Goldschmidt2013 Conference Abstracts 1661

Nanomineralogy of gemstones: From Granite compositions: Source vs. genesis to discovery process, revisited. An isotopic CHI MA* AND GEORGE R. ROSSMAN traverse across SE Australia Division of Geological and Planetary Sciences, California ROLAND MAAS1 AND IAN NICHOLLS2 Institute of Technology, Pasadena, CA 91125, USA. 1 School of Earth Sciences, University of Melbourne, Australia, *Email: [email protected] [email protected] 2 School of Geosciences, Monash University, Melbourne, Nanomineralogy is the study of Earth and planetary Australia materials at nanoscales, focused on characterizing nanofeatures (like inclusions, exsolution, zonation, coatings, Granite compositions are determined by source characteristics, pores) in minerals and rocks, and revealing nanominerals and by details of melting, melt extraction and transport through the nanoparticles [1]. With advanced high-resolution analytical crust, by magma mixing and assimilation at various scales and scanning electron microscope, we are now capable to depths, and by magma chamber processes. The importance of characterize solid materials easier and faster down to each factor is often difficult to ascertain. We examine this nanometer-scales. During our nanomineralogy investigation of issue using Sr-Nd-O isotope data for 430-370 Ma granites gemstones, nanofeatures are being discovered in many across the Paleozoic Lachlan Orogen (LO), SE Australia. commom gems, which cause color and other optical effects, S-types granites in the eastern LO show strong isotopic and provide clues to genesis. Presented here are a few colorful links with Lower Paleozoic low-! meta-turbidites which projects demonstrating how nanomineralogy works and plays Nd dominate the mid crust. Further west, geophysical data suggest a unique role in gemstone and geomaterial research. the presence of a greenstone-dominated, lower/mid-crustal Rose quartz contains nanofibers of a dumortierite-related Neoproterozoic block with a thickness of 25 km above Moho, phase that is pink, which is the true cause of rose color and the Selwyn Block. S-type granites in this area have higher !Nd, optical star effects [2,3]. Sub-micrometer inclusions of 18 87 86 " O and lower Sr/ Sr than those in the eastern LO, and ilmenite are the cause of color in blue quartz. links to the meta-turbidites – present above the block – are Why is obsidian black? Because most obsidians contain weak. In the far western LO where the mid crust comprises nanoinclusions of magnetite. ‘Fire’ obsidian, a variety of thick, imbricated Cambrian metabasalts overlain by meta- obsidian from Oregon, has thin layers showing varous colors. turbidites, S-types show the widest isotopic range (! -2 to - The layers, 300 to 700 nm thick, consist of concentrated Nd 9), consistent with links to both metabasalts and turbidites. nanocrystals of magnetite, giving rise to brilliant colors in I-type granites in the eastern LO show strong Sr-Nd isotope reflection due to thin-film interference [4]. Whereas ‘rainbow’ covariation; their large range in ! (+6 to -8) could reflect obsidian from Mexico contains oriented nanorods of Nd source rock heterogeneity (e.g. Cambrian greenstones hedenbergite, which cause the rainbow effects via thin-film underlying the meta-turbidites have a similar isotopic range), interference [5]. syn-magmatic mixing (crustal assimilation), or both. I-types in During a study of benitoite, the state gemstone of the western part of the orogen are isotopically diverse, with California, new mineral barioperovskite (BaTiO ) and two 3 distinct trends in Sr-Nd-O isotope plots in the various more new barium titanate minerals BaTi O and BaTi O were 2 5 3 7 structural zones, but links to known lower crustal features discovered to occur in a tubular inclusion within one benitoite appear to be weaker than for the S-types. crystal [6]. The data from this example suggest that heterogeneity in

source (isotopic) compositions is transferred to S-type [1] Ma (2008) Eos Trans. AGU, 89, abs MR12A-01. granite/volcanic compositions with little disturbance by post- [2] Goreva et al. (2001) American Mineralogist, 86, 466-472. melting processes, at least at an orogen-wide scale. I-type [3] Ma et al. (2002) American Mineralogist, 87, 269-276. petrogenesis appears to be more complex and probably [4] Ma et al. (2007) Canadian Mineralogist, 45, 551-557. involves mixing processes (mixed sources, syn-magmatic [5] Ma et al. (2001) Canadian Mineralogist, 39, 57-71. mixing). [6] Ma and Rossman (2008) American Mineralogist, 93, 154- 157.

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Temporal variations of atmospheric Application of clumped isotope helium isotopes thermometry to subsurface dolostone J.C. MABRY1*, T.F. LAN1, P. BURNARD1 AND B. MARTY1 samples 1CRPG-CNRS, 54501 Nancy, France (*correspondence: J. M. MACDONALD1*, C. M. JOHN1 AND J. P. GIRARD2 [email protected]) 1Carbonate Research, Dept. Earth Science and Engineering,

Imperial College London, SW7 2AZ (*correspondence: The isotopic composition of the atmosphere (3He/4He = [email protected]; 1.382±0.005 x 10-6) is distinctly different from crustal helium 3 4 -8 [email protected]) ( He/ He ~10 ). Several authors [e.g. 1, 2, 3] have proposed 2 TOTAL, CSTJF, Ave Larribau, 64018 Pau (jean- that the amount of excess crustal helium entering the [email protected]) atmosphere due to modern fossil fuel extraction may be

enough to upset the balance of the helium composition in the Platform carbonates are a major hydrocarbon reservoir atmosphere on a timescale short enough to detect with modern setting, and are often dolomitized. An important parameter in measurement techniques. Previous attempts failed to detect characterising these reservoirs is the palaeotemperature of the variations beyond the measurement precision [3, 4]. However, various carbonate phases during burial diagenesis. Clumped recent measurements by [5] from the Cape Grim Air Archive isotope analysis of CO from acid digestion of carbonate (CGAA) found a decrease of the atmospheric 3He/4He of 0.23- 2 phases may offer the best route to accurately and precisely 0.30‰ per year over the period 1978 to 2011. We will attempt determining this temperature. We apply the clumped isotope to replicate these results using a high-precision helium isotope palaeothermometer to natural dolostone samples from the measurement system we have devised. Northern Marion Platform (NMP, offshore NE Australia) and Air samples are collected in copper tubes which are sealed to dolostone samples from other subsurface locations. with steel clamps. Each sample is approximately 15-20 cm3 of Initially, five dolostone samples from the NMP collected air which is purified all at once and then measured in 11 between ~100-160 metres below sea floor (mbsf) were standard-bracketed aliquots. The amount of helium in each analysed. Petrographic analysis revealed that these samples sample aliquot is matched to the amount in an aliquot of the were all pervasively dolomitized: planar-s to planar-e dolomite standard to minimize pressure effects. Measurements are made forms 100% of the modal mineralogy. Initial clumped isotope on a Thermo Helix Split Flight Tube (SFT) multi-collector analysis (triplicate analyses; reaction at 90°C for 45mins; acid noble gas mass spectrometer. With this system we have a and non-linearity corrections applied; data transferred to long-term reproducibility of sample air of 0.05% (2!). universal reference frame [1]) yielded temperatures of 22 °C Our initial measurements of the 3He/4He in CGAA to 31 °C using the calibration of Ghosh et al. [2]. samples do not reproduce the results of [5]. They are As a second step, we analysed samples from subsurface consistant with no change in the helium composition over time wells where independent constraints using fluid inclusion with an upper limit (2!) of 0.16‰ per year decrease in thermometry exist. By testing clumped isotope thermometry 3He/4He. We will make further measurements of the CGAA on these well-constrained natural reservoir samples, we hope samples. to show that clumped isotope thermometry is an ideal Sample R /R (2!) # analyses air std technique to determine burial temperatures in carbonate CGAA 1978 1.0402 (0.0027) 3 reservoir rocks, as it overcomes some of the problems inherent CGAA 1979 1.0386 (0.0010) 7 in fluid inclusion and conventional "18O thermometry. CGAA 2008 1.0387 (0.0004) 4 CGAA 2011 1.0389 (0.0014) 4 [1] Dennis et al. (2011) Geochim. Cosochim, Acta 75, 7117–

7131. [2] Ghosh et al. (2006) Geochim. Cosochim, Acta 70, [1] Oliver et al. (1984) GCA 48, 1759-1767. [2] Pierson- 1439–1456. Wickman et al. (2001) EPSL 194, 165-175. [3] Sano et al. (2010) GCA 74, 4893-4901. [4] Lupton and Evans (2004) GRL 31, L13101. [5] Brennwald et al. (2013) EPSL 366, 27- 37.

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Hot CD-MUSIC Geochemical variations of basalts M. L. MACHESKY1*, D. J. WESOLOWSKI2, M. K. from petit-spot volcanoes in the RIDLEY3, M. P#EDOTA4, Z. ZHANG5, P. A. FENTER5 northwestern Pacific AND J. D. KUBICKI6 1, 2 3 2 4 1 S. MACHIDA *, N. HIRANO , Y. KATO , A. TAMURA Univ. of Illinois, Illinois State Water Survey, Champaign IL, AND S. ARAI4 USA, (*correspondence: [email protected] ) 2Oak Ridge National Laboratory, Oak Ridge, TN, USA 1 School Creative Sci. Engineer., Waseda Univ., Tokyo 169- ([email protected]) 8555, Japan (*correspondence: [email protected]) 3Texas Tech Univ., Dept. of Geosciences, Lubbock, TX, USA, 2 School of Engineer., Univ. of Tokyo, Japan ([email protected]) 3 Center NE Asian Studies, Tohoku Univ., Japan 4Univ. South Bohemia, !eské Bud"jovice, Czech Republic 4 Grad. School of Sci., Kanazawa Univ., Japan ([email protected]) 5Argonne National Laboratory, Argonne, IL 60439, USA Petit-spot, new type young volcanoes discovered on the ([email protected], [email protected]) old Pacific plate, originate from melting in the uppermost 6The Pennsylvania State Univ., University Park, PA 16802, mantle asthenosphere, and that the magma exudes where the USA, ([email protected]) plate flexes and fractures before subducting [1]. Our recent studies defined that alkaline basalt lavas from petit-spot show Among the many seminal contributions of Professor van (1) high concentrations of incompatible trace elements Riemsdijk is the CD-MUSIC model, which was developed in indicating extreme enrichment in highly incompatible collaboration with Professor Hiemstra, and has remained the elements (e.g., Rb, Ba, U, Th, and Nb) and REE, and depletion state-of-the-art Surface Complexation Model since its in heavy REE [1], and (2) extreme EM-1-like, Sr, Nd, and Pb publication in 1996[1]. Also in the mid-1990’s our group isotopic compositions [2]. These results indicate that melting began investigating ion adsorption phenomena (primarily of small-scale recycled plate material produces petit-spot cations) over a wide range of temperatures extending into the magma [2]. Thus, detailed geochemical investigation for these hydrothermal regime (10-250oC), mostly on rutile, but also on petit-spot volcanoes will provide key constraints on our several other metal oxides[2]. More recently, we have also understanding of the nature of heterogeneity of the complimented these macroscopic data with a variety of northwestern Pacific upper mantle. molecular-level information, including X-ray synchotron Basalts were collected from twelve petit-spot volcanoes at experiments, and static DFT as well as classical molecular a site in the Japan Trench (Site A), a site approximately 600 dynamics (MD) simulations. CD-MUSIC has proven to be a km ESE of the Site A (Site B), and a site approximately 200 sturdy framework within which we have been able to km S of the Site A (Site C). Five distinct compositional groups coherently interpret this assortment of data[3,4]. are identified on the basis of their major and trace element This contribution will summarize our efforts to rationalize compositions. The Group 1 basalts (G1), from the Sites A and adsorption data for rutile to 250oC within the CD-MUSIC C, are enriched in LILEs and LREEs. Then, they show model framework with particular focus on Sr2+ and Zn2+. Our negative U, Th, Nb, and Ta anomalies. The Group 2 basalts classical MD simulations suggest that the enhanced adsorption (G2) from the Site A show negative U, Th, Nb, Ta, Zr, and Hf observed macroscopically as temperature increases is due to anomalies, and higher alkali contents than G1. However, on adsorbed cations moving closer to the surface and shedding the basis of other major element characteristics, G2 are further more bulk hydration water in the process. CD-MUSIC can subdivided into three groups. G2-2 have lower SiO2 and mimic this behavior although the agreement is not perfect, higher FeO*/MgO than G2-1 (and G1). G2-3 show a similar suggesting extensions to CD-MUSIC may be warranted. major element signature to G2-2, except for lower CaO. The Group 3 basalts, obtained from Site B, show lower SiO2 and [1] Hiemstra & van Riemsdijk (1996) JCIS 179, 488-508. higher FeO*/MgO than G2-2, and negative Zr and Hf [2] Machesky et al. (2006) Interface Sci. Tech.11, 324-358. anomalies. Variation of Ba/Nb of basalts from all groups [3] Ridley et al. (2009) GCA 73, 1841-1856. correlates to Sr and Nd isotopic compositions. These [4] Ridely et al. (2012) GCA 95, 227-240. observations suggest that the source heterogeneity for petit- spot magma is regulated by degree of contributions of LILEs and LREEs-enriched material.

[1] N. Hirano et al. (2006) Science, 313, 1426-1428. [2] S. Machida et al. (2009) GCA, 73, 3028-3037.

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Using noble gases for real-time Co-evolution of the ocean- tracing of oxygen turnover in aquatic atmosphere-sediment system through systems Phanerozoic time LARS MÄCHLER1, MATTHIAS S. BRENNWALD FRED T. MACKENZIE*1 ROLF ARVIDSON2 AND ROLF KIPFER12 AND MICHAEL W. S. GUIDRY1 1Eawag, Dep. of Water Resources and Drinking Water, Swiss 1University of Hawaii, Dept. of Oceanography, Honolulu, HI, Federal Institute of Aquatic Science and Technology, USA *correspondance: [email protected], Switzerland [email protected] 2Institute for Geochemistry and Petrology, Swiss Federal 2Universitat Bremen, MARUM/Fachbereich Institute of Technology Zurich, Switzerland Geowissenschaften (FB5), Bremen, Germany [email protected] Our recent experimental developments on membrane inlet mass spectrometric systems allow the quasi-con-tinuous Attempts to unravel the history of seawater chemistry go measurements of dissolved gas concentrations in natural back as far as E. Halley [1] and J. Joly [2] and more recently

waters under field conditions. Dissolved He, Ar, Kr, N2, O2, W. W. Rubey [3] and H. D. Holland [4] among others. We

and CO2 concentrations can be quanti-fied within minutes with have shown previously [5] that seawater chemical changes on high precision [±1%, 1]. the multi-million year time scale through Phanerozoic time The method was employed in a peri-alpine river to analyze reflect the essential state of the ocean-atmosphere-sediment the temporal and spatial dynamics of oxygen turnover during system with respect to major lithophile and organic bank infiltration. component fluxes constrained by a number of observations During low river discharge, the measurements indicated from the sedimentary rock record. that aeration of groundwater is dominated by direct hyporheic Despite relatively rapidly changing periods like the end exchange, and that the transport of solutes and heat are Permian and PETM episodes, the system appears homeostatic

decoupled. The combined Ar-O2 analysis allowed the in-situ and self-regulating and produces two dominant chemostatic oxygen consumption rate and it’s dependence on the water modes despite apparent time lags among various variables that temperature to be to deter-mined. During high river discharge suggest different biogeochemical pathways leading to the

after a flood event, we found that significant amounts of modes: (Mode I) elevated atmospheric CO2 and depressed

excess air were produced in the vicinity of the studied seawater Mg⁄Ca and SO4⁄Ca ratios, pH and carbonate groundwater wells. The formation of excess air and the saturation states (the calcite-dolomite seas) versus (Mode II)

correspond-ing oxygen input into the groundwater varied depressed atmospheric CO2 and elevated seawater Mg⁄Ca and

according to the confining conditions within the aquifer and SO4/Ca ratios, pH and carbonate saturation states (the there-fore also co-varied with different ecological process aragonite seas). Transitions between the two modes are S. zones. modified and overprinted by irreversible evolutionary and Our results show that the combined analysis of noble and ecosystem changes. One example involves the shift of the biogeochemically active gases yields valuable in-formation on locus of biogenic carbonate sediment deposition through the dynamics and the importance of dif-ferent gas exchange radiation of pelagic calcifiers and the expansion of dolomite mechanisms in aquatic systems with respect to deposition enabling development of Mode I seawater biogeochemical oxygen turnover and thus groundwater quality chemistry in the Mesozoic. In addition, Paleozoic deep seas might have been sites of inorganic carbonate accumulation [1] Mächler et al. ES&T, 46, 7927-8522, 2012. “lost” via subduction. Without this accumulation it is difficult

to account for high atmospheric CO2 concentrations and Mode I seawater chemistry during much of Paleozoic time.

[1] Halley (1715) Phil. Trans.29, 296-300. [2] Joly (1899) Sci. Trans. Royal Dublin Soc.7, 23-66. [3] Rubey (1951) Geol. Soc. Am. Bull.62, 1111-1148. [4] Holland (1972) Geochim Cosmochim. Acta36, 637-651. [5] Arvidson et al. (2006) Am. J. of Sci.306, 135-190. Guidry et al. (2007) In: Evolution of Primary Producers in the Sea, 377-403. Mackenzie et al. (2008) Mineral. Mag.72, 329-332. Arvidson et al. (2011) Aquat. Geochim.17, 735-747.

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Alunite-Turquoise occurrence from Metal precipitation mechanisms in, Ali-Abad porphyry copper deposit, “low sulfide,” magmatic Cu-Ni-PGE Central Iran mineralization at Sudbury, Canada: M. A. MACKIZADEH1*, B. TAGHIPOUR2 AND L. GORGI1 First constraints on oxygen fugacity 1Department of Geology, Isfahan University, Isfahan, Iran MATTHEW A. MACMILLAN1, JACOB J. HANLEY2 ([email protected]) AND DOREEN E. AMES3 2 Department of Earth Sciences, Shiraz University, Shiraz, Iran 1 Saint Mary’s University, Halifax, NS, B3H 3C3 ([email protected]) (*correspondence: [email protected]) 2 Saint Mary’s University ([email protected]) The Ali-Abad porphyry copper deposit is situated in 3 Geological Survey of Canada ([email protected]) Central Iranian volcano-plutonic arc belt. The oldest rocks in the area are conglomerate and sandstones of Sangestan The Sudbury Igneous Complex (SIC), Ontario, Canada, is formation (late Cretaceous). They have been intruded by a large (~60km x 30km), elliptical mass of layered igneous Oligocene to Miocene porphyrtic granitodis. rock situated along the contact between the Superior & The widespread hydrothermal alteration has been taken Southern provinces of the Canadian Shield. The SIC is widely place in conglomerate and sandstones including: Quartz- accepted to have been produced by melting of lower crust and sercite, argillic, advanced argillic, silicification and skarn upper crustal veneer due to meteorite impact at ~1850 Ma [1], formation. The following mineral assemblage has been and is remarkably associated with world-class Cu, Ni & PGE detected: mineral deposits. Along the North Range of the SIC, Alunite+ turquoise + pyrite+ sercite+ garnet+ quartz+ “footwall-type,” deposits are subdivided into sharp-walled goethite + epidote+ calcite+ jarosite vein and low sulfide PGE rich Cu-Ni-PGE mineralization. According to field and mineralogical investigations the Low sulfide mineralization occurs as $decimetre-scale close associate of alunite-turquoise is well established in blebs, disseminations & stringers of sulfide minerals that alteration zones. Probably, the turquoise is formed in charge of generally comprise <3% of any sample and are mined due to alunite or other Al-rich mineral phase during latest stage of their anomalously high concentrations of precious metals alteration process. It seems that oxidation of sulphide minerals compared to other deposit styles at Sudbury. Sulfides in these (supergene environment) its responsible for generation of all samples are intergrown with each other, and consist of bornite, chemical reactions necessary for alunite-turquoise formation. chalcopyrite & millerite, and, as a result of their textural

equilibrium with a variety of hydrothermal phases (Qtz, Cal, [1]Taghipour, B., Moore, F., Mackizadeh, M. A., and Ep, Chl, Ttn, Grt), are inferred to have precipitated from a Taghipour, S (2013) Hydrothermal garnet in porphyry copper hydrothermal fluid. related skarn deposits, Ali-Abad, Yazd Province, Iran, Iranian Hydrothermal garnets, which are rare in the footwall J. Scie. Tech. accepted paper. systems, were separated from a sulfide-bearing Qtz-Cal-Ep

vein (also containing a CuO phase – tenorite) within the deep 153 ore body at the Coleman Mine and allow constraints to be placed on the formation conditions of low sulfide mineralization in this area of the SIC footwall. Garnets have been studied using include fluid inclusion methods, LA- ICPMS mapping, Lu-Hf/Sm-Nd isotopes and EMP (epidote- garnet equilibria oxythermobarometer) [2]. The results address the chemistry of fluids from which low sulfide mineralization

formed, and will constrain P, T & fO2 – conditions that have not been reported for low sulfide-style mineralization within the SIC footwall.

[1] Krogh et al. (1984), The Geology and Ore Deposits of the Sudbury Structure: Ontario Geological Survey, 431-447. [2] Donohue & Essene (2000), Earth and Planetary Science Letters 181, 459-472.

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Arc lithosphere imposes segmented, Micro-Chronology of the Earliest great circle volcano distribution in Solar System: Challenges for the the central Sunda Arc, Indonesia Future COLIN G MACPHERSON1, ADAM PACEY1,2 GLENN J. MACPHERSON* AND KEN JW MCCAFFREY1 *Dept. Of Mineral Sciences, Smithsonian Institution, 1Department of Earth Sciences, Durham University, Durham, Washington, D.C. USA 20560 UK, DH3 1LE. [email protected] (correspondence: [email protected]) 2 Department of Earth Science & Engineering, Imperial College London, South Kensington, London SW7 2AZ, During the first ~1-2 Ma of our Solar System’s history, as UK the Sun evolved from a Class 0 to a Class II protostar, solid matter in the innermost disk was heated, evaporated and The term island arc betrays the common assumption that recondensed, and extensively reprocessed (including melting). subduction zone magmatism occurs in curved zones, which Such solids are preserved in chondrites as calcium-aluminum- can be expressed by approximating arcs as segments of small rich inclusions (CAIs) and amoeboid olivine aggregates circles on a spherical surface. Such observations are used to (AOAs). Evidence for the original evaporation and relate arc volcano locations to their vertical separation from condensation is preserved mainly in the form of characteristic seismicity in the subducted slab and to conclude that the chemical and isotopic signatures, but rarely in the physical primary control on loci of magmatism lies in the slab or properties (e.g. textures) of the objects. In contrast, evidence mantle wedge. for repeated melting and re-heating is everywhere in the The small circle approximation ignores longstanding, petrology of most CAIs and AOAs. Advances in the analytical empirical observations that magmatic centres in many precision of mass spectrometry (MS), especially secondary subduction systems describe linear features i.e. segments of ionization (SIMS), thermal ionization (TIMS), and great circles. The Sunda Arc, Indonesia, is one system that has inductively-coupled plasma (ICP-MS), now permit proved difficult to accommodate in small circle models. We extraordinary time resolution of early solar system events that applied an objective line-fitting protocol; Hough Transform are recorded in the petrologic properties of CAIs and AOAs. image analysis, to explore the distribution of central Sunda Pb-Pb ages of CAIs yield a precision of < 500 Ka. ICP-MS Arc volcanoes. This shows that volcano distribution in the measurements of the 26Mg-26Al isotope system demonstrate central Sunda Arc is best described as en echelon, great circle that the primary fractionation (presumably via condensation) segments each of 500 – 750km length, rather than as small of Al from Mg took place within 20 Ka. SIMS determinations circles. of internal 26Mg-26Al extinct isochrons confirm that CAI Central Sunda Arc segmentation reflects weakness of the precursors formed within a very short time consistent with that arc lithosphere resulting from tectonic forces generated close determined by ICP-MS, but remelting and reprocessing of to the plate margin and/or by arc lithosphere flexure. To the CAIs continued for at least 200 Ka and possibly as long as 600 east of our study area the arc has collided with Australian Ka. The time resolution of such SIMS internal isochrons is continental crust while highly oblique convergence to the west now bettter than 50 Ka. The challenge now is to identify the has produced the Great Sumatran Fault. In both cases volcano nature of the processes that are recorded in this chronology. locations can be related to stress imposed upon the arc For example, the original fractionation event that made the lithosphere by these specific features. Furthermore, changing CAI precursors apparently was singular and of short duration locations, petrography and geochemistry of central Sunda whereas remelting occurred as a result of a process that magmatism since the late-Pliocene can also be attributed to happened repeatedly over 200 Ka or more. Nor is it clear if the evolving stress in the upper plate. formation of Wark-Lovering rims was a singular event We conclude that the arc lithosphere stress field is the affecting all CAIs simultaneously or a repeating event over primary control on distribution of Sunda Arc volcanoes. time. Finally, there is as yet no anchor that ties Solar Interplay between this stress field and the arc crust will chronology with CAI chronology. One recent suggestion is provide a major control upon pathways of magma from the that the last (or nearly so) FU-Orionis flare in the early Sun mantle wedge to the surface. was responsible for making the generation of CAIs we now see, but earlier generations were destroyed. Such linking of solar processes and chronology with nebular products is a major challenge for the future.

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Soluble Manganese(III) and a revised Study of droplet activation in thin Sedimentary Redox Cycle broken clouds A. S. MADISON1,#, A. MUCCI2, B. SUNDBY2, B. M. TEBO3 F. MADONNA1, M. ROSOLDI1 AND G. PAPPALARDO1 1, AND G. W. LUTHER * 1 Consiglio Nazionale delle Ricerche - Istituto di Metodologie 1 School of Marine Science and Policy, College of Earth, per l’Analisi Ambientale, Tito Scalo, Potenza, I-85010, Ocean and Environment, University of Delaware, Lewes, Italy DE 19958, USA (*correspondence: [email protected]); [email protected] #present address Golder Associates Inc., 200 Century Parkway, Mt. Laurel, NJ, USA 08054 The impact on climate of thin clouds is one of the most ([email protected]) uncertain. Their importance is related to their global mean 2 Department of Earth and Planetary Sciences, McGill cloud fractional coverage [1]. Moreover, they provide University, Montreal, QC, Canada H3A 2A7 significant information about the mechanisms leading to ([email protected]; [email protected]) clouds formation. Thin clouds are difficult to observe 3 Division of Environmental and Biomolecular Systems, accurately and large discrepancies exist among different Oregon Health and Science University, Beaverton, OR observation techniques [2]. A study to assess the behaviour of 97006, USA ([email protected]) macrophysical and microphysical properties of thin clouds is proposed. The study takes advantage of multi-wavelenght Recent field studies have confirmed the presence of lidar and microwave radiometer measurements performed at soluble manganese(III) or [Mn(III)]aq, which along with CIAO (CNR-IMAA Atmospheric Observatory), in Potenza, Mn(II) passes through a 0.2 µm filter, in natural waters of the Italy. Particular attention has been paid to optically thin Black Sea, the Baltic Sea and Chesapeake Bay. This species broken stratocumulus where it is possible to investigate the can account for a large fraction (up to 100%) of the dissolved fast change between non-saturation and saturation conditions Mn pool at the oxic/anoxic interface. We have applied a in an aerosol layer and the droplet activation. spectrophotometric method to determine the concentration and speciation of Mn in sediment porewaters of the St. Lawrence Estuary collected during cruises in 2009 and 2010. In all samples, [Mn(III)]aq accounts for up to 80% of the total dissolved Mn pool in the vicinity of the oxic-suboxic boundary, with concentrations ranging from the detection limit of 50 nM to 80 µM. We use flux calculations and a diagenetic model to explore the interaction of Mn(III) with other element cycles. Data collected along the Laurentian Trough of the St. Lawrence Estuary demonstrate that the reduction-oxidation capacity of the soluble Mn pool has been underestimated since Mn(III) can act as either an electron acceptor or an electron donor during interactions with the C, N, S, O and Fe cycles. In In the plot, it is reported the profiles of aerosol exctinction these (hemi)pelagic sediments, our data suggest that a coefficient integrated over 2 hours obtained including (black) significant fraction of the porewater Mn(III) is produced or excluding (red) clouds. The plot shows the seperation

through the oxidation of Mn(II) by O2. Soluble Mn(III) between the region where droplets are activated from that

intermediates are also produced during dissimilatory MnO2 where aerosol particles seems to be not affected by nucleation reduction upon organic matter mineralization and abiotic processes. The results of the mentioned study over two years

reduction of MnO2 by reductants such as Fe(II), FeS and H2S. of data, including aerosol, water vapour and liquid water Finally, our results reveal that soluble Mn(III) is likely measurements, will be presented. ubiquitous in porewaters, and, as such, is a key redox species in the global sedimentary cycles of carbon, oxygen, iron and [1] Rossow, W. B., and R. A. Schiffer (1999) ISCCP. Bull. sulfur. Amer. Meteor. Soc., 80, 2261–2287. [2] Turner, D. D., and Coauthors (2007), Bull. Amer. Meteor. Soc., 88, 177–190.

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Geochemical and mineralogical Lithium isotope evidence for characteristic of current roadside pervasive metasomatism of sub- pollution from experimental continental lithospheric mantle monitoring plots located in different T. MAGNA1, L. ACKERMAN1,2 AND P. )PA*EK3 countries 1Czech Geological Survey, Klárov 3, CZ-11821 Prague, Czech 1 2 Republic; [email protected] TADEUSZ MAGIERA , MARIOLA JAB%O&SKA , MARZENA 2 1 1 Inst. Geology, Academy of Sciences CR, Rozvojová 269, CZ- RACHWA% AND MA%GORZATA WAWER 16500 Prague, Czech Republic 1Institute of Environmental Engineering, Polish Academy of 3Inst. Geophysics, Academy of Sciences CR, Bo+ní II, CZ- Sciences, 34 M. Sk'odowskiej-Curie Str., 41-819 Zabrze, 14134 Prague, Czech Republic Poland (*correspondence: [email protected]) We present Li contents and isotope compositions in a suite 2 The Faculty of Earth Sciences, University of Silesia, 60 of spinel peridotite/harzburgite xenoliths, enclosed in Tertiary B#dzi$ska Str., 41-200 Sosnowiec, Poland alkaline lavas from three volcanic centres in the western part ([email protected]) of the Eger rift, Bohemian Massif, belonging to the European Cenozoic Rift System. Secondary features were observed in The aim of the study was characterisation of current subset of xenoliths implying metasomatism by alkali-rich particulate pollutants emitted by traffic sources and deposited melts with carbonate affinity [1]. Whole-rock xenoliths show on roadside topsoil. For this purpose 7 cm of topsoil were no to slight Li enrichment (1.4–5.8 ppm) coupled with removed and replaced by 30 plastic boxes filled with pure extreme 7Li depletion in some samples ("7Li from –9.7 to quartz matrix. Such experimental monitoring plots were 2.5‰), attesting to dramatic departure from "7Li of pristine installed in Poland, Germany, Finland, Tadjikistan, Greece mantle ("7Li=3–4‰). More complex co-variations are and China close to arteries with high traffic volume. observed for bulk "7Li and modal olivine, clinopyroxene and Geochemical analyses of some heavy metals (HM) were orthopyroxene for the three volcanic centres. "7Li values do conducted by AAS (Fe, Mn, Zn, Pb, Cu) and ICP (Cd, Co, Mo not correlate with parameters of magmatic fractionation and/or and W) after extraction in aqua regia. Additionaly SEM and fluid activity and are thus regarded as independent parameter X-ray diffraction analyses were conducted in soil layer of secondary metasomatism. However, carbonate-rich removed from monitoring place and in sand matrix after 1 and metasomatism does not impart specific Li signature to 2 years of exposition. xenoliths that carry distinctive Nb–Ti enrichments in melt Chemical analyses of removed topsoils have shown that pockets [2]. On the contrary, relics of oceanic crust preserved the highest contents of Fe, Mn, Zn, Pb, Cu were noted in as eclogites are ubiquitous in the wider area which may carry Poland and Germany, but the highest amount of W was strongly negative "7Li values [3]. Their melts can metasoma- detected in Finland. After 1 and 2 years of exposure a big tize the sub-continental mantle and erase its intrinsic Li sig- changes in HM content in quartz sand were observed. nature [4]. Therefore, we propose a scenario whereby xeno- Contents of Fe, Mn, Zn and Pb in most monitoring plots were liths from the sub-continental mantle beneath central Europe even three times higher after 2 years than after 1 year of were invaded by eclogitic melts formed at lower temperatures exposure. There was significant increase of W in sand matrix that carry distinctively light Li isotope compositions from after 2 years’ exposure in samples from Finland. earlier subduction of Saxothuringian lithosphere, operating in Mineralogical analyses revealed different iron forms: the area during the Devonian/Carboniferous although timing metallic iron ((-Fe), Fe oxides (mostly magnetite and of the metasomatic imprint remains uncertain. Host alkaline hematite), Fe-Zn and Fe-Cu oxides (ferrites) and other mineral basalts always have higher "7Li than the xenoliths, as also components as: barite, aluminosilicates glassy phases and reported for xenoliths with mantle "7Li signature [5], implying different kinds of spinels. In matrix from Finland plot tungsten uniform relationship of basalt–xenolith systems in continental carbide particles were also commonly observed. settings.

[1] )pa+ek et al. (2013) J Petrol, in press; [2] Ackerman et al. (2013) J Petrol, under review; [3] Magna et al. (2004) IJMS 239, 67-76; [4] Tang et al. (2012) Lithos 149, 79-90; [5] Magna et al. (2008) EPSL 276, 214-222

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Arsenic methylation in the bedrock Structure, dynamics, and aquifer of the Willamette Basin, spectroscopy of metalloproteins from Oregon, USA methanogenic and SCOTT C. MAGUFFIN1 AND QUSHENG JIN1 hydrocarbonoclastic microbes 11272 University of Oregon Eugene, OR, USA JOHN S. MAGYAR1*, WEI TING CHEN1, CHRISTINA L. CLEVELAND1, PAUL B. HARVILLA1 Groundwater arsenic contamination is a significant threat AND VICTORIA F. OSWALD1 to human health in many regions of the world. In aquifers, 1 Barnard College, Columbia University, New York, NY arsenic typically exists as arsenate or arsenite. Methylated 10027, USA arsenic, such as monomethylarsonate (MMA), (*correspondence: [email protected]) dimethylarsinate (DMA), and trimethyarsenate, are less abundant and often overlooked as potentially significant The increasing scarcity of conventional, easily accessible species of arsenic. Identifying biogeochemical processes that petroleum sources leads to an increasing dependence on hard control arsenic speciation is critical for developing to reach petroleum in deep, cold offshore waters. These remediation strategies and for predicting the mobility of extraction processes lead to significant environmental arsenic in groundwater. challenges, including unprecedented spills in deep water. We analysed arsenic speciation in the bedrock aquifer of Here, we report progress toward an understanding of the Willamette Basin, Oregon, USA. Our results show that molecular adaptations for life at low temperatures, based on arsenite is the main species, with concentrations up to several our study of cytochrome c from Colwellia psychrerythraea, a parts per million (ppm); DMA is the main methylated species, psychrophilic, hydrocarbonoclastic marine bacterium with concentrations up to 20 ppb. Significantly, the responsible for a large portion of the early bioremediation of concentrations of DMA correlate linearly with those of the 2010 Deepwater Horizon oil spill in the Gulf of Mexico. arsenite. Based on these observations, we hypothesize that in Although surface oil spill bioremediation is well-established, the aquifer 1) methylated arsenic species are produced from the biogeochemistry of deep marine oil spills is not yet well inorganic arsenic by prokaryotic methylation; and 2) understood. An understanding of psychrophilic metalloprotein prokaryotic methylation can be a significant process in the dynamics and thermodynamics is essential to a full cycling of arsenic. understanding of biogeochemical cycling in these To test our hypotheses, we incubated aquifer sediments in environments. reactors and monitored arsenic speciation over time. We also Further insights into microbial metal uptake processes are included sterlized sediments as a biological control. We gained from our parallel studies of a putative observed the accumulation of MMA and DMA in all but the metalloregulatory protein from the methanogenic archaeon sterilized control. To determine the in situ rate of arsenic Methanocorpusculum labreanum. We suggest that this protein methylation, we conducted a push-pull test in the bedrock is involved in regulation of nickel uptake, which is essential aquifer. Based on the field observations, we calculated that for methanogenesis. In addition, we have determined that this DMA accumulated at a rate of 1 to 3 ppb per day. Because protein is an iron-sulfur cluster-binding flavoprotein, DMA is produced and consumed simultaenously, this value suggesting a role in electron transfer processes as well. represents the minimum rate of DMA production in the For both Colwellia and Methanocorpusculum, we have aquifer. used genomic information to identify specific proteins of Our results demonstrate that DMA is produced in situ at a interest. The genes are either synthesized chemically or significant rate by indigenous aquifer prokaryotes. The results amplified from genomic DNA by PCR and cloned into E. coli. suggest that arsenic methylation is an important factor in The proteins have been overexpressed and purified, and we evaluating the occurence and mobility of arsenic in are currently characterizing them by a wide variety of groundwater. Because of the volatility of many methylated spectroscopic and other techniques, including UV-vis arsenic species, arsenic methylation may also constitute a absorption, circular dichroism, fluorescence, atomic significant pathway in the global cycling of arsenic. absorption and NMR spectroscopies; X-ray crystallography; differential scanning calorimetry; electrochemistry; and analytical HPLC.

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Isotopologue effects in the generation Coupling fluid residence times, and consumption of nitrous oxide erosion rates and weathering fluxes to PAUL M. MAGYAR1*, SEBASTIAN KOPF1, evaluate the operation of a hydrologic VICTORIA J. ORPHAN1 AND JOHN M. EILER1 thermostat 1California Institute of Technology, Pasadena, CA 91125, K. MAHER1* AND C.P. CHAMBERLAIN2 USA (*correspondence: [email protected]) 1Department of Geological and Enviornmental Sciences, Nitrous oxide in air and natural waters is produced and Stanford University, Stanford, CA, 94305, consumed by chemical and biochemical reactions that [email protected] fractionate isotopes by a variety of equilibrium and kinetic 2Department of Environmental Earth System Science, mechanisms. Previous measurements of "15N, "17O, "18O, and Stanford University, Stanford, CA 94305, position-specific 15N incorporation (‘site preference’) have [email protected] identified characteristic fractionations for many of these processes. In particular, site preference measurements have The Earth’s thermostat is thought to be a negative

successfully distinguished between N2O produced by bacterial feedback between atmospheric CO2 levels and chemical nitrification and denitrification. But there remain too few weathering of silicate rocks that keeps temperatures relatively constraints to fully characterize the sources and sinks of pools moderate over geologic time scales. To evaluate the operation

of N2O in complex natural settings, and no existing isotopic of this thermostat, we relate the weathering flux per area of tools distinguish among some biological sources, e.g., archaeal continent to the cooperation between runoff and tectonic and bacterial nitrification. It is possible additional progress processes. The two are linked here by the balance between the could be made by adding new constraints from the study of the time that water spends in the weathering zone (which depends

multiply substituted isotopologues of N2O [1]. on runoff, hydraulic conductivity and the length of the flow We use high resolution multi-collector gas source mass path) and the kinetics of mineral weathering (which depend on spectrometry to measure the relative proportions of six singly composition, temperature and erosion rate). We use two types and doubly substituted isotopologues of nitrous oxide, of equations: (1) a reactive transport equation that quantifies including 14N15N16O, 15N14N16O, 14N15N18O, 15N14N18O, weathering-derived solute as a function the fluid residence 14 17 14 18 N2 O, and N2 O [2]. Each of these species has unique time; and (2) an equation that relates erosion to the abundance chemical and physical properties that potentially lead to of fresh minerals in the soil. We calculate the weathering- distinctive isotope fractionations. Here, we describe the derived solute concentration (C) as a function of the

measurement of N2O produced by diffusion through a pinhole, Damköhler number (Da), which is modified to account for the which produces an isotope effect dependent only on molecular effect of erosion on the supply of fresh minerals. This mass. This tests our ability to accurately determine the 6- approach requires that as fluid residence time becomes shorter dimensional isotopic ‘fingerprint’ of a given fractionation. For than the equilibrium time, solute concentrations decrease and the mass 47 species, 14N15N18O and 15N14N18O, our measured solute fluxes plateau. This relationship is observed in modern result are within 0.1‰ of the expected value. In addition, we rivers draining tectonically inactive areas wheres solute fluxes

have analyzed N2O produced by pure cultures of a denitrifying are smaller and Damköhler numbers lower, because reduced

bacterium that lacks a N2O reductase enzyme. It has a site supply of fresh lengthens the equilibrium time. In contrast, in preference consistent with the expectation for denitrifiers [3]. active mountain ranges, high relief and rapid supply of fresh Measurements of site preference and of multiply-substituted minerals result in long fluid residence times and short isotopologues are both consistent with a kinetic isotope effect equilibration times such that solute concentrations and fluxes produced at the catalytic center of the nitric oxide reductase are high. This approach allows weathering rates to increase enzyme and distinct from the predicted equilibrium asymmetrically between tectonically active and inactive areas fractionation [4]. in response to changes in climate, to create a bimodal hydrologic thermostat. However, to fully evaluate this model [1] Kaiser et al. (2003) Geophys. Res. Lett 30, 1046, for weathering fluxes requires improved understanding of the doi:10.1029/2002GL016253. [2] Eiler et al. (2013) Int. J. reactive flow paths in large catchments and how they are Mass Spectrom. 335, 45-56. [3] Ostrom et al. (2007) J. moderated by physical/chemical erosion, the underlying Geophys. Res. 112, G02005, doi:10.1029/2006JG000287. [4] causes for variations in concentration-discharge relationships Wang et al. (2004) Geochim. Cosmochim. Acta 68, 4779- and the biogeochemical factors that influence the equilibrium 4797. time.

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Iron speciation and aging in organic- Microbial communities colonising rich aquatic systems bedrock outcrops in a Swedish forest P. MAHESHWARI1,2, Y. WANG2 AND T.D. WAITE2* S MAHMOOD*, A EKBLAD, D BYLUND AND RD FINLAY 1Civil Engineering, Indian Institute of Technology Uppsala BioCenter, Department of Forest Mycology and Plant Gandhinagar, Ahmedabad 382424, India Pathology, Swedish University of Agricultural Sciences, 2Water Research Centre, School of Civil & Environmental Box 7026, SE-750 07, Uppsala, SWEDEN Engineering, University of New South Wales, Sydney (*correspondence [email protected]) 2052, Australia (*correspondence: [email protected]) We are using mor-layer covered bedrock outcrops as a Iron is ubiquitous in natural environments and used widely model system to study patterns of microbial colonisation of in engineered treatment systems as a coagulant or adsorbent. rocks and biogeochemical processes that lead to mobilisation These systems typically contain dissolved organic matter of mineral nutrients essential for plant growth and ecosystem which may influence both speciation and time- dependent function. The nutrients released from the bedrock are utilised transformation of iron species present. In an attempt to by the microbial community, taken up directly by roots or understand the speciation and transformation of iron in transported to roots via mycelia of ectomycorrhizal fungi that organic-rich systems, a ferric salt was added in a controlled form symbiotic associations with tree roots. We are testing the way to supernatant from a bench-scale membrane bioreactor following hypotheses: (1) Microbial communities that have high in soluble microbial products (SMP) and the system the ability to weather minerals or capture mobilised nutrients allowed to age and the reductive reactivity of Fe examined. In will increase in relative abundance or activity on the rocks particular, for each aging time, ascorbate was added to these compared to the overlying organic mor-layer. (2) samples in varying concentrations. The formation of Fe(II) Ectomycorrhizal fungal communities make a major upon reduction of Fe(III) species by ascorbate was measured contribution to the biological weathering of minerals/bedrocks using ferrozine colorimetry [1]. in forest ecosystems. Bedrock outcrops colonised by Following Wang and Waite [2], we assumed the Fe(III) to ectomycorrhizal fungal mycelia/tree roots should therefore be present as either weakly bound Fe(III)SMP, strongly bound have a relatively higher concentration of organic acids than the Fe(III)SMP and AFO. The relative distribution of iron into rocks colonised by mosses or apparently bare rocks. (3) Since these forms and their rate constant for ascorbate reduction are the organic sources of C tend to have a very low "13C, we shown in Figure 1. It was observed that despite AFO being the expect that the rock surfaces that exhibit varying degrees of most stable form, dissolved Fe(III) mainly exists as strongly biological weathering would also reflect differences in their bound SMP complexes with weakly bound Fe(III)SMP "13C signatures depending on the level of biological activity turning negligible after extended aging. (deposition of C in the form of organic acids/microbial biomass, root exudates and solubilised organic matter etc). To test hypothesis 1, we are analysing fungal and bacterial communities colonising rocks using 454- pyrosequencing. To test hypothesis 2, the rock surface minerals are being used for analysis of organic acids using LC-MS/MS. To test hypothesis 3, the rock surface minerals are being used for analysis of "13C using IRMS.

Figure 1: Relative composition of Fe(III) species and their corresponding ascorbate reduction rate constants.

[1] Viollier et al. (2000) Appl. Geochem. 15, 785-790. [2] Wang & Waite (2010) Water Research 44, 3511-3521.

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Effect of N on microbially mediated Contemporaneous crustal records in weathering of primary minerals the eastern and western Dharwar S. MAHMOOD1, C. MARTINS1, M OLOFSSON2, craton: Evidence from U- Pb and D. BYLUND2 AND RD. FINLAY1* Lu - Hf isotope sytematics 1 Uppsala BioCenter, Dept Forest Mycology & Pathology, 1 2 3 B. MAIBAM *, A. GERDES AND J.N. GOSWAMI Swedish University of Agricultural Sciences, Box 7026, 1 Uppsala SE-750 07, Sweden. (*[email protected]) Department of Earth Sciences, Manipur University, Imphal, 2 Dept Natural Sciences, Technology & Mathematics, Mid India, e-mail: [email protected] (*Presenting author) 2 Sweden University, SE-85170 Sundsvall, Sweden. Institute of Geosciences, Goethe-University Frankfurt, Germany, e-mail: [email protected] 3 The aim of this study was to determine whether N addition Physical Research Laboratory, Ahmedabad, India, e-mail: affects: (a) composition of microbial communities in forest [email protected] soil responsible for mobilization of nutrients from primary minerals, (b) kinetics of organic acid production, (c) rate of Combined U - Pb and Lu - Hf isotope systematics of nutrient release from primary minerals and uptake by plants, detrital (metasedimentary) and magmatic (orthogneissic) and (d) C allocation patterns in the rhizosphere. We used zircon grains from the eastern and western Dharwar craton provide new insight on the tectonomagmatic evolution of this microcosms with pine seedlings growing in mor layer soil ancient crust in the Indian shield. This data set establish the from granite outcrops in a mixed pine-spruce-birch forest. antiquity and nature of the source magma (juvenile or Fungal mats often observed at the mor layer-rock interface recycled) sampled by the analyzed zircon grains and provide a harbor microbial communities that mobilize mineral nutrients better understanding of the Archean curstal evolution in the from granite rocks and/or capture and transport the mobilized Indian shield. For this study we have selected five samples nutrients to tree roots via mycelial networks of (three from the western and two from the eastern block) ectomycorrhizal fungi. The growth substrate was amended thatyielded reasonable number of zircon grains. with quartz, apatite, biotite or no minerals and two U - Pb ages for detrital zircon grains suggest presence of concentrations of a slow release N fertilizer in factorial $3.4 Ga crustal components in both the western block and the combinations. Microcosms were sampled destructively after 0, eastern block of the Dharwar craton. Zircon from magmatic 6, 12 & 60 weeks. Bacterial and fungal communities were rocks of the western block yielded ages ranging between 3.1 - analysed by DGGE & 454 pyrosequencing and soil solutions 3.2 Ga, while those from the eastern block show a bi-model sampled to study kinetics of organic acid production (LC-MS) distribution with records of older components (3.0 - 3.2 Ga) and for elemental analysis (ICP-AES) to determine weathering and presence of younger events (overgrowth at 2.7 and 2.5 rates. C allocation patterns were studied using 13C-RNA based Ga). Magmatic and detrital zircon grains of western Dharwar stable isotope probing (SIP) of rhizosphere microbial block exhibit !Hf(t) of +1 to +5 and Hf model ages of 3.25 - communities. After 12 weeks there were only small changes in 3.45 Ga suggesting formation of juvenile crust during this rhizosphere bacterial communities in response to N epoch. A predominant phase of crustal reworking during 2.85 - 3.1 Ga could be inferred from the subchondritic !Hf values (- application and/or mineral amendments but fungal community 5 to -0.9) for detrital zircon grains. structure exhibited larger changes. N had a negative effect on The age data for majority of the detrital and few magmatic mobilization of nutrients from these minerals into the soil zircon grains from the eastern Dharwar craton suggest solution, and also reduced plant nutrient uptake. Seedlings in formation of juvenile crust (!Hf of +1 to +4) during 3.2 to 3.6 apatite-amended substrates had higher biomass compared to Ga. A crustal reworking phase during 2.5 to 3.0 Ga could be those grown in biotite-treated substrates and also higher P inferred from the !Hf ranging from +4 to -16 in majority of concentrations. the magmatic and some detrital grains. The combined U–Pb- Hf isotope data is consistent with the idea that crust formation processes took place contemporaneously in both western and eastern blocks of the Dharwar craton.

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Effects of aqueous phosphate on The effect of Alkali-Feldspar U(VI) sorption composition on mineral-melt F. MAILLOT1*, V. MEHTA2, J.G. CATALANO1, partitioning of Trace Elements 2 3 D.E. GIAMMAR AND Z. WANG 1 2 3 M. MAIMAITI *, F. ARZILLI AND M.R. CARROLL 1 Earth & Planetary Sciences, Washington Univ., St. Louis, 1 Geology Division, University of Camerino, Via Gentile III da MO 63130, USA, (*correspondence: Varano Camerino (MC) Italy,62032 [email protected]) 2 (*correspondence:[email protected]) Energy, Environmental and Chemical Engineering, 2 Geology Division, University of Camerino Washington Univ., St. Louis, MO 63130, USA ([email protected]) 3Pacific Northwest National Lab., Richland, WA 99352 USA 3 Geology Division, University of Camerino

([email protected]) Uranium contamination of soils and groundwater has

resulted from past mining, processing, and waste disposal The aim of this work is to better understand how activities. Among the in-situ remediation strategies for oxic variations in Alkali-Feldspar composition can influence trace subsurface environments, phosphate-based treatments have elements substitution and mineral-melt partitioning. Feldspars generated significant interest [1]. The soluble uranyl ion are a group of very common and important rock-forming [U(VI)O 2+], stable in oxidizing environments, has a strong 2 minerals. Moreover Trace elements are useful as they are affinity for phosphate, which can potentially reduce its much more sensitive to partial melting, crystal fractionation aqueous concentrations by promoting the nucleation of low- and magma mixing, contamination processes, and thus Trace solubility U(VI)-phosphate minerals or by enhancing U(VI) elements can provide geochemical and geological information sorption to subsurface minerals. out of proportion to their abundance. We investigated the effect of aqueous phosphate on U(VI) To investigate systematically the trace element sorption on montmorillonite (Clay Mineral Society source clay partitioning between alkali feldspar and silicate melt, this SWy-2) and goethite. Both minerals are important components study examines Ba, Rb, Sr partition coefficient variations with in the reactive fine fraction of soils and sediments at sites feldspar Or, Ab, An content by using experimental data from contaminated with uranium [2]. We determined U(VI) Arzilli (2012), Mahood and Stimac (1990) and London (1996 adsorption isotherms at several pH conditions and initial ). We have discovered that for our experimental data, [PO 3-]. Uranium speciation was further investigated using U 4 exponential model fits better than simple linear regression L -edge EXAFS and Time Resolved Laser Fluorescence III model. We suggest that the relationship between partitioning spectroscopies. of Ba, Rb, Sr and feldspar Or, Ab, An content is not well A series of possible competing and cooperating reactions produced by a simple linear model and better results are may occur in the presence of U(VI) and phosphate, including obtained with an exponential model involving feldspar Or the formation of U(VI)-phosphate precipitates, U(VI)- content. phosphate ternary surface complexation [3], and surface site We are currently working more on the effect of Alkali- competition between U(VI) and phosphate. Formation of Feldspar crystal growth rate on trace elements partitioning as uranyl-phosphate minerals was observed in the presence of when the growth rate is fast, the crystal can be less selective in either goethite or montmorillonite. Before the onset of allowing trace elements to enter their structure. precipitation however, our results show contrasting behavior

between these two systems. While phosphate does not [1]Lofgren et al.(2006) American Min.91,1596-1606. substantially influence the extent of U adsorption on montmorillonite, it was found to enhance U sorption on goethite at pH 4 and to inhibit it at pH 8. These observed differences indicate that the specific mineralogy of a contaminated field site could greatly influence the applicability of phosphate-based uranium remediation.

[1] Vermeul et al. (2009) 300 Area Uranium Stabilization Through Polyphosphate Injection: Final Report. [2] Stubbs et al. (2009) Geochim. Cosmochim. Acta 73, 1563-1576. [3] Singh et al. (2012) Environ. Sci. Technol. 46, 6594-6603.

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Pseudomorphic replacement of Mineralogy and thermodynamics of diopside during interaction with secondary arsenic phases 1 2 3 (Ni,Mg)Cl2 aqueous solutions JURAJ MAJZLAN , PETR DRAHOTA AND MICHAL FILIPPI A. S. MAJUMDAR*, H. E. KING , T. JOHN, 1 Institute of Geosciences, Friedrich-Schiller-Universität Jena, C. KUSEBAUCH AND A. PUTNIS Germany, [email protected] 2 Institute of Geochemistry, Mineralogy and Mineral Institut für Mineralogie, Universität Münster, Corresstraße 24, Resources, Charles University, Prague, Czech Republic, 48149 Münster, Germany [email protected] *correspondance: [email protected] 3 Institute of Geology, Academy of Sciences of the Czech

Republic, Prague, Czech Republic, [email protected] Alteration of peridotite, including serpentinization, has a

special place among fluid rock interaction that not only Arsenic is an integral part of the toxic load of many types drastically changes rock properties at the ocean floor but also of mining waste. The parageneses of arsenic minerals in the leads to rich ore deposits worldwide. During peridotite primary assemblages (rocks, ores) and the secondary serpentinization, olivine and orthopyroxene are more reactive assemblages (oxidation zones, polluted soils, waste forms) are than clinopyroxene. Hence, it may be reasonable to assume quite variable. In this contribution, we will describe different that after initial serpentinization of olivine and orthopyroxene, mineral assemblages found at sites polluted by arsenic, the hot hydrothermal solution rich in metal ions (e.g. Ni) can including naturally polluted soil profiles, rocky mine dumps, open further possibilities for relict clinopyroxene to react. tailings, underground spaces, and caves. Here, the mineralogy We present a hydrothermal experimental study of is not only dictated by the bulk chemical composition but also diopside-(Ni,Mg)Cl solution interaction to clarify the 2 by the local conditions and shows surprising variations. For replacement mechanism and pattern of element mobilization example, although mining waste is commonly dominated by during alteration. Different chloride solutions were used with arsenic-rich hydrous ferric oxide and scorodite (FeAsO · Ni/Mg ratios of 0, 0.5 and 1. Experiments were carried out in 4 2H O), polluted soils contain more commonly cold seal pressure vessels at 300-600 °C and 1 kbar pressure 2 pharmacosiderite [(K,Na,Ba)Fe4(AsO4)3(OH)4·6-7H2O) and for 15 days in gold capsules. For 500-600°C NiCl2 18 Ca-Fe arsenates such as arseniosiderite. This difference could experiments solutions were also spiked with 50% H O to 2 arise from different availability of element due to different study the behaviour of isotopic exchange, hence, the time scales. If so, such differences could suggest how the replacement mechanism. Raman, SEM and microprobe waste forms could react and transform in the future. In waste analyses were performed on reactive samples to identify the forms from material processed by pressure oxidation contain phases and to observe textural and compositional features. yet different types of ferric arsenates, not known as minerals. The reactive samples show a sharp compositional and Little is known about their solubility and reactivity. The structural interface between diopside and the pseudomorph chemical composition of the whole system influences, of phases. A complex rim of Ni poor and Ni rich regions are course, the nature of the secondary arsenic minerals, and the present in NiCl and (Ni,Mg)Cl experiments. Here, the 2 2 link between the two can be easily established. precipitated phases are willemseite and/or nepouite. For In addition to the crystalline arsenate phases, As(V) can be MgCl experiments, only talc was detected. The experiment 2 also incorporated into the crystal structure of iron oxides, with 18O-enriched solution documents a shift in the Si- especially hematite, as epitaxially intergrown clusters with O(bridging)-Si band of willemseite towards lower angelellite-like local structure. This mode of occurrence may wavenumbers confirming that diopside pseudomorphism be found especially in older systems with relatively low occurs via an interface coupled dissolution precipitation, pollution loads. where the spatial coupling between dissolution-precipitation is Thermodynamic data suggest, not surprisingly, that dependent on temperature. The study also shows evidences for scorodite is the most stable phase in the system Fe O -As O - Ca transport in the opposite direction to Ni and/or Mg during 2 3 2 5 H O. Ka,kite, bukovsk-ite, As-rich hydrous ferric oxide, alteration. This may be important as a geochemical tracer for 2 FeAsO , and presumably also z-kaite are metastable. The data economic Ni deposits and Ca mobilization during 4 for more complex ferric arsenates (pharmacosiderite, serpentinization. arseniosiderite, yukonite) are missing; this work is in progress and could reveal interesting relationships between the simpler and more complicated ferric arsenates.

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Cathodoluminescence of Hematite scalenohedra –ancient barytocalcite CaBa(CO3)2 jewelry and a problem of M. MAKIO1, H. NISHIDO2, N. KUSANO2 sedimentary mineralogy AND K. NINAGAWA2 EMIL MAKOVICKY, MATTEO PARISATTO AND 1 Graduate School of Social and Cultural Studies, Kyushu FLEMMING HØJLUND123 University, 744 Motooka, Nishid-ku, Fukuoka, 819-0395, 1 Institute for Geoscience and Natural Resource Management, Japan University of Copenhagen, Østervoldgade 10, 1350 2 Department of Biosphere-Geosphere Science, Okayama Copenhagen, Denmark, [email protected] University of Science, 1-1 Ridai-cho, Okayama 700-0005, 2 Department of Geosciences, University of Padova, Via Japan (correspondence: [email protected]) Gradenigo 6, 35131 Padova, Italy,

[email protected] Anhydrous double salts of CaCO and BaCO have not 3 3 3 Moesgaard Museum, Moesgaard Allé 20, 8270 Højbjerg, been investigated with respect to CL properties up to date. In Denmark, [email protected] this study we have characterized CL emissions in barytocalcite CaBa(CO ) , of which structure is different from 3 2 In 1964 a scalenohedron of hematite was found in rhombohedral-calcite type. archaeological excavations of the bronze-age layer (1980- Single crystals of three barytocalcite (Blagill, UK; Fosters, 2020 BC) of the Tell of Qala’at al-Bahrain on the shores of the UK; Langban, Sweden) were selected for CL spectral Persian Gulf, together with faience and carnelian beads. We measurements at various temperatures. subjected the scalenohedron to X-ray tomographic CL spectra of barytocalcite at room temperature have a investigation using a Bruker microCT-Skyscan 1172 high pronounced emission peak at around 600 nm in red region. It resolution scanner. The system has a polychromatic can be assigned to an impurity center of divalent Mn ion (4G- microfocus X-ray source with a tungsten anode; it was run at 6S) as an activator, which occupies Ca site in barytocalcite o 100 kV and 10 W. 2000 radiographs were acquired over 360 , structure, where the centered wavelength is appreciably 9 radiographs were averaged for each angular position. smaller than the value of calcite (620 nm) due to different Scanning revealed considerable internal porosity of the crystal field. Barytocalcite has aragonite-like structural ‘crystal’, with a preferential concentration of small pores in configuration rather than calcite-like one. Therefore, various the central portions and with larger, elongated pores in the types of Ca sites substituted with Mn ions can be suggested for subsurface portions. The internal structure reveals that it is a this Ca-Ba series carbonates, which might modify the strength pseudomorph after a scalenohedral carbonate, composed of an of crystal field around activated Mn ions. Temperature intergrowth of hematite tablets and grains. Its geometry controlled CL measurements reveal that the CL intensity of coincides with that of calcite {21-34} scalenohedron, with Mn activated emission in barytocalcite decreases in an minor presence of {10-10} and {02-24}. increase of sample temperature, suggesting a temperature Mineral trade knows such ‘hematite scalenohedra’ from quenching effect especially pronounced in the range of the Arzanah and Hormuz Islands in the Persian Gulf. Both are .50~25 °C. The intensity at .189 °C is twice as much as that top portions of tall salt diapirs occluding fragments of at room temperature. Furthermore, an increasing temperature Precambrian Hormuz Formation: blocks of various volcanic results in a shift of the emission peak to shorter wavelengths, rocks, sediments and even iron ore, forming a jumbled mass. which might be attributed to an increase in the distance Specularite is reported in geological descriptions but not the between Mn ion and adjacent ligand. hematite pseudomorphs which look very much like our specimen. Our research revealed an extensive replacement of well-crystallized carbonates by hematite (may-be in relation to the formation of large hematite masses which in this pre-iron- age society were polished into hematite weights) but it leaves open the question at which geological stage the evaporite sequence produced perfect carbonate crystals and when were they pseudomorphosed by hematite. This may have practical importance, a number of these diapirs being connected with the Gulf gas and oil occurences.

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Fluid-induced redox processes at the Timing and distinct magma sources slab-mantle interface: insights from in ultramafic-mafic intrusions of the ultrahigh-pressure garnet peridotites Taimyr Peninsula (Russia) NADIA MALASPINA1, FALKO LANGENHORST2 K.N. MALITCH1, I.YU. BADANINA1 AND STEFANO POLI3 AND A.P. ROMANOV2 1Università degli Studi di Milano Bicocca, Milano, Italy 1Institute of Geology and Geochemistry of the Uralian Branch ([email protected]) of Russian Academy of Sciences, Ekaterinburg, Russia 2 Universitat, Jena, Germany ([email protected]) (*correspondence: [email protected]) 2 3Università degli Studi di Milano, Milano, Italy Krasnoyarsky Research Institute of Geology and Mineral ([email protected]) Resources, Krasnoyarsk, 660049, Russia

The slab-to-mantle volatile transfer is related to the fluid It is commonly assumed that ultramafic-mafic intrusions speciation, which in turn is a function of fO , in a system and associated PGE-Cu-Ni sulphide deposits of Northern 2 Siberia represent a small component of a major episode of buffered by equilibria involving redox-sensitive elements. The mafic activity at ~250 Ma, which included formation of the redox processes taking place in the portion of mantle wedge most extensive flood-basalt province on Earth [1]. Recent on top of the subducting slab is poorly investigated and the studies, however, advocated protracted evolution of the ore- oxidising power of fluids is still unknown. forming magmas parent to the Noril’sk-type intrusions [2-4]. A case study is represented by grt-orthopyroxenites and This report presents the results of uranium-lead ages of peridotites from Dabie-Shan (China) hosted by grt-coe zircons and whole-rock Nd-Sr isotope data for the same suite gneisses which contain an association of opx + grt ± cpx ± ol, of lithologies from the Binyuda and Dyumtalei ultramafic- formed at the expenses of a previous grt-peridotite. Grt mafic intrusions located in the limits of the Taimyr Peninsula includes primary polyphase inclusions corresponding to a (Russian Arctic). The rocks investigated comprise sulphide- solute-rich aqueous fluid enriched in LILE and LREE. rich varieties of (1) melanotroctolite and (2) ferrogabbro (i.e. Orthopyroxenites represent metasomatic layers produced after gabbro abnormally high in iron) occurring in bottom parts of the reaction of mantle peridotites with a Si-saturated fluid the Binyuda and Dyumtalei intrusions, respectively. phase sourced by the associated crustal rocks. The trace Zircons are characterized by similar U-Pb ages (248.5±11 element pattern of this fluid shows a peculiar LILE signature Ma at Binyuda and 244.4±2.4 Ma at Dyumtalei). In contrast, which is recorded by subduction grt-peridotites from Sulu silicate material show distinct Sr-Nd isotope signatures 87 86 (China). These samples show porphyroclastic grt, cpx and phl, (!Nd=3.5±0.7 and Sr/ Sri=0.70493±0.00021 at Dyumtalei, 87 86 and a younger paragenesis of fine-grained ol + cpx + opx + !Nd=-3.4±0.3 and Sr/ Sri=0.70585±0.00004 at Binyuda). phl ± magnesite equilibrated with neoblastic grt. The determined Nd-Sr variability is interpreted to represent a We measured the Fe3+ distribution of the major phases of primary source signature of the lithological units. An orthopyroxenite and peridotite with Flank Method electron important role of the juvenile component is clearly defined for probe microanalyses and EELS. Pyrope-rich metasomatic grt the Dyumtalei intrusion, whereas a major contribution from a

presents a complementary decrease in Al2O3, relative to the SCLM source is inferred for the Binyuda intrusion. 3+ increase of Fe2O3. Diopsidic cpx contains Fe //Fe up to 0.51 These signatures clearly manifest deviation from those and high Na, requiring the incorporation of an aegirine typical for the ore-bearing intrusions of the Noril’sk Province, component. The coupled Na-Fe3+ enrichment in cpx suggests a characterized by a significant time span of zircon and corresponding enrichment in the whole rock and could be baddeleyite U-Pb ages (from ca. 350 to 230 Ma), relatively favoured by the influx of alkali-rich metasomatic fluid phases. constant !Nd values (+1.0±0.5) and heterogeneous radiogenic 87 86 To investigate the role of deep fluids in the redox processes of Sr/ Sri (from 0.70552 to 0.70798). the suprasubduction mantle we also measured the Fe3+ in the The study was supported by RFBR (grant 13-05-00671) microprecipitates of polyphase inclusions using EELS on a and the Uralian Division of Russian Academy of Sciences TEM. The solute content of slab fluids may contain high Fe3+ (grant 12-5-9-019-Arctic). concentrations and surprisingly inclusion phases such as phl 3+ 255 may contain up to 0.70 of Fe //Fe. If net bulk rock oxidation [1] Campbell et al. (1992) Science , 1760-1763. [2] Malitch et al. (2010) Contrib. Mineral. Petrol. 159, 753-768. can be demonstrated, silicate-alkali-rich C-bearing fluids [3] Malitch et al. (2012) Russ. Geol. Geophys. 53, 123-130. could be regarded as potential carriers of oxidising [4] Malitch et al. (2013) Lithos 164-167, 36-46. components to the suprasubduction mantle.

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Effect of variable CO2 on andesite- Use of uranium, thorium and carbon lherzolite reaction: Implications for isotopes for thermal groundwater mantle hybridization and generation and travertine dating of alkalic basalts MALOV A.I., BOLOTOV I.N., ZYKOV S.B., DRUZHININ 1 1 AND S.V., POKROVSKY O.S. ANANYA MALLIK * AND RAJDEEP DASGUPTA Institute of the Ecologic Problems of the North, UB RAS, 1Rice University, Houston, TX, USA (*[email protected]) Naberezhnaya Severnoi Dviny, 23, Arkhangelsk, 163061,

Russia Presence of recycled oceanic crust, a major heterogeneity [email protected] in the Earth’s mantle, is invoked in the source of many ocean

island basalts (OIBs) [1]. However, andesitic partial melts The use of 14C dating in groundwater in some cases, is derived from oceanic crust, upon reaction with subsolidus facing serious difficulties. It first of all - reducing the specific peridotite, produce basanites [2] but cannot form strongly activity of 14C in groundwater due to dissolution of carbonate alkalic lavas such as nephelinites. In this study, we evaluate host rocks, overstates age, and mixing with younger water, whether such an andesite, with dissolved CO , can evolve to 2 substantially understates it. In this regard, we propose the more Si-deficient magma due to partial reactive crystallization sharing of 14C and 234U-238U for dating. However, 234U-238U in subsolidus peridotite. method now not enjoys great popularity. This is due to the We performed piston-cylinder experiments at 1375 °C, 3 need to determine a large number parameters. It should be GPa with homogenous mixtures of 25% or 33% of an andesite noted difficulty in defining SSA, and respectively, (-recoil and lherzolite KLB-1 with 1 to 5 wt.% CO in the starting 2 loss factor. For practical use of the 234U-238U method, we offer melts (0.25 to 1.62 wt.% bulk CO ). Upon reaction, with 2 to introduce in the calculation the generalized parameter increasing CO in the reacting melt: a) modes of reacted melt, 2 (probability of the transfer of 234U into water, or "effective (- opx and garnet increased while that of olivine and cpx recoil loss factor") derived empirically from geological decreased b) the andesite evolved from basanite to nephelinite benchmarks, hydrodynamic calculations, and paleo- c) the residual melts, on a volatile-free basis, showed variation hydrogeological reconstructions [1]. For hydrothermal system in SiO from 44-40 wt.% and 45-43 wt.%, TiO from 6-5 wt.% 2 2 located within mainland European Subarctic 14C age of and 7-6 wt.%, Al O from 14-11 wt.% and 13-10 wt.%, MgO 2 3 thermal waters is 9-12 ka, 234U/238U age - 6-11 ka. from 13-17 wt.% and 12-17 wt.%, CaO from 8-11 wt.% and Calibrated "13C age of travertine - to 3 ka. U-Th age of 8-11 wt.% and Mg# from 68-75 and 69-73, for 25% and 33% travertine -- up to 1.5 ka. Assessment calculations show that melt-added series, respectively and d) FeO* and Na O did not 2 when dating groundwater isotope of uranium, 10% admixture show significant variation. of young water (up to 100 years) reduces the age of ancient Our results show that with increasing CO in the andesite, 2 water (11 ka) by 11%. Joint dating of the groundwater and its reaction with lherzolite yields greater degree of Si- from them formed travertine possible to estimate the velocity undersaturation owing to dilution of melt SiO by CO and 2 2 of the groundwater in the hydrothermal system and the speed lowering of melt SiO by enhanced crystallization of opx at 2 of neotectonic uplift of the area. the expense of olivine. Increased precipitation of garnet lowers

Al O in the reacted melts. Increased CaO and MgO and no 2 3 [1] Malov ( 2013) Lithol. Miner. Resour. 48, 254-265. significant trend of FeO* and Na2O with greater bulk CO2 content confirm propensity of Ca2+ and Mg2+ over Fe2+ and Na+ in entering silicate melt as carbonates. Residues show

more opx-enrichment with greater CO2 in the system. We have developed a model for quantitative prediction of mineral modes in hybrid residues as a function of melt-rock ratio and

dissolved CO2 in the reacting melt. At a given MgO, the CO2- bearing reacted melts are better match for alkalic OIBs in

terms of SiO2, Al2O3, CaO, Na2O and CaO/Al2O3 than their volatile-free analogs.

[1] Hofmann & White (1982), EPSL 57, 421-436. [2] Mallik & Dasgupta (2012), EPSL 329-330, 97-108.

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Biogeochemistry of the Big Toroki What causes the rapid change of sapropel lake, Western Siberia Cenozoic magma sources in the A.E. MALTSEV*, G.A. LEONOVA, S.K. KRIVONOGOV, Pamir? AND V.A. BOBROV 1 1 1 N. MALZ* , L. RATSCHBACHER , J. A. PFÄNDER Institute of geology and mineralogy SB RAS, Koptyug Pr. 3, AND C. MÜNKER2 Novosibirsk 630090, Russia 1 Institut für Geologie, TU Bergakademie Freiberg, Germany (*coresspondence: [email protected])! (*correspondence: [email protected]) 2Institut für Geologie und Mineralogie, Universität zu Köln, We investigated a 1.8 m long sediment core of Lake Big Germany Toroki (N 55º 24', E 80º 36'). The lake has a closed basin of 2 9.57 km in area and a 1 m in depth and is overgrown by macrophytes [1]. Its water is low-mineralized (845 mg/l), and The Pamir mountains, building the western elongation of belongs to the hydrocarbonate Na-Mg class according to [2]. the Tibet plateau, were formed by the India-Asia collision ~55 Ma ago. Extreme shortening resulted in extremely thickened The sediments are organic-mineral sapropels (Corg 45.4 %) according to [3]. Water macrophytes are the main producers of crust making the Pamir an ideal natural laboratory to study the organic matter. The sediment sequence consists of a crustal melting processes. substrate, bluish-gray sandy silts (180–160 cm), blackish peat After the India-Asia collision, post-collisional granitoids (160–120 cm), coarse peaty sapropel with abundant mollusk appear at ~46 Ma and the magmatic activity in the Pamir was shells (129–122 cm), blackish peaty sapropel with random rather sparse until ~33 Ma. During this time, Sr- and Nd- gastropod shells (120–75 cm) and greenish macrophytic isotope compositions (initial 87Sr/86Sr: 0.7223 to 0.7067 and sapropel with random bivalve shells (75–0 cm). initial !Nd: -10.3 to -2.6) indicate a gradually increasing

Total organics, Corg and carbonates vary along the core in amount of mantle components, coupled with decreasing SiO2 compliance with its sediment units. Total organics is 40–50% contents (77 to 62 wt.%). At ~29 Ma, this trend reverses with in the sapropel, 60–61% in 120–130 cm and sharply declines an increasing crustal component up to ~14 Ma; initial 87Sr/86Sr below 140 cm. Corg is 14–18% in 0–70 and 120-135 cm compositions increase again from 0.7064 to 0.7203 and initial intervals, 9–13% in the middle and sharply declines from 6.4 !Nd decrease from -3.7 to -8.4. Apart from these highly to 0.47 % in 140–180 cm interval. Carbonates are low, 3–4 %, evolved granitoids, basaltic magmatism occurred in the upper 0–75 cm and progressively increases to 14–16 % contemporaneously. The youngest samples at ~11 Ma from below. The sediment pore waters showed variations in Fe, Mn, the easternmost region of the Central Pamirs are ultrapotassic Cu, Zn, Pb and Cd. Sharp peaks of Fe and Mn are in the lower tephrites to tephriphonolites, showing some of the least middle (90–130 cm), Cu, Zn and Cd in the upper middle (60– radiogenic Nd isotopic compositions (initial !Nd: -9.6 to - 80 cm) and Pb in the top (0–40 cm) parts of the core. Changes 12.3) together with rather radiogenic Sr isotope compositions 87 86 of H, N and S, which mostly compose the organic matter, (initial Sr/ Sr: 0.7100-0.7104). match variations of Corg. What triggers the variable proportions of mantle and This research was supported by the SB RAS Integration crustal components in the the sources of Cenozoic igneous Project no. 125. rocks over such short time intervals? The post-collisional magmatism in the Tibetan Plateau is supposed to be [1] Agricultural organic-mineral materials in the Novosibirsk influenced by a slab break-off at 55-40 Ma [1], leading to the Region (1990), Novosibirsk. [2] Alekin O.A. (1948), General ascent of asthenospheric material, thus triggering partial hydrochemistry. Leningrad, Gidrometeoizdat. [3] Korde N.V. melting in the ascending mantle and the lower crust. Such a (1960), Biostratigraphy and typology of Russian sapropels, scenario provides a viable explanation for the increasing Moscow, USSR Ac. Sci. amount of mantle component in the 46-33 Ma igneous suites of the Pamir. The ongoing (crustal) shortening led to an extremely thick crust, in which anatexis caused the 29-14 Ma magmatism. Moreover, the subducting cold Indian slab interrupted the asthenospheric upwelling. We will further test this genetic model by combined Lu-Hf and U-Pb measurements on igneous zircons.

[1] e.g. Kohn and Parkinson, 2002, Geology, 30, 591-594

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The Eastern Rift Zone through time: Fluids, subduction, and deep carbon A record of plume pulsing or magma CRAIG E. MANNING1*, YUAN LI2 AND JAMES EGUCHI1 plumbing evolution? 1Department of Earth and Space Sciences, University of 1 1 California, Los Angles, CA 90095, USA CHRISTINA J MANNING * AND MATTHEW THIRLWALL (*correspondence: [email protected]) 1Department of Earth Science, Royal Holloway University of 2Bayerisches GeoInstitute, Universität Bayreuth, 95440 London, Egham, Surrey. TW20 0EX Bayreuth, Germany (*correspondence: [email protected]) Studies of the deep carbon cycle have concluded that the Lavas from Öræfajökull volcano, SE Iceland, exhibit mantle is gaining C because more carbon is subducted than is isotopic compositions distinct from normal Icelandic enriched degassed by volcanism [1]. This relies on the assumption that

mantle, attributed to the presence of recycled sediment in their all CO2 lost from slabs is degassed at arc volcanoes, which is source [e.g.1, 2]. This distinctive source has recently been problematic because arc crust is permeable [2] and arc recognized in postglacial Eastern Rift Zone (ERZ) lavas [3], magmas may attain deep fluid saturation [3]. Support has also indicating the source is more widespread, as well as in the been drawn from models showing that slab fluids possess low

East Iceland Tertiary lavas (~13 Ma) [4], indicating that it is XCO2 [4]. But new theoretical and experimental results show also long lived. that C solubilities are likely higher than these models predict. A comprehensive suite of lavas from the ERZ; Si0a and Total dissolved carbon depends on the solubilities of all C - -2 Fljótshevrfi Groups (0.7 - 3 Ma) and Tertiary lavas from species (e.g., CO2aq, HCO3 , CO3 , etc), which are controlled

Skaftafell (3-5 Ma) have been analysed for Sr-Nd-Pb isotopic by pH, fO2, halogens, and dissolved cations. Controls on these ratios along with major and trace elements. Whilst both variables in subduction zones are likely to combine to elevate Skaftafell and ERZ lavas lie on correlations trending towards carbonate mineral solubility. For example, the calculated pH an enriched end-member similar to the Öræfajökull source, the of model slab mineral assemblages of jadeite, white mica and Skaftafell lavas trend to an end-member which has lower quartz [5,6] along the top of the Costa Rica slab [7] indicate 143 144 87 86 207 Nd/ Nd for a given Sr/ Sr and more positive 1 Pb and that the CaCO3 solubility is higher at mineral-buffered pH 208 1 Pb. This suggests a temporal change in the composition than at the more alkaline pH of otherwise pure H2O saturated

of the enriched mantle source in the past 5 Ma. Further, the only in CaCO3, or than in molecular mixing models. Si0a and Fljótshevrfi lavas (0.7 - 3 Ma) show more depleted Carbonate solubility is also enhanced by salts. At a given P-T, and less variable isotopic compositions suggesting the calcite solubility increases in proportion to the square of NaCl transition was not gradual, but that there was a distinct break mole fraction [8]. Our studies in KCl, LiCl, and their mixtures

in the supply of enriched mantle at ~3 Ma. Possible have similar form and, at fixed P, T and Xsalt, solubility mechanisms for this could be: 1. Supply of discreet blobs of decreases as LiCl > NaCl > KCl, consistent with Pearson enriched mantle from the plume [4], 2. Changes to the magma Hard-Soft Acid-Base rules. Metal-carbonate ion pairing and

plumbing regime resulting in a reduced contribution from the reduction of carbonate or CO2 to CH4 during mantle-wedge enriched source and greater homogenisation of melts between serpentinization will further increase solubility. Models 3 and 0.7 Ma. including the above effects yield 21 wt% total C in some slab fluids. C carried by subduction-zone fluids and deep degassed [1] Prestvik et al. (2001), EPSL 190, 211-220 [2] Kokfelt et magmatic volatiles likely play important roles in the deep al. (2006), J.Pet 47, 1705-1749 [3] Manning and Thirlwall carbon cycle, and must be taken into account in assessing the (2013), CMP in review [4] Kitagawa et al. (2008), J.Pet 49, gain or loss of carbon by the mantle. 1365-1396. [1] Dasgupta & Hirschmann (2010) Earth Planet. Sci. Lett. 298, 1-13. [2] Ingebritsen & Manning (2002) PNAS 99, 9113- 9116. [3] Blundy et al. (2010) Earth Planet. Sci. Lett. 290, 298-301. [4] Gorman et al. (2006) Geochem. Geophys. Geosys. 7, Q04007. [5] Manning et al. (2010) Earth Plant. Sci. Lett. 292, 325-336. [6] Wohlers et al. (2011) Geochim. Cosmochim. Acta 75, 2924-2939. [7] Syracuse et al. (2010) Phys. Earth Planet. Int. 183, 73-90. [8] Newton & Manning (2002) Am. Min. 87, 1401- 1409.

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A new lithospheric model for Spatial and temporal variability in southeastern Sicily (Italy) clay mineral and iron (oxyhdr)oxide

F.C. MANUELLA1, A. BRANCATO 1, S. CARBONE1, S. minerals of the Changjiang (Yangtze) GRESTA1 River suspended sediment: Monsoon 1Dipartimento di Scienze Biologiche, Geologiche e controlling weathering Ambientali, Sezione di Scienze della Terra, Università di 1, 2 1 Catania, Corso Italia 57, 95129, Italy (correspondence: CHANGPING MAO *, JUN CHEN , XUYIN YUAN , 2 2 [email protected]), [email protected], [email protected], YINXIAN SONG AND JUNFENG JI [email protected] 1 Institute of Isotope Hydrology, School of Earth Sciences and Engineering, Hohai University, Nanjing 210098 China An interdisciplinary approach for a new lithospheric (*correspondence: [email protected]) model for southeastern Sicily and the Sicily Channel has been 2nstitute of Surficial Geochemistry, School of Earth Sciences recently proposed by Manuella et al. [1], as retrieved from the and Engineering, Nanjing University, Nanjing 210093 integration of published petrologic and geophysical data. The model elaborated by Manuella et al. [1] points out the Clay mineral assemblages and iron (oxyhdr)oxide are existence of a Permo-Triassic oceanic lithosphere that sensitive to bedrock geology and chemical weathering, and broadens from the Hyblean Plateau to the Sicily Channel, therefore have long been regarded as a powerful indicator of underlying a thick Mesozoic-Cenozoic sedimentary and the nature of the source areas. The goal of the present work is volcanic sequence, in continuity with the adjacent Mesozoic to show quantitative spatial distribution and seasonal Ionian-Tethys ocean, thus confirming the hypothesis of variability pattern of clay mineral assemblages and iron Scribano et al. [2]. The Permo-Triassic basement consists of a (oxyhdr)oxide in river suspended sediments for the entire level of peridotites, affected by different degrees of Changjiang (Yangtze) basin. serpentinization (35–100 vol.%) ranging to a depth of 8–19 The Changjiang (Yangtze) River originates on eastern km, and a remarkable anomaly occurs at 19 km, corresponding periphery of the Tibetan Plateau and causes large continental to the Moho discontinuity, which has been considered as a masses from Tibet to the oceans. A large part of the serpentinization front. Changjiang Basin has a subtropical monsoon climate. The

suspended sediments of Changjiang River drainage basin were collected during the flood (July-August 2007) and dry (December 2007, January 2008) seasons. In the present work, river suspended sediment was investigated by quantitative mineralogical, geochemical analyses of bulk samples and single particles.The results indicate that an increasing trend of hematite% and goethite% were observed in the main channel from the upper to middle reaches. The concentration of illite has a ranges from 60% to 80% in summer and 40% to 60% in winter, both with a decreasing trend from the upper to lower reaches. The kaolinite contents of the lower stream abruptly increased from 10% to 30% in the dry seasons (winter) relative to the flood seasons (summer). This peak is probably associated with strong inputs of suspended material from the Poyang lake and its tributaries (located between middle and lower reaches of the Changjiang River) . Our results suggest that spatial and temporal variations in Figure 1. A schematic view of the new lithospheric model clay mineral and iron (oxyhdr)oxide minerals primarily reflect variations in the intensity of the monsoon, and which is the [1] Manuella et al. (2013), J. Geodyn. 66, 92–102. [2] principal forcing factor on the mechanical and chemical Scribano et al. (2006), Miner. Petrol. 86, 63–88. weathering processes between the different sub-catchments of Changjiang River.

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Element mobility from seafloor Isotopic composition of precipitation serpentinization to high-pressure in Ferrara Province dehydration of antigorite in MARCHINA C.1, VACCARO C.1*, FAZZINI M.1, subducted serpentinite: insights from DI ROMA A.1 AND BIANCHINI G.1 Cerro del Almirez (southern Spain) 1Dip. Fisica e Scienze della Terra, Università di Ferrara, Italy (*[email protected]) CLAUDIO MARCHESI1*, CARLOS J. GARRIDO1, 2 JOSÉ ALBERTO PADRÓN-NAVARTA , VICENTE LÓPEZ Ferrara province is located in the Po valley, a flat low-land SÁNCHEZ-VIZCAÍNO3 4 surrounded by the Alps and the Appennines. The particularity AND MARÍA TERESA GÓMEZ-PUGNAIRE of this area is represented by the proximity to the Comacchio 1IACT, CSIC-UGR, 18100 Armilla (Granada), Spain Valleys and the Adriatic Sea. It is interesting to note that, in (*correspondence: [email protected]; spite of the vicinity to the sea, the area is charaterized by [email protected]; [email protected]) continental climatic characteristics. Stable hydrogen and 2Géosciences Montpellier, UMR 5243, CNRS-UM2, 34095 oxygen isotope ratios are dynamic tracers for the cyclying of Montpellier, France ([email protected]) atmospheric moisture as influenced by water vapour 3Departamento de Geología, Universidad de Jaén, 23700 advection, condensation, and evaporation [1]. Linares (Jaén), Spain ([email protected]) The stations selected for this study include various sectors 4Departamento de Mineralogía y Petrología, UGR, 18002 of the Ferrara province and allow to characterize the isotopic Granada, Spain ([email protected]) fingerprint of the local meteoric water. The recorded "18O values ranging between -6.95 and -5.19, and "D values The Cerro del Almirez massif is composed of antigorite ranging between -46.21 and -31.82 are compared with serpentinite and chlorite harzburgite separated by a transitional Northern Meteoric water Line [2]. zone that marks the front of prograde serpentinite-dehydration These data will be implemented with the investigation of at high pressure in a paleo-subduction setting. Concentrations further local events in the selected stations in order to create of Sc and V indicate that the peridotite precursor of an hydro-archive, i.e. a data-set of stable isotope of meteoric serpentinite experienced up to 20% partial melting in the water in Ferrara province. This is important considering that FMQ spinel stability field at -2 < 1log fO2 < 0. Peridotites the stable isotopes provide a snapshot of the current climatic underwent intense seafloor serpentinization in a fluid- conditions to be compared with the literature data and with the dominated system. Olivine hydrolysis at ~ 200 °C and future composition, as a proxy to evaluate on-going climatic pyroxene serpentinization at > 350-400 °C remobilized Ca and changes. REE (especially LREE and Eu) and caused the progressive enrichment of Cs, Rb, Ba, U and Pb and locally the [1] H.Fudeyasu, et al. (2008) J. Geohys. Res, 113]. [2] crystallization of talc by silica fluid addition. Transformation Longinelli and Selmo (2003) Jour. Hydrol. 270, 75-88]. to antigorite serpentinite upon subduction led to Sr depletion, [3]Zuppi and Sacchi, (2004) Global Planet. Change 40 79– and Ti, Tm, Yb and Lu were remobilized at the sample scale 91]. during fluid-assisted crystallization of titanian clinohumite. The high-pressure prograde breakdown of antigorite to chlorite harzburgite preserved the REE fractionations and the characteristic negative Eu anomaly of precursor serpentinites. Relative enrichment of Th-U-Nb-Ta-Pb-Sr in chlorite harzburgite cannot be balanced by closed-system dehydration of serpentinite indicating that dehydration occurred in an open system involving external fluids equilibrated with crustal sources. Open-system fluid flux in the subducted slab results in the recycling into the deep convective asthenospheric mantle of prograde harzburgite enriched in Th, U, HFSE and Pb relatively to oceanic depleted peridotite.

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Bacterial phosphate acquisition from The energy budget of the mantle minerals in ultra-oligotrophic, JEAN-CLAUDE MARESCHAL1, CLAUDE JAUPART2, ferruginous environments STEPHANE LABROSSE3 AND FRANCIS LUCAZEAU2 1 1, 1 GEOTOP, University of Quebec, Montreal, Canada JULIA A. MARESCA *, MENGYIN YAO , CARRIAYNE 2 2 2 3 Institut de Physique du Globe de Paris, Paris, France JONES , SEAN A. CROWE , EDWARD F. DELONG 3 2 Ecole Normale Superieure de Lyon, Lyon, France AND DONALD E. CANFIELD

1Civil and Environmental Engineering, University of We have estimated the present total energy flow of the Delaware, Newark, DE USA. Earth to be 46 +/- 3 TW. The heat loss through the continents 2NordCEE, University of Southern Denmark, Odense, and their margins was obtained by integrating the available Denmark. heat flux measurements which yields 14TW. For the oceans, 3Civil and Environmental Engineering, Massachusetts Institute we have used a cooling plate model for the seafloor with of Technology, Cambridge, MA USA. parameters constrained by heat flux and bathymetry data *Correspondence: [email protected] (29TW), and we used the buoyancy flux to estimate the hotspots contribution (3-4TW). After removing the radiogenic Although ancient ferruginous environments were likely heat production in the continental crust and lithosphere (7- primarily anoxic, the abundant Fe2+ could have been oxidized 8TW), the total heat loss from the convecting mantle is 38+/3 to form iron oxyhydroxides by abiotic processes, iron TW. The mantle energy loss must be balanced by radiogenic oxidizing microbes, or free oxygen produced by oxygenic heat production in the Earth’s mantle, heat flow from the core, photosynthesizers within oxygen “oases”. Iron oxyhydroxides and secular cooling of the mantle. All the other possible are known to be strong adsorbents of phosphate. Thus, sources (tidal dissipation, differentiation of the crust from the microbes in ferruginous environments would have had to mantle, gravitational energy released by thermal contraction) contend with high Fe concentrations and low, sometimes account for < 1TW. Geochemical and cosmochemical vanishingly low, dissolved inorganic P concentrations. Lake estimates of the concentration in radioactive elements in bulk Matano, on Sulawesi Island, Indonesia, is a stratified silicate earth (crust and mantle) yield values in the range 13- ferruginous lake with less than 15nM soluble inorganic 24 TW, i.e. ~5-17TW for the heat production of the Earth phosphate. We have isolated 9 heterotrophic bacterial strains mantle. For our preferred estimate of 11TW, the mantle Urey from this lake, and most are capable of solubilizing phosphate ratio is 0.29. Recent measurements of the thermal conductivity from Fe oxyhydroxide minerals. All strains grow when of the core have led to a re-evaluation of the core heat flow provided with low concentrations of soluble inorganic with a lower bound of 9TW and a range 9-17TW. Subtracting phosphate, but some cannot tolerate high phosphate the mantle heat production and the core heat flow from the concentrations (30 mM). When goethite with adsorbed mantle energy loss, we obtain that the present cooling rate of phosphate is provided as the sole P source, all strains grow the mantle is ~16 TW with a very wide range (1-33TW). This quite well, and P is released into the medium. Measurements represents a cooling rate of ~100 K/Gy (7-220K/Gy), much of pH changes in unbuffered medium suggest that some higher than long term cooling rates obtained from petrological isolates produce acids that contribute to P desorption, though estimates of Archean mantle temperature (~70K/Gy). the variability in the amount of phosphate solubilized, consumed, and released suggests that these isolates have multiple mechanisms for P acquisition from Fe particles and subsequent intracellular storage. In addition to the physiological data from these isolates, metagenomic data from Lake Matano surface water indicates that a variety of phosphorus sources can be used, including inorganic phosphates, organophosphates, and phosphonates. These data from Lake Matano use extant pelagic bacteria to characterize microbial pathways for P acquisition from sinking Fe particles, how these pathways affect rates of growth, and how different P acquisition strategies may have regulated biological activity in ancient ferruginous oceans.

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206Pb/238U matrix induced bias in LA- Fe, S isotope systematics of the 3.24 ICP-MS: A multivariate study Ga old Mendon-Mapepe Formations, E. MARILLO-SIALER1, J. D. WOODHEAD1 AND J. HERGT1 Kaapvaal Craton, South Africa 1School of Earth Sciences, The University of Melbourne, JOHANNA MARIN-CARBONNE1, ELODIE MULLER1, Victoria, Australia VINCENT BUSIGNY1, CLAIRE ROLLION-BARD2 [email protected] AND PASCAL PHILIPPOT1 1 Institut de Physique du Globe de Paris, Sorbonne Paris Cite, Many studies acknowledge the occurrence of systematic Universite Paris 7 Diderot, UMR 7154 CNRS,France discrepancies between the 206Pb/238U ratios measured by LA- [email protected] ICP-MS and TIMS across different reference materials (e.g. 2 Centre de Recherches Pétrographiques et Géochimiques, Université [1, 2]). In order to investigate these effects further high- de Lorraine, UMR 7358, 15 rue Notre Dame des Pauvres, F- precision morphology and volume determinations of laser 54500 Vandoeuvre-lès-Nancy, France ablation pits, obtained in several zircon materials under

varying ablation conditions, have been achieved by confocal Variations of Fe and S isotope compositions of laser scanning microscopy (CLSM 700, Carl Zeiss). These sedimentary pyrites have placed important constraints on the provide detailed information on subtle differences in ablation chemistry and redox evolution of the Earth’s ocean and behaviour between different zircon matrices. We demonstrate atmosphere over geological time. In order to better constrain that small but significant differences in pit dimensions and the paleo-environmental conditions and potential biological laser penetration rates exist between zircons. Subsequent role on these pyrite formations, we developed coupled Fe and evaluation of the 206Pb/238U values reveals an association S isotope and trace element compositions analyses in 28 between ablation behaviour and deviations in the 206Pb/238U samples from the Barberton Barite Drilling Project (BBDP). downhole fractionation patterns observed during ablation - a The BBDP intercepted the transition from deep-water black finding that has major ramifications for studies of U-Pb cherts and komatititic basalts of the Mendon Formation to geochronology employing laser ablation. shallow-water sulfate deposits and terrigeneous and The differences in ablation behaviour between zircons, volcanoclastic sediments of the 3.24 Ga old Mapepe however, cannot be ascribed to a single variable. Based on Formation. In situ Fe and S isotope compositions of pyrite our initial observations the measured laser penetration rates were measured with ims 1280 HR2 at CRPG, with a may also be partially dependent on the crystallographic reproducibility better than 0.2 ‰ (2!) in both "56Fe and "34S. orientation of the crystals. Multivariate analysis of all possible Iron and S isotopes of bulk-rocks were analysed at IPGP, with parameters involved in the ablation process (zircon chemistry, 56 34 a reproducibility better than 0.1 ‰ (2!) in " Fe, " S and crystallographic orientation, accumulated radiation damage, %33S. topographical and morphological data, and ablation cell spatial In situ and bulk-rock analyses reveal a large range of variations) will be used to identify the most important causes 56 variation from -4.3 ‰ to +3.2‰ for " Fe, from -6.6 ‰ to of these artifacts, and thus hopefully provide a means of +3.5 ‰ for "34S and from -3.5‰ to 1.8‰ for %33S. Although correcting the results. Our ultimate goal is to offer researchers mean in situ pyrite Fe and S isotope compositions are a method for producing high-accuracy U-Pb ratio generally well correlated with bulk-rock values, there are measurements by LA-ICP-MS. some offset depending on the presence of other Fe and S

mineralogical phases (sulfates, carbonates, clays). This is well [1] Klötzi et al. (2009) Geostand. Geoanal. Res. 33, 5-15. [2] illustrated by co-variations between Fe and S isotope Allen & Campbell (2012) Chem. Geol. 332-333, 157-165. compositions with some major and trace elements (SiO2, Al, U…). Pyrites of all samples show a clear correlation between in situ "56Fe and %33S values. Pyrite from sedimentary rocks display a rough trend between negative "56Fe and %33S values and positive "56Fe and %33S values (mostly in BIFs). These large Fe and S isotope variations may reflect a mixing between different sources and record pyrite formation pathways. Coupled S and Fe isotope composition at µm-scale provides new insights into the origin of isotope variations in Archaean pyrites and its link to ocean chemistry.

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Mineralogical and geochemical Chemical geothermometry of zoning at high-temperature contacts geothermal fluids: past, present, and as a fonction of CO2 pressure: An future example from Romanian skarns LUIGI MARINI STEFAN MARINCEA1*, DELIA-GEORGETA DUMITRAS1, Consultant in Applied Geochemistry, I-55049, Viareggio ANGELA MARIA ANASON1, CRISTINA GHINET1 (LU), Italy ([email protected]) AND AURORA MARUTA IANCU1 Most water geothermometers, including the Na-K and Geological Institute of Romania, 1, Caransebes Str., silica functions were initially derived on a purely empirical Bucharest, Romania, RO-012271. (*correspondence: basis. Long ago, geochemists observed a general decrease in [email protected]) Na/K ratio and a general increase in SiO concentration of 2 Obviously mineral zoning occurs in two high- thermal waters with increasing temperatures. The first temperature skarn deposits: Cornet Hill and M3gureaua Va4ei geothermometers were based on these empirical correlations. (Metaliferi Massif, Apuseni Mountains, Romania). In both Studies of hydrothermal alteration mineralogy developing in occurrences, an extensive metasomatism affected Tithonic - high-temperature hydrothermal systems as well as modeling of Kimmeridgian reef limestones of the C3pâlna5-Techereu unit. both mineral-solution equilibria and irreversible mass transfer The magmatic Upper Cretaceous intrusions at the contact are taking place during water-rock interaction suggested that monzodioritic to quartz-monzodioritic. geothermometers are governed by equilibrium reactions The metasomatic mineral zoning is defined by the between hydrothermal minerals and the aqueous solution predominance of a mineral species and is, from the outer to under reservoir conditions. A new generation of the inner part of the metasomatic area: (1) calcite (marble) / geothermometric techniques was consequently proposed and a tilleyite / spurrite + perovskite / wollastonite + gehlenite + theoretical justification for water geothermometers was found. vesuvianite / wollastonite + grossular / quartz monzonite at Moreover, a different approach to geothermometry, based Cornet Hill (CH) and (2) calcite (marble) / wollastonite + on speciation-saturation calculations carried out at different titanian andradite + vesuvianite / gehlenite + grossular at temperatures, was also suggested. It was shown that the M3gureaua Va4ei (MV). Differences in mineral zoning and in saturation indexes with respect to a number of plausible crystal chemistry of mineral species are principally due to the hydrothermal alteration minerals converge to 0 at the different pressures of volatile components (i.e., CO , SO , 2 3 equilibrium temperature, if the geothermal water is in H2O) which are higher at MV and lower at CH. Silicate- carbonates (e.g., spurrite, tilleyite) and hydrous or hydroxyl- equilibrium with the considered minerals. bearing silicate-carbonates (e.g., scawtite, fukalite) are Also gas geothermometers were initially empirical or restricted to the CH skarn area. Sulfate-bearing mineral partly empirical and were later improved by introduction of species (i.e., ellestadite-OH, thaumasite) are more common at vapor-liquid distribution coefficients into equilibrium CH, whereas a silicate-bearing apatite occurs at MV. relations. The importance of addition to or removal from The hydrothermal alteration results in a restricted equilibrium liquids of equilibrium vapors was thus association of hydroxyl-bearing minerals at MV (i.e., demostrated. This approach was later extended to fumarolic xonotlite, hibschite, thomsonite), whereas at CH the gas discharges. Besides, geothermometric functions involving

association also includes afwillite, gismondine, tobermorite, the H2/Ar and H2/N2 ratios were proposed, based on the

riversideite. hypothesis that Ar and N2 are present in hydrothermal fluids in relative contents close to those of air-saturated groundwater. In addition to provide a condensed history of chemical geothermometry, this presentation also intends to review main geothermometers and related graphical tools, trying to emphasize advantages and limitations and to give practical hints to the user. Future developments are also briefly considered.

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How to protect geochemists working Radionuclides (10Be, 210Pb, 137Cs and on environmental issues 7Be) to Determine Anthropogenic from litigation? Impact on Erosion Rates

LUIGI MARINI J. MARQUARD1*, R.E. AALTO1 AND T.T. BARROWS1 Consultant in Applied Geochemistry, I-55049, Viareggio 1College of Life & Environmental Sciences, Univ. of Exeter, (LU), Italy ([email protected]) EX4 4RJ, UK (*correspondence: [email protected])

Four researchers working on environmental geochemistry Short lived radiometric isotopes (210Pb, 137Cs and 7Be) at the Dept. of Env. Sciences of Siena University are involved have been used widely for determining sediment sources and in litigation. In December 2002, their institution was entrusted deposits [1-3]. However, little research has combined short by the Italian Ministry of Defense to perform a geochemical- and long term radiometric isotopes for this purpose. Here we environmental study of two Sardinian firing ranges, due to combine short lived radionuclides with the long lived meteoric their experience on the environmental impact of Depleted 10Be to evaluate anthropogenic impacts on sediment erosion Uranium (DU) gained through previous investigations carried and redistribution during American colonial times (late 16th out in Kosovo. The geochemical-environmental study was century) and longer timescales (within the Pleistocene). This focused on the distribution of U and other toxic heavy research is based in the Christina River Basin, Pennsylvania elements in soils, but active stream sediments, natural waters, (USA) within the Critical Zone Observatory (CRB-CZO). and wild and cultivated plants were also investigated. Anthropogenic impacts are being evaluated on soil Unfortunately, in contrast with the expectations of several redistribution and river channel development by using fallout inhabitants of the area, the Siena researchers did not find any radionuclides. Pre-colonial soil profiles and erosion rates are evidence on the presence of DU in the surveyed area. The being quantified to gain information about natural erosion in study of the Siena researchers was harshly criticized by the the catchment. Sediment redistribution during colonial public prosecutor of Lanusei, technically advised by a full settlement is being evaluated to see the effects of land clearing professor in physics of Brescia University, who is also and stream damming for mill use. Floodplain development member of the CERN of Genève. The crime of aggravated within the last century is being investigated to identify intentional omission of precautions against accidents and changes in the source of sediment erosion due to afforestation disasters was ascribed to the Siena researchers. In particular, and mill dam breaching. In addition, suspended loads in the they have been charged with: (a) not denouncing the danger of streams from various storm events are being analysed to anomalous concentrations of Th present in the firing range; (b) determine the present main source of erosion. using the knowledge gained in Kosovo to select methods that Initial results show changes in the concentration of the prevented to highlight the possible presence of DU. Actually, meteoric 10Be tracer in river sediment of different ages. for what concerns point (a), there is no Th anomaly as Th Millpond deposits that were in the streams at colonial times contents in local soils are comparable with the values found in have a relatively high 10Be concentration. Floodplain sediment other areas of the Sardinia Region and elsewhere. For what that was deposited within the last century and present concerns point (b), it is totally different, in terms of adopted suspended loads have a lower 10Be concentration. This clearly investigation tactics, to study a small area, in which one indicates a response of the erosional source in the streams to knows that DU-shell were used and see the explosion craters the environmental changes in the watershed. Deforestation and (like in Kosovo), and to investigate a large area, in which one the increase in agricultural land-use enhances sediment surface does not know if DU-shell were used or not (like in the erosion with high 10Be and therefore lead to high 10Be Sardinian firing ranges). These facts demonstrate that sediment deposits from that time. Afforestation and the technical advisors must be selected among experts in increase in urbanisation in the catchment within the last 200 geochemistry to ensure a fair trial. The international yrs in turn led to a decrease in upland erosion. geochemical community is urged to play an active role on this crucial point. [1] Wallbrink & Murray (1996) Water Res 32 (2), 467-476. [2] Zapata (2003) Soil Till Res 69, 3-13. [3] Aalto & Nittrouer (2012) Phil. Trans.370, 2040-2074.

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Ni diffusion in small angle grain Magma Signatures in the Terceira boundaries of forsterite Rift Azores: a melt inclusion study MARQUARDT, KATHRINA1 AND DOHMEN, RALF2 A FILIPA A MARQUES 1, ZOLTAN ZAJACZ 2, PEDRO 3 4 1 MADUREIRA AND STEVEN D SCOTT Deutsches GeoForschungsZentrum Potsdam 2Instsitut für Geologie, Mineralogie und Geophysik, Ruhr 1CREMINER (LARSyS), University of Lisbon, Portugal Universität Bochum 2ETH Zürich, Switzerland 3EMEPC & University of Évora, Portugal Defects such as grain boundaries and interfaces are potent 4University of Toronto, Dept. Earth Sciences, Canada pathways for the transport of elements in rocks [1]; therefore they strongly affect large-scale physical properties of rocks, The Terceira Rift (TR) is a 550km long ESE trending line e.g. viscosity, electrical conductivity and bulk diffusivity. Yet of volcanic reliefs (Graciosa Island, Terceira Island, D. João data for geo-relevant materials are rare. The dependence of de Castro Bank, S. Miguel Island) alternating with deep basins diffusion on the grain boundary structure e.g. defined by the (e.g. E of Terceira, Hirondelle) that define the plate boundary lattice misfit, in silicates is unknown [p.954, 2]. Limited between the European and African plates on the Azores experimental studies in material sciences indicate major plateau [1]. Seismic tomography suggests that the Azores effects of grain boundary orientation on diffusion. Lately, plume is centered NE of Terceira supplying upwelling plume synthetic georelevant bicrystals became available. Thus only material SW of Terceira (e.g. Faial) [2]. now, first diffusion data on single grain boundaries have been Melt inclusions (MI) are small portions of melt trapped produced [e.g. 3]. during crystal growth. Their study allows the characterization The effect of grain boundary orientation on diffusion in of the composition of primary melts, mantle heterogeneity, forsterite tilt grain boundaries (misorientations of 17° and 11°) magma sources and timescales. This study presents the first was characterized by transmission electron microscopy geochemical dataset of olivine-hosted unexposed MI sampled (TEM). The site specific TEM-foils were cut using the from submarine and subaereal lavas along the TR. Plots of focused ion beam technique (FIB). To study diffusion we incompatible trace element ratios (Fig.1) confirm the presence

prepared amorphous thin-films of Ni2SiO4 composition of distinct mantle signatures showing a mixing trend between perpendicular to the grain boundary using pulsed laser two end-members that represent extreme topographic deposition. Annealing (800-1000°C) leads to crystallization of domains: Terceira and Hirondelle Basin. These findings will the thin-film and Ni-Mg inter-diffuse into the crystal volume be discussed considering recent geophysical and geochemical and along the grain boundary. The interdiffusion profiles were data obtained in the area. measured using the TEMs energy dispersive x-ray spectrometer standardized using the Cliff-Lorimer equa. and EMPA measurements. We obtain volume diffusion coefficients that are consistent with earlier studies of Ni-Mg interdiffusion in forsterite at comparable temperatures. Contrasting to [4] our volume diffusion data are about an order of magnitude slower, while having similar activation energies. Grain boundary diffusion perpendicular to the dislocation lines of the small angle grain boundaries proved to be max. an order of magnitude faster than volume diffusion. The difference deceases markedly at temperatures above 1000°C. Fig. 1 Incompatible trace element plots of olivine-hosted MI from the TR. (square symbols: aereal lavas; circles: submarine lavas) [1] Hartmann, Wirth & Markl (2008) Contributions to Mineralogy and Petrology 156, 359-375. [2] Dohmen & AFA Marques research is funded by CREMINER/LA Milke (2010), Reviews in Mineralogy and Geochemistry 72, UI101 POSC (co-financiado FEDER) and FCT’s project 921-970. [3] Marquardt, Petrishcheva et al. (2011), TerRiftic (PTDC/MAR/111306/2009). Steve Scott’s research Contributions to Mineralogy and Petrology. 162, 739-749. [4] is funded by the NSERC. [1] Vogt PR, Jung WY (2004) EPSL Ito, Yurimoto, et al. (1999). Physics and Chemistry of 218:77-90. [2] Yang T, Shen Y, van der Lee S, Solomon SC, Hung Minerals 26, 425-431. SH (2006) EPSL 250:11-26

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Buried lava paleosol in NW Fogo Bottom up approach for the island (Cape Verde) – chemical and predictive modelling of sorption mineralogical evolution isotherms on argillaceous rocks R. MARQUES1,2, M.I. PRUDÊNCIO1,2, J. C. M. MARQUES FERNANDES1*, R. DAEHN1, N. VER2 WAERENBORGH1,3, J. T. COUTINHO1, F. ROCHA2,4, E. AND B. BAEYENS1 2,4 1,2 FERREIRA DA SILVA AND M.I. DIAS 1 Paul Scherrer Institut, CH-5232, Villigen, Switzerland 1Campus Tecnológico e Nuclear, IST/UTL, EN10, Sacavém, (*correspondence: [email protected]) Portugal ([email protected]) 2Hungarian Academy of Sciences, H-1525, Budapest, 2GeoBioTec, Univ. Aveiro, Aveiro, Portugal Hungary 3Centro de Física da Matéria Condensada - Univ. Lisboa, Portugal Sorption in natural argillaceous rocks is inherently too 4Dep. de Geociências, Univ. de Aveiro, Aveiro, Portugal complex and multi-faceted to be mechanistically predicted. The so-called “bottom up” approach for argillaceous rocks is In Fogo island (Cape Verde archipelago), buried based on the hypothesis that the uptake of sorbates in such paleosoils developed between alkaline lava flows occur. Six complex systems can be quantitatively described based on the samples (from parent rock to paleosurface) were collected understanding of the sorption mechanisms on 2:1 type clay from a 1 m thick profile. Weathered samples vary in colour minerals [1]. Illite and illite/smectite mixed layers are the from dark brown to yellowish. Chemical and mineralogical major clay mineral components of many argillaceous rocks, analyses were performed by instrumental neutron activation and their properties are supposed to be responsible for the analysis, Mössbauer spectroscopy and X-ray diffraction. radionuclide uptake in these systems. The aim of this work is to test the capabilities of the 2SPNE SC/CE sorption model [2] and of the generalised sorption model for Cs [3] to make blind predictions of the sorption isotherms in two argillaceous rocks, Boda Clay Formation (BCF) and Opalinus Clay (OPA). As a complementary tool Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy is used to verify the assumptions made in this approach. Sorption isotherms of Cs(I), Ni(II), Co(II) and Eu(III) were measured on BCF and OPA rock samples in their respective pore-waters. The sorption prediction on these argillaceous rocks was then carried out using the mechanistic sorption models developed for illite [2, 3], and the results scaled over the illite and illite/smectite weight content in the Fig. 1 – Chemical variations with depth/weathering degree sample. Generally a good agreement between the measured (after normalization to Sc) data and the predicted values was found. However, some discrepancies were observed, e.g. for Ni(II) on BCF at higher The main minerals of the parent rock identified by XRD Ni(II) equilibrium concentrations. EXAFS was therefore used are pyroxenes, olivines and phyllosilicates. In the paleosol to verify the sorption mechanisms along the isotherm at the only pyroxenes, quartz, phyllosilicates and in the most molecular level. In the isotherm region, where prediction and weathered/surficial samples hematite, were clearly identified. measurement coincide, sorption was in fact the only uptake- Except for Cr a general enrichment of the studied controlling mechanism. In contrast, EXAFS showed chemical elements occurs with increasing weathering (Fig.1). precipitation as additional uptake processes in the isotherm The ancient surficial level has a significant enrichment in Na, regions where prediction and measurement deviated. K, Rb, Cs, Ba, REE, Ta, Th and U. Bromine variations may be mainly related with the presence of fluorapatite detected by [1] Bradbury & Baeyens (2000) Appl. Clay Sci. 52, 27-33. [2] XRD. Iron has a conservative behaviour. As the weathering Bradbury & Baeyens (2009) Geochim. Cosmochim. Acta 73, degree increases the Fe3+/Fe2+ ratio increases from 35% up to 1004-1013. [3] Bradbury & Baeyens (2000) J. Contam. 85% and hematite is formed. Hydrol. 42, 141–163.

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Open-pit coal mining effects on rice paddy Sectoral contributions to black soil composition and metal bioavailability to carbon concentrations and radiative Oryza sativa L. plants in Cam Pha, forcing in Delhi northeastern Vietnam 1, 2 2 J. EDUARDO MARQUEZ, RAUL E. MARTINEZ HOÀNG TH6 PALLAVI MARRAPU , YAFANG CHENG , GREGORY 1, 2 3 2 BÍCH HÒA AND RETO GIERÉ R.CARMICHAEL , GUFRAN BEIG , SCOTT SPAK , MICHAEL DECKER4, MARTIN G SCHULTZ4 Institut für Geo- und Umweltnaturwissenschaften, Albert- 3 AND SAROJ K.SAHU Ludwigs-Universität, Albertstraße 23b, D-79104 Freiburg, 1 Germany. Chemical and Biochemical Engineering, The University of Iowa, Iowa city, IA, United States. 2 This study quantified Cd, Pb, and Cu content, and the soil- Centre for Global and Regional Environmental Research, plant transfer factors of these elements in rice paddies within The University of Iowa, Iowa city, IA, United States. 3 Cam Pha, Quang Ninh province, northeastern Vietnam. The Indian Institute of Tropical Meteorology , Pune, Maharastra, rice paddies are located at a distance of 2 km from the largest India. 4 Coc Sau open-pit coal mine. Electron microprobe analysis and Forschungszentrum Juelich GmbH,Juelich, Germany. energy-dispersive spectroscopy revealed a relatively high proportion of carbon particles rimmed by an iron sulfide In this study we evaluate the air pollution levels in Delhi mineral in the quartz-clay matrix of rice paddy soils at 20-30 and their impacts on weather and climate. The two way cm depth. Bulk chemical analysis of these soils revealed Cd, interactions between pollution and meteorology are evaluated Pb, and Cu in concentrations exceeding calculated background using the WRF-Chem model. The analysis period is focused concentrations by 2500, 1226, and 979 %, respectively. Metals on October 2010, the time period of the Commonwealth and metalloids in Cam Pha rice paddy soils, including As, Cd, Games. The model is compared to BC and PM2.5 Cr, Cu, Hg, Mn, Ni, Pb, and Zn, ranged from 0.2 ± 0.1 to 140 measurements at 11 sites. A sector based analysis is performed ± 3 mg/kg, in close agreement with toxic metal contents in to assess the contributions to pollution and direct radiative mine tailings and Coc Sau coal. Native and model Oryza forcing from transport, residential, power and industrial sativa L. rice plants were grown in the laboratory in presence emissions. The contributions from emissions outside of Delhi of 1.5 mg/kg of paddy soil from Cam Pha to investigate its are also evaluated to see the extent that regional emissions effects on plant growth. A decrease in growth of 60% with need to be controlled to meet air quality targets in Delhi. respect to a control was found for model plants, whereas a Results of simulations for emission scenarios for 2030 decrease of only 10% was observed for native rice plants. This generated by the GAINS model that address air quality and result suggests an adaptation of native Cam Pha rice plants to climate strategies are also discussed. toxic metals in the agricultural lands. The Cd, Cu, and Pb contents of the native rice plants from Cam Pha paddies exceeded permitted levels in foods. Cadmium was highest in the rice-grain endosperm at 0.09 ± 0.01 mg/kg, compared to the allowed content in foods of 0.05 mg/kg. Along with rice plant adaptation to contaminated soils, bioaccumulation of trace metals, such as Cd and Pb, poses a severe health risk to the population of Cam Pha. The adaptation of native rice plants, combined with bioaccumulation ratios of 1 ± 0.6 to 1.4 ± 0.7 calculated for Cd transfer to the rice-grain endosperm, strongly suggest a continuous input of toxic metals from coal- mining to agricultural lands in Cam Pha. In addition, our results imply a sustained absorption of metals by native rice plant varieties, which may lead to metal accumulation (e.g. Cd) in human organs and in turn to severe disease.

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Competitive effect of Al(III) on Deep ingression of meteoric water in Eu(III) sorption to illite late-metamorphic veins: a LA- R. MARSAC*1, A. SCHNURR1, T. KUPCIK1, T. RABUNG1, ICPMS fluid inclusion study from the T. SCHÄFER1, N.L. BANIK1, C.M. MARQUARDT1 , Rhenish Massif, Germany M. MARQUES-FERNANDEZ2, B. BAEYENS2, 1 2 1 M.H. BRADBURY2 AND H. GECKEIS1 A. MARSALA *, T. WAGNER AND M. WÄLLE 1Karlsruhe Institute for Technology, Institute for Nuclear 1 ETH Zurich, Department of Earth Sciences, Institute of Waste Disposal, D-76021 Karlsruhe, Germany. Geochemistry and Petrology, Clausiusstrasse 25, 8092 (*correspondence: [email protected]) Zurich, Switzerland (*correspondence: 2Paul Scherrer Institut, Laboratory for Waste Management, [email protected]) 5232 Villigen PSI, Switzerland 2 Division of Geology, Department of Geosciences and Geography, University of Helsinki, P.O.Box 64 (Gustaf Clay rock formations present low permeability and strong Hällströmin katu 2a), FI-00014 Helsinki, Finland sorption capabilities for cations, two properties that make them suitable as host rocks for nuclear waste disposal. The fluid evolution of late-metamorphic quartz vein Accurate description of radionuclide sorption onto clay rock systems in the fold-and-thrust belt of the Rhenish Massif has based on geochemical sorption modelling is required to assess been investigated by microthermometry and LA-ICPMS radionuclide migration properly. Examining published studies microanalysis. The quartz veins are hosted in very low-grade on trivalent actinide/lanthanide (An/Ln(III)) sorption to Illite organic-matter-rich metapelites of the Hunsrückschiefer and batches (Illite du Puy) reveals data sets showing different record two major stages of textural evolution: (1) a massive metal ion sorption behavior [1-3] (and own experimental vein filling assemblage with elongate-blocky quartz, chlorite, data). Surface complexation constants can differ by more than albite and apatite, and (2) an open space filling assemblage s one order of magnitude (log K1=1.9 vs. 3.1). with euhedral crystals of quartz, ankerite/dolomite and minor Comparing Eu sorption data implies that in one case calcite and sulfides. The euhedral quartz crystals host well (stronger sorption) [3] the description of isotherms by the 2 preserved fluid inclusion assemblages and permitted to SPNE SC/CE model requires the consideration of strong and reconstruct the evolution of the fluid system with time. The

weak sites, where binding to strong sites prevails at low [Eu]tot fluid inclusions, all aqueous two-phase with low salinity,

and sorption to weak sites at higher [Eu]tot. In the other cases belong to three successive generations. They show a Eu(III) sorption appears to be linear over a wide range of systematic decrease in salinity from 4.7-5.3 to 3.1-3.9 and 1.4-

[Eu]tot, suggesting strong sites being absent or blocked. We 1.7 wt.% eqv. NaCl, and a decrease in homogenization explain this observation by slightly different Illite purification temperatures from 210-225 °C to 148-164 °C and 124-139 °C. procedures notably by the effect of an acid washing step [1-3]. LA-ICPMS microanalysis of individual fluid inclusions If Illite batches are washed at pH=3.5 with HCl during 1 week yielded reproducible concentrations of Li, Na, K, Rb, Cs, Mg, before Eu addition, we exclusively found weaker Eu sorption. Ca, Ba, Sr, B, Al, As, Sb, S, Cl and Br. Alkali metals and A possible explanation for this observation is the incongruent boron, arsenic and antimony are correlated with the fluid Illite dissolution resulting in the release of Al(III), which in salinity. Element concentrations are highest in the early fluid turn can compete with Eu(III) for sorption sites. In order to generation and decrease systematically in the latter two confirm this hypothesis we contacted Illite during 1 week with generations. Changes in salinity, homogenization temperature a solution containing 10-4 M of Al(III) (i.e. equal to [Al] due to and elemental concentrations are explained by fluid mixing illite dissolution at pH=3.5) at different pH. Again, we found between a hot metamorphic fluid (moderate salinity and Eu sorption behaviour similar to that of the acid treated clay. elevated concentrations of B, As and Sb) and a cooler dilute Taking the competing effect of Al(III) species into account meteoric fluid during late-metamorphic exhumation and uplift. can explain the different Eu(III) sorption data sets. Cl/Br ratios of the fluid inclusions extend from close to seawater to values that are substantially below seawater. [1] Gorgeon (1994) Ph.D. thesis University Paris 6. [2] Because evaporitic rocks are absent in the shallow-water Bradbury & Baeyens (2009) Geochim. Cosmochim. Acta 73, marine sequence of the Rhenish Massif, the elevated Br 990-1003. [3] Bradbury et al. (2005) Geochim. Cosmochim. concentrations and Cl/Br ratios below seawater are best Acta 69, 5403-5412. explained by fluid-rock interaction and uptake of Br from the organic matter in the metasediments.

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Mélange formation, mantle-wedge Raman hyperspectral imaging of diapirs and subduction zone carbonaceous materials and magmatism hematite: potential HORST R. MARSCHALL1 AND JOHN C. SCHUMACHER2 misinterpretations 1 Dept Geology & Geophysics, WHOI, Woods Hole, MA, CRAIG P. MARSHALL1 AND ALISON OLCOTT MARSHALL1 USA, [email protected] 1Department of Geology, University of Kansas, Lawrence, 2 Dept Earth Sci., University Bristol, Bristol, UK, KS, 66045, USA [email protected] and [email protected] [email protected]

Raman hyperspectral imaging is becoming increasingly Components derived from the subducting slab contribute popular in geoscience applications, as geologists, to the source region of magmas produced at convergent plate paleontologists, and planetary and space scientists discover the margins. The characteristic range of compositions of these wealth of non-destructive mineral data that Raman magmas is commonly attributed to three-component mixing in spectroscopy can provide. One common application of Raman the source regions of these magmas: hydrous fluids derived hyperspectral imaging is identification of optically similar from subducted altered oceanic crust and components derived minerals within thin sections and their spatial distribution. For from the thin sedimentary veneer are added to the depleted 2 example, hematite, disordered sp carbonaceous material, and peridotite in the mantle wedge, where melt is produced. We graphite can co-occur within a sample and often appear as recently proposed an integrated physico-chemical model of black opaque minerals that are challenging to distinguish subduction zones that includes mélange formation at the slab- optically [e.g., 1,2]. In order to distinguish between these three mantle interface as the dominant physical mixing process, as minerals geologists will typically collect a Raman spectrum in well as low-density mantle-wedge diapirs that transport the the carbon first-order region between 900-1800 cm-1. well-mixed materials into the hot corner of the mantle wedge Coincidently the hematite 2LO (which appear due to point beneath arcs [1]. -1 defects of the &-Fe2O3 lattice) at ca. 1320 cm is located in the The strong petrologic and chemical contrast at the slab- 2 same frequency region of the disordered sp carbonaceous mantle interface leads to the production of hybrid rock material D band (A1g mode active due to disorder and compositions by metasomatic reactions, diffusion and -1 decreasing crystallite size) at ca. 1350 cm . While some mechanical mixing. The rise of low-density plumes in the geologists are cognizant of the overlap between the broad 2LO mantle wedge provides a mechanism to transport these 2 hematite mode and the broad D band of disordered sp carbon, buoyant hybrid rocks from the slab-mantle interface toward many however remain unaware [e.g., 3,4,5,6], identifying the source region of arc magmas. The mélange plumes may hematite by examination of the mineral fingerprint region partially melt in the hot corner of the mantle wedge due to -1 (200-800 cm ) only [e.g., 7]. We suggest that rather than heating and decompression, or their interior parts may examining the mineral fingerprint region and the carbon first- dehydrate and flux-melt the overlying mantle-wedge order region separately for hyperspectral 2D and 3D imaging, harzburgite. The combination of these processes may produce -1 the entire spectral region from 200-1800 cm should be used the large range of major and trace-element compositions found in order to eliminate further false identification of these two in modern island arc volcanic rocks. minerals. Furthermore we suggest caution when interpreting Consequences and predictions from our model include the the carbon first-order region as the G band (E mode in-plane following: low-velocity zones at the slab-mantle interface and 2g2 C-C stretching LO phonon mode of an infinite crystal) from in the mantle wedge may represent layers and diapirs of fluid- carbon is always present whatever the degree of structural rich mélange material instead of hot, melt-bearing mantle. The 2 order that the carbon sp lattice has. slab components are transported as solid matter into the source region of arc magmas rather than through the classically [1] Marshall et al. (2011) Nat Geosci.4, 240-243. [2] Marshall invoked fluids and melts. The temperatures and timescales for and Olcott Marshall (2011) Spectrochimica Acta.80, 133-137. the generation of arc magmas determined from isotope and [3] Lu et al. (2007) Adv. Funct. Mater.17, 3885-3896. [4] Lu trace-element ratios need to be revisited, as these may reflect et al. (2008) J. Phys. Chem. C.112, 7069-7078. [5] Torporski processes in the head of the mélange diapirs rather than in the et al. (2004) GIT Imaging Microsc.4, 38-40. [6] Schopf et al. subducting slab or the harzburgitic mantle wedge. (2005) Astrobiology.5, 333-371. [7] Schopf et al. (2010) Precamb Res.179, 191-205. [1] Marschall, Schumacher (2012) Nature Geosci. 5: 862–867

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A new model for emerald Crustal evolution during granite mineralisation and boiling as a emplacement: inheritance and mechanism for emerald zoning and development of heat-producing colouration. element enrichment DAN MARSHALL1*, LARA LOUGHREY2, V. MARSHALL1,2*, K. KNESEL2, S. E. BRYAN3, MEGHAN HEWTON3 AND GABRIEL XUE4 C. M. ALLEN4 AND I. T. UYSAL1 1Earth Sciences, Simon Fraser University, Burnaby, BC, 1Queensland Geothermal Energy Centre of Excellence, Canada (correspondence: [email protected]) [email protected] (*presenting author) 2Teck Resources Ltd., 550 Burrard St, Vancouver, BC, 2School of Earth Sciences, The University of Queensland Canada ([email protected]) 3Earth, Environmental & Biological Sciences, Queensland 3Teck Alaska Inc., Red Dog Mine University of Technology Anchorage, AK, USA( [email protected]) 4Institute of Future Environments, Queensland University of 4Callinex Mines Inc., Vancouver, B.C., Canada Technology ([email protected]) The Big Lake Suite (BLS) granite in central Australia is Emerald forms in a number of geological environments [1] one of the most prospective hot-dry rock geothermal resources from a wide variety of fluids, dominated by water, generally worldwide. We have undertaken LA-ICP-MS 206Pb/238U dating comprising a variety of salts, and compressible gases [2]. of ~500 spots in 431 zircons across two plutons to shed new Geological environments are variable but unique in that they insights into petrogenesis and the relationship between offer mechanisms that allow for the combination of emplacement age and elemental enrichment; heat-producing berrylium-rich fluids to interact with chromium- and element (HPE) enrichments vary from 144–28 ppm Th and vanadium-bearing fluids or rocks. Our more recent work has 30–8 ppm U between plutons. concentrated on a relativey new occurrence of emerald in the New emplacement ages were obtained for drill holes Big Northwest Territories of Canada. Emerald from this deposit Lake 1 (299 ± 6 Ma, MSWD 1.6, n=33) and Moomba 1 (324 ± has precipitated from saline brines via inorganic sulphate 5 Ma, MSWD 0.71, n=42) in the southwest pluton, and reduction. Habanero 1 (315 ± 5, MSWD 1, n=38), Jolokia 1 (319 ± 13, MSWD 0.75, n=5) and McLeod 1 (306 ± 5 Ma, MSWD 1.8, n=74) in the northeast pluton. 206Pb/238U ages suggest protracted magmatism ~325–300 Ma, reinforcing the idea of piecemeal accumulation of granitic bodies. Inherited 427–414 Ma ages for igneous zircons were identified in all wells (except Jolokia 1) indicating a recycled Silurian magmatic component in the BLS. Although there is overlap, inherited zircons have (on average) lesser trace- element enrichment (~250 ppm U) than emplacement-aged zircons (~870 ppm U). This suggests the emplacement-aged magma had undergone a greater degree of differentiation, thereby enriching it in HPE relative to magma compositions from which the inherited zircon population crystallised. Protracted magmatism over ~25 Myr, and differences in emplacement history, can help explain variations in U and Th enrichment across the two plutons. Samples from the southwest pluton exhibit a difference in emplacement age of Figure 1. Zoned emerald from the Byrud deposit. ~25 Myr, yet exhibit similar maximum Th and U enrichment implying initial elemental composition and differentiation Zoned gem emerald occurs in a number of deposits controls allowed the magma to differentiate to the same level. worldwide. The best known occurences of zoned emerald are Comparatively, in the northeast pluton, greater variability in the Emmaville-Torrington in Australia, Erongo in Namibia, final Th and U enrichment suggests slight differences in and the Byrud deposit in Norway. Recent fluid inclusion source controls over the crystallisation history of the pluton. studies indicate that the zebra striping or zoned emerald (Fig. 1) is related to alternating precipitation of clear beryl and emerald in the vapour and liquid conjugates of (two-phase) boiling systems respectively.

[1] Groat et al. (2008) Ore Geol. Rev. 34, 87-112. [2] Roedder (1972) U.S.G.S. Prof. Paper 440 JJ, 164 p.

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Magmatic volatiles and mantle source Helium isotopes signature of mafic lithology in the Hawaiian Plume: a volcanics at Stromboli (Italy) view from olivine-hosted melt during its magmatic evolution. inclusions, glasses, and osmium M. MARTELLI1, A. RIZZO1, A. RENZULLI2, F. RIDOLFI2, I. isotopes ARIENZO3 AND A. ROSCIGLIONE4 1 1 1 2 Istituto Nazionale di Geofisica e Vulcanologia, Sezione di JARED MARSKE , ERIK HAURI , MICHAEL GARCIA 3 Palermo, Palermo, Italy, [email protected] AND AARON PIETRUSZKA 2 Dipartimento di Scienze della Terra, della Vita e 1j5241 Broad Branch Rd, Washington DC, [email protected] dell’Ambiente - University of Urbino, Italy 25241 Broad Branch Rd, Washington DC, [email protected] 3 Istituto Nazionale di Geofisica e Vulcanologia, Sezione di 31680 East-West Rd, Honolulu HI, [email protected] Napoli Osservatorio Vesuviano, Napoli, Italy 4Box 25046 DFC, Denver, CO, [email protected] 4 Dipartimento DiSTeM, Università di Palermo, Italy

Variations in radiogenic isotopes (e.g. Pb,Nd) and A study on fluid inclusions of mafic minerals from magmatic volatiles (e.g. CO2,H2O) in Hawaiian volcanoes selected volcanics is conducted to characterize the He and Ar reveal important processes (i.e. source heterogeneity, melting, isotopes of Stromboli. We also measured trace element in magma degassing). Shield-stage lavas likely originate from a clinopyroxenes of selected samples and Sr-Nd isotopes. The plume source containing peridotite and ancient recycled samples belong to (i) the present-day activity of Stromboli; (ii) oceanic crust (pyroxenite). The source region may also be the extreme terms among the magmatic series erupted heterogeneous with respect to volatile concentrations. (calcalcaline CA and potassic KS); (iii) the ultramafic However, shallow degassing makes it difficult to determine if xenoliths outcropping in the island. The gas content trapped in there is a link between mantle source composition and volatile mafic crystals is consistent with magma crystallization and budget. Here we present Os isotopic ratios and volatile fluid entrapment from mantle depths to progressively contents on olivines and glasses for 33 samples from Koolau, shallower conditions. All samples have 3He/4He in the range Mauna Kea, Mauna Loa, Hualalai, Kilauea, and Loihi to 4.0-4.9 Ra, except the KS (3He/4He < 3.5 Ra), associated to determine if volatiles in magmas correlate with geochemical higher Sr and lower Nd isotope ratio. Overall, He isotopes are tracers of source lithologies. For a given volcano, most well associated to lithophile element isotopes. The whole set osmium isotopic compositions of olivines are similar to the of helium isotope data indicates ratios lower than those whole-rock values, yet some Mauna Loa and Loihi olivines measured in the most uncontaminated Aeolian lavas (i.e., display the significantly low 187Os/188Os values (~0.117) Alicudi, ~ 7 Ra) and in common volcanic arcs, due to that may reflect partial melts of ancient recycled mantle subduction-related contamination beneath Stromboli. 3He/4He lithosphere. SIMS analyses on Hawaiian glasses reveal a range from mafic minerals are compared to those of currently in abundances of CO2 (10-251 ppm), H2O (0.2-1.2 wt.%), S geothermal fluids, with the latter ranging between 3.9 and 4.5 (38-2960 ppm), and Cl (39-2960 ppm). However, most Ra. The maximum 3He/4He ratio measured in LP fluid samples have low CO2 contents (<100 ppm) indicating they inclusions (i.e., 4.6 Ra) would thus correspond to the upper experienced degassing. Olivine-hosted melt inclusions may limit that should be expected for surface gases during or better preserve pre-eruptive concentrations and we will present before high-intensity eruptive events, when a deep gas new volatile contents on Hawaiian melt inclusions from the component is released from the magma. same olivines analyzed for Os isotopes.

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Developing the comminution age Fayalite oxidation processes at technique: Isolating the detrital Obsidian Cliffs, Oregon minerals A.M. MARTIN1*, E. MÉDARD2, B. DEVOUARD2, L.P. 1 1 2 1 KELLER , K. RIGHTER , J.-L. DEVIDAL AND A.N. MARTIN* AND A. DOSSETO 1 1Wollongong Isotope Geochronology Laboratory, School of Z. RAHMAN Earth and Environmental Sciences, University of Wollongong. 1 Johnson Space Center, 2101 NASA Parkway, Houston, TX (*correspondence: [email protected]) 77058 USA (*correspondence: [email protected]) 2 Clermont Université, UBP/CNRS/IRD, Laboratoire Magmas The uranium-series isotopes can be used to quantify the et Volcans, 5 rue Kessler, 63038 Clermont-Ferrand, timescales on which Earth-surface processes operate; this is France essential before we can begin to try to understand how the erosion of the Earth’s surface responds to climate change. Fayalite Fe 2+SiO , the ferrous end-member of olivine, is The traditional uranium-series methodology analyses the 2 4 present in terrestrial rocks and in primitive meteorites [1]. A isotopic composition of the bulk sediment; however, this ferric fayalite, laihunite Fe2+Fe3+ %(SiO ) , has also been requires complex modelling to account for the variable 2 4 2 reported in terrestrial [2, 3, 4, 5] and martian [6] samples. In isotopic composition of authigenic phases, such as carbonates order to constrain the oxidation processes of fayalite, we have and organic material [1]. The accuracy of the calculated ages studied crystals found in lithophysae from the Obsidian Cliffs can be improved by focussing on the isotopic evolution of rhyolite using EMPA and SAED+EELS on a TEM, and made only the detrital minerals. One such example is the emerging thermodynamic modelling. comminution age technique which calculates a radiometric age ! by relating the (234U/238U) of the detrital minerals to the surface area [2]. Sequential extraction procedures are currently used to remove the non-detrital fraction but these procedures are unreliable and suffer from a lack of reproducibility and completeness. To overcome this, the isolation of the detrital minerals can be monitored by analysing the (234U/238U) of the sediment throughout the procedure. This is possible as there !!!! are three domains of (234U/238U) in sediment: 1. (234U/238U) = 1 ! for the inner-core of detrital minerals, (234U/238U) < 1 in the Figure 1: (a) picture of an oxidized fayalite crystal (approx. outer-rind (ca. 50 nm) of sediment due to the effects of alpha- 1.6 mm tall) (©B.Lechner) (b) HRTEM image of the recoil, and (234U/238U) > 1 for the non-detrital fraction [3]. The fayalite/laihunite interface. minimum (234U/238U) of the sediment therefore represents the ! optimum isolation of the detrital minerals. Fayalite crystallized at 800-900°C and low pH2O. This study evaluates existing sequential extraction Temperature decrease to 650°C induced the oxidation of 2+ 3+ procedures and proposes an optimised procedure based on the fayalite into a “laihunite” zone Fe Fe 2%(SiO4)2 composed of above methodology. This will be presented in addition to the nano-lamellae of various oxidation phases (Fig.1). Further implications of the results upon ages calculated using the cooling, H2O exsolution from rhyolite lava and/or infiltration comminution age technique. of meteoric water caused the oxidation of the “laihunite” zone 2+ 3+ into an “oxyfayalite” zone Fe 0.26Fe 1.16%0.58(SiO4) also made [1] A.J. Plater, M. Ivanovich, R.E. Dugdale (1992), Applied of nano-lamellae. Geochemistry, 7 101-110. [2] D.J. DePaolo, K. Maher, J.N. Fayalite oxidation reactions can be used to constrain the Christensen, J. McManus (2006), Earth and Planetary Science emplacement and cooling history of the lava flow. Our data Letters, 248 394-410. [3] V.E. Lee (2009), “Radiogenic also hint at the existence of a ferric fayalite phase that is more Isotope Geochemistry and the Evolution of the Earth’s Surface oxidized than laihunite. and Interior”, PhD Thesis, University of California, Berkeley. ! [1] Jogo et al. (2009) EPSL 287, 320-328 [2] Laihunite Research Group (1982) CJG 1, 105-115 [3] Schaefer (1983) Nature 303, 325-327 [4] Kitamura et al. (1984) AmMin 69, 154-160 [5] Shen et al. (1986) AmMin 71, 1455-1460 [6] Noguchi et al. (2009) JGR 114, E10004.

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Heating from within and without, Carbon budget during alteration of tales of contrasting long-lived crustal the oceanic crust hots spots I. MARTINEZ*1, S. SHILOBREEVA2, V. BUSIGNY1, 3 4 1 1 C. LAVERNE , J. ALT AND P. AGRINIER M. HAND 1 IPGP, PRES Sorbonne Paris Cité, Paris, France (* South Australian Centre for Geothermal Energy Research, correspondence: [email protected]). University of Adelaide, S.A., 5005 Australia. 2 Vernadsky Institute, Moscow, Russia. (correspondence: [email protected]) 3 Univ. Aix-Marseille III, Marseille, France.

4 Univ. of Michigan, Ann Arbor MI, USA. High thermal gradient conditions in the crust can be

generated by a number of mechanisms: direct advection of Although it is largely accepted that volatile elements are heat via magmatism, high basal heat flow associated with incorporated into the oceanic crust during alteration, the flux extension/removal of lithospheric mantle, rapid exhumation of of carbon involved in this transfer remains poorly known. The deeply buried rocks and high rates of internal heat generation. detailed study of altered rocks is a key to better constrain the While each of these mechanisms may have characteristic time C uptake during alteration. In this work, we studied carbon and length scales, the duration of metamorphism as perceived concentrations and isotopic compositions in altered basaltic by geologists is generally controlled by the exhumation samples drilled from 2 different sites. We first selected a potential in the system which determines the thermal record of young section of altered oceanic crust (15 Ma): the an individual rock. Therefore long-lived high-T ODP/IODP Hole 1256D, providing a large variety of rocks metamorphism generally points to thermally anomalous from lavas down to the gabbroic rocks. The second set of conditions in crust with low exhumation potential where samples, which is of Jurassic age (Site 801, 150 Ma), was material stays within the system for an extended period of selected to evaluate C uptake variations during aging of the time (e.g. orogenic plateaus). crust. All samples are enriched in carbon relative to fresh More intriguing is apparently long-lived (~ 100 Ma) high- basalts. For 1256D samples, total CO ranges between 564 and T “hot-spot” metamorphism that appears to have operated on a 2 2823 ppm with "13C values from -14.9‰ to -26.6‰. The sub-orogenic (~ 100km) scale length scale. This sub-orogenic carbon isotope compositions are interpreted in terms of a scale means that rocks can potentially easily move out of the mixing between two components: (1) carbonate with "13C = - high-T region curtailing the duration of their high-T history. 4.5‰ and (2) organic compound with "13C = -26.6‰ Such systems can be plausibly be driven by high rates of representing more than 75% of the total C in most of the internal radiogenic crustal heat generation in chemically samples. Jurassic samples are enriched in carbon relative to anomalous crust undergoing limited deformation. For 1256D samples (with total CO between 0.3 and 2wt%). example in parts of central Australia, crustal heat generation 2 -3 Although the organic carbon concentration and isotope rates are regionally in excess of 8µWm , and are spatially composition remains constant in these samples, the carbonate associated with high-T low-P granulite metamorphism. concentration strongly increases. A possible explanation is “Long-lived crustal “hot spots” can also be generated in that higher atmospheric CO in the Mesozoic [1] may have led highly localised rift basins developed in thick continental 2 to higher carbonate contents in the old 801 basement. lithosphere. Continental rift basins may accumulate in excess Alternatively, we propose a two-step model for carbon cycling of 25km of sediment fill associated with voluminous mafic during crustal alteration: (i) organic compounds are formed magmatism. This creates a logical setting for high-T, medium close to ridge axis, either through recycling of biogenically- P metamorphism associated with on-going basin development, derived material or Fischer-Tropsch-type reactions; (ii) away including high-grade intrabasinal deformation. from the ridge axis, the organic production decreases and We discuss salient features of internally and externally carbon uptake is dominated by carbonate precipitation from driven crustal “hot spots”. seawater. The total flux of C stored in the altered oceanic

crust, as carbonate and organic compounds, is estimated at

2.9±0.4 1012 molC/yr with a mean "13C of -4.7‰.

[1] Gillis & Coogan (2011) EPSL 302,385-392.

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Modelling of rare earth element The conditions of formation of the sorption to Bacillus subtilis bacteria Castro de Rei reduced W-skarn RAUL E. MARTINEZ1, OLIVIER POURRET2 I. MARTÍNEZ-ABAD1* AND A. CEPEDAL1 3 AND YOSHIO TAKAHASHI 1 Department of Geology, University of Oviedo, Arias de 1 Insitut für Geo- und Umweltnaturwissenschaften, Albert- Velasco s/n, 33005, Oviedo, Spain. Ludwigs Universität, Albertstraße 23b, D-79104, (*correspondence: [email protected]) Freiburg, Germany. [email protected] 2 HydrISE, Institut Polytechnique LaSalle Beauvais, 19 rue The reduced W-skarn of Castro the Rei (Villalba Gold Pierre Waguet, 60026 Beauvais Cedex, France. District, NW Spain) is hosted by marbles and calc-silicate 3 Department of Earth and Planetary Systems Science, hornfels of the contact aureole of a blind poskinematic Hiroshima University, Higashi-Hiroshima, Hiroshima Variscan granitoid [1, 2]. A hornblende-hornfels facies 739-8526, Japan. metamorphism is related to these granitoids, at pressures up to 2 kb [3]. Prograde skarn developed in marble is characterized In this study, rare earth element (REE) binding constants by garnet (Gr41-77), pyroxene (Hd33-100), quartz and calcite with and site concentration on the Gram+ bacteria surfaces were minor scheelite, K-feldespar and apatite. Locally, it can be quantified using a multi-site Langmuir isotherm model, along formed by wollastonite, garnet (Gr62-82) and piroxene (Hd43-70). with a linear programming regression method (LPM). This Prograde skarn and calc-silicate hornfels were overprinted by approach found one discrete REE binding site on the Gram+ two stages of retroskarn. The first stage consists of Bacillus subtilis surface for the pH range of 2.5 to 4.5. ferrotremolite, epidote (Ps19-31), zoisite (Ps0-19), quartz, calcite, Average log REE binding constants from 1.08 ± 0.04 to 1.40 ± K-feldspar and sulfides and the second stage is characterized 0.04 for the light REE (LREE: La to Eu), and from 1.36 ± 0.03 by prehnite or chlorite, quartz, calcite and sulfides. Based on to 2.18 ± 0.14 for the heavy REE (HREE: Gd to Lu) at 1.3 g/L mineral associations, fluid inclusion and stable isotope studies, of Bacillus subtilis bacteria. Similar values were obtained for a T-X(CO2) isobaric (2kb) diagram with selected phase bacteria concentrations of 0.39 and 0.67 g/L Within the equilibria [4] was used for establishing the conditions of the experimental pH range in this study, Bacillus subtilis was skarn formation. shown to have a lower affinity for LREE (e.g. La, Ce, Pr, Nd) Fluid inclusions in garnet and quartz indicate that the and a higher affinity for HREE (e.g. Tm, Yb, Lu) suggesting prograde skarn was formed from a low-CO2 (<0,06 mole an enrichment of HREE on the surface of Gram+ bacteria. fraction) aquocarbonic fluid. At this X(CO2) the minimum Total surface binding site concentrations of 6.73 ± 0.06 to 5.67 formation temperature of the wollastonite-bearing skarn is ± 0.06 and 5.53 ± 0.07 to 4.54 ± 0.03 moles/g of bacteria were 555ºC. For the garnet (Gr41-77) and pyroxene (Hd33-100) skarn, observed for LREE and HREE respectively, and a log KREE,j of the formation temperature is above 520ºC, in agreement with 1.46 ± 0.02 for a biomass content of 1.3 g/L. The difference in the 18O fractionation between quartz and garnet that yields a these values (e.g. a lower affinity and increased binding site temperature of 534ºC. Ferrotremolite, epidote (Ps19-31) and concentration for LREE, and the contrary for the HREE) zoisite (Ps0-19) from the first stage of retroskarn are formed at suggests a distinction between the LREE and HREE binding lower X(CO2) (<0.04 mole fraction) and a temperature below modes to the Gram+ bacteria reactive surface at low pH. A 450ºC. For the second stage of retroskarn, fluid inclusions and multisite Langmiur isotherm approach along with the LPM occurrence of prehnite indicate near 0 X(CO2) and regression method, not requiring prior knowledge of the temperatures below 385ºC. This is consistent with the number or concentration of cell surface REE complexation maximum formation temperature calculated for the chlorite sites, were able to distinguish between the sorption constant [5], up to 325ºC. and binding site concentration patterns of LREE and HREE on the Gram+ Bacillus subtilis surface. This approach quantified [1] Martínez-Abad et al. (2011) In: Ediciones Universidad the enrichment of Tm, Yb and Lu on the bacteria surface and Católica del Norte. Antofagasta, Chile, 2, 550-552. [2] it has proven to be a useful tool for the study of natural Martínez-Abad et al. (2012) Geo-Temas, 13, 414. [3] Bellido- reactive sorbent materials controlling REE partitioning in the Mulas et al. (1987) Memoria del IGME. 157 pp. [4] Berman natural environment. (2007) Geol. Surv. Can. open file rep., 5462, 41pp. [5] Cathelineau, M (1988) Clay Minerals, 23, 471-485.

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Surface ocean "11B-pH Elemental ratios as proxies for reconstructions and insights into the paleoclimate reconstruction in the ocean-atmosphere carbon exchange western Mediterranean during the last deglaciation F. MARTINEZ-RUIZ*1, M. RODRIGO-GAMIZ2, V. 3 1 1 2 1 NIETO-MORENO , F. J. JIMENEZ-ESPEJO , D. M.A. MARTÍNEZ-BOTÍ *, G. MARINO , G.L. FOSTER , 1 4 2 1 2, 3 GALLEGO-TORRES AND M. ORTEGA-HUERTAS P. ZIVERI , M.J. HENEHAN , P.G. MORTYN AND D. VANCE4 1Instituto Andaluz de Ciencias de la Tierra (CSIC-UGR), 1 Spain (*correspondence: [email protected]) Ocean and Earth Science, National Oceanography Centre 2Royal Netherlands Institute for Sea Research, NIOZ, The Southampton, University of Southampton, Southampton Netherlands ([email protected]) SO14 3ZH, UK (*correspondence: M.A.Martinez- 3Biodiversität und Klima Forschungszentrum BiK-F, Germany [email protected]) ([email protected]) 2 Institut de Ciència i Tecnologia Ambientals, Universitat 4Dept. Mineralogía y Petrología (UGR), Spain Autònoma de Barcelona, 08193 Bellaterra, Barcelona, ([email protected]) Spain 3 Department of Geography, Universitat Autònoma de The western Mediterranean region has provided excellent Barcelona, 08193 Bellaterra, Barcelona, Spain 4 marine archives for paleoclimate reconstructions. In particular, Institute of Geochemistry and Petrology, ETH Zürich, the Alboran sea basin where exceptional high sedimentation Zürich, Switzerland rates allowed high-resolution analyses for reconstructing past climate variability. Elemental ratios have revealed as reliable There is a long-standing debate about the causes of the proxies for such reconstruction and have served to glacial-interglacial fluctuations in atmospheric CO 2 characterize arid/wet fluctuations, intensity of atmospheric concentrations (pCO ). One of the most established 2 fluxes and dust deposition, as well as bottom-water oxygen hypotheses involves the “storage” of CO in the deep ocean 2 conditions. Over the past 20,000 cal yr BP, ratios mirroring during glacial periods, and the subsequent re-communication eolian input (Zr/Al, Ti/Al and Si/Al) evidenced a major input of this deep carbon reservoir with the surface ocean and of dust from the offset of the Last Glacial Maximum to the atmosphere during deglaciations (mainly via upwelling in the Oldest Dryas. Mg/Al, K/Al and Rb/Al ratios have provided Southern Ocean), thereby causing atmospheric pCO to 2 information on fluvial contribution, and record humid increase [1-3]. Yet direct evidence for carbon leakage from the conditions during the subsequent Bolling-Allerod warm ocean into the atmosphere during deglaciations is currently period, further supported by the decrease of Zr/Al ratio. These lacking. 11 ratios have also allowed a detailed reconstruction of Boron isotopes (" B) in planktic foraminifera are a paleoclimate conditions during the Younger Dryas and the proven proxy for past surface oceanic pH [4,5], which has Holocene. Ratios of redox sensitive elements such as U/Th, provided valuable insights into past changes in the ocean Zn/Al, Cu/Al, and V/Al ratios have also supported fluctuations carbonate system, and ultimately into past atmospheric pCO2. 11 in oxygen conditions at time of deposition, although these Here we will present new planktic foraminifera " B results elements are particularly susceptible to diagenetic from sediment cores retrieved from the Eastern Equatorial remobilization that could alter the original records. Regarding Pacific and Subantarctic Atlantic Ocean that yield novel productivity fluctuations, reconstructions based on Ba proxies, insights into the causes and mechanisms of pCO rise during 2 including Ba/Al ratios, have shown a significant increase in the last deglaciation. the Ba/Al ratio during cold periods, i.e., H1 and Younger

Dryas (derived from authigenic marine barite) evidencing [1] Anderson et al. (2009) Science 323, 1443-1448. [2] enhanced marine productivity. In contrast, during the early Skinner et al. (2010) Science 328, 1147-1151. [3] Burke & Holocene the Ba/Al ratio indicate decreasing productivity. Robinson (2012) Science 335, 557-561. [4] Sanyal et al. However, the biogeochemistry of Ba is not yet fully (2001) Paleoceanography 16, 515-519. [5] Foster (2008) understood and mechanisms for barite precipitation in the EPSL 271, 254-266. water column still require further investigation.

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Isotope geochemistry in waters Limestone-based technosols. A affected by mining activities in remediation technique for sediments Portman bay (Spain). contaminated by heavy metals. M.J. MARTÍNEZ-SÁNCHEZ1; M.L. GARCÍA-LORENZO2; C. M.J. MARTÍNEZ-SÁNCHEZ1; M.L. GARCÍA-LORENZO2; C. PÉREZ-SIRVENT1* AND M. HERNANDEZ-CORDOBA3. PÉREZ-SIRVENT1*; E. GONZÁLEZ1; V. PÉREZ1; S. 1 1 1 1 MARTÍNEZ ; M.D. BELANDO , L. MARTINEZ Department of Agricultural Chemistry, Geology and AND C. HERNANDEZ1. Pedology. Faculty of Chemistry, University of Murcia, Murcia, Spain. [email protected] 1Department of Agricultural Chemistry, Geology and (*presenting author García-Lorenzo, M.L. Pedology. Faculty of Chemistry, University of Murcia, [email protected]) Murcia, Spain. [email protected] (*presenting author) 2Department of Petrology and Geochemistry. Faculty of 2Department of Petrology and Geochemistry. Faculty of Geology, Unibersity Complutense of Madrid, Madrid Geology, Unibersity Complutense of Madrid, Spain. (Spain) 3Department of Analytical Chemistry. University of Murcia. The aim of this work was to assess the suitability of limestone-based technosols for decreasing the toxicity of the The objective of this work was to characterize processes leachates caused by rain in sites contaminated by heavy affecting waters from Portman bay by way of isotopic metals. For such a purpose, 64 technosols were prepared in analysis, particularly H and O stable isotopes from water containers of 0.75m3, filled with 4 types of sediments molecule and S and O from dissolved sulfates were studied. collected from Portman Bay and subjected to different Portman bay is situated close to the mining region of La Unión stabilizer proportions (limestone filler), different thickness of and was subject to mining from the time of the Roman Empire a drainage layer and presence/absence of a topsoil cover. The to 1991, when the activity ceased. From 1957 to 1991, the technosols were then submitted to different humidity/dryness Peñarroya Mining and Metallurgical Society performed ore cycles simulating the usual rain conditions in the zone and extraction on a large scale. From Lavadero Roberto, the waste percolates were analyzed using a bettery of bioassays. materials were discharged directly into the sea in the inner part Portman bay is situated close to the mining region of La of the bay, and later they were also discharged to sea at a Unión. The entire area around the bay was subject to mining distance of the shore. These wastes mainly consisted in ore from the time of the Roman Empire to 1991. Since 1957, the materials (sulfides as galena, pyrite and sphalerite), wastes from mining operations were discharged directly into phyllosilicates in addition to siderite, iron oxides and the sea in the inner part of the bay, while later on, they were sometimes alteration products such as jarosite, alunite, also discharged to sea at a distance of the shore. These wastes kaolinite and greenalite. mainly consisted in ore materials (galena, pyrite and Mining activities have produced great amount of wastes, sphalerite), phyllosilicates, in addition to siderite, iron oxides characterized by high trace elements content, acidic pH and and sometimes alteration products such as jarosite, alunite, minerals from weathering processes. According to the isotopic kaolinite and greenalite. These materials have suffered a analysis, the origin of waters from Portman Bay is not marine, concentration process by floatation with sea water and as a they are meteoric waters subjected to evaporation except for result of the discharge, the whole of the bay has filled up with two superficial samples from Portman Bay, where seawater wastes which also extend into the Mediterranean Sea. remained stagnated in impermeable sediments. The possible The obtained results suggest that selected remediation marine infiltrations only take place in the deepest layers (>17 technique reduces significantly the toxicological effect of the m) because below this depth materials showed low percolate to the tested organisms. The ecotoxicological testing permeability. Superficial waters from Portman bay have may be a useful approach for assessing the toxicity as a undergone evaporation while deep waters showed no evidence complement to chemical analysis. In addition, the use of a of this process. The isotopic results suggested that the sulfates battery of bioassays allows diminishing problems related to mainly come from sulfide oxidation and transport of produced false positive results. The use of limestone filler constitutes an sulfosalts. The oxygen isotopes of water and sulfates were excellent option in sediments polluted by trace elements, used to indicate the mechanisms of this oxidation, being Fe3+ because of risk for human health or ecosystems does not exist the principal oxidant of pyrite. Moreover, there is evidence after the intervention. in addition, the designed experience showing that sulfate oxygen is derived from water under allow to optimize stabilizer quantities, and may suppose a big aerobic and anaerobic conditions. Isotopic data also suggested cost-saving project in areas affected by mining activities. that a reduction process is taking place under anaerobic conditions, favored by the depth.

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The composition of zircon in Sr and Pb isotopes in surface water peraluminous Variscan granites from and bottom sediments from a public Northern Portugal water supply reservoir, São Paulo, HELENA C.B. MARTINS1* AND JOANA ABREU1 Brazil 1 DGAOT, Centro de Geologia, Faculdade de Ciências V.T. S. MARTINS.1* ; C. S. D. MURAKAMI2 Universidade do Porto, Portugal, [email protected] (* AND C. H. GROHMANN3 presenting author) 1 Institute of Geosciences, University of São Paulo, São Paulo, SP, 05508-080, Brazil (*correspondence: A group of peraluminous Variscan plutons were selected [email protected]) from the study of zircon composition. The selected plutons 2 [email protected] are: the post-D3 Vila Pouca de Aguiar and the Lavadores 3 [email protected] plutons [1, 2] and the late-D3 Vieira do Minho pluton [3]. The zircons occur as euhedral to subhedral crystals and exhibit São Paulo is the biggest city of South America, with finely concentric oscilatory zoning in BSE imaging. Internal almost 20 million people living in its metropolitan area zoning is mainly related to variations of Hf, Y, U and Th (MASP) of almost 6000 km2. This population is mainly concentrations. Compositional ranges in zircon from all supplied by public surface water reservoirs, one of them being granites are present in Figure 1. the Guarapiranga Dam, which provides water to 3,7 million people that live in the southeast of MASP. The Guarapiranga Dam surroundings are occupied by more than 800 thousand people that may compromise the quality of its waters. In order to investigate the existence of anthropogenic influences on the surface water of Gurapiranga Dam, the chemical composition of water and the surroundings rocks and sediments, as well as the Sr and Pb isotopic ratios of them, were analysed. The results obtained from samples of water and sediment (bottom or margins), indicate that the water collected in only one point showed evidence of sewage contamination with the presence of high nitrate (>20 mg/L). In the sediments and bottom margin appeared high concentration of copper in the Figure 1: Compositional variation of zircons. Bar shows the closest points of catchment water by the supply company. The complete range of zircon composition (vertical line), including the presence of copper may be associated with the use of copper median (short horizontal line). sulfate as algicide to prevent the eutrophication process of the The zircon crystals have Zr/Hf ratio varying reservoir and occurs mainly in the deepest parts of the dam. between 29 to 56, with no significant differences between the The Sr isotope data indicated as well as the Pb isotopes, different granites. These values are in the same range of other that the surface waters isotopic ratios are similar to the peraluminous granites [5] and are in accordance with a crustal leachate (nitric and hydrochloric acids 3.5 M) from the bottom signature of zircon as suggested by several authors [4, 5].The and margins sediments, that exhibited high content of copper range of Zr/Hf values in zircon crystals of the studied granite (0.717) and organic matter, or with higher clay content. plutons overlaps with that of the potential protholits proposed Furthermore, the Sr isotope ratios are also similar to those of in the genesis of these peraluminous granites, namely meta- rainwater (0.715). As for the Pb isotopes, the Sr isotopes do igneous crustal sources at different levels [1, 3]. not clearly distinguish anthropogenic sources from natural sources, since both sources have similar ratios to surface [1] Martins et al. (2009) Lithos 111, 142-155 [2] Martins et al. waters in this case. Further studies should indicate that (2011) CR Geoscience 343, 387-396 [3] Martins et al. (2013) isotopes can be used as monitors of safe drinking water. Lithos 162-163, 221-235 [4]Pupin (2000) Trans. R. Soc. Edinb.: Earth Science 91, 245-256 [5] Pérez-Soba et al. (2007) The Canadian Mineralogist 45, 509-527. This work has been financially supported by PTDC/CTE- GIX/099447/2008 (FCT-Portugal, COMPETE/FEDER).

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Emerging organic pollutants removal Nitrogen isotopes in lunar soils: from water using high silica zeolites A record of contributions to A. MARTUCCI1, L. PASTI2, E. SARTI2 AND R. BAGATIN3 planetary surfaces in the inner solar 1Dept. of Physics and Earth Sciences, Univ. of Ferrara, 44100 system Ferrara, Italy; (*correspondence:[email protected]) 1 1 1 2 2 B MARTY , M. CHAUSSIDON , E. FÜRI , K. HASHIZUME , Dept. of Chemistry and Pharmaceutical Sciences, Univ. of 3 4 1 F. PODOSEK , R. WIELER AND L. ZIMMERMANN Ferrara, 44100 Ferrara, Italy; [email protected] 3Eni Donegani Env. Technologies, San Donato Milanese 1CRPG-CNRS, Université de Lorraine, Vandoeuvre, France, 20097,Italy, [email protected] [email protected] 2Osaka University, Japan Zeolites are environmentally compatible crystalline 3Washington University, St Louis, USA aluminosilicates, which have well defined micropore 4ETH, Zürich, Switzerland dimensions and composition in a rigid crystal lattice.
The shape of their internal pore structure can strongly affect their The nitrogen isotope composition of inner planets ("15N = adsorption selectivity toward host molecules [1-3]. In the 0 ‰ for the terrestrial atmosphere) and meteorites (between - present work, organophilic synthetic zeolites which are cheap 40‰ and +40‰ for most meteorite clans) differs drastically and available on the market, differing in topology, channel from both Solar ("15N = -386 ‰ [1]) and Cometary ("15N systems and free window apertures, and emerging organic 7+800 ‰ for CN and HCN) values. On Earth, 15N/14N ratios contaminants (i.e. pharmaceuticals, fuel-based-pollutants) span over less than 40 ‰. In contrast, values measured in differing in chemical properties and molecular dimensions, lunar soils and rocks vary by up to 400 ‰. Since trapped lunar were tested. A combined diffractometric, thermogravimetric, noble gases are exclusively sourced by the solar wind, these and gas chromatographic study was used to: (i) measure the variations were initially interpreted as a temporal evolution of sorption capacity of hydrophobic zeolite materials weighed the solar wind N isotope composition [2]. Ion probe against organic pollutants dissolved in water; (ii) quantify measurements and N-Ar systematics of soil grains have shown aspects of their removal efficiency for potential use in that these N isotope variations instead result from mixing wastewater and groundwater remediation; (iii) understand between light N from the solar wind and a 15N-rich component zeolite structural features for the adsorption of emerging of non-solar origin [3,4]. The latter could have originated from organic pollutants from aqueous solutions. Coupling the implantation of ancient atmospheric N from the Earth, when information gathered from these approaches can help in the terrestrial magnetic field was weaker than Today [5]. selecting adsorbent materials for water treatment. However, the analysis of fluid inclusions in 3.5 Ga-old quartz is consistent with a N content and isotopic composition of the [1] D. Löffler et al. (2005) Environ. Sci. Technol. 39, 5209- Archean atmosphere comparable to modern values [6], which 5218. [2] A. Martucci et al. (2012) Micropor. Mesopor. Mater. suggests that the terrestrial magnetic field was strong enough 148, 174-183. [3] L. Pasti et al. (2012) Micropor. Mesopor. to retain atmospheric N since at least 3.5 Ga. Thus escape of Mater. 160 182–193. [4] B.A. De Moor et al., J. Phys. Chem. atmospheric N should have occurred before 3.5 Ga ago, e.g., C (2011) 115, 1204–1219. in the Hadean, which is difficult to reconcile with the exposure ages and antiquities of lunar soils generally lower than 2-3 Ga. The secular varations of the N isotope composition of lunar soils are better accounted for by mixing solar wind N with asteroidal (IDPs, micrometeorites, meteorites) nitrogen, and temporal N isotope variations are consistent with a marked increase of the meteoritic flux in the last few hundreds of Ma. The N isotope systematics of lunar soils permit to constrain the fraction of cometary impactors to less than 13%, and the water flux to the lunar surface to about 600 tons/yr [7].

[1] B. Marty et al., Science, 332, 1533 (2011). [2] J.F. Kerridge, Rev. Geophys. 31, 423 (1993). [3]. Hashizume et al., Science 290, 1142 (2000). [4]. R. Wieler et al., EPSL 167, 47 (1999). [5] M. Ozima et al., Nature 436, 655 (2005). [6] B. Marty et al., submitted. [7]. E. Fueri et al., Icarus 218, 220 (2012).

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The composition of the Archean Ectomycorrhiza-bacterial atmosphere as a tracer of volatile interactions in weathering echange between the mantle, the MARUPAKULA S*, MAHMOOD S AND FINLAY RD surface and the outer space Uppsala BioCenter, Dept Forest Mycology & Pathology, 1 1,2 3 1 Swedish University of Agricultural Sciences, Box 7026, B. MARTY , M. PUJOL , R. BURGESS , E. HEBRARD , 1 4 Uppsala SE-750 07, Sweden. L. ZIMMERMANN AND P. PHILIPPOT (*[email protected]) 1CRPG-CNRS, Université de Lorraine, Vandoeuvre les Nancy, France. [email protected] The role of ectomycorrhizal fungi in mobilising nutrients 2Present address : Total E&P, Pau, France from organic polymers is widely accepted but the function of 3Manchester University, UK mycorrhizal fungal mycelia in mobilising and transferring 4IPG Paris, France nutrients from mineral substrates to the host trees is less well understood [1]. In addition to increasing the nutrient absorbing The terrestrial atmosphere evolved through time as a result surface area of their host plant root systems, the extraradical of exchanges of volatile elements with the mantle, the crust, mycelia of ectomycorrhizal fungi also provides a direct and the outer space. Measurements of noble gases and pathway for translocation of photosynthetically derived carbon nitrogen in Archean rocks (barite, hydrothermal quartz, cherts) to microenvironments in the soil. The continuous provision of give insights into the composition of the atmosphere at the energy-rich compounds, coupled with the large surface area of time of rock formation. Trapped fluids consist of a mixture of the mycelium, suggests that it may constitute an important one or several hydrothermal component(s) with an niche for bacterial growth and colonization, however the role atmospheric end-member, presumably contributed as of these microbial interactions in weathering is still poorly atmospheric gases dissolved in fresh- or sea-water. The understood. It has been shown that different soil horizons isotopic compositions of Archean neon, argon and krypton harbour different ectomycorrhzal fungi [2] and that the appear similar to the present-day ones for radiogenic or ectomycorrhizal fungi allocate organic acids to mineral fissiogenic isotopes. Compared to extraterrestrial precursors, substrates. In this study we use high-throughput sequencing to Archean atmospheric xenon is enriched in its heavy isotopes study the distribution of different bacterial and fungal taxa in by 1-2 %/amu, and intermediate between chondritic and O, E or B-horizon soil from a podzol collected from Jädraås, modern atmospheric [1]. We interpret this difference as Sweden. Bacterial microbiomes from single mycorrhizal root resulting from a preferential escape of Xe backwards through tips colonised by different fungi were also examined to time [1,2], due to its increasing photoionization by hard UV determine whether distinct bacterial communities were light from the young Sun deep into the atmosphere and a more associated with particular mycorrhizal fungi. efficient trapping interaction with the primitive organic haze [3]. 3.5 Ga ago, the 40Ar/36Ar ratio was 143±24, which, when [1]. Finlay RD, Wallander H, Smits M, Holmström S, van integrated into a 3-box (mantle, crust, atmosphere) K-Ar Hees PAW, Lian B. Rosling A. (2009). Fungal Biology model, is consistent with a significant volume of felsic crust Reviews 23: 101-106. [2]. Rosling A, Landeweert R, Lindahl between 30% and 55% of its present-day volume at that time BD, Larsson K-H, Kuyper TW, Taylor AFS, Finlay RD. [4]. The partial pressure of atmospheric N2 was similar to, or (2003). New Phytologist 159: 775-783. lower than, the present-day one, and the Archean N isotopic composition was similar within 2-3‰ to the modern one [5]. These results indicate efficient magnetic shielding of the atmosphere since 3.5 Ga, and, together from estimates of the density of the Archean atmosphere [6], set constraint on the

PCO2 in the Archean atmosphere at <0.7 bar.

[1] M. Pujol et al., EPSL 308, 298 (2011). [2] B. Marty, EPSL 313, 56 (2012). [3] E. Hébrard & B. Marty, AGU Fall meeting (2012). [4] M. Pujol et al., Nature, in the press. [5] B. Marty et al., submitted. [6] S.M. Som et al., Nature 484, 359 (2012).

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Simulating magma ascent: An Direct link between end-Triassic experimental challenge CAMP volcanism, C-cycle H. MARXER*, P. BELLUCCI, S. ULMER AND M. NOWAK perturbation and mass extinction

1,2 1 University of Tuebingen, Department of Geosciences ANDREA MARZOLI , JACOPO DAL CORSO , FABIO *correspondence: [email protected] TATEO2, HUGH C. JENKYNS3, HERVÉ BERTRAND4 AND NASRRDDINE YOUBI5 Isothermal decompression experiments with H O-bearing 2 1Dipartimento di Geoscienze, Università di Padova, Italy – e- phonolitic melt (synthetic Vesuvius AD 79 “white pumice” mail:[email protected], [email protected] composition) were conducted at super-liquidus T (1323 K) in 2 IGG-CNR, Padova, Italy; [email protected] an internally heated argon pressure vessel. The samples were 3Department of Earth Sciences, University of Oxford, decompressed from 200 MPa at true and interpolated -1 UK; [email protected] decompression rates (DRs) of 0.0028-4.8 MPa·s , applying a 4 Université Lyon1 and Ecole Normale Supérieure de Lyon, novel continuous decompression (CD) [1] as well as former France; [email protected] stepwise decompression (SD) techniques to investigate the 5 Department of Geology, Cadi Ayyad University, Marrakech, effect of decompression path on melt degassing. At target P Morocco; [email protected] the samples were quenched rapidly. The comparison of the vesiculated glass products in terms The eruption of continental flood basalts of the Central of bubble number density (BND), size distribution of bubbles Atlantic Magmatic Province (CAMP) is coeval with mass and residual H O-content in the glass reveals a massive 2 extinction at the Triassic–Jurassic (Tr–J) boundary. In order to influence of the applied decompression path on the degassing define the role of CAMP volcanism in triggering the biotic behavior of the melt. Decompression of the H O-bearing melt 2 turnover, it is crucial to define whether or not onset of CAMP induces supersaturation with H O. At a certain 1P, bubbles 2 preceded the main end-Triassic climate disruption marked by will nucleate homogeneously within the melt and grow by a significant negative Carbon isotope excursion (CIE) of up to H O diffusion into the bubbles to regain equilibrium. The 2 – 8 ‰. However, the temporal relationships between extent of supersaturation is controlled by the actual volcanism and CIE still remain circumstantial due to the decompression rate, because the diffusion distance of H O is 2 difficulty in correlating a continental event (volcanism) with limited within a certain time. The experiments have shown one recorded in marine sediments (CIE). Sediments that the BND increases with decompression rate, whereas underlying CAMP basalts in Morocco are characterized by average size decreases. At low CD rates of $0.024 MPa·s-1 high contents of MgO (10–32 wt.%) and of mafic clay only few bubbles nucleate in the melt, because the minerals (11–84%). This geochemical signature must be decompression rates provide sufficient time for H O diffusion 2 linked to deposition of mafic clay minerals derived from early- into existing bubbles. Bubble growth is the predominant erupted CAMP basalts. The measured C-isotope compositions degassing process. Residual H O-contents in the glasses 2 of bulk organic matter show marked negative CIEs (up to - indicate that an equilibrium degassing path can be simulated at 6‰) in association with the highest MgO peaks. This low decompression rates. In comparison to CD, all geochemical anomaly can be readily correlated with the initial corresponding SD run products feature higher BNDs and negative CIE shortly preceding the Tr–J boundary. Our data smaller bubble diameters for low decompression rates. SD show that the end-Triassic CIE and associated mass extinction results in instantaneous supersaturation due to rapid P drop, occurred when CAMP had already been active and supports which can only be reduced by a massive nucleation event. The the hypothesis that the cause of the mass extinction was differences between the decompression techniques decrease CAMP volcanism. with increasing nominal decompression rate due to the effect of a rapid P drop, enhancing bubble nucleation. SD techniques are not suitable to investigate the dynamic processes during continuous magma ascent, at least at low nominal decompression rates. Ongoing experiments with CD will give new insights into the dynamic processes within ascending magma prior to eruption.

[1] Nowak et al. (2011): Am. Mineral., 96, 1373-1380.

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Interaction of nanoparticles with Characterization of woody biomass microorganisms ashes and their utilization potential S. MASAKI1 , H. SHIOTSU1, F. SAKAMOTO2 , T. OHNUKI2 CHRISTOPH MASCHOWSKI1, RETO GIERÉ1 AND S. UTSUNOMIYA1 AND GWENAELLE TROUVÉ2 1 Department of Chemistry, Kyushu University, Fukuoka 812- 1 Albert-Ludwigs-Universität Freiburg, Germany 8581, Japan ([email protected]) ([email protected]) 2 Advanced Science Research Center, Japan Atomic Energy 2 Université de Haute-Alsace, Mulhouse, France, Agency, Tokai, Ibaraki 319-1195, Japan ([email protected])

Due to ubiquitous and abundant occurrence of Ash from biomass combustion is typically considered a nanoparticles (NPs) and microorganisms in the surface and waste product. Bottom ashes, however, are sometimes used as subsurface environments, they encounter and interact in source of nutrients in fertilizer additives. Fly ashes may be aqueous systems. Microorganisms can also form NPs on the enriched in hazardous constituents (e.g., heavy metals, cell surfaces by uptaking or releasing ions from/to solutions. dioxins, and chlorides). Therefore, they should not be Despite numerous studies reported biomineralization of NPs, distributed into the environment but rather be land-filled. knowledge on the interaction between micoorganisms and NPs In this study, bottom and fly ashes from two different is still limited. Here we report the response of microorganisms types of solid biomass fuel, wood chips and Miscanthus grass,

to NPs using S. cerevisiae (yeast) and CeO2 NPs (CeNPs). were sampled on site at a district heating plant and a power Yeast was harvested in a YPD media prior to the plant, respectively. These ashes were investigated by using X- experiment or a YPD media containing 250 ppm CeNPs (7 ray diffraction and subsequent pattern analysis by Rietveld nm). The yeast was then contacted with a 1 mM NaCl solution refinement method to gain semi-quantitative results for (P-free) for 0-120 h at four pHs: 2, 3, 5 and 7. A variety of crystalline phases. The results were compared with those from analytical techniques have been employed to investigate analogous ashes, which have been produced under controlled substances released from the cells, including inductively laboratory conditions from pellets of wood and Miscanthus. coupled plasma mass spectrometry (ICP-MS), ion Furthermore, the samples were characterized by laser chromatography (IC), high performance liquid diffraction to determine their particulate size distribution. chromatography (HPLC) and total organic carbon analyzer The main focus was put on the calcium oxides (mainly (TOC). The cytotoxicity of CeNPs was determined by the lime), which are present in both types of ashes and could bear classical methylene blue straining technique and the mutated utilization potential as CO2-neutral clinker substitution in proteins were identified by peptide mass fingerprinting (PMF) cement production. Main sources of lime in the ashes of both analysis. fuel types are extraneous calcite (present as grains in the fuels The solution analysis revealed that yeast released ortho- and then decomposed during combustion) as well as biogenic phosphate, organic phosphorous compound and various Ca phosphates and oxalates, as indicated by SEM/EDX analysis and elemental maps. The Miscanthus fuel used in the organic matters (<3 kDa) in all solutions. Phosphate released power plant, however, was co-combusted with 2 wt% of from the cells adsorbed on CeNPs at greater extent than limestone in order to minimize fouling and slagging and inorganic phosphate by a factor of two. Although dissolved certainly contributed to the lime content of the Miscanthus organic carbon (DOC), in general, inhibits phosphate ashes. Another component of the ashes is SiO2, mainly under adsorption to mineral surfaces, the released organic substances quartz specie. In the wood fuel, the silicon originates from enhanced anion adsorption in the present study and possibility extreaneous quartz grains, whereas in Miscanthus it is changed surface property of CeNPs. No cytotoxicity of CeNPs probably also of biogenic origin. was detected; however, CeNPs induced an excess expression The second focus of this study was on alkali and alkaline of two proteins: Eno2p and Rps24bp. In addition, the earth metal species. They can help to classify the fuel type. abundance and type of released substances were modified by Potassium contents were relatively low for both fuel types, CeNPs. Because Eno2p is related to the glycolytic system, indicating a diminished fouling and slagging potential on CeNPs can affect the yeast’s metabolism. That is, stimulating combustor walls and convection tubes. glycolytic system, which is the fastest step in the energy Both ash types contain similar crystalline phases, and our production process, lead to the decrease of tricarboxylic acid data are close to literature. These results may be used to cycle via the electron transport chain, resulting in the evaluate the potential of such ashes as secondary raw modification of the released substances. The phenomena materials. elucidated in the present study provided new insights to the fundamental process in the interaction between microorganisms and NPs in the Earth surfaces.

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The influence of the elemental Long-term effects of CO2-charged composition on the cubanite brine on caprock integrity and mineralization existing heterogeneities within the A. V. MASHUKOV*, V. G. MIKHEEV Entrada Sandstone, Green River, AND A. E. MASHUKOVA Utah Siberian Federal University, Krasnoyarsk, Russia, 1 1 ALEXANDRA MASKELL , NIKO KAMPMAN , MIKE (*correspondence: [email protected]) 1 1 1, BICKLE , HAZEL CHAPMAN , KATHERINE DANIELS ([email protected]) 2 5,6 ANDREAS BUSCH , MORGAN SCHALLER ([email protected]) 7 AND JAMES P. EVANS

1 Using the methods of X-ray and Mössbauer spectroscopy, Department of Earth Sciences, University of Cambridge, scanning electron microscopy, there were studied the samples Downing Street, Cambridge CB2 3EQ, UK of Norilsk ore types in order to identify compounds containing 2Shell Global Solutions International, Kessler Park 1, 2288 GS cubanite. Depending on elemental composition there were Rijswijk, The Netherlands singled out sample series. 3British Geological Survey, Keyworth, Nothingham, NG12 The concentration of selected elements varied from 5GG, UK sample to sample and reached maximum values in percent 5Department of Earth and Planetary Sciences, Rutgers age: for Cu - 23.0, Fe - 41.7, S - 34.0, O - 1.1. The relative University, 610 Taylor Road, Piscataway, NJ 08854-8066 6 magnetization (I/I0) of the samples at different temperatures Department of Geological Sciences, Brown University, 324 are shown in Table 1 Brook St., Providence, RI 02912 o t C 20 200 240 300 400 500 560 7Department of Geology, Utah State University, 4505 Old 1 0.61 0.84 0.38 0.14 0.06 0.02 Main Hill Logan, UT 84322-4505 16 I/I0 0,67 0.40 0.15 0.12 0.08 0.03 0.02

Table 1: The temperature dependence of the relative Natural CO2 has been escaping through geysers related to magnetization, for I/I0 line 1 - heating, line 2 - cooling. fault zones at Green River, Utah for at least 400 ka [1]. A The samples have a complex and diverse composition of a scientific drilling project in 2012 to sample the CO2 system, wide range of values having the remanent magnetization and showed that the uppermost formation, the Entrada Sandstone, its resistance to various demagnetizing factors. contained zones with high CO2 pressures, despite this unit Magnetization changes irreversibly with the change of being exposed at surface. Core revealed that The Entrada temperature. This fact, as well as the discrepancy of Curie sandstone comprised bleached sandstone layers interbedded temperature in the cycle «heating - cooling», indicates the with variably bleached and carbonated thin siltstone layers presence of a mechanical mixture, consisting of two and which have acted as aquitards. more ferromagnetic phases. Results from mineralogical, petrological, and geochemical The magnetic phase has the spectrum composed of two analysis of the CO2-reservoir rocks and sealing siltstone layers six-linear spectrums. The peaks on the spectrum borders show from the Entrada Sandstone core are presented together with a the iron oxide presence. The sample magnetism is caused by reactive transport model of the mineralogical changes. We the presence of the minerals of sulphide and oxide groups, determine the length scales and mechanisms of CO2 containing Fe2+ and Fe3+ as the main components. penetration of the sealing siltstone caprocks, and especially the Phases containing Cu, Fe, S have complex composition: significance of carbonate precipitation on its sealing

cubanite I (36,1% CuFe2S3), cubanite II (54,8% CuFe2S3), properties. chalcopyrite (5,0% CuFeS2), magnetite (2,22% Fe3O4), magnetite (1,64% Fe2O3). The position of the absorption lines [1] Burnside et al. (2013). Geology. 41, 471–474. in the magnetically ordered areas indicates the presence of CuFeS2. Some of the samples of this group have broadened lines, indicating the existence of various positions of the Fe ions in the sublattices. Intergrowths of chalcopyrite (CuFeS2) are characterized by the isomer shift of 0,058 mm/s and the absence of quadrupole splitting. Thus, the presence of the characteristic structures of the solid solutions decomposition shows a wide temperature range of sulphide crystallization.

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Mineral and chemical evolution of Accurate measurement of diffusion fragmental massive sulfide ores profiles in altered wellbore cement V.V. MASLENNIKOV1 *, R.R. LARGE2, using XMCT 1 2 S.P.MASLENNIKOVA AND L.V.DANYUSHEVSKIY 1, 1 HARRIS E. MASON *, WYATT L. DUFRANE , 1Institute of Mineralogy UB RAS, Miass, Russia STUART D.C. WALSH1 AND SUSAN A. CARROLL1 (correspondence: [email protected]) 1 Physical and Life Sciences Directorate, Lawrence Livermore 2CODES, Tasmania University, Hobart, Australia National Laboratory, 7000 East Ave, Livermore, CA (Ross. [email protected]) 94551

(*corresponding author: [email protected]) The styles of mineral and chemical evolution of

fragmental massive sulfide ores at the Urals and Rudny Altai Recent, intense effort has been focused on characterizing VMS deposits depends on the primary composition of sulfide and modeling the degradation of wellbore cements exposed to clasts and impurity of adjacent sediments. CO -rich brines due to their role in geologic carbon storage. In the early diagenetic stage, pyrrhotite fragments are 2 Scanning electron microscopy (SEM) and micro X-ray replaced by sooty pyrite with increasing grades of Au, Ag, V computed micro-tomography (XCMT) show the development and U. Pseudomorphic chalcopyrite-2 and sphalerite-2 have of three discrete alteration layers in the reacted wellbore inherited Ni, Mn, As, Pb, Tl, Au, Ag, and Te from replaced cement: a portlandite depleted zone, a Ca-carbonate zone, and colloform pyrite fragments. In the submarine supergene zone, an amorphous zone. Alteration models have assumed discrete, chalcopyrite-2 may be partly replaced by bornite or tennantite sharp contacts between these layers where the chemistry and enriched in Ag and Bi. In pyrite-rich fragmental ores, mineralogy change drastically. Despite the power of XCMT sphalerite-1,2 is commonly dissolved, but in sphalerite-rich to provide detailed 3D images of these alteration zones, little classtic sediments, sphalerite-2 is a dominant product of the has been done to refine the geometrical models of wellbore sulfide evolution. In submarine supergene zones, all sulfides cement alteration using these data. can be replaced by oxyhydroxides and then transformed to Interpretation of XCMT images of wellbore cement can be hematite and magnetite in later metamorphic stages. In the last problematic given the large distribution in grain and pore sizes stage of diagenesis, fine grained pyrite is overgrown by pyrite as well as similarities of the mineral compositions and euhedra while chalcopyrite-2 and sphalerite-2 are densities. Application of simple grayscale thresholds to recrystallized to twin crystal aggregates depleted in most of XCMT data to identify alteration zones is problematic because the trace elements. These mineral concequences are typical of of the zones span a narrow range in composition and density. clastic sulfides associated with jasper at the margins of the Instead of thresholding, we rely on an advanced user-guided massive sulfide. In calcareous and serpentitite-rich clastic segmentation method which extracts the reaction zones by sulfide sediments, pyrite nodules are commonly the products looking for not only differences in greyscale, but also in of diagenesis. In carbonaceous clastic sulfide sediments, texture. This method allows us to more accurately define diagenesis results in nodular as well as framboidal pyrite. Fine reaction boundaries and their extent in three dimensions. grained diagenetic pyrite inherits high contents of trace With the reaction zone extents as guides, we take the elements from ore clasts. In the metamorphic stage, the analysis a step further and build 3D maps of mineral and diagenetic pyrites are replaced by pyrrhotite and euhedral elemental abundances. Using the geochemical model [1] and pyrite. The range of submarine supergene and metamorphic specific mineral linear X-ray attenuation coefficients we alteration assemblages of fragmental massive sulfide ores is calculate what phases are present and their relative due to dissolution of clastic and diagenetic sulfides or their abundances in each zone. The end result shows that the recrystallization and refining. reaction regions are defined by rather diffuse regions where This mineral research was supported by Program N23 of multiple reactions can occur simultaneously, rather than by Presidium RAS (project 12-P5-1003) and LA-ICPMS analyses sharp regions. of sulfides were carried out at CODES, University of

Tasmania [1]. [1] H.E. Mason et al., Environ. Sci. Technol. 2013: 47, 1745

[1] Danyushevsky, Robinson, Gilbert, Norman, Large, McGoldrick, Shelley (2011) Geochim Explor Environm Anal This work was performed by LLNL under Contract DE- 11: 51–60. AC52-07NA27344.

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Hydrocarbon Source Appraisal in A physicochemical approach to the PM2.5 in Rio de Janeiro early generation of continental crust C. MASSONE,1,2 , A. WAGENER1*, A. GIODA1 by melting of oceanic crust 1 AND A. SCOFIELD 1 H.-J. MASSONNE 1 Chemistry Department, PUC-Rio, 22453-900 RJ, Brazil 1 Universität Stuttgart, Azenbergstr. 18, D-70174 Stuttgart, (*correspondence: [email protected]) ([email protected]) Germany ([email protected]) ([email protected]) 2IEAPM, 28930-000 RJ, Brazil ([email protected]) The phase relations of three rocks (basalt, Archaean

greywacke, and quartz diorite) each with different H O The work aimed at characterizing hydrocarbons present in 2 contents were studied by thermodynamic calculations for the atmospheric particulate matter (2.5 8m) in urban and rural P-T range 0.5-4.5 GPa and 550-1300°C using the computer areas. For this HV sampling of PM over 24h occurred 2.5 program PERPLE_X [1] and the haplogranitic melt model by weekly along 12 months. Determination included 45 PAHs, n- Holland & Powell [2]. The obtained P-T pseudosections were alkanes, UCM, hopanes and steranes. Amongst the 16 USEPA contoured by the following parameters: volume, K/(Na+Ca), PAH m/z 252 and 276 predominated, however in urban centers Na/Ca and Si/Al of melt, and density of the total rock and alkylated homologues were as well important (Fig 1). The restite. The melt and restite formed in the three studied rocks presence of mature hopanes (Fig 2) and homologue n-alkane could be reasonably well characterized with these parameters series confirm the petrogenic component derived from and the obtained phase relations. For instance, melts vehicular emission of unburned fuel. The ratio representing TTGs are generated in the basaltic protolith in the B(a)Py/(B(a)Py+B(e)Py near 0.5 indicates moderate pressure range 1.2-2.0 GPa between temperatures of 600- fotodegradation of B(a)Py independently of the season. 3 1000°C. The restite shows densities above 3.3 g/cm at Acephenanthrylene, Bz(c)phenanthrene, diBz(a,j)chrysene, pressures in excess of 1.3 GPa when more then 5 vol.% of pentaphene, Bz(a)chrysene, picene and indene(7,1,2,3- melt has formed in a low-H O basaltic composition and at cd)chrysene were also found and used for source appraisal. 2 >1.0 GPa and with >20 vol.% melt (T > 850°C) in a more hydrated basalt. TTG melts can also form in the two other studied rocks at a slightly elevated pressure range compared to the basaltic compositions. However restite densities exceed 3.3 g/cm3 only in the stability field of coesite. The obtained calculation results suggest the following geotectonic scenario which is capable to form considerable volumes of continental crust in Archaen times. The formation of relatively thick plates of oceanic crust, the hydration of their surface and final collision leads first to thickened oceanic crust and the generation of a granitic protocrust by partial melting in the hydrated realm of the underthrust oceanic plate during the collisional process. Subsequently, the protocrust is, Figure 1. (1) City center; (2) rural area in fact, further thickened by this process, but TTG melts are predominantly formed in the underthrust oceanic plate at a later stage. The restites in this partially melted regime reach densities above those of the mantle to be delaminated. The suggested crust-forming process could have occurred until late Proterozoic times.

[1] Connolly, J.A.D. (2005) Earth Planet. Sci. Lett. 236, 524-541.[2] Holland, T.J.B. & Powell, R. (2001) J. Petrol. 42, 673-683. Figure 2. Mature hopanes and Gamacerene

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A multi-component model for the Multiple sulfur isotopic evaluation of partial melting in presence of CO2 porewater sulfate profiles 1 2 and H2O in the mantle ANDREW L. MASTERSON , WILL BERELSON 1 1 2 AND DAVID T. JOHNSTON MALCOLM MASSUYEAU , YANN MORIZET AND FABRICE GAILLARD1 1Dept. of Earth and Planetary Sciences, Harvard University, 1 Cambridge MA 02138: [email protected] ISTO CNRS- Univ. Orléans, ORLEANS, France 2 Dept of Earth Sciences, USC, Los Angeles CA (*correspondence: [email protected]) 2 !Université de Nantes, Nantes Atlantique Universités, Modern marine sediment porewater sulfate concentration Laboratoire de Planétologie et Géodynamique de Nantes profiles provide information about total and depth dependent ! (LPGN), UMR CNRS 6112, NANTES, France rates of organic carbon remineralization. These profiles only provide net rates, however, as oxidative sulfur cycling is a The link between volatiles and mantle melting has so far challenge to uniquely quantify. Researchers have been illuminated by experiments revealing punctually, at a demonstrated active oxidative sulfur cycling in organic rich given P-T condition and under a specific chemical system, sediments (where sulfate reduction otherwise dominates) properties such as solubility laws, redox equilibria, and phase using the "18O of porewater sulfate. The utility of this equilibria. The aim is to establish a multi-component model approach, which still carries great promise, relies on a robust describing the Gibbs free energy of melt produced by mantle understanding of in situ sulfur oxidation processes. melting in presence of CO -H O: Carbonatite-carbonated melt 2 2 Furthermore, recent work targeting the oxygen isotopic and basalts. consequences of the sulfate reduction network, and Near solidus melts are dominated by carbonate-rich experimental work on oxygen isotope exchange with sulfur compositions, evolving towards basaltic compositions at intermediates, demonstrates a complexity to interpreting these higher temperatures. However, this carbonate-silicate records that is to date not fully explored. transition is complex, abrupt, and dependent on temperature, Aimed at improving the estimates of net and gross sulfate pressure and the chemical composition of the system. In order reduction derived from porewater sulfate profiles in organic to simulate partial melting in a variety of mantle conditions, rich sediments, we present multiple S (34S/32S & 33S/32S) and we established a parameterization of the mixing properties sulfate oxygen (18O/16O) isotopic profiles from 5 anoxic basins allowing the complex activity-composition relationships for within the California Borderlands and Mexican Margin multi-component hydrated carbonated melts to be accounted (Alfonso, Mazatlan, Soledad, Santa Monica, San Blas). All for. Using the Margules formalism, this parameterization is sites exhibit linear sulfate concentration profiles that are used calibrated on crystal-liquid, redox, fluid-liquid and liquid- to infer rates of methanotrophy using simple flux balance liquid equilibria obtained by experimental studies in the P-T models, and thus extracting rates of sulfur recycling range 1-10 GPa and 900-1800°C (more than 500 data points). complements those estimates. We discuss the utility of We so far adjusted the activity of the SiO and CO melt 2 2 applying coupled minor sulfur isotope (33S/32S) and 18O/16O components which constitutes the main part of the silicated systematics in improving estimates of sulfur reycling and carbonated frameworks. The SiO -CO interaction reveals 2 2 processes in these oxidant limited systems, and their a strong non-ideality requiring a strongly asymetric Margules implications for improving early diagenetic models of sulfur formulation. We also determined the standard thermodynamic mediated remineralization reactions. properties for the CO2 melt component. As applications, we define the composition of incipient melts as a function of depth underneath MORs and Hot-Spots

and identify regions of CO2 saturation for kimberlitic melts.

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Groundwater chemistry in 2012 in A model study on the effects of Miyagi Prefecture including Tsunami polyacrylic acid added in geothermal affected area water on the growth of silica scale at HARUE MASUDA1, SHINJI NAKAYA2, REO IKAWA3 a geothermal power plant 4 AND NAOATSU MARUI 1 1 SACHI MASUNAGA *, MAYUMI ETOU , 1Osaka City University, [email protected] YOSHIHIRO OKAUE1 AND TAKUSHI YOKOYAMA1 2 Shinshu University, [email protected] 1 Faculty of Science, Kyushu University, Fukuoka, 34AIST, [email protected], [email protected] 812-8581,Japan

[email protected] (*presenting author) Geochemical characteristics of the surface and ground waters (total 238 samples) in Miyagi Prefecture, of which Polyacrylic acid (PAA) has been added as an inhibitor of coastal area was damaged by Tsunami occurred in association calcium carbonate scale at the Takigami geothermal power with the giant earthquake on the 11th March, 2011, was plant, Oita prefecture, Japan. In the geothermal power plant, documented to figure out the situation of aqueous environment since the addition of PAA, the amount of silica scale formed in 2012 and assess the future risk of groundwater by the from geothermal water has been reported to incerase Tsunami deposits and Fukushima-Daiichi nuclear disaster. compared with that before the addition. Anthropogenic impact on the studied water was not Alminum (Al) is extremely concentrated into the silica scales obvious for whole studied area, and all the studied waters were in spite of its low concentration in geothermal water. free from radiogenic Cs. Salinization is prominent in the Therefore, it is considered that Al plays an important role for groundwaters located in the Tsunami affected area, especially the formation of silica scale from geothermal water[1]. the shallow well waters from <10m depths in the southern part Moreover, Al forms a stable Al-PAA complex[2]. As a result, of the prefecture. The highest Cl concentration is 14000 it is necessary to consider the interaction among Al, PAA and mg/L, while the rate of seawater is commonly less than 3 % silicic acid in geothermal water. (500 mg/ L) one year after the Tsunami. Fe and Mn are In this study, some model experiments were carried out to occasionally higher than the standards of drinking water (0.3 elucidate wheather PAA accelerates the growth of silica scale and 0.05 mg/L respectively) in the Tsunami affected in geothermal water containig Al, PAA and slicic acid. groundwaters, while, minor toxic element concentrations (As, At pH 8.5, which is pH value of the geothermal water, Cd, Se, Pb, CrVI, Zn, F-) are generally lower than the standard PAA didn’t affect the polymerization of silicic acid, while Al values for drinking water. Those elements were released from and Al-PAA inhibited the polymerization between monosilicic the host sediments probably due to the reduction of acid and polysilicic acid (M-P reaction). From 27Al NMR, we groundwater in association with seawater contamination by found that 4-coordinated Al in supersaturated silicic acid the Tsunami, and Tsunami deposits do not seriously cause the solution can convert into 6-coordinated Al by the addition of contamination at present. However, the groundwater PAA, indicating the formation of Al-PAA complex. The Al- chemistry must be monitored in the future to assess the PAA complex adsorbed on the surface of silica gel and groundwater as water resources since the recharging age of the retarded the dissolution of the silica gel. It can be deduced that studied groundwaters are generally 20 to 50 years. the growth of silica scales from geothermal water is accelerated due to the inhibitions of M-P reaction and of dissolution of silica by the Al-PAA complex.

[1]Takushi Yokoyama et al., (1993) Geochem. J., 27, 375-384 [2]Mayumi Etou et al., (2011) Anal. Sci., 27, 111-115

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Iron mobilisation from volcanic Volcanic ash and aerosol ash/glass by atmospheric processing TAMSIN A. MATHER1 E. MATERS1*, P. AYRIS2, C. JACQUES1, A. GUEVARA1, R. 1Dept. Earth Sciences, University of Oxford, South Parks HENLEY3, S. OPFERGELT1 AND P. DELMELLE1 Road Oxford OX1 3AN, UK, [email protected] 1 Earth and Life Institute, Université catholique de Louvain, Volcanoes are an important source of silicate particles Louvain-la-Neuve, Belgium (e.g., ash) and aqueous aerosol (e.g., sulphate) to the Earth’s (*correspondence: [email protected], atmosphere and environment. Persistent emanations represent [email protected], a key background flux to the atmosphere maintaining its [email protected], characteristics and composition, while sporadic large-scale [email protected], eruptions have the potential to perturb the atmosphere’s [email protected]) 2 chemical and radiative balance as well as having other direct Department of Earth and Environmental Science, Ludwig effects on the Earth’s environment. The recent travel chaos in Maximilian University, Munich, Germany Europe during the Icelandic eruptions of Eyjafjallajökull and ([email protected]) 3 Grimsvötn in 2010 and 2011 has also brought into sharp focus Research School of Earth Sciences, Australian National the vulnerability of highly developed societies, remote from University, Acton, Australia volcanoes, to their far-flung effects. ([email protected]) In this talk I will explore some of the nature and impacts

of volcanic ash and other volcanic particles and how Deposition of volcanic ash can provide a source of volcanologists study them. I will cover topics such as the bioavailable Fe to remote regions of the ocean where Fe generation of particles during volcanic activity, their effects in deficiency limits primary production. Understanding controls the plume (e.g., lightning generation and the scavenging of of ash Fe solubility is essential for assessing volcanogenic Fe gases), their fall out and their environmental effects (e.g., the input to the marine environment. It is well known that potential of volcanic ash to fertilize the oceans). Recent work interaction with acids (e.g., H SO , HNO ) and exposure to 2 4 3 has also shown the importance of understanding the cloud condensation/evaporation cycles during transport relationship between volcanic emissions and cloud properties increase Fe solubility in mineral dust. Airborne volcanic ash in order to understand the perturbation that anthropogenic particles, which act as cloud condensation nuclei and are co- emissions represent in terms of the Earth’s radiative budget emitted with volcanic acids (e.g., H SO , HCl, HF), are 2 4 via the indirect aerosol effect. similarly expected to undergo atmospheric processing. We

investigated the influence of such processing on ash Fe

solubility by i) exposing six ash samples (57-74 wt.% SiO2) to

pH 1 H2SO4 for 336 h to mimic contact with acid during

transport, and ii) subjecting a glass sample (58 wt.% SiO2) to

three 12-h cycles of alternating pH 2 and 6 H2SO4 to simulate pH changes during cloud evaporation and condensation, respectively. Solution sub-samples were analysed for Si, Al, Fe, Mg, Ca, Na and K concentrations by ICP-AES. Changes in sample surface compositions were assessed by X-ray photoelectron spectroscopy, and untreated ash surfaces were examined by scanning electron microscopy. Results suggest that surficial Fe salts do not constitute a significant fraction of the soluble Fe mobilised from ash in acid. The Fe release trend is consistent with leaching/dissolution of silicate components in the ash. We propose that ash surface properties imparted by eruption plume processing, including oxidation in a water- or HCl-rich environment or interaction with HF, are key in governing ash Fe release. The preliminary findings of the pH cycling experiment suggest that Fe release over 36 h is driven by dissolution and precipitation of Fe(III) at pH 2 and 6, respectively. Acid mobilisation of Fe does not appear to increase significantly over multiple cycles.

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High Cesium Concentrations in Control of oxygen fugacity in piston Groundwater in a Coastal cylinder experiments Granitoidic Fracture Network V.MATJUSCHKIN1*, B.TATTITCH1 AND J.D.BLUNDY1 F. MATHURIN1*, H. DRAKE1, B. KALINOWSKI2, 1 University of Bristol, Wills Memorial Building, AND M. ÅSTRÖM1 Quenn's Road, Bristol, BS8 1RJ, United Kingdom 1 (*[email protected]) Linnaeus University at Kalmar, Sweden,

(*presenting author: [email protected]) 2 Controlled oxygen fugacity experiments in a piston Swedish Nuclear Fuel and Waste Management Co, Sweden cylinder apparatus can be carried out using a double capsule technique and different solid oxygen buffers as suggested by This study aims to increase the understanding of the Eugster (1957) and Jakobbson (2012). However both the sources and mechanisms by which elevated Cs concentrations capsule designs used in these studies as well as the choice of build up naturally in deep and low temperature (<20"C) the spacer in the piston cylinder assemblage can affect the ƒO groundwater residing in fractured crystalline bedrock. 2 in the experimental charge. The main goal of our study was The hydrochemical monitoring program carried out by the concentrated on minimizing variability in ƒO by testing Swedish Nuclear Fuel and Waste Management Co (SKB) 2 different types of spacers, capsule materials and filling revealed that high variability in natural Cs concentrations, materials. In order to control and/or read the achieved ƒO in with values up to several 8g/L (Fig. 1), occurs in fracture 2 the capsule we have examined the reaction of 3 different ƒO groundwater at the Äspö Hard Rock Laboratory (Äspö HRL) 2 sensors: NiPd, CoPd and magnetite-ilmenite. All experiments and the nearby Laxemar area (Sweden) down to 1155m depth. were carried out at 1GPa and 1000°C using the same piston Related to the various types of water residing into the bedrock cylinder apparatus. [1], the highest Cs concentrations were found in both old The results show that use of Al O as spacer material in deep-seated saline and marinogenic groundwater (Fig. 1). The 2 3 combination with noble metals such as Pd and Pt can lead to SEM-EDS and XRD analyses of fracture coatings reveal that oxidation of experimental charge up to 1NNO+5 as Pd or Pt high Cs concentrations (>50 ppm) in the bulk fracture coatings do not prevent enough hydrogen loss during experiment. correlate with a mineral enrichement in illite, together with Alternatively, using wet spacer materials (e.g pyrophyllite) mixed-layer clays and chlorite. Based on hydrochemical may reduce the experimental by diffusion of hydrogen into the modelling, intrusion of Baltic Sea water (K and NH rich 4 capsule. Applying MgO spacer with Pt and AuPd (80/20) water), together with cation exchange, constitute a consistent capusles we could achieve consistent ƒO between 1NNO+2.5 explanation for the high Cs concentrations observed in the 2 and +3.5 for experiment durations up to 72 hours. In contrast, marinogenic groundwater at the Äspö HRL. the use of pyrex (borosilicate glass) sleeve as spacer material The Cs sorption mechanism and results presented here are in combination with AuPd capsules showed minimal loss of relevant for recognition of conditions of importance in term of hydrogen (water) as well as no detectable boron diffusion bedrock disposal of toxic waste materials as fractured bedrock through the capsule walls. As result, both NiPd and CoPd constitutes the last retention barrier separating radionuclides 134 137 internal sensors indicated consistent ƒO values of 1NNO+1 (including Cs and Cs) from the biosphere if the release of 2 (±0.2) for experiments tested up to 26 hours. radionuclides in the repository occurs. A further important factor we tested is the reaction of

different solid buffers depending on the ƒO2 we aspire to achieve. The metal sensors such as NiPd or CoPd are suitable for short and long time experiments (given the presence of an appropriate amount of water) and are able to register the

changes of ƒO2 already after first 12 hours of experiment. In contrast, magnetite-ilmenite oxide sensor needs more time for equilibration showing consistent results only after 24-72 hours runs.

Fig. 1. Vertical distribution of the Cs concentrations in the fracture [1] Eugster (1957) J. Chem. Phys. 26: 1760-1761 groundwater. [2] Jakobsson (2012) Contrib. Mineral. Petrol. 164: 397-406

[1] Mathurin et al. (2012) EST journal 46, 12779-12786.

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Geomicrobiology of ancient Chemical composition of chromian polymetallic Kupferschiefer black spinel of Podiform chromitite, shale - minireview Sangun Zone, southwest Japan. R. MATLAKOWSKA* AND A. SK%ODOWSKA ICHIRO MATSUMOTO Laboratory of Environmental Pollution Analysis, Faculty of 1 Faculty of Education, Shimane University, Matsue, Japan. Biology, University of Warsaw, Miecznikowa 1, 02-096 [email protected] (corrspondence) Warsaw (*correspondance: [email protected]) There are many chromitite pods in the Sangun zone belongs to inner zone of Southwest Japan. Most many The highly mineralized upper Permian Kupferschiefer chromitite pods enclosed by dunite rich ultramafic portion black shale located in the Fore-Sudetic Monocline (SW were discovered and outputted in this Zone, in Japan. Poland) is a polymetallic, organic-rich sedimentary rock. It Maximum size of chromitite-pod called “Nanago-ore body” belongs to one of the largest copper and silver deposits in the which is 40*210*25m (2.1*105m3) in size from Wakamatsu world but it contains also large amounts of precious and rare chromite mine of the Tari-Misaka ultramafic complex. In this elements such as nickel and platinum. study, I summarized the relationships between chromian Indigenous microorganisms occurring in the black shale spinel in chemistry and size of chromitite-pods for its origin play a role in the biotransformation of the rock. The which controls a size. significant impact of heterotrophic bacteria represented by Chromitite-pods are divided into two groups by Cr# Pseudomonas sp. Acinetobacter sp. Bacillus sp. and (Cr/(Cr+Al)) of chromian spinel from chromitite that are Microbacterium sp. [1] includes such activity as: (i) relatively high-Cr# (Cr#: 0.55<) group and low-Cr# (Cr#: degradation of sedimentary organic matter and metalloorganic 0.47-0.55) group. High-Cr# groups are from “Nanago-ore compounds [2], (ii) bioweathering of rock-forming and ore body” and “10th ore body” of Wakamatsu mine from Tari- minerals [3, 4], (iii) complexation of elements by bacterial Misaka ultramafic complex and chromitite pods from Takase extracellular metabolites such as siderophores and organic and Ashidachi ultramafic complexes. Low-Cr# groups are acids. All these activities strongly influence redistribution of from 51st, 52nd, 53rd, 54th, 55th, and 56th ore bodys of carbon and other elements in the rock and are of Wakamatsu mine from Tari-Misaka ultramafic complex and environmental significance of the global biogeochemical cycle chromitite-pods from Inazumiyama, Mochimaru, Yagami, of elements in deep underground environment. Ashidachi, and Yanomine ultramafic complexes. Cr# of chromian spinel in dunite-harzburgite host rock of [1] Matlakowska & Sk'odowska (2009) J Appl Microbiol 107, chromitite varies from 0.45 to 0.65 in “Nanago-ore body” and 858-866. [2] Matlakowska & Sk'odowska (2011) “10th ore body” of Wakamatsu mine and 0.40 to 0.60 in the Chemosphere 83, 1255-1261. [3] Matlakowska et al. other chromititite-pods. (2012)9FEMS Microbiol Ecol 81, 99-110. [4] Matlakowska et Relationships Cr# of chromian spinel from chromitite- al. (2010) Environ Sci Technol 44, 2433-2440. pods and from dunite-harzburgite indicated that it was a relatively large-scale chromitite which shows high Cr# of chromian spinel in this area. The results of above characteristics clearly show that spinel precipitation and concentration are more intense at “Nanago-ore body” than at the other chromitite bodies of the Wakamatsu mine and the other chromitite-pods of other ultramafic complexes. That is supposing the origin of chromitite is the magma mixing which continues with melt and the reaction of a wall rock ultramafic rocks [1], the reaction ratio and reaction stage are important. Matsumoto et al., (2002) [2] also pointed out this importance by resarch of Wakamatsu chromitie mine. This study support the idea.

[1] Arai and Yurimoto (1994): Econ. Geol., 89, 1279-1288. [2] Matsumoto et al. (2002): Shigen-Chishitsu, 52, 135-146.

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Ion irradiation experiments to Improved understanding of sources olivine: Comparison with space and processes of metal mobilization weathering rims of Itokawa and from sulfidic mine wastes through the lunar regolith particles application of post-transition stable

1 2 2 T. MATSUMOTO *, A. TSUCHIYAMA , A. TAKIGAWA , K. isotopes 3 3 4 4 YASUDA , Y. NAKATA , N. WATANABE , A, KOUCHI , 1,2 1 MATTHIES, R * AND BLOWES, D W M. NAKAMURA5, A. MIYAKE2 1 AND M. OHTAKE6 Department of Earth and Environmental Sciences, University of Waterloo, 200 University Avenue West, Waterloo, ON 1Department of Earth and Space Science, Osaka University, Canada N2L 3G1 (*correspondence: Machikaneyama-cho 1-1, Toyonaka, Osaka, Japan. [email protected]) (*correspondence: [email protected]) 2 2 School of Civil Engineering and Geosciences, Newcastle Division of Earth and Space Science, Kyoto University. ! 3 University, Newcastle upon Tyne, NE1 7RU, UK The Wakasa wan Energy Reserch Center, Japan. 4Institute of Low Temperature Science, Hokkaido University, The generation of metalliferous mine waters can result in Japan. potentially harmful impacts on environmental receptors. We 5Department of Earth Science, Tohoku University, Japan. conducted a 30 week lab-scale humidity cell test with sulfidic 6ISAS/JAXA, Sagamihara, Japan tailings from the Kidd Creek massive sulfide deposit, Canada.

In 7-day cycles, the mine waste was exposed to three days of Surface morphologies of regolith particles of asteroid dry and moisturized air to accelerate sulfide-mineral Itokawa recovered by the Hayabusa missions have important oxidation. On day seven, metals were mobilized through imformation about phenomena on the surface of an airless flushing with deionized water. For the first time, we combined celestial body. In previous studies, space weathering rims this prediction technique with a detailed study on the were found on Itokawa particles by TEM and STEM [1, 2]. fractionation of stable zinc isotopes to i) identify principal Especially, vesicles were identified in thick space weathering metal sources and ii) improve understanding of the rims probably caused by solar wind He+ implantation [2]. geochemical processes leading to metal mobilization. The Blister structures corresponding to the vesicles were also dissolution of secondary and tertiary oxyhydroxisulfates at the observed on the particle surfaces by FE-SEM [3]. beginning of the study led to considerable changes in zinc In this study, we carried out ion irradiation experiments to isotope ratios, potentially indicating kinetic fractionation of olivine particles (Fo ) at the Wakasa Wan Energy Research 70 zinc isotopes. Thereafter, zinc was primarily mobilized Center and Institute of Low Temerature Science in order to through the oxidation of primary sulfide minerals with little or understand relationship between space weathering processes 66 no change in " Zn values. The limited isotope fractionation and surface nano-morphological changes of Itokawa paricles. observed may assist in the use of zinc isotopes as a tracer of The fragments were irradiated by H+, H + and He+ ions at 4 to 2 anthropogenic, metal mine sources in future studies. 50 keV with fluences of 1 : 1016 to 1 : 1018 ions/cm2. Irradiated samples were observed by FE-SEM. Ultra-thin sections of the samples prepared by FIB were observed by TEM and STEM. Lunar regolith particle surfaces were also observed by FE-SEM for comparison. Blister structures and numerous bubbles, which have silimar structures to the Itokawa particles, were observed on the irradiated olivine samples. The blister structues were also observed on the lunar particles. The mean size and number density of blisters on lunar and Itokawa regolith particles are within almost the same range, suggesting that blisters formed on lunar and Itokawa particles by the same process.

[1] Noguchi et al. (2011) Science, 333, 1121-1125. [2] Noguchi et al. (2013) Met. Planet. Sci. accepted. [3] Matsumoto et al. (2013) LPSC XLIV, 1441.

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Inter-laboratory calibration of Zn Across-arc geochemical variations in isotopic compositions for organic and Central America subduction zone: inorganic reference materials evidences from Honduras basalts N. MATTIELLI1*, A. E. SHIEL2,3, K. GORDON2, D. WEIS2, MICHELE MATTIOLI1, SAMUELE AGOSTINI2 J. PETIT4 AND E. COUDER1. AND ALBERTO RENZULLI1, 1G-Time, Université Libre de Bruxelles, 1050 Brussels, 1 Dipartimento di Scienze della Terra, della Vita e Belgium (*[email protected]) dell’Ambiente, Università di Urbino “Carlo Bo”, Campus 2PCIGR, EOAS, University of British Columbia (UBC), Scientifico “Enrico Mattei”, 61029 Urbino (PU), Italy Vancouver, B.C. Canada 2 Istituto di Geoscienze e Georisorse, Consiglio Nazionale 3Dept. of Geology, University of Illinois at Urbana- delle Ricerche, Area della Ricerca di Pisa, Via G. Champaign, Urbana, IL USA Moruzzi, 1, 56124 Pisa (PI), Italy 4UMR 5805 EPOC-OASU, TGM, Université de Bordeaux1, 33405 Talence cedex, France The across-arc geochemical data on the subduction zone of Central America are relatively scarce in Honduras where Significant inaccuracy in MC-ICP-MS measurements of the active volcanic front does not occur inland but few km Zn isotopic composition may be caused by inorganic and offshore the Pacific Ocean coast. In order to fill this gap we organic resin-derived components added to samples during selected quaternary basalts from a arc to back-arc transect, column chemistry or/and to incomplete separation of the enclosing (i) El Tigre, a stratovolcano in the Gulf of Fonseca, analyte from the sample matrix [1]. In addition, previous (ii) Yojoa Lake and Sula Graben back-arc volcanism, and (iii) studies [1, 2] have shown that mass bias corrections, using Utila, a quaternary volcanic island near the strike-slip sample-standard bracketing and external normalization, fail to boundary between the North-American and Caribbean plates, accurately correct for these matrix effects. about 200 km behind the front. The present work aims to calibrate several organic and We found systematic variations in trace elements and inorganic reference materials to assess the accuracy of Zn isotopic compositions of basalts across this Honduras transect. isotopic measurements. Analyses of a broad compositional Lavas from El Tigre are calc-alkaline with a significant LIL range of USGS rock reference materials, including the basalts enrichment and Nb depletion, a strong slab signature and BCR-2 and BHVO-2 and the gabbro HRM-27, and organic incompatible element contents similar to those in the main reference materials, including the lichen BCR-482, the rye front of the adjacent volcanoes from El Salvador and grass BCR-281, the San Joaquin soil SRM 2709, the light Nicaragua (e.g. Ba/La up to 80). The back-arc quaternary sandy soil BCR-142 and the lobster hepatopancreas TORT-2, volcanism of Yojoa Lake, Sula Graben and Utila is Na- have been systematically performed on two Nu Plasma MC- alkaline, with a wide range of composition at Yojoa (basalts, ICP-MS (Nu 015 at ULB and Nu 021 at PCIGR). hawaiites, mugearites, benmoreites, trachytes) and a more Two anion exchange chromatography procedures have restricted, mafic composition at Sula and Utila (basalts and been compared for Zn isolation using 0.2 mL or 2 mL of AG hawaiites). The back-arc basalts have similar major-trace 1-X8 resin. Elemental concentrations were determined by element compositions to OIBs, such as relative enrichment in ICP-MS for each digested sample and Zn eluate cut to monitor Nb and Ta, depletion in Pb and no pronounced peaks of fluid– both Zn recovery and the presence of potential matrix mobile incompatible elements (Ba/La < 20). interferences. Zn isotopic ratios have been corrected both by The Sr and Nd isotopic data show a clear systematic external normalization using Cu and by sample-standard variation passing from arc to back-arc, with El Tigre lavas bracketing with IRMM 3702 and Lyon JMC Zn standard characherized by higher 87Sr/86Sr (70.7038), and lower solutions. The lightest and heaviest "66Zn values (±2SD; 143Nd/144Nd (70.51301), Utila basalts having typical values of relative to Lyon JMC) of the study are exhibited by the lichen a Depleted Mantle unaffected by any subduction imprint BCR-482 (+0.09±0.06‰) and the lobster hepatopancreas (70.7028 and 0.51310, respectively), whereas Sula and Yojoa TORT-2 (+0.49±0.07‰), respectively. have intermediate values. 208Pb/204Pb and 206Pb/204Pb isotope ratios of El Tigre are [1] Shiel, A.E., Barling, J., Orians, K.J. & Weis, D. (2009). very similar to arc volcanoes of El Salvador and Nicaragua Analytica Chimica Acta 633, 29–37. [2] Petit J.C.J., Taillez, (38.2 and 18.5, respectively), whereas back-arc samples have A. & Mattielli, N. (2013). GGR. DOI: 10.1111/j.1751- higher 206Pb/204Pb (18.6-18.7 for Sula and Yojoa, 18.7 for Utila 908x.2012.00187.x. island).

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Modal metasomatism in upper Oxidation state of iron in a primary mantle from Eastern part of Central Martian basaltic melt European Volcanic Province (SW A. K. MATZEN1*, J. R. BECKETT2, A. B. WOODLAND3 Poland). AND B. J. WOOD1 1 1 1 Oxford Deptartment of Earth Sciences, UK, OX1 3AN MAGDALENA MATUSIAK-MA%EK , JACEK PUZIEWICZ , 2 3 (*correspondence: [email protected]) THEODOROS NTAFLOS AND MICHEL GRÉGOIRE 2 California Instute of Technology, Pasadena, CA 91125 1University of Wroc'aw, 3 Goethe-Universität, D-60438, Frankfurt am Main [email protected] 2University of Vienna, Austria Olivine is an extremely important mineral in the 3University Toulouse III-CNRS, France generation and evolution of basaltic melts. Roeder and Emslie [1] concluded that the olivine (ol) silicate liquid (liq), 2+ ol liq Cenozoic volcanic rocks of mafic affinity occur exchange coefficient, KD,Fe -Mg = (FeO/MgO) /(FeO/MgO) aboundantly in central Europe forming the Central European (by weight), is 0.30±0.03, independent of temperature (T) and 2+ Volcanic Province. The ascending magmas intentsively liquid composition. An accurate KD,Fe -Mg is predicated on a sampled upper mantle peridotites. Mantle xenoliths from the precise measurement, or calculation, of the abundances of Eastern part of CEVP (SW Poland) are in general strongly Fe2+ and Fe3+ (expressed as Fe3+/;Fe) in the liquid. It is well depleted and nominaly anhydrous. known that major-element composition can affect Fe3+/;Fe Small amounts of hydrous phases (mostly pargasitic [e.g., 2], and very few measurements have been made on amphibole) in xenoliths from Lutynia and Wilcza Góra were primitive liquid compositions relevant to Martian reported in literature (Blusztajn and Shimizu, 1994, petrogenesis. We measured the Fe3+/;Fe ratios of a series of Chem.Geol; Matusiak-Ma'ek et al., 2010, Lithos). The first experimentally-produced glasses to better constrain the 2+ locality with significantly higher amounts of amphibole was appropriate KD,Fe -Mg(s) to use for Martian systems. described by Nowak et al. (e.g. 2010, EGU2010-9299) from One-atmosphere, super-liquidus (1450°C) experiments Wo'ek Hill. were performed on a synthetic basalt modeled after the

Mafic and ultramafic xenoliths from Wilcza Góra basanite primitive magmas found near Home Plate (50% SiO2; 10%

form four compositional groups. Almost half of the xenoliths Al2O3; 18% FeO*; 12% MgO) [3] at logfO2s ranging from -10 contain pargasitic amphibole with modal compositions up to to -0.68. Fe3+/;Fe of the resulting glasses were measured 5%. Amphibole forms: (1) integranular grains; (2) amphibole- using Mossbauer and XANES spectroscopy. Fe3+/;Fe vary spinel-clinopyroxene clusters in host peridotite; (3) cores of from 0.06 to 0.68, and compare favorably with estimates clinopyroxene II; (3) lamellae in pyroxenes and (4) based on terrestrially-relevant experiments [4]. Our results amphibole-olivine vein. Composition of amphibole follows appear to contrast with much lower Fe3+/;Fe reported for compositional variations of host peridotite. The mg-number in similar experiments on a Zagami bulk composition [5]. amphibole occuring in peridotitic xenoliths is 0.910, the TiO2 One-atm experiments on model Martian compositions 2+ content is 0.262-0.413 wt.%. Amphiboles in xenoliths affected provide the tightest constraint on KD,Fe -Mg because T and fO2 by “Fe-metasomatism” have mg-number from 0.892 to 0.852, are well known, allowing us to use [4] to predict the amount of while in cumulative xenoliths the latter is 0.854-0.734. The Fe2+ present in each liquid. The median of 17 published 1-atm 2+ TiO2 content is 0.533-2.220 and 2.915-3.508 wt.%, experiments yields KD,Fe -Mg= 0.354±0.008 (error is one mean 2+ respectively. One xenolith contains vein formed of high mg- absolute deviation). Applying this KD,Fe -Mg to the ol-phyric number 0.860-0.908 and TiO2-rich (3.253-3.705 wt.%) shergottites, leads to the possibility that Y980459, NWA 5789 amphibole. The REE pattern of the vein amphibole is LREE- and 2990 are liquid compositions (others appear to have enriched with negative inflection from Nd to La. It perfectly accumulated olivine), identical to the results of [3]. mimics REE composition of coexisting clinopyroxene. Amphibole in Wilcza Góra xenoliths stands for local [1] Roeder & Emslie (1970) CMP 29, 275-289. [2] Sack et al. modal metasomatism in upper mantle beneath SW Poland. (1980) CMP 75, 369-376. [3] Filiberto & Dasgupta (2011) Composition of the amphibole suggest that it was introduced EPSL 304, 527-537. [4] Jayasuriya et al. (2004) Am. Miner. 89 to the host peridotite together with clinopyroxene I due to 1597-1609. [5] Righter et al. (2013) Am. Miner. 98 616-628. reaction with hydrous mafic alkaline melt(s).

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Geochemistry of rare earth element Bioavailability of metals associated (REE) in weathered crust from the with aquatic natural organic matter granitic rocks in Sulawesi Island, PATRICIA A. MAURICE1*, KESHIA KUHN1, Indonesia LISA NEUBAUER2, THILO HOFMANN2 AND FRANK VON DER KAMMER2 1 2 3 ADI MAULANA *, KOTARO YONEZU , AKIRA IMAI 1 4 Civil & Environmental Engineering & Earth Sciences, Univ. AND KOICHIRO WATANABE of NotreDame, Notre Dame, IN 46556 USA 1 Faculty of Engineering, Kyushu University, Fukuoka 819- *corresponding: [email protected] 0395, Japan (*correspondence: [email protected] 2Dept. of Environmental Geosciences, Univ. of Vienna, u.ac.jp) Vienna, Austria 2 Faculty of Engineering, Kyushu University, Fukuoka 819- 0395, Japan ([email protected]) This research focused on the bioavailability of trace metals 3 Faculty of Science, Akita University, Japan associated with natural organic matter (NOM) to aerobic ([email protected]) bacteria, using abiotic experiments with the siderophore 4 Faculty of Engineering, Kyushu University, Fukuoka 819- desferrioxamine B (DFOB) and live-culture experiments with 0395, Japan ([email protected]) aerobic Pseudomonas mendocina. Trace metal contents and distributions in reverse osmosis, XAD-8 and XAD-4 isolates We report for the first time the geochemistry of rare earth from the Suwannee River (SR), were measured prior to and elements (REE) in weathered crusts of I-type and calc-alkaline following reaction with DFOB using field flow fractionation to high-K (shoshonitic) granitic rocks at Mamasa and Palu (FFF) with in-line UV/vis, fluorescence, and ICP detection. region, Sulawesi Island, Indonesia. The weathered crusts can Results showed that Fe is preferentially associated with be divided into horizon A (lateritic profile) and B (weathered intermediate to high molecular weight (MW) components at horizon) in the Mamasa region with the present of horizon C both the native pH of the SR (3.4) and pH 7, Al is fairly (weathering front) in the Palu region. Quartz, K-feldspar, uniformly distributed, and Cu is preferentially associated with kaolinite, halloysite and montmorrilonite with Ca-amphibole lower MW components. Reaction of SR XAD-8, XAD-4 and prevail in the weathered crust. The total REE content of the RO samples with excess of the microbial siderophore DFOB weathered crust are relatively elevated (40 to 75%) compared removes ~75% of Fe within 1 hour. Al and Cu are also to the parent rocks, particularly in the lower part of horizon B decreased, but not as efficiently. Upon reaction with DFOB, in Mamasa profile and in horizon C in Palu profile. This loss of some higher MW components and addition of more suggests that REE-bearing accessory minerals may be resistant low to intermediate MW components suggests that Fe, and against weathering and may remain as residual phase in the perhaps also Al, likely bridges organic components. Live- weathered crusts. The mass transfer illustration using isocon culture experiments showed that while siderophores are useful diagram shows a different transfer trend from Mamasa and for Fe acquisition from NOM by P. mendocina, they are not Palu weathering profile. The positive Ce anomaly in the required. Overall, our research shows that metals bound to horizon A of Mamasa profile indicated that Ce is rapidly NOM are likely highly bioavailable, and further emphasize precipitated during weathering and retain at the upper soil that trace metals need to be considered in any study of aquatic horizon, suggesting the occurrence of redox-controlled process NOM. which leading to the CeO2 precipitation.

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Linking soil chemistry, treeline shifts Mg isotope fractionation during and climate change: a scenario hydrothermal carbonation of CHRISTIAN MAVRIS1*,2,5 , SUSANNE P. ANDERSON2, serpentine 1 3 4 MARKUS EGLI , ALEX E. BLUM , GERHARD FURRER 1, 2 3 5 V. MAVROMATIS *, A. BEINLICH , H. AUSTRHEIM AND AND DENNIS DAHMS 1 E.H.OELKERS 1 Dept. of Geography, University of Zurich, CH-8057 1 GET, CNRS, UMR 5563, Toulouse, France, (*correspondence: [email protected]) 2 2INSTAAR, University of Colorado, Boulder, CO 80301, [email protected](*), [email protected]. MDRU, EOS, University of British Columbia, Canada, USA [email protected]. 3 PGP, University of Oslo, Norway, 3US Geological Survey, Boulder, CO 80303, USA [email protected] 4Inst. Biogeochemistry & Pollutant Dynamics, ETH Zurich,

CH-8092 As (i) the Mg isotope compostition of seawater is lighter 5Dept. of Geography, University of Northern Iowa, Cedar than that of the mantle and (ii) Mg isotopic composition of the Falls, IA, USA mantle is considered homogeneous [1], significant

fractionation processes must be ocurring during the alteration Global warming can destabilize our fragile ecosystems. As of the continental crust [2,3]. This study has been initated to cold areas become warmer, both flora and fauna must adapt to explore possible processes accounting for this fractionation. new conditions [1]. It is widely accepted that climate changes Here we present new observations of Mg isotope deeply influence the treeline shifts. But there is little fractionation during the carbonation of the Linnajavri knowledge about what happens to the soil chemistry when Ultramafic Complex, N-Norway. Carbonation of the ecosystems tend to replace each other. Will elemental serpentinite in this complex ocurred at closed system availability become a crucial factor in progressively warming conditions (except for the volatiles) at ~275 oC resulting in the conditions? formation of mainly magnesite and talc [4]. Textural The Sinks Canyon and Stough Basin - SE flank of the observations and reaction path considerations indicate that Wind River Range, Wyoming, USA - offer a case study to mineral replacement began with magnesite precipitation answer these questions. Conceptually, the areas were divided resulting in an increasing Si activity in the alteration fluid into three main subsets: tundra, forest and subarid eventually saturating talc. The original serpentine has an environment, all with soils developed on granitoid moraines. isotopic composition of "26Mg (DSM3) =-0.11±0.05, whereas From each subset, a liquid topsoil extract was produced and talc is enriched in 26Mg with average "26Mg =0.17±0.08 and mixed with the solid subsoil samples in batch reactors at 50 magnesite is depleted in 26Mg with average "26Mg =- °C. The batch experiment was performed over 1800 h, and the 0.95±0.15. These observations indicate that Mg isotopes are progress of the dissolution was regularly monitored by efficiently fractionated at mid-crustal PT conditions. analysing liquid aliquots with IC and ICP-OES. The observed fractionation has significant implications for The nutrients are released within the first hours of the the Mg isotope distribution in natural waters due to the large experiment. Si and Al are continuously released into the difference of the dissolution rates of Mg bearing silicates solution, while some alkali elements – i.e. Na - show a more relative to Mg-bearing carbonates – the dissolution rates of complex trend. Organic acids (acetic, citric) and other ligands magnesite are ~3 orders of magnitude faster that that of talc at produced during biodegradation play an active role in mineral 25 oC and pH=8 [5,6]. Our observations suggest that Mg dissolution and nutrient release. Furthermore, the mineral isotope fractionation during carbonate formation and their colloids detected in the extract (X-ray diffraction) can faster erosion rates at Earth’s surface conditions may explain significantly control surface reactions (adsorption/desorption) the enrichment of seawater in 24Mg compared to that of fresh and contribute to specific cationic concentrations. mantle Mg and that Mg-bearing hydrous silicates may The experimental set up is then compared to a computed represent the missing sink for residual the 26Mg. dissolution model using SerialSteadyQL and PHREEQC

software. [1] Teng et al., (2007) EPSL 26, 84-92. [2] Tipper et al., Decoding the mechanisms driving mineral weathering is (2006) EPSL 247, 267-279. [3] Wimpenny et al., (2010) GCA the key to understand the main geochemical aspects of 74, 5259-5279. [4] Beinlich et al. (2012) Terra Nova 24, 446- landscape adaptation during climate changing conditions. 455. [5] Saldi et al. (2007) GCA 71, 3446-3457. [6] Pokrovsky

et al., (2005) Chem. Geol. 217, 239-255. [1] Burga et al. (2010) Flora 205, 561-576

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Tracing the movement and fate of Adsorption of 109Cd onto metaloxide injected CO2 in a mature oil field nanoparticles using geochemical, isotopic and NATALIA MAYORDOMO1*, JUAN-LUIS LOPEZ-GOMEZ1, modeling approaches URSULA ALONSO1 AND TIZIANA MISSANA1 1 1 1,2 1 CIEMAT, Avenida Complutense, 40. C.P 28040 Madrid B. MAYER , G. JOHNSON , C. DALKHAA , M. 1 1 1 (Spain) *[email protected] SHEVALIER , M. NIGHTINGALE AND I. HUTCHEON

1University of Calgary, 2500 University Drive NW, Calgary, To reduce the environmental impact of hazardous Canada, T2N 1N4. pollutants, as the highly toxic metal Cd, geochemical barriers 2Midland Valley, 144 West George St, Glasgow, UK, G22HG providing confinement are required. To enhance contaminant *Correspondance: [email protected] retention in geochemical barriers, different nanoparticles (NPs) are being analysed, taking into account their inherent Carbon capture and geological storage is a potential retention properties, either single or combined with other technology to reduce CO2 emissions into the atmosphere. materials. Monitoring of CO2 storage sites is required by many of the To assess which NPs better prevent the risk of emerging regulations with specific interest in accounting of contaminant leakage, detailed experimental and theoretical injected CO2 in various target reservoirs. At the Pembina sorption studies in a wide range of geochemical conditions, Cardium CO2 Monitoring Project in central Alberta (Canada), are demanded. The stability of the NPs, upon contaminant we have used chemical data and carbon and oxygen isotope adsorption in different environments, is an aspect that must be ratios of produced water and gases sampled repeatedly from also evaluated. various observation wells to trace the movement of injected In this study, the retention capability of two metaloxide

CO2 and assess pore space saturation with CO2. The distinct NPs (Al2O3 and CuO) as candidate sorbents for Cd carbon isotope ratios of injected CO2 in association with gas immobilisation in geochemical barriers was analysed. compositional and flux data were used to determine the Sorption experiments have been carried out in different

percentage of injected CO2 produced at several observation electrolytes (NaNO3, NaHCO3, Na2SO4 and NaClO4) and in a wells using two end-member mixing calculations [1]. Changes wide range of pH and ionic strengths, to simulate different of "18O values of produced water of up to 4 ‰ were caused by environmental and salinity conditions. Sorption isotherms at oxygen isotope exchange between CO2 and H2O following different Cd concentration were also performed. 18 CO2 injection [2]. The changes in the " O values of water In addition, particles size and surface charge were were used for a quantitative assessment of CO2 dissolved in systematically measured in all experiments to assess NPs the fluids and of free phase CO2 in the pore space of the stability, essential to predict their performance. reservoir. Subsequently, we combined seismic and Geochemical modelling of a wide set of experimental geochemical information with reservoir modeling approaches sorption data contributes to probe the capability of selected 109 in an attempt to determine a carbon budget for injected CO2 in NPs as Cd adsorbents in geochemical barriers and the mature oil field. Results of partitioning calculations contamination risk assessment. indicate that two years after commencement of CO2 injection the majority of the CO2 remained in a free phase within the Acknowledment: The research leading to these results has reservoir, while smaller amounts of injected CO2 were received funding form the Spanish Government under the dissolved in water and oil. In April 2010, CO2 injcetion at this project NANOBAG (CTM2011-27975). N. Mayordomo pilot site was stopped but geochemical monitoring acknowledges the FPI BES-2012-056603 grant from commenced for an additional 2 years until June 2012. We MINECO (Spain). observed continued increases of "18O values of formation water suggesting increases in CO2 pore space saturation in the vicinity of two observation wells. The obtained results indicate that chemical and isotopic techniques can play a crucial role in

monitoring the movement and the fate of CO2 in geological

reservoirs during and after CO2 injection.

[1] Johnson et al. (2011), IJGGC 5, 933-941; [2] Johnson et al. (2011), Chem Geol 283, 185-193.

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Paleo-methane emission events in Thermal structure of the Sgurr Beag Krishna-Godavari basin, Bay of thrust, NW Scotland Bengal: Geochemical signatures S.E. MAZZA1*, R.D. LAW1 AND M.J. CADDICK1 ANINDA MAZUMDAR 1 Dept. of Geosciences, Virginia Tech, Blacksburg, VA 24061, USA (*correspondence: [email protected]) Gas Hydrate Research Group, Geological

Oceanography,National Institute of Oceanography, In the Caledonides of NW Scotland, well-understood Goa - 403004, India metamorphic temperatures (Tm) and deformation temperatures (Td) [i.e. 1, 2] progressively increase up structural section in Marine cold seep associated authigenic carbonates are known the Moine thrust sheet at the foreland edge of the orogenic from modern and past geological records. Cold seeps are characterized wedge. However, the thermal history of the hinterland thrust by expulsion of fluid enriched in methane, hydrogen sulfide, and sheets is less well-constrained [3]. This study is focuses on bicarbonate from the seafloor that results in the precipitation of determining Td and Tm for the Sgurr Beag thrust sheet in the calcium carbonates and pyrite at or below the sediment-water hinterland of the Scottish Caledonides, to test whether interface, often associated with a proliferation of chemosynthetic potentially thrust-related inversion continues into the communities. Cold seeps are known to be associated with methane structurally higher thrust sheets that are penetratively hydrate deposits. Methane hydrate, a crystalline, ice-like form of deformed at higher (upper amphibolite) temperatures. methane and water (molar ratio 1:6) exists within the marine Preserved microstructures imply a wide range of possible sediments at suitable temperature-pressure conditions [1]. In deformation temperatures, which are quantified with the the Krishna-Godavari (K-G) Basin (Bay of Bengal), seismic data quartz c-axis fabric opening angle thermometer [4]. Td from show the regional presence of gas hydrates manifested in the form of a quartz opening angle thermometry increases up section, bottom simulating reflector (BSR). BSRs represent a phase boundary ranging from 395°C to 583°C ± 50°C. This indicates that if the where low-velocity gas-charged sediments occur below the hydrate isothermal surfaces dip towards the hinterland, thrust-related stability zone. Recent drilling and logging activities on-board JOIDES thermal inversion continues into the Sgurr Beag nappe. This study also presents new metamorphic P-T constraints for the Resolution in the Indian margin under the aegis of Indian National Sgurr Beag nappe, based on garnet-biotite thermometry and Gas Hydrate Program (NGHP) have confirmed the existence of GASP barometry, indicating Tm of ~620°C at 5.8 to 7.4 kbar. massive gas hydrate deposits in the K-G Basin [2]. Extensive fault and Together, Td and Tm indicate that deformation continued past fracture zones in K-G basin sediments are apparently responsible for peak metamorphic conditions in the Sgurr Beag thrust sheet. the advective transportation (focussed flow) of methane rich fluid from the base of gas hydrate stability (BGHSZ) to the sediment water [1] Read (1931) B.G.S Memoir, 238. [2] Johnson & Strachan interface. The sharp perturbation in sulfate, sulfide and bicarbonate (2006) JGS. 163, 579-582. [3] Thigpen et al. (submitted) concentrations at the sediment -water interface is attributed to the JMG. [4] Kruhl (1998) JMG 16, 142-146. anaerobic oxidation of methane (AOM) performed by a syntrophic

consortium of CH4-oxidizing archaea and sulfate-reducing bacteria [3]. Here we report repeated evidence of such methane expulsion events in K-G basin in the quaternary period. Highly 12C enriched authigenic carbonates in the form of chimneys, massive crusts, chemosynthetic clams and other faulnal records indicate cold seep events[3]. Destabilization of deep seated methane hydrate is one possible cause for these sudden methane pulses. Shale tectonics induced fault and fracture opening and change in geothermal gradient could be one of the plaussible reson for focussed gas emission events.

[1] Kvenvolden (1988) Chem. Geol., 71, 41-51. [2] Ramana et al. (2004) International Jour. Enviormental Studies 64, 675- 693. [3] Boetius et al. (2000) Nature, 407, 623– 626. [4] Mazumdar et al. (2009) Geophy.Geochem.Geosys., 10, 1-15.

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New applications of dissolved gallium Experimental dissolution of FeCO3 in the oceans: Promoting increasingly under controlled sulfidic conditions routine measurement ALISON MCANENA1* AND SIMON W. POULTON2 JASON A. MCALISTER1* AND KRISTIN J. ORIANS1 1Institute of Marine and Coastal Science. Rutgers, The State 1 University of New Jersey, New Brunswick, 08901 NJ, University of British Columbia, Vancouver, Canada USA (*correspeondence: [email protected]) (*Correspondence: [email protected]) 2 School of Earth and Environment, University of Leeds, Leeds, LS2 9JT, UK Dissolved gallium (Ga) is present in the oceans at

picomolar concentrations, consistent with more routinely In modern sedimentary environments, reduced Fe minerals measured dissolved trace metals such as iron and aluminum, (e.g. siderite; FeCO ) tend only to precipitate under anoxic yet Ga exhibits comparatively less contamination risk, 3 conditions in environments where high Fe(II) pore water therefore easing sample collection and analysis. Shown here aq concentrations are accompanied by low rates of sulfide are three applications utilizing dissolved Ga concentrations in fixation. In contrast, siderite-rich sediments are extensively the ocean to study carbon dynamics, climate change, and observed throughout the Precambrian rock record, both in mechanisms controlling sources and sinks of trace elements marine shales and banded iron formations. However, rising and isotopes (TEIs) in the ocean. Dissolved Ga is applied to atmospheric oxygen and the gradual rise in oceanic sulfate 1) development of a model utilizing dissolved Ga profiles to concentrations through time ultimately led to the increased estimate particulate abundance, 2) utilization of dissolved Ga sulfidation of reactive Fe minerals, and hence less preservation as a new parameter differentiating Pacific and Atlantic source of siderite in marine sediments. Nevertheless, high waters to the western Arctic Ocean, and 3) identification of concentrations of siderite, particularly during the Precambrian, differentially sourced plume waters of the Columbia River. persist in sediments that contain pyrite, likely due to sulfate Particulate abundance is vital to estimates of carbon flux and limited conditions during diagenesis. However, the reactivity drawdown of CO from the atmosphere. Dissolved Ga 2 of siderite towards dissolved sulfide is currently unknown. profiles are utilized here to model relative particulate We investigate the kinetics of siderite dissolution in the abundance of CaCO and opal, complimenting established 3 presence of sulfide under varying conditions. The rate of sediment trap and U-Th methods, and providing potential for Fe(II) carbonate dissolution was measured experimentally on particulate abundance to be estimated on an increasingly samples of synthetic and natural FeCO , under controlled routine basis. Arctic inputs from the Atlantic, identified by a 3 initial sulfide concentrations, mineral surface area and pH. We strong dissolved Ga gradient, represent comparatively warm propose a reaction mechanism where carbonate species waters that threaten sea ice melt and CO release if able to 2 undergo direct substitution with dissolved sulfide on the permeate Pacific source water stratification via upwelling over mineral surface, ultimately producing FeS as a major reaction the extensive shelf area of the Arctic Ocean. Finally, the product. The rate constant (k ) determined by the sulfidation Columbia River plume provides a spatially and temporally Fe of siderite is similar to other highly reactive Fe minerals,such unique environment, combining the plume induced salinity as ferrihydrite, but up to 5 orders of magnitude faster than gradient with dynamic winds resulting in upwelling and more crystalline Fe(III) oxides; with complete siderite downwelling conditions oscillating on the order of days. A dissolution occurring over just tens of minutes. plume endmember mixing model developed here utilizes Our data suggest siderite in marine sediments is highly dissolved Ga to identify offshore waters associated with reactive towards dissolved sulfide, even in the presence of low formation under divergent wind conditions, influencing sulfide concentrations. FeS formation is limited by sulfide scavenging reactions and therefore concentrations of dissolved (and hence, initial sulfate) availability, with experimental TEIs. Oceanographic study of complex multiparameter results explaining the stability of co-precipitating FeS and problems such as climate change requires a broad suite of FeCO species observed within some sedimentary variables including trace elements and isotopes. Results of 3 environments. We therefore conclude that the remobilization this work encourage increasingly routine measurement of of reduced Fe(II) minerals by sulfide may have contributed dissolved Ga concentrations and application to oceanographic greatly to Fe cycling in both modern and ancient anoxic research, including future GEOTRACES cruises. environments.

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Chromium isotope fractionation Seafloor massive sulfide exploration during pedogenesis: Influence of in SW Pacific - A commercial redox recycling perspective C.N. MCCLAIN*, K. MAHER, K.L. WEAVER TIMOTHY F. MCCONACHY1 AND J.L. DRUHAN 1 SVP Science & Exploration, Neptune Minerals, Inc., Suite 3, Department of Geological and Environmental Sciences, Level 7, North Tower, 1-5 Railway Street, Chatswood, Stanford University, Stanford, CA 94305, USA NSW, 2067, Australia (*correspondence: [email protected]) [email protected]

Tracking the fate of Cr and "53Cr during physical and The discovery and recovery of seafloor massive sulfides chemical weathering of soils is central to investigating both near Galapagos and black smokers at 21oN on the East Pacific naturally occurring Cr(VI) drinking water contamination and Rise in the late 1970s is arguably one of the great natural the use of Cr as a paleoredox proxy. Cr is a unique system to science discoveries of the 20th Century. Since then, black study because it is possible to monitor variations of both the smokers have been found in all the world’s oceans. Because fluid "53Cr(VI) as well as the solid "53Cr(III) in space and time of the high concentrations of copper, lead, zinc, silver and to interpret modern and ancient (bio)geochemical cycling. gold associated with seafloor massive sulfides, they have However, determining fractionation factors from observed gone, in the space of less than 30 years, from being a scientific isotope patterns is difficult due to multiple transformation curiosity to a potential new source of metals for commercial pathways, recycling, and inherent heterogeneity in soils. The use, attracting significant speculative investment by private coupling of Cr-, Fe- and Mn- cycling and the presence of and public companies and state-owned enterprises. One secondary minerals such as Fe-Cr-oxyhydroxides and Mn- commercial Mining Licence has been granted in the Bismarck oxides in soils indicates that Cr(III) available for oxidation Sea by the Government of Papua New Guinea and further may have been recycled (oxidized and reduced multiple mining licences are likley to follow in other countries’ waters times). Here we present a theoretical study that quantitatively along the SW Pacific Ring-of-Fire. tracks Cr isotopes during pedogenesis by modeling oxidation, The SW Pacific region is attractive to explorers for two reduction, fluid flow and physical denudation. We apply the main reasons: firstly, it has convergent plate boundaries with model to a corresponding field study of solid and fluid associated volcanic arcs and back arcs which host deposits of speciation, isotope composition, physical and chemical massive sulfide that generally contain superior metal grades gradients occurring in a modern serpentine mollisol developed due to complex crustal melting and fractionation processes; on ultramafic bedrock in the Putah Creek watershed of the and secondly, countries in the region are able to grant secure northern California Coast Range. The model is parameterized title to explore within their territorial waters and Exclusive using both field and published data. Results demonstrate that Economic Zones under existing legislation. increased recycling changes apparent fractionation, depending Land-based explorers are finding that new deposits are on fractionation factors assumed. These simulations show that hard to discover and difficult to permit; and drilling, it is difficult to attribute in-situ fractionation factors to specific feasibility, construction and stripping typically takes 10 years reactions without careful evaluation of phases, mechanisms or more. By contrast, on the seafloor, new deposits are and rates. Our modeling methods can also be applied to other relatively easier to find, they are high grade, have no or little elements (such as Fe) and environments (such as groundwater overburden and mining does not require high levels of aquifers) to evaluate the spatial variability in isotopic infrastructure or capital; and mine scheduling is flexible. composition imposed by redox recycling. Neptune Minerals holds granted licences and licence applications in seven countries in the SW Pacific. It has completed exploration programs using a combination of hydrothermal plume survey, moderate to high-resolution acoustic seabed mapping, ROV mapping and sampling, geophysics, drilling and spot sampling, making and assessing a number of new discoveries. The company’s ‘baby step’ approach to its exploration, environment and social licences is akin to adopting a precautionary approach.

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Black carbon concentrations and Transformational science with a new fluxes during recent millennia from a global volcanic gas emissions developing array of Arctic ice cores database J.R. MCCONNELL1*, D. DAHL-JENSEN2, D. FRITZSCHE3, B. MCCORMICK1, E. COTTRELL1, T. FISCHER2, M. NOLAN4 AND M. SIGL1 G. CHIODINI3 AND C. CARDELLINI4 1Desert Research Insitute, Reno, NV 89509, USA 1Department of Mineral Sciences, National Museum of (*correspondence: [email protected], Natural History, Smithsonian Institution, Washington, DC, [email protected]) USA 2University of Copenhagen, Copenhagen Denmark 2Department of Earth and Planetary Sciences, University of ([email protected]) New Mexico, Albuquerque, NM, USA 3Alfred Wegener Institute, Potsdam, Germany 3Istituto Nazionale di Geofisica e Vulcanologia, Osservatorio ([email protected]) Vesuvio, Napoli, Italy 4University of Alaska, Fairbanks, AK, USA 4Dipartimento di Scienze della Terra, Università di Perugia, ([email protected]) Perugia, Italy

Short-lived aerosols such as black carbon (BC) and dust Volcanic degassing is regularly monitored at many are important components of climate forcing, although volcanoes worldwide, with direct sampling and both ground- warming from increased carbon dioxide and other greenhouse and satellite-based remote sensing techniques. Recent years gas concentrations is the long-term driver of climate change. have seen a sea-change in instrument sophistication and With their short lifetimes in the atmosphere, aerosol capability. The literature contains a wealth of additional data concentrations and deposition rates are dominated by regional arising from campaign measurements of degassing. However, – rather than global – sources and intra- and inter-annual there is currently no existing inventory of volcanic gas variability is high. Such aerosols in snow are especially emission measurements in an easily accessible form, such as important in the high latitudes because of their strong impact an online relational database. on albedo. Inspired by the Deep Carbon Observatory's DECADE

Because most BC aerosols in high latitudes originate in initiative to estimate global volcanic CO2 flux, we are building lower latitudes, changes in long range transport processes and a new database incorporating all published degassing and pathways may dominate over changes in source strength in volatile data for Earth's volcanoes. Appropriate metadata will determining concentrations and deposition rates in these be carefully defined and attention paid to data quality. regions. However, detailed understanding of past and present Numerous factors influence the accuracy of gas emission concentrations, deposition rates, sources, and transport measurements, and some categorisation or quantification of pathways of BC to and within the Arctic is lacking. Here we the uncertainty present in each data entry is crucial. Emissions present and discuss detailed records of BC measured in a fluxes and relevant metadata will be incorporated into the developing array of ice cores widely distributed around the database of Smithsonian’s Global Volcanism Program as we Arctic. We use a range of elemental and chemical tracers aim to directly link gas emissions to volcanic activity. Gas measured in the same ice cores to identify likely sources and compositions will be incorporated into the EarthChem to investigate spatial and temporal patterns of BC deposition database with the intent to make these two databases during recent centuries and millennia. interoperable. Our vision is for the database to become an essential tool of the volcanological community, and we seek close collaboration with the volcanic emissions community from the onset. Close consultation with gas geochemistry and monitoring experts will ensure that the data and metadata types defined and implemented in the database are fit-for- purpose, and that the proposed database search capabilities, visualisation schemes and output standards meet the user needs of these researchers. We will build on lessons learned from the Italian volcanic gas database, GOOGAS. We are also working closely with cyber-infrastructure specialists to ensure the new database is fully inter-operable with existing online resources (e.g. EarthChem, WOVOdat, Global Volcano Model, GOOGAS, IRIS) and can be extended beyond gas emissions into other monitored parameters in the future.

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HIMU lithospheric mantle in the Abundance and ubiquity of H2O in Southwest Pacific: Tracing the roots the martian interior of Zealandia FRANCIS M. McCUBBIN* ALEX J. MCCOY-WEST1*, VICKIE C. BENNETT1 Institute of Meteoritics, 1 University of New Mexico, MSC03- AND YURI AMELIN1 2050, Albuquerque, NM 87131, USA 1 ([email protected]) Research School of Earth Sciences, Australian National

University email: [email protected] There is substantial evidence supporting the past existence of abundant flowing water on the martian surface, however the The existence of a widely sampled HIMU reservoir in the source for this water remains elusive. Earlier studies of Southwest Pacific is well documented from the Pb isotopic 206 204 martian meteorites resulted in estimates of less than about 35 compositions of intraplate basalts with Pb/ Pb>19.5. The ppm H O [1], which is incompatible with an internal source origin of this signature however, remains controversial with 2 for the surface water. These earlier studies primarily relied proposed sources including metasomatised subcontinental upon bulk rock water contents of the meteorites and were lithospheric mantle and ancient oceanic lithosphere stored in likely affected by magmatic degassing [2]. Even modern the deep mantle [e.g. 1-3]. Here we further investigate the efforts to estimate H O abundances in martian melt inclusions origin of HIMU characteristics through a combined petrologic 2 likely suffer from volatile loss [i.e., 3]. and Sr-Nd-Pb isotopic study of a suite of mantle xenoliths We have revisited the abundance and distribution of H O assembled from 12 localities throughout New Zealand. Prior 2 in the martian interior through studies of volatile bearing Re-Os isotopic study of this suite [4] demonstrated that a mineral phases in martian meteorites [4-5], which are more substantial portion of the lithospheric mantle underlying likely to retain their OH components during magmatic southern New Zealand is Paleoproterozoic in age (c. 1.7 Ga) degassing. There are water contents available for amphibole and thus > 1 b.y. older than the oldest overlying crustal rocks. and biotite in the Chassigny meteorite [5-7] and apatite in a For this investigation Sr, Nd and Pb isotopic compositions number of enriched and depleted shergottites [4]. If the water were determined from leached clinopyroxene mineral in these minerals was primary to the parental melts, the separates of the xenoliths using ID-TIMS methods. Pb 202 205 magmatic source regions from which the parental melts were isotopic compositions were determined using a Pb- Pb derived likely have 70-300 ppm H O. This would imply that double spike. Initial results show a narrow range of measured 2 both geochemically depleted and enriched sources on Mars 206Pb/204Pb between 19.5-21.1 and with no simple correlation 238 204 87 86 have elevated H O abundances and Mars’ ancient surface with U/ Pb or with Os isotopic composition. Sr/ Sr 2 water could be internally derived. isotopic compositions show a narrow range centered about

0.7025-0.7028, with 143Nd/144Nd isotopic data having more 206 204 [1] Mysen, B.O. (1998) Am Min, 83, 942-946. [2] McSween variability. The CPX leachates had lower Pb/ Pb, showing H. et al. (2001) Nature, 409, 487-490. [3] Usui T. et al. (2012) that the HIMU signature does not result from contamination EPSL, 357-358, 119-129. [4] McCubbin, F.M. et al. (2012) by the host basalts. Geology, 40, 683-686. [5] McCubbin, F.M. et al. (2010) The Pb isotopic results are consistent with a widespread EPSL, 292, 132-138. [6] McCubbin, F.M. et al. (2013) MAPS, HIMU component residing in the lithospheric mantle beneath In Press, DOI: 10.1111/maps.12095. [7] Watson, L.L. et al. Zealandia. The homogeneous measured Pb isotopic (1994) Science, 265, 86-90. compositions and lack of correlation with Os model ages imply a multi-stage history for lithosphere development in the region, with Paleoproterozoic melt extraction as reflected in Os isotopic signatures followed by an extensive, but much younger metasomatic event generating the Pb isotopic characteristics.

[1] Panter et al. (2006) JPet 47, 1673-1704. [2] Timm et al. (2009) JPet 50, 989-1023. [3] McCoy-West et al. (2010) JPet 51, 2003-2045. [4] McCoy-West et al. (2013) Geology 41, 231-234.

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Bio-calcification and its response to Continuous measurement of methane ocean acidification: new insights from emissions from a landfill using a new boron isotopes laser-based open path instrument 1,2 1 1,2 M.T. MCCULLOCH , J.A. TROTTER , M. HOLCOMB DAYLE MCDERMITT1*, LIUKANG XU1, XIAOMAO LIN2, 3 AND P. MONTAGNA JIM AMEN3, KARLA WELDING3, TYLER ANDERSON1 1 1 AND ANATOLY KOMISSAROV Oceans Institute and School of Earth and Environment, The University of Western Australia, Crawley 6009, Australia. 1LI-COR Biosciences, Lincoln, NE USA 68504 2 ARC Centre of Excellence in Coral Reef Studies, UWA. *correspondence: [email protected], 3 ISMAR-CNR, via Gobetti 101, I-40129 Bologna, Italy. [email protected], [email protected], [email protected], [email protected] Bio-calcification is not only responsible for building the 2 Dept. Of Agronomy, Kansas State Univ., Manhattan, KS majestic coral reefs of the tropics, but is also a determinant of USA [email protected] 3 the oceans carbonate chemistry and ultimately the CO2 content Bluff Road Landfill, City of Lincoln, Lancaster County, NE of the biosphere upon which life depends. By its very nature, USA 68517 [email protected] biomineralisation occurs within a restricted, physiologically controlled environment, whose connectivity to external A new laser-based open path methane analyzer (LI-7700, seawater is poorly known. Understanding these factors is thus LI-COR Biosciences) was used to measure methane emission fundamental to quantifying the response of this key group of rates by eddy covariance from June to December 2010 at the

organisms to CO2 driven climate change and ocean municipal landfill in Lincoln, NE USA. The instrument acidification. Boron isotopes are an ideal tool to interrogate provides continuous measurements at 10 Hz with minimal these processes, as its speciation is pH dependent, and maintenance and can operate on solar power. High frequency biocalcifiers specifically incorporate the isotopically distinct corrections for effects of temperature and water vapor on borate species into their carbonate skeleton. methane absorption spectra, and operation in dusty Using boron isotope systematics we show how biological environments present special challenges that will be discussed. up-regulation of the pH of the calcifying fluid is a Methane concentrations varied sharply from near background characteristic of both azooxanthellate and zooxanthellate to more than 60 ppm. Methane emission rates varied as much aragonitic corals. Scleractinian corals up-regulate pH at their as 35-fold from day to day and depended strongly on changes site of calcification such that internal changes are in barometric pressure (P), increasing with falling P and approximately one-half of those in ambient seawater [1]. decreasing with increasing P. Emission rates were Although the absolute magnitude of the pH-buffering capacity systematically higher in December than during the summer is species-dependent, it provides a mechanism to raise the period. Higher rates were associated with changes in P that saturation state of the calcifying medium, thereby potentially were larger in magnitude and longer in duration in winter than increasing calcification rates at relatively little additional in summer, and with lower mean temperatures, which energy cost. This is especially evident in deep-sea corals appeared to reduce methane oxidation rates. Power spectrum where high degrees of pH up-regulation has facilitated and ogive analysis showed that 10 days of averaging were calcification at, or in some cases below, the aragonite required to capture 90% of the variance in emission rate. saturation horizon. Models [2] combining biologically induced Implications of these results for estimating landfill emission pH regulation with abiotic calcification, (IpHRAC) now make rates will be discussed. it possible to unravel the effects of increased temperature and reduced seawater saturation states on bio-calcification. Up- regulation of pH is not however ubiquitous among all calcifying organisms; those lacking this ability may undergo

severe declines in calcification as CO2 increases.

[1] Trotter et al., (2011) Earth Planet. Sci. Lett. 303,163-173. [2] McCulloch et al. (2012) Nature Climate Chg. 2, 623-627.

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The Earth and its building blocks Remarkably hot quartz in resurgent W. F. MCDONOUGH1 intrusions associated with the 18.8 1 Dept of Geology, University of Maryland, College Park, Ma Peach Spring Tuff supereruption MD, 20742-4211, USA. 1 1 2 S.M. MCDOWELL *, C.F. MILLER AND J. WOODEN

The composition of the Earth was shaped by the chondritic 1Vanderbilt University, Nashville, TN 37235, USA building blocks that most likely populated the inner solar (*correspondence: [email protected]) system. The observed isotopic composition of the available 2Stanford University, Palo Alto, CA 94305 chondrites, which are few and only recently (<10^5 years) ([email protected]) delivered, reveal an enstatite chondrite (EC) match, or similarity, to that of the Earth. However, and in stark contrast, The Silver Creek caldera (southern Black Mountains, the Earth does not match EC for their volatile element western Arizona) is the source of the 18.8 Ma, >700 km3 abundances, nor their mineralogical attributes. Based on the Peach Spring Tuff (PST), the only supereruption deposit in the planetary mass fraction of Fe in the Earth’s core, the planet is Colorado River Extensional Corridor (CREC) [1]. A 30 km2 strongly reduce, intermediate in redox potential between intrusive complex within the caldera records ~200 ka of post- ordinary (OC) and EC. Increasingly, it is observed that the PST resurgent magmatism and consists of two primary units: niningerite and oldhamite in EC, as well as other phases, is the the intermediate to felsic Moss porphyry (62-68 wt% SiO2; the alteration product of sulfidation of ferromagnesian silicates 18.81 ± 0.09 Ma [TIMS U-Pb zircon age]) and the felsic and not a primary feature[1]. Times porphyry (>72 wt% SiO2; 18.63 ± 0.08 Ma) [2]. Both The 142Nd isotope data [2] has opened up a new vista in units intrude trachytic, densely welded intracaldera PST. revealing aspects of solar system history and the nature and To investigate epizonal magmatic processes during and distribution of the early building blocks. A fundamental immediately after the PST supereruption, and to constrain the observation from this isotope system is that the three thermal history of the PST magmatic center, we applied Ti-in- domainant classes of chondrites, CC, OC and EC, have clear quartz thermometry [3] to two samples of Moss, one sample of differences in their average 142Nd/144Nd compositions and Times, and one sample of a younger (18.21 ± 0.07 Ma) the Earth is most similar to the EC class [3]. Interpretation of crosscutting quartz porphyry dike. Quartz in the Moss yields the 142Nd signature of the Earth include a deep hidden conspicuously high Ti concentrations (~60 to 340 ppm; avg. reservoir [4] or loss of the equivalent reservior to space by an 160 ppm), corresponding with Ti-in-qtz temperatures of ~730- ablation process [5]. Alternatively, the data are consistent 980ºC (avg. 840°C, aTiO2 = 0.7). Ti-in-qtz concentrations for with early solar system heterogeneity [6]. the Times (~45-150 ppm; avg. 95 ppm) and quartz porphyry Neutrino geoscience, the detection of electron anti- dike (~50-110 ppm; avg. 70 ppm) give mean Ti-in-qtz neutrinos from beta-decays of Th and U series, is now temperatures of 780°C and 745°C, respectively. Quartz providing data on the amount and distribution of U and Th temperatures are broadly consistent with trends in zircon inside the Earth. The latest results from the KamLand and saturation and Ti-in-zircon temperatures for the same units. Borexino experiments were reported earlier this year [7,8] and Moss temperatures are higher than those for all other units in demonstrate that the Earth contains a considerable amount of the CREC except intracaldera PST, which yields comparable primordial heat and favors both cosmochemical [9] and Ti-in-zircon temperatures [4, 5]. geochemical models [10]. Combined with data for the Mineral thermometry suggests that the Moss records a composition of the continental crust, these models will be brief period of exceptionally hot magmatism that coincides interpreted in terms of the residual amount of heat producing temporally and spatially with the PST eruption. Quartz data power left in the mantle needed for mantle convection and are consistent with the hypothesis that influx of anomalously driving plate tectonics. warm and/or voluminous mafic magma led to rapid production and accumulation of massive, high-T PST magma [6]. [1] Lehner et al. 2013, GCA 101; [2] Boyet & Carlson 2005, Temperatures of successive post-PST intrusions fell at a rate Science 309; [3] Gannoun et al. 2011, PNAS 108; [4] Boyet & of ~0.25ºC/k.y. Carlson 2006, EPSL; [5] O’Neill & Palme 2008, Phil. Trans. R. Soc. A 306; [6] Qin et al. 2011, GCA 75; [7] Bellini et al. [1] Ferguson et al. (2013) Geology 41, 3-6. [2] McDowell et 2013, arXiv:1303.257; [8] Gando et al. 2013, al. (2012) GSA AbsProg 44, 320. [3] Watson & Wark (2006) arXiv:1303.4667v2; [9] Javoy et al. 2010, EPSL 293; [10] ContMinPet 152, 743-754. [4] Claiborne et al. (2010) McDonough and Sun 1995, CG 210. ContMinPet 160, 511-531. [5] Pamukcu et al. (2013) JPet.

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Not so hot and not so salty microbes RESOChron: ELA-ICP-He-MS and their role in oil recovery and instrument for in situ U-Th-Pb-He corrosion geothermochronology MICHAEL J. MCINERNEY1 BRENT IA MCINNES1, NOREEN J EVANS1, MIKE 2 1 3 1 SHELLEY , BRAD MCDONALD , DAVID GIBBS , ASHLEY Department of Microbiology and Plant Biology, University of NORRIS4, ED ROBERTS3, CLIFF GABAY4 Oklahoma, Norman, OK 73019 USA; AND DES PATTERSON5 [email protected] 1AuScope GeoHistory Facilty, John de Laeter Centre for Diversifying the global energy portfolio with carbon-free Isotope Research, Applied Geology, Curtin University, or carbon-neutral fuels is critically needed. However, fossil Perth WA Australia; [email protected] fuels will likely be the dominant energy source for several 2Laurin Technic Pty Ltd., Canberra ACT, Australia decades. 3Australian Scientific Instruments Pty Ltd, Canberra ACT 4Resonetics Ltd, Nashua NH, USA "#$%#&#'(%)!(*+,%)-!+&!+#.!/0*(#%!0%)/(1102!#%!+#.!+ 5Patterson Instruments Ltd, USA /0-0/3+#/-4!*(%5!+&!67#'7!(/0!%+)!)++!7+)!89:!)+!;: <=4!>,)! (/0!-(.)5!8-(.#%#)#0-!/(%$#%$!&/+*!?!)+!@AB=C!D0!'+%2,')02! The development of an in situ microanalytical instrument (!)0-)!+&!(!*#'/+>#(.!1.,$$#%$!1/+'0--!#%!(!7510/-(.#%0!+#.!+ capable of rapid automated U-Th-Sm-Pb-He isotope analysis /0-0/3+#/! 8@EF@AB! -(.#%#)5G! 9; <=C! H70! #%I0')#+%! +&! of multiple grains will permit a more detailed interrogation of *+.(--0-! (%2! %#)/()0! -)#*,.()02! #%! -#),! *#'/+>#(.! $/+6)7! the time-temperature history of apatite, zircon, rutile, titanite (%2!*0)(>+.#-*4!67#'7!>.+'J02!(!*(I+/!6()0/!'7(%%0.!(%2! and other accessory phases. Previous work1-3 has demonstrated '+//0')02! #%)0/60..! 10/*0(>#.#)5! 70)0/+$0%0#)#0-C! H70! the technical feasibility of this approach, while this project 0&&#'('5!+&!>#+-,/&(')(%)F*02#()02!+#.!/0'+30/5!6(-!)0-)02!!"#$%%&' advances the field via the development of a prototype system #%!(!'+%)/+.!�.2!)/#(.C!H6+!60..-!/0'0#302!(%!#%+',.,*!+&! that integrates four existing commercial components: (i) a >#+-,/&(')(%)F1/+2,'#%$! ! -10'#0-! (%2! KL! ',>#'! helium mass spectrometry module based on the AlphachronTM *0)0/-! +&! %,)/#0%)-! 8$.,'+-04! -+2#,*! %#)/()04! (%2! )/('0! design, (ii) an ICP-MS module (Agilent 7700), (iii) an excimer *0)(.-=G! )6+! 60..-! /0'0#302! I,-)! %,)/#0%)-G! (%2! +%0! 60..! laser ablation module based on the RESOlution design, and /0'0#302! +%.5! &+/*()#+%! 6()0/C! H70! .#1+101)#20! (iv) swappable ultra-high vacuum and flow-through analytical >#+-,/&(')(%)! 6(-! 20)0')02! +%.5! #%! )70! 1/+2,'02! &.,#2-! cells designed by Laurin Technic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

!"#$%&'()**+' '+$" 1/+2,'0/-! #%!+ (! '+//+2#%$! +#.! 1/+2,')#+%! &('#.#)5! 8*(/#%0! -(.#%#)5G! ;; <=C! Q%/#'7*0%)-! '+%)(#%#%$! ! '" -10'#0-! '(,-02! ! -#$%#&#'(%)! '+//+-#+%! +&! *0)(.! '+,1+%-! '" $'''" /''''" /$'''" 0''''" 0$'''" -''''" -$'''" 1''''" 1$'''" 670%! 50(-)! 0R)/(')! (%2! )7#+-,.&()0! 60/0! 1/0-0%)C! ! S,/! ,-.&/0"1'2$0'34#%&"-'(*%5$*'&$*64&"06"-+' 6+/J! -7+6-! )7()! *#'/+>#(.! 10/*0(>#.#)5! 1/+&#.0!

*+2#&#'()#+%! (%2! #%! -#),! >#+-,/&(')(%)! 1/+2,')#+%! (/0! Initial in vacuo laser ablation testing on a large Mud Tank 1+--#>.0C! T0/*0%)()#30! )7#+-,.&()0! ,-0/-! (/0! #*1+/)(%)! zircon indicate that: (i) the DL for radiogenic 4He, is exceeded *02#()+/-!+&!'+//+-#+%!#%!-+*0!+#.!1/+2,')#+%!&('#.#)#0-! when ablation volumes are >780 µm3 corresponding to a 10 µm deep ablation pit with 5µm radius; (ii) U-Th-Pb-He mapping/profiling is feasible with this new approach.

[1] Boyce J. W. et al., 2006, GCA 70, 3031–3039; [2] Boyce J. W. et al., 2009, G-cubed 10. doi:10.1029/2009GC002497; [3] Vermeesch, P. et al., 2012, GCA 79, 140-147.

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Evaluating the role of arc volcanism Initiation and 35 Myr duration of S- on Neoproterozoic to Early Paleozoic type granitic magmatism in an climate accretionary orogen N. RYAN MCKENZIE1*, NIGEL C. HUGHES2, BENJAMIN C. SEANN J. MCKIBBIN1, BILL LANDENBERGER2, GILL3 AND PAUL M. MYROW4 WILLIAM J. COLLINS3 AND C. MARK FANNING4 1Department of Geological Sciences, Jackson School of 1Vrije Universiteit Brussel, Brussels, Belgium; Geoscience, University of Texas at Austin, Austin TX, [email protected]; 78712 2, 3University of Newcastle, Newcastle, Australia; 2Department of Earth Sciences, University of California, [email protected]; Riverside, Riverside CA, 92521 bill.collins@newcastle.edu.au 3Department of Geosciences, Virginia Polytechnic Institute & 4Australian National University; [email protected] University, Blacksburg VA, 24061 3Department of Geology, Colorado College, Colorado Springs Granites in circum-pacific igneous provinces can often be CO 80903 divided into ‘S-’ and ‘I’-types on the basis of elemental and *Corresponding author: [email protected] isotopic characteristics [e.g. 1]. This division reflects a dominance of sedimentary or igneous source components, and Identifying the driving mechanisms for major climatic dating of granites allows tracking of the relative contributions shifts deep in Earth history is challenging. Here we use a to growing batholiths in accretionary orogens. In the Lachlan global compilation of detrital zircon age data to evaluate and New England Orogens of Eastern Australia, a progression spatiotemporal variation in continental arc volcanism and from S-type through I-type to A-type granites occurs

tectonic outgassing of CO2 to the atmosphere during the repeatedly over ~100 Myr periods. S-type intrusion occurs Neoproterozoic and Early Paleozoic. This data set reveals a during the first major extensional event following major

direct link between tectonically driven CO2 emissions and the compression, while later I-type intrusion reflects a diminished dramatic episodes of climate change observed in this interval: sedimentary source and increasing mantle contribution. The the Cryogenian “Snowball Earth” and the “hothouse” world of timing of S- and I-type granites is therefore related to the the Cambrian. Importantly, these climatic events had tectonic evolution of orogens [2]. profound affects on early animal evolution. Specifically, our The S-type phase of intrusion in the New England data show the following trends: (1) a global reduction in accretionary orogen (~300-280 Ma) records an environment continental arc volcanism occurred around the transition into switching from compression to extension and back to the “Snowball Earth” whereas widespread arc systems compression as part of this process. We have undertaken U-Pb initiated near the terminal Cryogenian and its glacial interval; dating of zircons extracted from small (~backarc) gabbroic (2) Continental arc systems stayed active and further expanded and dioritic bodies (Bakers Creek Supersuite), recalculated the dramatically during the Ediacaran and into the Cambrian. This ages of S-type granites (Hillgrove Supersuite), and compiled corresponding to an extreme greenhouse climate and chronological data for the New England Orogen in order to protracted interval of global environmental stress; and (3) A investigate the establishment of magmatism in this area. We global reduction in arc volcanism during the early Ordovician find a progression through: (1) diverse magmatism involving is associated with a period of global cooling and the onset of gabbroic, dioritic, S- and I-type during establishment of the Great Ordovician Biodiversification Event (GOBE). These magmatism (305-295 Ma); (2) a major pulse of S-type data demonstrate that global variation in plate tectonic regimes magmatism (295-285 Ma), ending with; (3) I-type and HREE- plays a major role in steering Earth’s climate and evolutionary depleted (deep crustal) magmatism around the time of the patterns on million year time scales. Hunter-Bowen orogenic event (~285-266 Ma). Magmatism occurs over a ~35 Myr period in the region of most voluminous intrusion, but timing varies along-strike and may reflect assymetric rifting of the orogen. Together, these data time the heating, melting, depletion, and exhaustion of the S-type magma source. [1] Kemp, A. I. S. & Hawkesworth, C. J., 2003. Treatise on Geochemistry 3, 349-410. [2] Collins, W. J. & Richards, S. W., 2008. Geology 36, 559-562.

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Identifying the sources of iron in EARTHTIME: Past, Present, and reservoir fluids at a CO2 injection Future pilot in Alberta, Canada NOAH MCLEAN1 BREEGE MCKIERNAN1* MICHAEL WIESER1 1NERC Isotope Geosciences Laboratory, Keyworth, MICHAEL NIGHTINGALE2A AND BERNHARD MAYER2 Nottingham, UK 1 [email protected] Department of Physics and Astronomy, University of

Calgary, 2500 University Drive NW, Calgary, AB, The last ten years have seen a revolution in T2N1N4, Canada ([email protected] (*presenting geochronology. Recognizing that the apparent precision author) achievable by a new generation of mass spectrometers and 2Department of Geoscience, University of Calgary, 2500 laboratory techniques outstripped inter-laboratory agreement University Drive, NW Calgary, AB, T2N1N4, Canada and revealed unrecognized inter-chronometer biases, the ([email protected], [email protected]) EARTHTIME initiative was formed to move science forward

through community engagement and collaboration. A series The Pembina oil field is situated in western-central of inter-related experiments in the U-Pb and Ar-Ar Alberta, Canada. After decades of water-flooding, a CO 2 communities, including inter-lab comparisons, community injection pilot project was constructed to enhance tertiary oil tracer calibration and distribution, and adoption of software recovery. A detailed geochemical monitoring program was and data reduction norms, have been broadly successful, in conducted to study the impact on the geochemistry of large part due to international cooperation. reservoir fluids and rocks [1]. Increased iron concentrations, The success of the U-Pb and Ar-Ar experiments have up to 144 g/g, were measured at observation wells in the since inspired the same approach from other chronometers vicinity of the two CO injectors after CO injection 2 2 whose increasing measurement precision and proliferation of commenced.U laboratories has elicited the same questions. The U-series Iron isotopic compositions were measured and two community is now embarking on a large international inter- possible sources of iron were investigated: leaching from the laboratory comparison, in conjunction with first-principles production pipes and siderite dissolution. Iron isotope data are calibration efforts; the LA-ICP-MS U-Pb community has summarized in Figure 1. completed an inter-laboratory comparison and is presently Data suggest that neither siderite dissolution nor iron engaged in software package comparison and development of leaching are the only processes occurring at the site. Either a data reduction norms; and the EarlyTime initiative, focused on third source of iron or BSR are responsible for the measured geochronology of meteorites, is organizing an inter-laboratory iron delta values. comparison. These efforts seek to replicate, and strive to be informed by, the progress made by EARTHTIME. As these parallel projects advance and the accuracy of each system improves, it is worthwhile considering both the limiting uncertainties and the ultimate goals involved. Minimizing and correctly estimating inter-laboratory biases by measuring multiple ‘secondary’ standards across many laboratories yields a community-wide measure of the external reproducibility of each method. As measurement uncertainties and internal repeatability improve, along with our ability to estimate them, this external reproducibility and the ability to tie each system back to first principles measurements define accuracy and precision for each system. These uncertainties also determine how well we can compare between isotopic systems, an ultimate goal of Figure 2: Iron isotope data obtained for reservoir water EARTHTIME and the larger geochronology community. obtained from observation wells, siderite samples from the Decay constant uncertainties dominate our ability to combine reservoir and production the pipe. data from multiple chronometers, and active research and debate is focused on inter-relating these decay constants [1] Michael Nightingale (2010). Unpublished MSc. Thesis. through geologic comparisons, for instance dating the same University of Calgary. discrete event in time with multiple chronometers.

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Did the Moon Form at 4.36 Ga? Magma-mixing processes recorded in CLAIRE L. MCLEOD1* AND ALAN BRANDON1 compositionally zoned titanite from 1Department of Earth and Atmospheric Sciences, University of the Ross of Mull Granite, Scotland Houston, Science and Research Building 1, Houston, TX, 1 2 G. W. MCLEOD * AND T. J. DEMPSTER 77204, *[email protected] 1Earth & Environment, University of Leeds, Leeds, LS2 9JT, Magma ocean crystallisation is an important stage of early UK (*correspondance: [email protected]) planetary differentiation and evolution. Estimates for the 2Geographical and Earth Sciences, University of Glasgow, timing of lunar magma ocean (LMO) crystallisation, and G12 8QQ, UK ([email protected]) consequent formation of the lunar crust (ferroan anorthosites; FANS, and the Mg suite), is not well constrained with ages Accessory minerals play a significant role in the control of spanning from 4.57 Ga to 4.18 Ga[1,2,3,4]. More recent trace element behaviour and consequently may be crucial in studies[5,6] on lunar crustal samples are consistent with a late c. deciphering magma genesis and crystallization histories. 4.36 Ga age for the moon from Sm-Nd, Rb-Sr and Lu-Hf Titanite is characterised by slow diffusion of trace elements, isotopes. The Sm-Nd isotopic systematics of KREEP samples and as such may preserve magmatic zoning. The incorporation and lunar mare basalts constrains the age of LMO of REE and HFSE within titanite makes it ideal for assessing crystallisation from 4.49 Ga to 4.31 Ga[7], while the Lu-Hf petrogenetic processes. system suggest that the KREEP reservoir also formed c. 4.36 In plutonic environments the detail of petrogenesis is often Ga[8]. The U-Pb ages of lunar zircons indicate a potentially lost as slow rates of cooling! allow minerals to chemically re- older age for LMO solidification at c. 4.42 Ga[9]. equilibrate during sub-solidus diffusion. The Ross of Mull To further examine LMO crystallisation and its Granite displays a variety of plutonic level magma-mixing relationship to the timing of lunar formation, a suite of mare phenomena and represents an excellent site to test the potential basalts that span the range of petrologic types from the Apollo of titanite to preserve geochemical fingerprints of its genesis. collection will be evaluated for their Sm-Nd systematics. A textural and! geochemical investigation of titanite from the High-precision 142Nd/144Nd to date indicate a closure age of c. pluton reveals that zoning in trace elements strongly correlates 4.34±0.04 Ga for the Sm-Nd mare basalt source reservoirs[7,10]. with field evidence of magma-mixing processes. Diorite With the additional new 142Nd/144Nd data presented here, we enclaves contain a range of textures indicative of variable will test whether the previously obtained correlation with states of interaction with the host granite and suggest that a 143Nd/144Nd represents an isochron with an age c. 4.36 Ga, the number of discrete mixing events have occurred, both prior to implication of this being that the mantle source closure time emplacement at the present level and in situ. for the basalts is consistent with a rapid LMO solidification Titanites from both the enclaves and the host granite show following a late lunar formation time. Alternatively, if these compositional zoning dominated by fine-scale oscillatory new data do not lie on a coupled 142Nd-143Nd isochron, this types as well as major discontinuities linked to dissolution would indicate multistage histories for their lunar mantle events associated with changes in titanite, and associated sources[11]. In the latter case, the coupled 142Nd-143Nd data for ilmenite, stability. The zones reflect growth during changing lunar basalts implies a more protracted differentiation history melt chemistry and correlate with variations in REE and and are likely more consistent with an early formation time of HFSE. Introduction of fresh diorite magma into the granite the Moon. host, and the subsequent mixing processes, induced compositional, temperature and oxygen fugacity changes to [1]Papanastassiou & Wasserburg (1976) 7th LSC 2035-2054; which titanite responded. Processes recorded by titanite [2]Carlson & Lugmair (1988) EPSL 90, 119-130; [3]Alibert et zoning include; (i) homogenisation of crystal free melts; (ii) al. (1994) GCA 58, 2921-2926; [4]Borg et al., 2011) Nature crystal transfer and scavenging between partially crystallised 477, 70-72; [5]Borg et al. (2013) LPSC #1563; [6]Carlson et al. magmas; (iii) melt segregation and transfer from crystalline (2013) LPSC #1621; [7]Boyet and Carlson (2007) EPSL 262, enclaves; and (iv) late-stage diffusive exchange. Titanite thus 505-516; [8]Gaffney et al. (2013) LPSC #1714 [9]Nemchin et records both localised and distal mixing activity and is capable al. (2009) NatureGeo 2, 133-136; [10] Brandon et al. (2009) of revealing many otherwise hidden events within the magma GCA 73, 6421-6445 [11]Munker (2010) GCA 7340-7361. chamber.

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Trace element partitioning between Iron supply and cycling on the carbonate globules and silicate glass Oregon-California shelf: in volcanic carbonatites Comparisons with the Gulf of Mexico S. C. MCMAHON1*, E. R. HUMPHREYS-WILLIAMS2, C. E. hypoxic zone 1 1 2 L. GILDER , R. A. BROOKER , T. E. JEFFRIES 1 2 1 JAMES MCMANUS *, MOUTUSI ROY , SILKE AND M. J. WALTER 3 4 5 SEVERMANN , ZANNA CHASE , WILLIAM BERELSON , 1School of Earth Sciences, University of Bristol, BS8 1RJ, CLARE REIMERS1, MIGUEL GOÑI1, APRIL ABBOTT1 UK (correspondence: [email protected]) AND JESSE MURATLI1 2Department of Earth Sciences, Natural History Museum, 1Oregon State University, CEOAS, 104 CEOAS Admin Bldg, Cromwell Road, London, SW7 5BD, UK Corvallis, OR, 97331 (*correspondence: ([email protected]) [email protected],

[email protected], The origin of globular-shaped carbonate in silicate glass in [email protected], carbonatites is subject to much debate. Whether such [email protected], ‘globules’ represent immiscible carbonatite melts or rounded [email protected]) calcite crystals has important implications for calcio- 2 Arizona State University, Tempe, AZ, 85287 carbonatite genesis. Here we present major and trace element ([email protected]) analyses of carbonate and silicate glass from volcanic 3 Rutgers University, New Brunswick, NJ, 08901 carbonatites in the Calatrava Volcanic Province (CVP), Spain ([email protected]) and the Auvergne, France, as well as new experiments 4 University of Tasmania, AU ([email protected]) reproducing the CVP textures. 5 University of Southern California, Los Angeles, CA, 90089 Compelling textural evidence for liquid immiscibility ([email protected]) includes curved menisci against silicate melt, and budding of

globules (suggestive of coalescence) [1]. However, The riverine supply of fine-grained sediment to coastal experiments have shown that similar globules can form as regions along the Northeast Pacific margin generates a patchy solid carbonate crystals in equilibrium with silicate melt [2]. "depositional" setting with sediments containing varying Experimentally produced immiscible carbonate melts also do amounts of sands and muds. The mid-shelf adjacent to the not reproduce the stoichiometric calcite and dolomite Umpqua River, features a mud-rich sediment patch that is compositions observed in the natural volcanic carbonatites. relatively rich in operationally defined reactive iron. Reactive One way to resolve whether the globules formed as melts iron concentrations here covary with the distribution of or solids in natural and experimental samples is to investigate organic material, suggesting that there may be a coupling the way elements are distributed between the two phases. LA- between their delivery and burial. ICP-MS has been employed for in-situ trace element analysis Downcore profiles of dissolved iron from a number of of both carbonate and glass. Partitioning into a crystalline locations along the Oregon margin shows that sediments can phase is controlled by the characteristics of the lattice site range from being relatively enriched to depleted in dissolved where the element resides, subject to strictly defined iron concentrations. Although this pattern may point to a constraints related to the element size (ionic radius) and the connection between the diagenesis of continentally derived charge. Classic Onuma parabolae are observed, suggesting a sediment and the iron supply to coastal waters from the crystal control over the partitioning in some volcanic sediments, other factors such as rates of fluid advection, carbonatites, with calcite globules representing crystalline bottom water dissolved oxygen contents, and the availability carbonate crystallised from carbonate-rich silicate melt. of fresh organic material likely influence net iron transport Experimentally we have reproduced these pure calcite across the sediment-bottom water boundary. In an effort to ‘globules’, as well as more complex immiscible alkali-bearing separate some of the factors that might influence dissolved carbonate melts. We report on the partitioning characteristics iron input to the overlying water column, we compare iron for both and draw comparisons with the natural samples in benthic fluxes along the Oregon and California margin with order to elucidate their origin as solids or melts. fluxes from the "hypoxic" shelf region in the Gulf of Mexico.

Our results do not suggest significantly greater benthic iron [1] Bailey et al. (2005) Min Mag 69, 907-915 [2] Brooker & fluxes within the Gulf of Mexico compared to the Oregon and Kjarsgaard (2011) J. Pet 52, 1281-1305 California margins.

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Materials from geochemically Secondary organic aerosol formation inspired studies : from Titan's tholins in aerosol water: Impact on aerosol to extremophile bacteria physical properties PAUL F MCMILLAN1 V. FAYE MCNEILL1 1Dept. of Chemistry, University College London, 20 Gordon 1Department of Chemical Engineering, Columbia University, St., London WC1H 0AJ, UK New York, NY, USA 10027 [email protected]

Geochemistry and experimental geology studies have long The chemistry of atmospheric aerosols influences their been linked to the identification and processing of new direct and indirect effects on climate. Inorganic aerosols may materials with great technological importance and high acquire an organic component via in situ interactions with societal impact. Examples range from hydrothermal and sol- volatile organic compounds (VOCs), a family of processes gel synthesis of ceramics to development of techniques for in known as secondary organic aerosol (SOA) formation. SOA situ studies of functional materials under extreme conditions. formation is one of the greatest sources of uncertainty in New research extending from planetary sciences to deep life estimations of aerosol climate forcing. Pathways for aqueous- geochemistry are leading to new developments in phase SOA formation have been identified in which water- nanomaterials technology and biochemical processing with soluble VOCs dissolve into cloud droplets or wet aerosols, medical and forensic applications. Here we describe and followed by aqueous-phase reactions which lead to the discuss recent results that extend from fundamental studies formation of SOA material. Our recent laboratory studies and interplanetary based observations of Titan's atmosheric show that particle-phase chemical reactions between organics aerosols to new materials being developed for efficient charge and inorganic salts can lead to secondary organic products storage and energy use applications on Earth, to the which absorb light in the UV and visible, thus changing the involvement of new studies of extremophile bacteria in the optical properties of the particle. We have also shown that deep Earth enviroment to development of nanotechnology and aqueous-aerosol SOA products may be surface-active, biomedical applications. These examples will illustrate the therefore potentially enhancing the ability of small particles to continued and emerging links between geochemistry, nucleate cloud droplets (CCN activity). In addition to these advanced materials science and biology, with enormous bulk surfactant effects, our work demonstrates that the surface benefits to society. adsorption of methylglyoxal and acetaldehyde from the gas phase can depress aerosol surface tension and increase CCN activity. Finally, I will introduce a photochemical model of coupled gas and detailed aqueous aerosol chemistry that we have developed in order to study the formation of secondary organic aerosol material in aerosol water and the associated changes in aerosol physical properties. I will present results for atmospheric scenarios and highlight needs for additional experimental work.

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Production of archaeal lipid Reconstructing the magma feeding biomarkers in stable isotope labeled system of the Cappadocian incubations of MCG-rich sediments ignimbrites (Turkey) through T. B. MEADOR1*, G. KUIPPERS1, C. LAZAR1,2, M. amphibole thermobarometry 1 2 1 KÖNNEKE , A. TESKE AND K-U. HINRICHS 1 1 1 E. MEDARD , J.-L. LE PENNEC , J.E. FRANCOMME 1MARUM Center for Environmental Sciences and Department A. TEMEL2 AND F. NAURET1 of Geochemistry, University of Bremen, 28359 Bremen, 1 Clermont Université, UBP/CNRS/IRD, Laboratoire Magmas Germany (*correspondence: [email protected]) et Volcans, 5 rue Kessler, 63038 Clermont-Ferrand, 2Department of Marine Sciences, Univ. North Carolina at France ([email protected]) Chapel Hill, Chapel Hill, NC 27599-3300, USA 2 Hacettepe University, Faculty of Engineering, Department of

Geological Engineering, 06800, Beytepe-Ankara, Turkey The Miscellaneous Crenarchaeota Group (MCG) exhibit a global-distribution in anoxic, aquatic sediments and occur The Cappadocia area of Central Turkey superbly exposes throughout a variety of distinct geochemical sediment regimes a succession of Neogene dacitic to rhyolitic ignimbrites and [1]. Several researchers have proposed that MCG live fallout deposits, recording 10 Ma of magmatic activity. This heterotrophically on organic carbon sources that are buried in provides an excellent example of long-lived, relatively low the seafloor [1, 2], and Lloyd et al. [3] recently identified frequency magmatic system, with a low average magma peptidases within the MCG genome; however, there is still no production rate (about 10-3 km3/a), but short-lived large direct evidence of the metabolic strategy employed by these 3 eruptions (up to 300 km for the Cemilköy ignimbrite). Most archaea. We incubated MCG-rich sediments from the White of the ignimbritic and fallout units share a very similar, low- Oak River estuary anaerobically with deuterated (D) water and variance, phenocryst mineralogy (plagioclase + biotite + 13C-bicarbonate [cf. 4], and determined the growth response of amphibole + magnetite + quartz), which makes them perfect the MCG community in response to the addition of various targets for Al-in amphibole barometry. organic substratres by quantifying the production of archaeal An accurate Al-in hornblende barometer has been intact polar lipid (IPL) biomarkers, including compounds recalibrated from literature data and new experiments on the thought to be specific for MCG. Kızilkaya ignimbrite. This new barometer takes into account After a period of 145 days, evidence of D uptake into IPLs the effect of both edenite and Tschermack substitutions on Al containing crenarchaeol indicated that several substrates concentrations. Our data, combined with existing litterature stimulated benthic Crenarchaeota, which was supported by data, show a very good pressure-dependence of the increases in the relative abundance of MCG clones in archaeal Tschermack substitution (correlation coefficient of 0.95) for 16s rRNA clone libraries by up to 30%. The incubations amphibole in equilibrium with biotite, plagioclase and quartz. amended with monosaccharides, peptone, or with yeast extract Our new barometer reproduces experimental pressures with an and acetate showed the highest label incorporations, average error of 36 MPa in the 100-400 MPa range. More translating into an ~ 5-fold increase in cell production rate, experiments are underway to improve the barometer’s relative to a control incubation with no substrate accuracy. ammendment. Given that only minimal 13C was incorporated Pre-eruptive temperatures are relatively stable for most into archaeal lipids, our data are consistent with heterotrophic units, between 700 and 760 °C. Amphiboles crystallized in the growth by MCG. Furthermore, these findings provide new upper crust, between 9 and 14 km depth, hinting at a constant evidence for the benthic production of crenarchaeol, likely by depth of magma storage beneath the Cappadocian ignimbrite MCG, which is in conflict with the presumed planktonic field. Detailed investigation of one of the youngest unit, the source of this biomarker [e.g., 5]. Kizilkaya ignimbrite, produces a tight unimodal pressure

distribution at 260 ± 20 MPa (9.8 ± 0.8 km depth), with a [1] Kubo et al. (2012) ISME J. 10, 1949-65. [2] Biddle et al. maximum data dispersion lower than the 2! uncertainty of the (2006) PNAS 103, 3846-51. [3] Lloyd et al. (2013) Nature barometer. If the erupted reservoir was homogeneous, as doi.10.1038/nature12033. [4] Wegener et al. (2012) Environ. suggested by the absence of magma mixing, and amphibole Microbiol. 14, 1517-27. [5] Sinninghe-Damsté (2002) J. Lipid was present in the entire reservoir, the aspect ratio of the Res. 43, 1641-51. magma chamber would be relatively low, with a minimum

diameter of 7.5 km and a 1.5 km maximum height.

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From small-scale chemical processes The structural determinants of silicon to long-term (radioactive) fractionation properties of silicate contaminant migration predictions minerals: a First-Principles Density JOHANNES C.L. MEEUSSEN1, THOMAS J. SCHRÖDER1 Functional Study 2 AND JORIS J. DIJKSTRA 1 2 M. MÉHEUT * AND E. A. SCHAUBLE 1Nuclear Research and Consultancy Group Petten, The 1GET, Université Paul Sabatier, Toulouse, France Netherlands. (* Correspondence: [email protected]) 2 (*correspondence: [email protected]) Energy Research Centre of the Netherlands, Petten The 2 ESS Dept., UCLA, Los Angeles, USA Netherlands([email protected])

Silicon is among the new isotopic systems that are Migration rates of (radioactive) contaminants in porous emerging due to recent analytical progress in mass materials, such as soil rock and concrete, are dominated by spectrometry. Thorough understanding of the parameters distribution of ions over pore solution and solid phase. influencing natural Si-isotope variation is therefore of great Precipitation and adsorption are small-scale chemical importance to assess potential geochemical applications. processes that determine the distribution and in this way Ab initio methods based on density functional theory have control migration rates at larger scales. The often proven successful in predicting equilibrium fractionation multicomponent nature of such interactions results in a strong factors as a function of temperature (e.g., 1). We use the PBE dependence of single element behaviour on chemical functional, combined with norm-conserving pseudopotentials conditions, which complicates the translation of experimental and plane wave basis sets. We focused on phyllosilicate results to field conditions. Credible contaminant migration minerals: kaolinite, lizardite, talc and pyrophyllite, which predictions require a model that contains the major soil appear to span a wide range in fractionation properties despite reactive phases / surfaces, e.g. the different oxide and organic having the same basic silicate polymerization. In this family matter surfaces, dissolved organic carbon, including their of silicates, calculated Si isotope fractionation appears to be mutual chemical interactions in a thermodynamic consistent correlated with chemical composition: way[1]. The combined CD-MUSIC model for oxides, the NICA-DONNAN model for organic matter, and the LCD model go a long way achieving this. To accommodate these

combined models an advanced numerical framework is eq. with X representing the cation equivalents of X=Al, Mg, required[2]. It is, however, important to realize that whatever Si, i.e. the number of <(SiO ), &(Al O ), (MgO) units in the the assumed sophistication of the conceptual- or numerical 2 2 3 mineral, and a (T) is a parameter depending on temperature. model, careful evaluation of model accuracy is essential for its X Further analysis leads us to interpret this relationship as an usefulness in practice. Such an evaluation can only be done by electron donation effect, such that a (T) should increase with testing the model on truly independent data [3]. X decreasing electronegativity of X. To assess the generality of

this relationship, we computed fractionations for a more [1] Schröder et al. (2005), Environmental Science &. diverse suite of minerals. Within the MgO-Al O -SiO system, Technology 39, 7176-7184. [2] Meeussen, 2 3 2 relation (1) continues to hold for quartz, pyrope and enstatite (2003), Environmental Science &. Technology 37, 1175- (R2 = 0.99, n=7), but forsterite is strongly anomalous. To 1182. [3] Dijkstra, et al. (2009) Environmental Science & assess the effects of Ca2+, Na+, K+ and tetrahedral Al3+ on Si technology 43 , 6196-6201. fractionation, we computed the properties of albite, anorthite,

microcline, diopside, wollastonite, jadeite, grossular, and the

three Al2SiO5 polymorphs. Preliminary results suggest almost all of these minerals follow relation (1) reasonably well (excepting wollastonite), if tetrahedral Al3+ is assumed to have no effect on Si fractionation (�����/�012 ). These results suggest that particular attention should be given to chemical compositions in Si isotope studies.

[1] Meheut et al. (2009) Chem. Geol. 258, 28

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Protein-silica interactions: The effect Speciation and thermodynamic of lysozyme on the structure of properties of palladium chloride and amorphous silica bisulfide complexes: insights from D.B. MEIER1*, D.J. TOBLER2, C.L. PEACOCK1 experiments and ab-initio molecular AND L.G. BENNING1 dynamics simulations 1 School of Earth and Environment, University of Leeds, 1,2 3 1,4 United Kingdom (*correspondence: [email protected]) YUAN MEI , T. M. SEWARD , JOËL BRUGGER , 2 2 5 Nano-Science Center, Department of Chemistry, University STEPHEN J. BARNES AND MARCO L. FIORENTINI of Copenhagen, Denmark 1School of Earth and Environmental Sciences, The University of Adelaide, Australia ([email protected]) Amorphous silica is one of the two dominant biominerals 2 CSIRO Earth Science and Resource Engineering, Australia in the world’s oceans where it is precipitated by diatoms, 3 Victoria University of Wellington, New Zealand radiolarians or siliceous sponges. Furthermore, in geothermal 4 South Australian Museum, Australia settings microorganisms can become quickly silicified through 5 CET/CCFS, The University of Western Australia, Perth, the precipitation of silica from under- or oversaturated Australia geothermal waters. In both cases, the interaction between amorphous silica and cell internal or cell wall Characterising the speciation and solubility of platinum macromolecules, like proteins, are crucial for templating the group elements (PGE) in hydrothermal fluids is useful in siliceous structures or for enhancing microbial silicification [1, understanding the formation of PGE deposits, and for 2]. However, how and if proteins affect the structure, supporting the development of new exploration tools for high composition and morphology of amorphous silica at the value magmatic nickel sulfide deposits, whose small footprints molecular level is only poorly understood may be extended by hydrothermal remobilisation of PGE. A number of experimental studies have investigated Pd Here, we quantified the effect a typical protein (lysozyme) speciation and solubility in hydrothermal chloride solutions, has on the atomic structure and composition of amorphous with reasonable agreement over the nature and stability of silica that was precipitated from supersaturated aqueous Pd(II) chlorocomplexes (Barnes and Liu, 2012). In contrast, solutions in the absence or presence of variable lysozyme there are significant discrepancies among the available concentrations (0 – 10’000 ppm). thermodynamic properties for the predominant Pd bisulfide Synchrotron-based pair distribution function (PDF) analyses species. This uncertainty severely hinders numerical showed only a minor change in the short range ordering (>15 modelling of PGE mobility in hydrothermal fluids. Å) of amorphous silica precipitated in the presence of 2 1000 Ab-initio molecular dynamics (MD) simulations were ppm lysozyme. This suggests limited structural interactions performed to investigate the stability of possible Pd-Cl and and hardly any incorporation of the lysozyme within the Pd-HS complexes in hydrothermal fluids. The simulations amorphous silica structure. Fourier Transform Infrared (FTIR) revealed the preference of four-fold square planar structures of spectroscopic analyses however, indicate significant both chloride and bisulfide complexes at high P,T (300 ˚C, incorporation and surface interaction between lysozyme and 500 bar). We are building a geochemical model for Pd amorphous silica at all lysozyme concentrations. transport via thermodynamic integration (Mei et al., 2013). The species geometry and thermodynamic properties derived Further PDF and FTIR experiments are underway to test from the MD simulations will be compared with the existing for artifacts and to confirm the findings reported above. thermodynamic properties (Boily and Seward, 2005) and with Moreover, thermogravimetric analyses, X-ray diffraction, total new EXAFS measurement of Pd chloride complexes in carbon analyses and high resolution microscopy will help to hydrothermal brines up to 340 ˚C. quantify the ratio of incorporated to adsorbed protein contents, the water contents, and the morphology of amorphous silica as [1] Barnes and Liu (2012) Ore Geol. Rev., 44, 49–58. [2] a function of protein content. Boily and Seward (2005) Geochim. Cosmochim. Acta., 69, [1] Perry & Keeling-Tucker (2000), Journal of Biological 3773–3789 [3] Mei, Sherman, Liu, Brugger (2013) Geochim. Inorganic Chemistry, 5, 537-550. [2] Tobler, Stefansson & Cosmochim. Acta., 102, 45–64. Benning (2008), Geobiology, 6, 481-502.

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Multi-element 2D analysis of drilling H2O-adsorption at the (100)-pyrite cores containing mining residues surface: Forcefield simulation studies using LIBS and chemometric analysis supporting GIXRD-experiments J.A. MEIMA S. MEIS1*, U. MAGDANS2, X. TORRELLES3 AND H. GIES1 Bundesanstalt für Geowissenschaften und Rohstoffe (BGR) 1Institute of GMG, Ruhr-University Bochum, 44780 Bochum, Hannover, Germany ([email protected]) Germany, (*correspondance: [email protected]) 2IA Physics, RWTH Aachen, 52056 Aachen, Germany, Laser-induced breakdown spectroscopy (LIBS) is a type ([email protected]) 3 of atomic emission spectroscopy that uses a laser-generated ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra, Spain, plasma to ablate, atomize, and excite material from a sample [email protected] surface. LIBS has potential for rapid non-destructive and in- situ geochemical analysis. However, quantitative analysis with It is of great importance to study mineral-adsorbate LIBS, especially of heterogeneous materials, is very interfaces, because in natural processes mineral surfaces are challenging; matrix effects and plasma variations influence the able to function as templates for the ordering of organic LIBS signal. These limitations have succesfully been molecules and water. The periodically ordered surface atoms overcome using multivariate chemometric methods and induce an ordering of the adsorbates, so that specific chemical repetitive measurements in other applications [e.g. 1]. reactions can take place near surfaces. The (100)-pyrite (FeS2) This study tries to estimate limits of detection and surface plays an important role in many environmental, accuracy for multi-element LIBS analysis of drilling cores biological and mineralogical processes, e.g. in acid mine containing mining residues (Harz, Germany) with the LIBS drainage processes and in the Iron-Sulphur world scenario, system described below. The LIBS system uses a Nd:YAG 50 that describes one possibility for the origin of life [1]. mJ 1064 nm laser and an Echelle spectrograph with CCD The structure of the (100)-FeS2-H2O interface was detector (285-960 nm, resolution 28-94 pm). On the drilling determined with grazing incidence X-ray diffraction cores, nine meter in total and each one cut in halve, 1000 x experiments under environmental conditions, previously[2]. 12.5 mm large surface strips were measured, representing An adsorption model for H2O at the (100)-FeS2 surface was 20000 individual (5 accumulated laser shots each) LIBS determined including three adsorption layers in a distance of measurements. Over 100 alternating layers consisting of 1.9(1)Å, 3.0(3)Å and 5.4(4)Å to the surface, a transitional sludge, Pochsand or wall rock were found; all layers were zone of partial ordered H2O molecules and H2O molecules that sampled and analysed by XRF as reference samples. A occupy vacancies of the topmost FeS2-layer. calibration model was developed with Partial Least Square Here we report about molecular dynamic (MD) Regression (PLSR) analysis. simulations of the H2O-adsorption on the (100)-FeS2 surface, A qualitative LIBS analysis based on characteristic carried out with the program package Materials Studio 5.0, emission lines for heavy metals and major elements has particularly the program “Adsorption locator”, from Accelrys shown, that significant chemical differences may exist Inc. Using the forcefield COMPASS27 we confirmed the between layers. Inside a layer of sludge or wall rock, the LIBS experimental achieved adsorption model of H2O. Additionally signal appears to be relatively constant. On the other hand, we determined the orientation of H2O-molecules within the Pochsand layers that consist of very course sand appear to be adsorption layers, the exact positioning of the H-atoms and we very heterogeneous; heavy-metal enrichment is clearly related get information about the influence of the H2O-density on the to distinct particles. Multivariate chemometric analysis on the ordering within the adsorption layers. The comparison of the relatively homogeneous layers is currently applied to build experiment and different MD simulations is well suited to get and test calibration models for a quantitative interpretation of detailed information about the atomic structure of the (100)- the LIBS measurements. FeS2-H2O-interface and to get information about interface systems under perfect adsorption conditions compared to [1] Sirven et al. (2006) Anal. Chem. 78, 1462-1469. interface systems exposed to higher entropy.

[1] G. Wächtershäuser, C. Huber (1998), Science 281 670- 672. [2] S. Meis, U. Magdans, X. Torrelles (2011), Acta Cryst. A67, C338-C339.

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Osmium isotope and PGE reference Early diagenetic quartz formation at materials OKUM and MUH-1 a deep iron oxidation front in the T. MEISEL1*, O.M. BURNHAM2 , C. KRIETE3 Eastern Equatorial Pacific 1 4 SYED N. H. BOKHARI AND T. SCHULZ 1 2 3 2 P. MEISTER *, B. CHAPLIGIN , A. PICARD , H. MEYER , 1 Montanuniversität, 8700 Leoben, Austria (*correspondence: C. FISCHER4, D. RETTENWANDER5, G. AMTHAUER5, [email protected]) C. VOGT4 AND I.W. AIELLO6 2 Geoscience Laboratories, Ontario Geological Survey, 1Max-Planck Institute Marine Microbiology, 28359 Bremen, Sudbury, ON Canada P3E 6B5 3 Germany (*correspondence: [email protected]) Federal Institute for Geosciences and Natural Resources, 2 Alfred Wegener Institute, 14473 Potsdam, Germany 30655 Hannover, Germany 3 4 Eberhard Karls University, 72076 Tübingen, Germany University of Vienna, Austria 4University of Bremen, 28359 Bremen, Germany 5University of Salzburg, 5020 Salzburg, Austria As for many isotope systems, certified reference materials 6 Marine Laboratories Moss Landing, CA 95039-9647, USA. (CRM) of real samples are very sparse. Solutions with known isotopic composition exist for QA/QC purposes, but for the Diagenetic quartz formation at low temperature is still not evalution of the combined standard measurement uncertainty well understood. Lithified chert consisting of microcrystalline matrix matched CRM need to applied. For method validation, quartz was recovered at ODP Site 1226 in the Eastern calibration and verification purposes of Os isotopic Equatorial Pacific [1] near the base of a 420 m thick Miocene- composition and platinum group element content (PGE) two Holocene sequence of nanofossil and diatom ooze. ultramafic RM with different matrices have been prepared. Precipitation temperatures calculated from oxygen isotope OKUM, an ultramafic komatiite and MUH-1, a depleted values in the cherts are near to present porewater harzburgite (Kraubath, Austria) have been prepared and are temperatures, and a sharp depletion in dissolved silica occurs already certified for major and trace elements by an at 385 m, indicating that silica precipitation is still going on. interlaboratory certification process lead by the International It has been observed that quartz forms in experiments in Association of Geoanalysts (IAG). Whereas the dominant the presence of fresh precipitated iron oxyhydroxides [2]. PGE bearing phases in lherzolites are sulfides, the dominat Indeed, a deep iron oxidation front occurs above 400 m phases in harzburgites are alloys and laurites. As a result, the sediment depth, which is caused by upward diffusing nitrate homogeneity of harzburgites with respect to PGE distribution from an oxic seawater aquifer in the underlying basaltic crust. is generally much worse than for lherzolites and komatiites. Sequential iron extraction and analysis of the X-ray absorption Initial homogeneity tests with 2 g and smaller test portion near-edge structure (XANES) revealed that iron in the cherts sizes demonstrate this significat difference. predominantly occurs as illite and amorphous iron oxide,

whereas iron in the nanofossil and diatom ooze occurs mainly

in smectites. Mössbauer spectroscopy confirmed that the

amorphous iron in the cherts is largely oxidized.

Two possible mechanisms may be operative during early

diagenetic chert formation at iron oxidation fronts: (1) quartz

precipitation may be initiated by adsorption of silica to freshly

precipitated iron oxides. (2) Iron oxidation lowers the pH,

which brings the reactive surfaces of iron oxides closer to the

zero point of charge, facilitating the binding of SiO . We 2 suggest that the formation of early-diagenetic chert at iron

oxidation fronts is an important process in suboxic zones of This test already demonstrates that validated methods with silica-rich sediments. The largest iron oxidation front ever lherzolitic RM such as UB-N cannot be applied to occurred during the great oxidation event ca. 2.5 Ga ago, when harzburgites as these are generally heterogeneous. large amounts of iron and chert beds were deposited. Both RM show PGE distributions typical for mantle restites and komatiite melts with 187Os/188Os of 0.127 and 0.27 respectively and thus ideal matrix RM for mantle studies. [1] D’Hondt et al. (2002) Proc. ODP, Init. Repts. 201. [2] Harder & Flehmig (1970) Geochim. Cosmochim. Acta 34, 295-305.

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B content and " 11B from cultured Investigation of the processes of diatoms (Thalassiosira weissflogii & organic matter diagenesis in T. pseudonana): Relationship to sediments of Lake Beloye, West pHseawater and diatom C acquisition Siberia, by the pyrolytic methods! 1 2 2 *L.M. MEJÍA1, J. FIETZKE2, K. ISENSEE1, A. MÉNDEZ1, J. V.N. MELENEVSKY *, G.A. LEONOVA , V. A. BOBROV , 4 5 PISONERO1, N. SHIMIZU3, C. GONZÁLEZ1, A.S. KONYSHEV AND A.E. MALTSEV 3 1 B. MONTELEONE AND H. STOLL 1,4 A.A. Trofimuk Institute of Petroleum Geology and 1Universidad Oviedo, C/ Arias de Velasco s/n, 33005 Oviedo, Geophysics, Siberian Branch of the Russian Academy of Spain. *correspondence: [[email protected]] Sciences, Russia (*coresspondence: 2Helmholtz Centre for Ocean Research Kiel, Wischhofstr. 1-3. [email protected]) 24148 Kiel, Germany 2,3,5Institute of Geology and Mineralogy, Siberian Branch of 3WoodsHole Oceanographic Institute, Woods Hole, USA the Russian Academy of Sciences, Russia

Despite the importance of diatoms in regulating climate, During diagenesis, biopolymers (proteins, fats, most geochemical records are based on carbonates. Among carbohydrates, lignin, etc. synthesized by animals and plants) 11 of organic matter (OM) transform into a geopolymer - the so- them, B content and " B has been widely used to reconstruct called kerogen composing most of the OM of ancient pH from foraminifera and coral fossils. We present sediments. Starting from the sedimentation and deposition of preliminary results of "11B on diatom opal and compare them OM of plant and animal genesis, many biochemical and to "11B on inorganically precipitated opal. We measured B chemical reactions run in it. content in opal with the aim of determining if [B] can be used Study of the Holocene sediments of Lake Beloye (West as a pH proxy or to identify physiological responses to Siberia) in the depth range 0 — 137 cm gave an insight into the transformation of organic matter (OM) at the early stages acidifying pH. of diagenesis. Analysis of OM was performed by pyrolytic Thalassiosira pseudonana and Thalassiosira weissflogii methods (Rock Eval (RE) and pyrolysis + gas were cultured at varying pH and Si and C quotas were chromatography-mass spectrometry (Pyr-GC-MS)). RE determined. Frustule B content was measured by LA-ICPMS pyrolysis is intended for the identification of oil source rocks, and ion probe. Cells of both species grown at higher pH have but owing to its simplicity and reliability, this method has higher [B] and higher Si requirements per fixed C. If this trend been widely used for the study of immature OM in soils and is representative of diatom silicification in a future more acidic recent lacustrine and marine sediments [1, 2]. The Pyr-GC-MS ocean, it could contribute to changes in the efficiency of is the main method for the study of the molecular composition of protokerogen. It consists in conducting the flash-pyrolysis diatom ballasting and C export, as well as changes in the at >600 ºC with a subsequent gas chromatography-mass- diatom abundance in the phytoplankton community in Si- spectrometry analysis of the products [3]. Using RE and Pyr- limited regions. If B enters the cell through the same GC-MS methods, 15 and 8 samples have been studied, - - transporter employed for HCO3 uptake, an increased HCO3 respectively. The results of the work are presented in detail in requirement with decreasing CO2 concentrations, and higher [4]. - B(OH)4/HCO3 ratios would explain the observed increase in The work has shown that the macromolecular aliphatic frustule B content with increasing pH. structure of the kerogen and the precursors of sterane and With current analytical precision, frustule [B] is unlikely hopane geomolecules — sterenes and hopenes — form at the to resolve ocean pH with a precision of paleoceanographic early stages of diagenesis. We suggest that macrophytes and interest. However, if B content was controlled mainly by bacteria are the main sources of OM for the studied lacustrine - sediments. HCO3 uptake, then B content measurements might reveal the - varying importance of active HCO3 acquisition in the past. 11 [1] Disnar et al. (2003) Org. Geochem. 34, 327—343. [2] Though as occurs with B content, " B may depend either on Sebag et al. (2006) European J. Soil Sci. 57, 344—355. [3] seawater pH and/or biomineralization processes, preliminary 11 Jocteur- Montrozier and Robin, (1988).Revue d’Ecologie et de " B results show very low values, which agrees with the very Biologie du Sol. 24, 203—214. [4] Melenevskii et al. (2011) low pH at the site of silicification ('5). At this acidic pH, it is Russian Geology and Geophysics 52, 583—592. very unlikely that "11B provides enough sensitivity to 11 reconstruct pHseawater. Conversely, " B in diatom opal may be 11 used to constrain " Bseawater, which is very important for foram-based pH reconstructions.

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Geochemistry of the Salma eclogites Geochemical characteristics of (Belomorian mobile belt, Baltic volcanic and plutonic rocks in the 36 Shield) Ma Organ Mountains caldera, USA:

A.E. MELNIK Are they telling the same story? Institute of Precambrian geology and geochronology RAS, V. MEMETI1* AND J. DAVIDSON1 St. Petersburg, Russia ( [email protected]) 1Durham University, Dept. of Earth Sciences, Durham, DH1

3LE, UK, (email: [email protected]) In the north-western part of the Belomorian mobile belt

were found numerous bodies of an eclogitic rocks, which were Volcanic and plutonic rocks are often studied as separate named Salma eclogites [1]. Salma eclogites include two types magma systems as they naturally represent different crustal of eclogitic rocks (after basic and after ultrabasic rocks) which depth levels. Results from such studies have often led to occur as tectonic blocks of various size and shape in gneisses. inconsistent interpretations regarding the geochemical Sm-Nd (grt-cpx-wr) and a local zircon U-Pb dating give the processes and the time scales responsible for the eclogites ages of 1.9 Ga [2]. The data have not proved compositional variations. This has resulted in a blurred previously published the Archean values of eclogite understanding of the connection between these two sub- metamorphism age. The eclogites are variably affected by systems and how magma plumbing systems operate over time. overprinted amphibolization. So, rims of Salma eclogite We are examining the ~36 Ma Organ Moutains caldera in bodies are commonly strongly amphibolized and also some New Mexico, USA, where contemporaneous volcanic and bodies are completely replaced by amphibolites. Geochemistry plutonic rocks of the same arc magma system are juxtaposed of REE and trace elements in the eclogites and garnet due to extensional tectonics along the Rio Grande Rift. amphibolites (completely retrogressed eclogites) were Detailed geologic and structural mapping [1] and high investigated using ICP-MS. Both basic and ultrabasic less precision 40Ar/39Ar ages of both volcanic and plutonic rocks retrograded eclogitic rocks have an almost flat chondrite- [2] provide an excellent framework to study the geochemical normalised REE patterns (YbN/LaN – 1,15-1,96) (Fig. 1). evolution and connection of both rock types for >2.5 myrs of Retrogressed Salma eclogites and garnet amphibolites after active magmatism. Three caldera-forming ignimbrites erupted eclogites in comparison with fresh rocks are enriched in REE within 600 kyrs [2] from this system with a total erupted (especially in LREE) and trace elements (U, Th, Nb, Ti, Zr). 3 volume of 500-1,000 km next to less voluminous pre- and The enrichment in REE and high field strength elements is postcaldera trachyte and andesite lavas. The ignimbrite caused by fluid affection during retrograde metamorphism. sequence is zoned from a crystal-poor, high-SiO rhyolite at 2 the base to a crystal-rich, low-SiO2 rhyolite at the top. This compositional zoning pattern of increased silica is also seen from the top downward in the main intrusion, the Organ Needle batholith, which has been interpreted to be the source for the ignimbrites [1]. The plutons are composed of granodiorite and syenite, and minor diorite and leucogranite. We will present major oxide, trace element and Sr, Nd and Pb isotope analyses of whole rocks for all plutonic and volcanic units as well as CL images and electron microprobe analyses on individual minerals and discuss 1) the geochemical relationship at rock and mineral scales of all rocks including pre- and postcaldera forming units, 2) the magmatic process(es) responsible for the compositional Figure 1: REE distribution in Salma eclogites (solid symbols - variations in both rock types, and 3) the possible cause(s) for ultrabasic eclogites; gray symbols - basic eclogites; open the large ignimbrite eruptions as well as the smaller sized lava symbols - retrogressed eclogites and garnet amphibolites after flows if they were derived from the underlying intrusions. eclogites). [1] Seager (1980), NM Bureau of Mines and Min. Res. [1] Konilov et al. (2004) 32nd IGC Abstracts (pt. 1) 108. Memoir 36, 97 p. [2] Zimmerer & McIntosh (2013) Journal of [2] Skublov, Berezin, Melnik (2011) Petrology 19, 470-495. Geophysical Research, v. 93, p. 4421–4433

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Insights into boron volatility in Early diagenesis of sulfur and trace magmatic systems element pyritization in sediments of a G. MENARD1*, I. VLASTELIC1 , E. F. ROSE-KOGA1, J. L. tropical upwelling system: Cabo Frio, PIRO1 AND C. PIN1 southeastern Brazil 1 Laboratoire Magmas et Volcans, Université Blaise Pascal, 1 1 1 1 U. MENDOZA *, R. DIAZ , M. MOREIRA , N. AMORIM , Clermont-Ferrand, France 2 1 M.E. BÖTTCHER , W. MACHADO , (*correspondence : [email protected]) 1 3 S.R. PATCHINEELAM , R. CAPILLA 1 AND A.L. ALBUQUERQUE1 It is generally accepted that boron behaves as a volatile element in magmatic systems but the amount of B leaving 1Geoquímica Ambiental, Universidade Federal Fluminense, magma (i.e. the absolute volatility) is poorly known [1]. In the RJ 24020-150, Brazil (*correspondence: aim to quantify the losses due to magmatic degassing, B [email protected]) concentration of recent (1977-2010) lavas from Piton de la 2Marine Geology, Leibniz Institute for Baltic Sea Research Fournaise volcano (Réunion Island) were measured by Warnemünde, D-18119 Warnemünde, Germany isotope-dilution ICP-MS, using a new method avoiding 3Petrobras–Cenpes, RJ 21941-915, Brazil sample evaporation. Twenty-three samples were selected based on three criteria: 1) samples are highly fresh and not The early diagenesis of sulfur and the potential effects of contamined; 2) they are cogenetic (they show tiny variations sedimentary pyrite re-oxidative cycling on the degree of trace in Pb-Sr-Nd isotopes); 3) samples cover a wide range of metals pyritization (DTMP) were assessed in short sediment eruption and degassing conditions, with an order of magnitude cores from the continental shelf under the influence of a variation in magma effusion rate. Samples include massive tropical upwelling system (Cabo Frio, Brazil). Under these basalts with variable amounts of cumulative olivine and depositional conditions, the degree of reactive iron pyritization naturally quenched samples (including Pélé’s hairs and was limited by both dissolved sulfide availability and pyrite scoria). oxidation events. Textural analyses of pyrite framboids B content varies from 1.15 to 3.98ppm. B behaving as a provide evidence of re-oxidation processes, reflecting dynamic highly incompatible during magmatic processes, ratios redox conditions in the sediments. The total sulfur, the involving B and another highly incompatible elements such as chromium reducible sulfur (CRS), and degree of pyritization B/Nb have to be constant in our suite of cogenetic lavas [2]. (DOP) values are relatively low, and showed an increase with However, while most samples show uniform B/Nb of 0.14, depth at all stations. The isotope composition of pore-water few samples show anormalous high (quenched samples) or sulfate (+18.7‰ to +23‰) remained close to the seawater low (first lavas of April 2007) B/Nb ratios. Because the value, but very light stable sulfur isotope signatures of the samples are fresh and unaltered and do not include exotic CRS fraction (-25.2‰ to -40.8‰) are found that reflect minerals potentially holding B, we interpret these subtle intense bioturbation-induced sulfur re-cycling. Relations variations as related to degassing processes. The amount of B between DTMP and stable isotope signals are found, loss in each sample has then been estimated taking the suggesting high (Pb, As, Cd and Mn), low (Zn and Cu) or composition of a primitive olivine-hosted melt inclusion as negligible (Cr and Ni) influences by iron sulfide re-oxidation. representative of the undegassed melt composition. Boron loss Pyrite-richer sediments provide an apparent threshold for varies between 10% for less-degassed samples to almost 30% intense pyrite re-oxidation, while CRS generally becomes for the first lavas of the April 2007 eruption. Moreover, the more depleted in 34S with increasing depth. This depletion was knowledge of eruptive history allows us to distinguish B loss greatest and becomes less variable when CRS contents exceed during 1) continuous open-system degassing in the magma ~0.1 wt% (with "34S values averaging " 40‰ ± 1‰), after chamber (10%), 2) lava emplacement and cooling (4-10%) which most trace elements (Pb, As, Cd, Mn and Zn) presented and 3) shallow closed-system degassing due to a vapor more accentuated DTMP values. Before the stabilization of accumulation at the top of the magma chamber prior to the the pyrite re-oxidation, the release of Mn and Fe into pore April 2007 eruption (5-8%) [3]. water was evidenced, indicating reduction of these elements. Sulfur isotope signatures of pyrite formed under the oxic [1] Rubin (1997) Geochim. Cosmochim. Acta 61, 3525-3542. bottom water conditions at Cabo Frio are similar to those [2] Hofmann et al. (1986) Earth Planet. Sci. Lett. 79, 33-45. observed in euxinic sedimentary environments, as the modern [3] Vlastélic et al. (2013) J. Volcanol. Geotherm. Res. 254 94– Black Sea. It is also indicated, that a superimposition of 107. sulfate reduction and intense oxidative sulfur cycling leading to pyrite re-cycling can affect benthic trace element fixation.

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Essential aqueous geochemistry of Evaporation of Mg- and Si-rich Pb(II) solid formation melts: evolution of chemical and A. MENDOZA-FLORES1 AND M. VILLALOBOS1* isotopic compositions of FUN CAIs 1Environmental Bio-Geochemistry Group, Geochemistry R.A. MENDYBAEV1*, F.M. RICHTER1, F.-Z. TENG2, Department, Geology Institute, UNAM, Coyoacan, CU, R.B. GEORG3 AND A.V. FEDKIN1 Mexico 04510, D.F. (*correspondence: 1 University of Chicago, IL, USA (* [email protected]) [email protected]) 2University of Washington, Seattle, WA, USA 3 Trent University, Peterborough, ON, Canada Lead is a biologically non-essential toxic metal whose biogeochemical cycle has been affected considerably by anthropogenic activities [1]. Its mobility in aqueous Extremely large mass-dependent fractionations of Si, Mg environments is determined by its abillity to form soluble and O isotopes in FUN CAIs suggest that their precursors lost complexes with organic matter [2], adsorbed complexes on Fe, significant amount of matter by evaporation. Chemical and Mn and Al oxide surfaces [3], and most of all a great variety Mg, Si and O isotopic compositions of the residues produced of solids with major anions such as O2-, hydroxyl, carbonate, by evaporation of forsterite-rich melts (FUN1 and FUN2) in sulfate, and nitrate [4]. However, the essential aqueous vacuum at 1900ºC suggest that the evaporating component is geochemistry of lead has serious gaps of knowledge. In Mg2SiO4 [1]. The evaporation trajectories of FUN1 and FUN2 particular, a dubious Pb(OH)2 solid phase has been proposed pass close to the compositions of C1 and Vig1623-5 FUN [4,5], but never identified, and solubility product constant CAIs, and the measured Mg and Si isotopic compositions of values with up to four orders of magnitude differences have most natural FUN CAIs also plot close to the correlation lines been reported [6] and incorporated in the databases of the established by the evaporation residues [1]. different geochemical speciation codes available. The goal of To test if evaporation of melts with compositions different this work was to test the existence of this hydroxide phase and from the forsteritic melts would result in residues with the validity of its solubility constants. chemical and isotopic compositions of C1 and 1623-5, we The solids formed in perchlorate and nitrate electrolyte conducted new sets of experiments in which FUN3 and FUN5 systems, under closed and open atmospheric CO conditions, 2 melts were evaporated at the same conditions as earlier. were identified by X-ray diffraction and other spectroscopies. Starting FUN3 and FUN5 compositions were obtained by We show that no solid phase of Pb(OH)2 is formed at any pH value, and thus the concentrations of aqueous Pb(II) are adding MgO and SiO2 to the C1 (FUN3) and 1623-5 (FUN5) controlled by the solubilities of solid oxide phases and in the amounts required by enrichments in heavy Mg and Si combinations of carbonates and hydroxi-carbonates, isotopes in these CAIs. depending on the conditions imposed on the system. Therefore, widespread geochemical databases must be corrected to exclude Pb(OH)2 as an actual Pb(II) solid phase forming, to yield more accurate aqueous Pb(II) solubility behavior predictions.

[1] Boutron et al. (1983) Geochim. Cosmochim. Acta 47, 1355-1368. [2] Pinheiro et al. (1999) Environ. Sci. Technol. 33, 3398-3404. [3] Mckenzie et. al. (1980) Aust. J. Soil Res. 18, 61-73. [4] Elkhatib et al. (1991) Environ. Pollut. 69, 269- 276. [5] Liu et !al. (1989) J. Colloid Interface Sci. 130, 101- 111. [6]Liu et al. (2003) J. Colloid Interface Sci. 268, 266- 269. After initial predominant loss of Si (FUN3) or Mg (FUN5), further evaporation results in loss of Si and Mg in

forsteritic proportions (constant aMgO/aSiO2 in the melt) and the evaporation trajectories are the same as established by FUN1 and FUN2 melts.

[1] Mendybaev et al. (2013) 44th LPSC, Abstract #3017.

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The microbial compelling attraction Protolith and tectonic implications of for hydrogarnets in the oceanic crust the Changhai metamorphic B. MENEZ1; V. PASINI1,2; D. BRUNELLI2,3; C. PISAPIA1, P. supracrustal sequence in southeast LE CAMPION1, C. LAVERNE4 AND E. GERARD1 Liaoning Province, NE China: 1 Institut de Physique du Globe de Paris, 1, rue Jussieu - 75238 Constraints from zircon U–Pb and Paris cedex 05, France ([email protected]; [email protected]; [email protected]; [email protected]) Lu–Hf isotopic and whole-rock 2 Università di Modena e Reggio Emilia, L.go St. Eufemia 19, geochemical evidences 41100 Modena, Italy ([email protected]; 1 1 1 2 [email protected]) E. MENG , F.L. LIU , J. CAI , Y. C 3 1 Istituto di Scienze del Mare – CNR, Via Gobetti 101, 49100 Institute of Geology, Chinese Academy of Geological Bologna, Italy Sciences, Beijing 100037, China ([email protected]; 4 Laboratoire de Pétrologie Magmatique, Universite´ Paul [email protected]; [email protected]:) 2 Cézanne Aix-Marseille III, Faculté des Sciences et School of Earth and Space Sciences, Peking University, Techniques, Avenue Escadrille Normandie-Niemen, Beijing 100871, China ([email protected]) 13397 Marseille cedex 20, France ([email protected]) The Changhai metamorphic supracrustal rocks, located in the eastern–central part of the Jiao–Li–Ji Belt in the North Microbial life appears to develop deep in the oceanic China Craton, are mainly composed of various types of crust, taking advantage of the redox gradients locally garnet–mica schists, along with minor quartzites and marbles. generated during hydrothermal alteration of the crystalline Geochemical results indicate that the source rocks were rocks. Nonetheless everything does not seem to be everywhere mainly granitoids with a possible minor contribution from and habitats are proving to be highly specific, mineralogically1 clastic sediments with an active continental margin signature. speaking. Notably, hydrogarnets were recently shown to Detrital zircons have U–Pb age peaks at approximately 1887, represent microbial niches hosted in serpentinized mantle- 2174, 2552, 2765, and 3212 Ma, !Hf values of –11.1 to +13.0, derived rocks from the Mid-Atlantic ridge. These and three major time windows of average continent crustal 3+ model ages (TDM) of 2.04–2.33, 2.48–2.56, and 2.72–2.93 Ga. hydroandraditic garnets (Ca3Fe2 (SiO4)3.x(OH)4x with trace amounts of Al, Ti, Cr) serve as metabolic substrates likely These results suggest that sediments of the Changhai metamorphic supracrustal rocks were mainly sourced from providing oxidized iron and calcium to the attached microbial nearby basement granitoid rocks and, to a lesser extent, from community2. Far from being anecdotic, such occurences can Paleoproterozoic metamorphosed strata such as the North and be found in other geographically-distant locations along the South Liaohe groups. Furthermore, the source rocks of the ridge system as for example in the South Western-Indian magmatic zircons analyzed in this study appear to have ridge, likely signing an extensive process. In addition, the originated from interaction between old continental crust and extent does not appear to be limited to the peridotitic portion juvenile material. The youngest concordant zircon age peak at of the oceanic crust. We present here results obtained on 1879 Ma coincides with the timing of formation of regionally hydroschorlomite, a Ti-, Ca-, Fe-rich andraditic garnet hosted widespread granitoids, mafic igneous rocks, and in altered basalts drilled in Hole 1256D during ODP Leg 206 metamorphism of the South Liaohe and Ji’an groups in the (Equatorial East Pacific)2. In situ characterizaton of the Jiao–Liao–Ji Belt, and requires the sedimentary protoliths of organic carbon speciation at the microscale reveals the the Changhai metamorphic supracrustal rocks to have been presence of microbiologically-derived material in close deposited after this time. The results regarding association with the hydrogarnets found in the deepest cores of lithostratigraphy, provenance, and depositional age indicate basalts (661–749 mbsf). The specificity of these microhabitats that the Archean Northern Liaoning–Southern Jilin Complex will be discussed and compared in terms of chemical and in the north, and the southern Liaoning–Nangrim Complex in mineralogical characteristics, inferred hosted metabolisms the south were already a single continental block by 1887 Ma, along with their potential as shaping low temperature and that the Changhai metamorphic supracrustal rocks was deposited at an active continental margin. alteration processes. This research was financially supported by research grants

[1] Ménez et al., 2012, Nature Geoscience, 5: 133-137. [2] from the Natural Science Foundation of China and Chinese (Grant 41202136 and Laverne et al., 2006, Geochemistry, Geophysics, Geosystems, Geological Survey Program s 1212011120150) 7(10), doi:10.1029/2005GC001180. .

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Multimodal and multiscale Application of a novel microscopies to study microfluorination technique to biomineralization and crystallization quantify biogenic opal " 18O processes ANTHONY J. MENICUCCI1, HOWARD J. SPERO2 3 1 1 1 AND JOY MATTHEWS NICOLAS MENGUY *, KARIM BENZERARA , JINHUA LI , LAURENT CORMIER1, OLIVIER DARGAUD1 1Department of Geology, University of California Davis, AND GUILLAUME RADTKE1 Davis CA USA ([email protected]) 2 I Department of Geology, University of California Davis, Institut de Minéralogie et de Physique des Milieux Condensés Davis CA USA (*correspondence: [email protected]) (IMPMC), UMR 7590 CNRS–UPMC–IRD, 3Department of Plant Sciences, Stable Isotope Facility, 4 place Jussieu, 75252 Paris Cedex 05, France, University of California Davis, Davis CA USA [email protected] (* presenting author) ([email protected]) For years, imaging and spectroscopic methods have been 18 intensively used to obtain information on properties of " O data from organisms that precipitate biogenic silica, minerals present on Earth and the processes involved in their such as diatoms or grass phytoliths, are relatively rare in the 18 formation. Recently, dramatic improvements have been made literature. The paucity of opal " O data is due to the difficulty in terms of spatial and spectral resolutions. For instance, a in isolating, purifying, and analyzing the covalently bound resolution better than 0.1 nm may now be achieved on oxygen for geochemical analysis, which typically involves crystalline compounds using Z-contrast on STEM-HAADF dangerous fluorination reagents and/or IR laser systems. We imaging mode. It is also possible to combine both high have developed a new microfluorination technique for opal spectral (0.1 eV) and spatial resolutions (20 nm for STXM, and quartz analysis that utilizes polytetrafluoroethylene better than 1 nm for EELS). Moreover, owing to the FIB powder (PTFE, C2F4, Teflon) as a fluorine source. Cleaned sample preparation method, these highly local techniques can and purified samples are dehydrated-dehydroxylated at be associated with complementary large scale analytical 1060ºC in vacuum prior to analysis and 0.4 mg of sample is methods allowing a multi-scale approach. then mixed with PTFE and graphite in silver foil capsules. Here, we shall present recent studies focused on the nm- Samples are analyzed at 1450ºC with a vario PYRO cube scale processes involved in the formations of (i) aragonite in TC/EA and IRMS in continuous flow mode. All data are corals, (ii) intra-cellular magnetite in magnetotactic bacteria calibrated to VSMOW using NBS-28 quartz. Acceptable data and (iii) crystal nucleation in glasses. For coral were obtained when sample yields exceeded 88% (>80% of biomineralization, combined nano-diffraction studies, >300 samples analyzed), yielding replicate precision better HRTEM and polarization-dependent synchrotron-based than ± 0.4‰ (1(). STXM imaging, have evidenced the biological control exerted Utilizing this method we analyzed a suite of diatom by the organism leading to a hierarchically structured solid samples from a sediment trap time series collected in the Gulf material [1]. Concerning the intracellular magnetites, we of California, Guaymas Basin. Samples were collected in the focused on asymmetric crystals formed by bacteria belonging late fall/early winter during three different years (1993, '94, 18 to the Nitrospira phylum [2]. Atomic scale processes and '96). Diatom " O ranged between 35 and 36.2‰ (VSMOW) crystal shape control involved during crytal growth will be (n=7). Five samples span a single fall through early winter discussed on the basis of ultra-high resolution observations period and when converted to temperature using the Labeyrie performed on an aberration corrected STEM. In addition, we (1974) relationship, record surface water temperatures will present some results related to nanoscaled heterogeneities between 25-27ºC that are in good agreement with in glasses leading to the crystal nucleation [3]. The ability to temperatures during the peak fall opal flux. These data suggest identify directly the crystallized phase from the image will be sinking diatom frustules remain suspended in the deep also addressed. pycnocline through early winter and data from sediment cores are likely to be seasonally biased. [1] Benzerara et al. (2011) Ultramicroscopy, 111, 1268 - 1275. [2] Li et al. (in prep) [3] Dargaud et al. (2012) J. of [1]Labeyrie (1974), Nature 248, 40-42. Non-Cryst. Solids, 358, 1257–1262

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U-series isotope composition of Superheating water to model soil primary minerals to determine “immobile” water regolith production rates on three LIONEL MERCURY1,*, KIRILL I. SHMULOVICH2, AND different lithologies PATRICK SIMON3 1 1 1 Institut des Sciences de la Terre d'Orléans, UMR 7327 D. MENOZZI AND A. DOSSETO Université d'Orléans-CNRS-BRGM, 45071 Orléans 1Wollongong Isotope Geochemistry Laboratory; GeoQuEST Cedex, France (* [email protected]). Research Centre, School of Earth and Environmental 2 Institute of Experimental Mineralogy, Russian Academy of Science, University of Wollongong, Wollongong, NSW, Science. 142432 Chernogolovka, Russia. Australia. ([email protected]; [email protected]) 3 CEMHTI, UPR3079 CNRS-Université d'Orléans, 45071 Orléans Cedex 2, France. The complex interaction between weathering, erosional and biological processes converts bedrock into regolith, Superheating namely the ensemble of soil and saprolite. Assessing rates of The superheated liquids are less stable than their vapour, regolith formation is necessary to evaluating soil sustainability while their criteria of internal stability are met. They can be and investigating landscape’s past history and future produced when an increasing T or a decreasing internal P evolution. (including negative pressure, or liquid tension) beyond the Recently, uranium-series isotopes have been used to stable values is produced in liquid in such conditions that quantify independent time-integrated regolith and soil vapor does not nucleate. This nucleation suppression can be production rates [e.g. 1, 2, 3]. This is because their abundance reached in nature either during a short time by a very rapid P in regolith is function of time and weathering. However, until or/and T variation (phreatomagmatism, for instance), or by now this method has been applied to bulk material, without decreasing the air humidity at a liquid-air interface located in distinguishing among primary minerals, secondary phases and infra-micronic container (soil capillarity, for instance). The other soil components. The overall research goal is to improve method of choice to experimentally probe superheating is the the U-series method accuracy, measuring regolith production micro-thermometry of fluid inclusions [1], that can be rates on primary mineral phases in place of bulk material. designed in terms of composition and density of occluded Three weathering profiles developed over basalt, granite liquids (in quartz). Their volumes are intermediate between and sandstone in NSW, Australia, have been sampled from macro-systems, in which superheating is restricted to low flat-topped areas chracterized by comparable climatic regime tensions with very short lifetime, and nanosystems, wherein and low erosion. Separation of primary minerals along the the host matches the size of the critical vapor nucleus. weathering profiles and their uranium-thorium isotopic composition will provide rates of regolith production. This Properties and behaviours of interest will contribute to improving U-series technique and will The first property available from the present experiments emphasize the role of parent material in determining soil are the surface of the metastable PT domain available for formation rates. aqueous solutions, that depends on the liquid composition and densities [2]. A second property of interest is the ability of this [1] A. Dosseto, H.L. Buss, P. Suresh, Earth and Planetary in-pores tensioned liquids to change the mechanical tensor in Science Letters 337 (2012) 47-55. [2] A. Dosseto, S.P. Turner, the surrounding solid, by recording the SiO2 Raman bands in J. Chappell, Earth and Planetary Science Letters 274 (2008) quartz during a microthermometric cycle. The third property is 359-371. [3] L. Ma, F. Chabaux, E. Pelt, E. Blaes, L. Jin, S. the transmission of the liquid tension to the dissolved solutes, Brantley, Earth and Planetary Science Letters 297 (2010) 211- again through recording characteristic Raman shifts of solutes 225. with known liquid tension. Consequently, the solubility of gases and minerals in such superheated mixtures changes, and in general increases, with consequences on weathering and

external gas cycles. At last, the superheating lifetime, the energy of the critical boiling, and the direct consequences of this return-to-equilibrium to local paragenes are explored.

[1] Roedder (1967) Science 155, 1413-1417. [2] Shmulovich K.I., Mercury L., Thiéry R., Ramboz C., and El Mekki M. (2009) Geochim. Cosmochim. Acta 73, 2457-2470.

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Crustal sources of peraluminous Rates of Natural silica precipitation granites: the Montes de Toledo through time batholith, Iberian Hercynian Belt R.MERLE1, A.NEMCHIN1, S. SIMONS1, F. TOMASCHEK2, 2 1 1 AND T. GEISLER MERINO, E. *, VILLASECA, C. , PÉREZ-SOBA, C., OREJANA, D.1, BELOUSOVA E2 AND ANDERSEN, T.3 1Curtin University, Department of applied geology, Perth 1 Australia [[email protected]; Facultad CC. Geológicas, Univ. Complutense de Madrid, [email protected]] Spain (*correspondence: [email protected]) 2 2 Universitat Bonn, Steinmann Institut, Bonn, Germany GEMOC, Macquarie University, NSW, Australia 3 [[email protected]; [email protected]] Dpt. of Geosciences, Univ. of Oslo, Blindern, Oslo, Norway

Significant deposits of amorphous and cryptocrystalline silica The Montes de Toledo batholith (MTB) is a composite (opal) in the Northern Yilgarn Craton are closely associated Hercynian plutonic array (~ 200 km long) located within the with the formation of calcrete. Precipitation of this calcrete Central Iberian Zone (CIZ). The MTB magmatism lasted from occurs in the areas of summer rainfall, where rapid water 316 to 297 Ma with prevailing monzogranitic to leucogranitic infiltration and high evaporation rates limit prolonged periods compositions and a marked S-type character. Two contrasted of dampness and plant respiration. The high U concentration segments are distinguished according to their geochemical and accompanied by low initial Pb and Th concentrations shown isotopical signatures: the eastern (E-MTB) and the western by some common varieties of opal facilitates the application of (W-MTB; Villaseca et al. [1]). Restitic and metamorphic the U-Pb and U-series techniques for high precision age enclaves are commonly found, though in the E-MTB are also determination of opaline silica. frequent mafic microgranular enclaves. The E-MTB granites We used SHRIMP (sensitive high resolution ion are enriched in Ca, Fe, Na, Sr and Y-HREE, whereas the W- microprobe) U-series dating of two common opal samples MTB granitoids display higher ACNK ratios and higher P, K, found in calcretes from the weathering profile in the Yilgarn 87 86 Rb and LREE contents. The wide whole-rock ( Sr/ Sr)300 Craton (Western Australia) to determine the timing of one of isotopic variation (0.706 – 0.723) and the abundance of the latest silicification events in the area and to investigate inherited Neoproterozoic zircons in the granitoids imply the variations of silica precipitation rates during the late involvement of a heterogeneous crustal source. =Hf values of Pleistocene. All analyses indicate that 238U, 234U and 230Th are the Neoproterozoic zircons from the W-MTB granites overlap not in secular equilibrium, allowing the calculation of those from the Schist-Greywacke Complex (=Hf up to +10 and 230Th/238U-234U/238U ages. +11, respectively), suggesting a major contribution of these An apparent symmetrical decrease of ages from centre of metasediments to the granite source. This is also supported by the opal veins towards their contacts with the calcrete suggests the similar range of their =Nd whole-rock isotopic that the precipitation of silica did not take place in an open composition (from -3 to -6) and Nd model ages (1.3 – 1.4 Ga). space fissures, but rather as replacement of carbonate. The In contrast, the Neoproterozoic zircons of the E-MTB granites opal growth rate was not constant during the entire time show lower =Hf values (< +5) suggesting a different protolith. interval between 150 and 40 kyr recorded by the two samples A meta-igneous source is consistent with the common and the age patterns can be interpreted to represent several presence of inherited zircons in those granites with the same episodes of very fast growth of opal interrupted by periods of Ordovician age range as in the outcropping CIZ peraluminous absence or relatively slow silica precipitation. The estimated augen orthogneisses (i.e., from 460 to 480 Ma). precipitation rate variation obtained from both opal samples shows three maxima with one near 90 kyr that is visible in [1] Villaseca et al. (2008). J Geosci 53, 263-280 both samples. In addition, we found increased precipitation rates at about 135 kyr and 117 kyr in one sample, whereas in the other samples the highest precipitation rates occurred at about 70 and 45 kyr. These rates appear to exhibit systematic variations through time that can be linked to the major orbital cycles of the Earth, suggesting that silica precipitation rates in the Yilgarn craton and perhaps in whole Australia are controlled by climate variations.

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Shells of Corbicula fluminea mussels Time resolved monitoring of and the bioavailability of Uranium contamination of oak trees anthropogenic Rare Earth Elements DIRK MERTEN1*, DIETRICH BERGER1, ARNO MÄRTEN1, in river water AND MIRKO KÖHLER2 1 1 1,2 Friedrich-Schiller-University, Institute of Geosciences, 07749 GILA MERSCHEL AND MICHAEL BAU Jena, Germany (*correspondence: Dirk.Merten@uni- 1 Earth and Space Sciences Program, Jacobs University jena.de, [email protected], Bremen, 28759 Bremen, Germany [email protected]) 2 Integrated Environmental Studies Program, Jacobs University 2Wismut GmbH, 09117 Chemnitz, Germany Bremen, 28759 Bremen, Germany ([email protected])

Rare Earth Elements (REE) of anthropogenic origin can be Monitoring organisms such as higher plants are used for found in river water and drinking water all around the world qualitative and quantitative detection of contaminants in the [1]. The Rhine River and the Weser River in Germany both environment because they take up nutrients and contaminants carry an anthropogenic Gd anomaly that results from the use via air, water and soil. Since trees in temperate regions form of Gd in MRI contrast agents that are introduced into the annual rings, chronological records of environmental pollution rivers with the effluents from waste water treatment plants for the near vicinity of the trees can be obtained by spatially [2,3]. In addition, the Rhine River also carries an anthropogenic La anomaly (and most recently an resolved analysis of the tree rings. anthropogenic Sm anomaly [4]), downstream of the Town of In the current work a simple and minimal-destructive Worms, where industry effluents with high concentrations of method for sampling and the spatially resolved (about 200 µm La (and Sm) are discharged into the river [3]. The shells of resolution) analysis of trees was developed. Concentration of invasive freshwater mollusk Corbicula fluminea were nutrients and pollution of trees with U and other heavy metals collected from both rivers to investigate the bioavailability of was measured by laser ablation-inductively coupled plasma- these anthropogenic REE. As the aragonite shell of Corbicula mass spectrometry (LA-ICP-MS) in annual rings of oak trees grows from the epithallial fluid of the mussel, anthropogenic grown in a former uranium mining area in Thuringia. The area metals have to be taken up by the mussel organism in order to was contaminated with heap material during active mining and eventually be available for incorporation in the shell. was elaborately remediated by Wismut GmbH in 2002 after Corbicula shells from the Weser River and from the upper termination of mining. Rhine River incorporate the geogenic REE from the river For quantification the standard reference material Virginia water, with slight preferential incorporation of LREE over Tobacco Leaves CTA-VTL-2 was pressed and used for HREE. Anthropogenic La is readily incorporated into the calibration while C was used as internal standard. Thus, it was shells, reflecting La-REE relationships in ambient river water. possible to deduce a temporally resolved depiction of the In contrast, anthropogenic Gd could not be detected in any of the Corbicula shells. These results show that anthropogenic element concentrations reflecting the history of uranium Gd is not bioavailable, probably due to the persistence of the contamination for the last 50-60 years and also to indicate highly stable Gd-DTPA complex that is used as MRI contrast remediation success. agent. Potential effects of high doses of REE should be The U concentrations in the analyzed tree cores could be investigated, because fish are known to bioaccumulate REE directly related to mobile U concentrations in the substrate [5] and anthropogenic REE have been found in tap water [2]. thus verifying the applied method as a successful biomonitoring tool for U contamination in soils. [1] Kulaksız & Bau (2011) Appl Geochem 26 1877-1885 [2] Kulaksız & Bau (2007) EPSL 260 361-371 [3] Kulaksız & Bau (2011) Environ Intern 37 973-979 [4] Kulaksiz & Bau (2013) EPSL 362 43-50 [5] Sun et al. (1996) Chemosphere 33 1475-1483

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The physical and chemical Effect of atmospheric organics on characteristics of marine primary iron bioavailability organic aerosol MESKHIDZE, N.1, M. S. JOHNSON2, D. HURLEY1, AND M. D. PETTERS1 MESKHIDZE, N. AND B. GANTT 1North Carolina State University, Raleigh, NC, USA North Carolina State University, Raleigh, NC, USA, [email protected], [email protected], [email protected], [email protected] [email protected] 2NASA Ames Research Center, matthew.s.johnson@nasa.gov Knowledge of the physical characteristics and chemical

composition of marine organic aerosols is needed for the Iron (Fe) delivered to the surface ocean through quantification of their effects on solar radiation transfer and atmospheric pathways is of specific interest for the marine cloud processes. This presentation examines research pertinent environment and plays a vital role in the earth’s to the chemical composition, size distribution, mixing state, biogeochemical cycle. The deposition of atmospheric Fe to the emission mechanism, photochemical oxidation, and climatic ocean’s surface may be an important control on primary impact of marine primary organic aerosol (POA) associated productivity in vast areas of the global oceans. Mineral Fe at with sea spray. Numerous measurements have shown that the source regions is primarily in the form of Fe- both the ambient mass concentration of marine POA and size- oxyhydroxides and aluminosilicate minerals. Once airborne, resolved organic mass fraction of sea spray aerosol are related Fe can be mobilized from the minerals through the effect of to surface ocean biological activity. Recent studies have also acids, organics, and sunlight initiating a complex cycling indicated that fine mode (smaller than 200 nm in diameter) between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe. marine POA can have a size distribution independent from Here mineral dust and dissolved Fe (Fe ) deposition rates sea-salt, while coarse mode aerosols (larger than 1000 nm in d are predicted using GEOS-Chem with a comprehensive dust- diameter) are more likely to be internally-mixed with sea-salt. Fe dissolution scheme. The model simulates Fed production Modeling studies have estimated global submicron marine -1 during the atmospheric transport of mineral dust taking into POA emission rates of ~10 ± 5 Tg yr , with a considerable account inorganic and organic (oxalate)-promoted Fe fraction of these emissions occurring over regions most dissolution processes, Fe(II)/Fe(III) photochemical redox susceptible to aerosol perturbations. Climate studies have cycling, dissolution of Fe-containing minerals (hematite, found that marine POA can cause large local increases in the goethite, and aluminosilicates), and detailed mineralogy of cloud condensation nuclei concentration and have a non- wind-blown dust. Calculations suggest that during the negligible influence on model assessments of the yearlong simulation ~0.26 Tg of Fe was deposited to global anthropogenic aerosol forcing of climate. Despite these signs d oceanic regions[1]. Compared to simulations only taking into of climate-relevance, the source strength, chemical account proton-promoted Fe dissolution, the addition of composition, mixing state, hygroscopicity, cloud droplet oxalate to the dust-Fe mobilization scheme increased total activation potential, atmospheric aging, and removal of marine annual model-predicted Fe deposition to global oceanic POA remain poorly quantified. d regions by ~75%. During the daytime, a large fraction of The current presentation will also summarize results from [1] model-predicted fluxes of Fed are in the Fe(II) form, while the recent marine aerosol workshop held in Raleigh, NC , nocturnal fluxes of Fed are largely in the Fe(III) form[1]. where workshop participants identified the most critical open In addition to model simulations, laboratory experiments questions regarding sea spray aerosol and developed a list of were also conducted to quantify the effects of atmospheric priorities for conducting and facilitating novel research. The organics on Fe bioavailability after deposition to the surface rankings of the most pressing science questions based on their ocean. Fe(II) was detected by absorbance spectrophotometry feasibility impact on reducing the current uncertainty ranges using the Ferrozine technique and total soluble iron was for different processes will also be discussed. The workshop determined by addition of hydroxylamine to reduce Fe(III) to presentations are available online at: Fe(II). This presentation will refine the concept of what http://www4.ncsu.edu/~nmeskhi/Marine_Aerosol_Workshop/ constitutes soluble Fe in atmospheric waters and bioavailable WEBSITE.html. Fe in the oceans. The important role of atmospheric organics [1] Meskhidze et al. (2013) Atmos. Sci. Lett., in review. for marine biogeochemistry and carbon cycling will also be discussed.

[1] Johnson, M.S. and N. Meskhidze (2013), Geosci. Model Dev. Discuss., 6, 1901-1947.

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It’s getting hot on Earth - The Middle Stability behaviour of silver Eocene Climatic Optimum in a nanoparticles in different aqueous terrestrial sedimentary record media K. METHNER1,2, U. WACKER2, J. FIEBIG1,2, A. MULCH1,2,3 G. METREVELI* AND G. E. SCHAUMANN AND C. P. CHAMBERLAIN 4 Universität Koblenz-Landau, Institute of Environmental 1 Biodiversity and Climate Research Centre, Frankfurt am Sciences, Environmental and Soil Chemistry, Landau, Main, Germany; [email protected] Germany (*correspondence: [email protected]) 2 Goethe Universität, Frankfurt am Main, Germany 3 Senckenberg Research Institute and Natural History Due to the wide application of engineered nanoparticles Museum, Frankfurt am Main, Germany (ENP) in different industrial products, in the last years, the 4 Stanford University, Stanford, CA, USA risk potential for their release in the environment is increased as never before. Mobility and toxicological behaviour of ENP The Middle Eocene Climatic Optimum (MECO) is an in aquatic systems is strong depending on their stability and enigmatic global warming event interrupting the protracted aggregation properties [1]. Furthermore, the changes in the Cenozoic cooling. It is marked by a negative shift in marine chemical composition of the aqueous phase can influence the oxygen isotope records that indicate an increase of water aggregation reversibility [2], which can lead to the temperatures by up to 5 to 6 °C and thus, documents an remobilisation of previously aggregated and immobilised increase in temperatures on top of the warm Eocene climate. nanoparticles. Despite the increasing amount of studies on the This makes the MECO one of the hottest phases during environmental behaviour of ENP, there is a lack of Earth’s climate history, but the questions, if and how the information about reversibility of the aggregation. MECO affected continental sites are still unresolved. In this study, aggregation of citrate stabilised silver Here, we present a stable isotope record ("18O) and nanoparticles (Ag NP) was investigated in synthetic aqueous

clumped isotope (147) temperatures from an Eocene mammal media and natural river water (Rhine). The influence of pH fossil locality in southwestern Montana, USA. The sampled value, sodium and calcium cations and humic acid (HA) on section (Upper Dell Beds, Sage Creek Basin) comprises about the stability of Ag NP was characterised. The reversibility of 60 m of stacked paleosols that were correlated to Chron C18r the aggregation was studied after reducing of ionic strength by paleomagnetic and biostratigraphy. The oxygen isotopic (by centrifugation and washing) and applying of ultra sound at record of pedogenic carbonates range from -12 to -18 ‰ different energy levels. (SMOW) and reveals prominent shifts of oxygen isotope Ag NP showed high aggregation at high sodium and + 2+ ratios of up to 6 ‰ within 3 m of section. The associated 147- calcium concentrations (c(Na ) > 40 mmol/L, c(Ca ) > 0.5 temperatures indicate an increase in temperatures of about 5 mmol/L), at low pH values (pH <3) and in river water. HA °C, reaching peak temperatures of 31 ±2 °C, and a rapid drop stabilised Ag NP and the stabilisation effect was much higher in temperatures of about 9 °C. Thus, we think that this record for pH induced aggregation than for sodium and calcium has the potential to (1) document the MECO in a terrestrial cation induced aggregation. After reducing of ionic strength, record, (2) yield realistic temperature changes between the the aggregation of Ag NP was reversible especially after MECO event and the post-MECO cooling phase, and (3) help applying of shear forces, but the disaggregation was not fully to track the isotopic evolution of precipitation during a short complete. After treatment, small aggregates remained in the term climatic event in continental interiors. dispersions, which were more stable, than the big aggregates. The results of this study show that the reduction of ionic strength and the presence of shear forces can lead to the partial disaggregation of previously aggregated nanoparticles. As a consequence, the probability of nanoparticle remobilisation can be increased.

[1] Morones et al. (2005) Nanotechnology 16, 2346-2353. [2] Fabrega et al. (2009) Environ. Sci. Technol. 43, 7285-7290.

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Artificially induced migration of Lateral carbon isotope homogeneity redox layers in Adriatic sediment in a Late Ordovician epeiric sea E. METZGER1*, D. LANGLET1, E. VIOLLIER2, N. KORON3, J. GARRECHT METZGER1* AND DAVID A. FIKE1 4 4 4 B. RIEDEL , M. ZUSCHIN , M. STACHOWITCH , 1 Washington University, St. Louis, Missouri 63130, USA J. FAGANELI3, M. THARAUD2, 1 1 (*correspondence: [email protected]) E. GESLIN AND F. JORISSEN 1 13 LUNAM Université, Université d’Angers, UMR CNRS 6112 Carbon isotope ratios of marine carbonate rocks (" Ccarb) LPGN-BIAF, Angers, France (*edouard.metzger@univ- can be used to correlate coeval ancient strata. Detailed angers.fr) correlation requires that the carbon isotopes of the carbon 2 13 Université Paris Diderot, Sorbonne Paris Cité, UMR CNRS source, the oceanic dissolved inorganic carbon pool (" CDIC), 7154 LGE-IPGP, Paris, France be homogenous on the mixing time of the ocean, (~1,000 3 Marine Biology Station, National Institute of Biology, Piran, years). Previous reports have suggested that apparent large 13 Slovenia (21.5‰) offsets in " Ccarb observed for Late Ordovician 4 Department of Marine Biology, University of Vienna, carbonate strata of North America are the result of large scale Vienna, Austria (i.e., 100s-1000s km) lateral gradients in the isotopic composition of DIC in the surface ocean (e.g., from the open Long term experimental studies suggests that, under Iapetus Ocean to shallow Laurentian epeiric seas [1,2]. An 13 anoxic transient conditions, redox fronts within the sediment alternative interpretation is that apparent offsets in " Ccarb are shift upwards causing sequencial rise and fall of benthic fluxes in large part the result of the differential admixture of of reduced species (Mn(II), Fe(II) than S(-II)) (e.g; Kristiansen secondary carbon incorporated into the rocks resulting in 13 et al., 2002). In order to study such processes in a more variable and lower " Ccarb values in diagenetically altered realistic system, benthic chambers were deployed on the locations [3]. 13 seafloor of the Northern Adriatic and sampled after 9, 30 and Here, we present Late Ordovician " Ccarb data covering 315 days of incubation. High resolution porewater profiles >1,400 km and spanning multiple depositional environments, were sampled by DET probes and redox sensitive species were from shallow cratonic sea to deeper foreland basins. Multiple 2- 2+ 2+ analysed (Alk, SO4 , Mn , Fe ). transects through the same interval across the study area reveal 13 Results show that anoxia was reached after 7 days. Mn no systematic " Ccarb gradients (maximum offsets between and Fe started diffusing towards the water column giving a any coeval strata are ~0.6‰). Detailed sampling has rusty color to the seafloor. Infaunal species appeared at the identified discrete stratigraphic intervals with characteristic 13 surface. After 20 days (fig. 1), all macro-organisms were dead. " Ccarb values resolvable at sub-permil levels. The work Porewater chemistry showed expected redox shifts. However, discusses the stratigraphic as well as biogeochemical bottom water chemistry followed a peculiar evolution: after 1 implications of these findings. month, sulfide had a higher concentration in the overlying water than in the porewater leading to a diffusional flux into [1] Holmden et al. (1998) Geology 26, 567-570. [2] Panchuck the sediment. The source of sulfide was attributed to the et al. (2006) J. Sed. Research 76, 200-211. [3] Metzger and decomposition of dead macroorganisms laying on the seafloor. Fike (2013) Sedimentology in press: doi: 10.1111/sed.12033. Our results suggest that the sulfide rise in the water column in coastal waters is strongly controlled by the biomass of benthic macrofauna and can be decoupled from sedimentary geochemical processes.

Figure 1: left: chamber after 20 days of incubation; right: chamber after 10 months of incubation.

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The contribution of phytoliths in Laboratory Study of Nitrate improving the understanding of Si Photolysis in Antarctic Snow: cycling Quantum Yield, Mechanism, Isotope J.D. MEUNIER*,AND C. KELLER Effects and Wavelength Dependence Aix-Marseille Université, CNRS, IRD, CEREGE UM34, CARL MEUSINGER1#, TESFAYE A. BERHANU2#, 13545 Aix en Provence, France (*correspondance: JOSEPH ERBLAND2, JOEL SAVARINO2 [email protected]) AND MATTHEW S. JOHNSON1* 1 Copenhagen Center for Atmospheric Research, CCAR, The Si cycle is remarkably affected by biomineralisation Department of Chemistry, University of Copenhagen, processes through the formation of diatoms and other Copenhagen, Denmark microorganisms in aquatic systems, and through the formation 2 Laboratoire de Glaciologie et G´eophysique de of phytoliths that constitute the main form of Si storage in l’Environnement, CNRS/Universit´e Joseph Fourier- terrestrial plants. After translocation from the roots to the Grenoble 1, Grenoble, France shoots as silicic acid, the main form of Si in soil sotutions, Si # CM and TAB contributed equally to the work. is polymerized through the elimination of water by *Corresponding author [email protected] evaporation and the formation of phytoliths occurs. Phytoliths are composed of opal A (XRD-amorphous phase) particles Post-depositional processes alter the nitrate concentration although some authors have suggested the presence of and isotopic composition at low accumulation sites. Available crystalline silica. Contrary to many nutrients, Si cannot be nitrate ice core records can only provide input for studying subsequently redistributed within the plant because the past atmospheres and climate if such processes are fully phytoliths remain insoluble until the litter falls and understood. Reported quantum yields for the main reaction decomposes. The beneficial effects of Si have been differ by orders of magnitude. The experimental system demonstrated by many studies using pots, hydroponic and included a Xe lamp with optional UV filters, an environmental field experiments and are particularly remarkable in plants chamber with temperature control and a N flow system to exposed to biotic or abiotic stresses. 2 flush gas phase products and used natural snow from Dome C, During litter decomposition phytoliths are either dissolved Antarctica. Irradiated snow was sampled in 1 cm sections and and constitute a source of recycled Si for plants or preserved analyzed for nitrate concentration and isotopic composition from weathering and their morphoscopy may then be helpful 15 18 17 (" N, " O and 1 O). Observed values for the quantum yield for reconstructing the past vegetation. After presenting some lie in the middle of the range of previously reported values and evidences that phytoliths can control the biogeochemical cycle can be explained using two types of nitrate: one easily of Si at ecosystem or watershed levels, several issues accessible (photolabile) and one of trapped or buried nitrate. concerning phytolith research are discussed. A few recent The quantum yield changes from 0.45 to 0.05 within what studies have provided some evidences that agriculture corresponds to weeks of UV exposure in Antarctica. An practices can deplete ASi pools of soil. Because phytoliths 15 average photolytic isotopic fractionation of = = -15±0.01 ‰ constitute one of the most rapidly bio available source of Si was found for the experiments without a wavelength filter. for crops, the consequence of soil erosion and straw These results are ascribed to excitation of the intense exportation on crop yield should be more studied in cultivated absorption band of nitrate around 200 nm. No fractionation areas In order to better integrate the phytoliths in the global was observed in the oxygen isotopes. An experiment with the models of Si cycling there is a need for a better quantification 305 nm UV filter, close to the actinic flux spectrum in Dome of soil phytolith pool (ASi). Extraction using gravimetric 15 C, showed a photolytic isotopic fractionation of = = -38±2.2 methods are time consuming and poorly correlated with ‰ slightly more positive than the fractionation determined in extractions using alcaline dissolution protocoles such as the the field (-40 to -74.3‰, Erbland et al., In review). We DeMaster's (1981), initially used for diatom test quantification demonstrate that the photolytic fractionation of nitrate isotopes in aquatic systems. We have recently shown that alkaline in snow is very sensitive to the actinic flux spectrum, leading extraction may not be strong enough to dissolve aged to the reinterpretation of previous laboratory studies. In order phytoliths, and may underestimate ASi by a factor of 4. to directly apply results from laboratory studies to ambient conditions the wavelength of irradiation has to match that in the field, as the photolytic fractionation changes significantly depending on the impinging spectrum.

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The biological pump and evolution of Preliminary U-series dating results marine animal ecosystems from the GISP2 ice core K.M. MEYER1*, A. RIDGWELL2 AND J.L. PAYNE1 K.W. MEYER AND S.M. ACIEGO 1Department of Geological and Environmental Sciences, University of Michigan, Ann Arbor, MI 48109-1005, USA Stanford University, Stanford, CA 94305, USA (*correspondence: [email protected]) (*correspondence: [email protected]) 2School of Geographical Sciences, University of Bristol, Ice core climate proxy records often lack precise age Bristol, BS8 1SS, UK ([email protected]) constraints on the geochemical variations they record in trapped gases and/or dust inclusions. Currently, few The export of organic matter from the surface ocean and geochronological methods exist to determine the age of the its respiration at depth creates gradients in nutrient and oxygen disturbed sections of deep and basal ice. Recent work on availability that influence the structure and distribution of material from the Antarctic EPICA Dome C core has marine ecosystems. Today the strength of the biological pump demonstrated advances in a radiometric dating method based is strongly influenced by mineral-ballasted phytoplankton. In on 234U/238U measurements and dust surface area [1]. Our Earth’s past, however, mineralized phytoplankton were less work has focused on applying these same methods to ice common and, consequently, the biological pump was likely samples from the Greenland Ice Sheet Project (GISP2) drill weaker. Here we use the GENIE model to explore the impact core. Given that the bottom 10% of the GISP2 core consists of of a changing biological pump on marine chemistry and disturbed deep ice argued to be 240 ka or older, external ecosystem structure. We find that under a weaker biological dating methods are necessary for confirming the absolute age pump likely typical of the Paleozoic and early Mesozoic, the of these samples and to further extend Northern Hemisphere position of the oxygen minimum zone shallows and anoxia is climate reconstructions [2]. more prevalent near the surface. In this scenario, less oxygen The U-series method depends on determining three is available to benthic ecosystems on shelf environments. If variables: (1) the initial concentration of 234U in the soluble so, these results imply that the mid-Mesozoic radiation of fraction of the ice, (2) the parent concentration (238U) in the phytoplankton with mineralized tests spread oxygen demand dust and (3) the precise surface area of the dust grains to more evenly through the oceans and reduced the spatial extent account for the loss of 234U from the grain by (-recoil. of anoxic regions. Thus, we hypothesize that the Phanerozoic One of the critical assumptions of the dating method is trend toward greater animal abundance and metabolic demand that the the dust is of marine origin, possessing an initial was driven more by increased oxygen availability than by 234U/238U activity ratio of 1.14 ± 0.01 [3]. Other studies have greater food availability. In fact, a reduction in productivity determined that there is a significant presence of soluble dust may have been required to generate sufficient oxygen from sea salt deposition on the Greenland Ice Sheet by 87 86 234 238 availability in the shallow oceans to make the oceans more Sr/ Sr, U/ U, and !Nd measurements [4]. Our initial habitable for animals. measurements yielded 87Sr/86Sr values ranging between 0.709439 ± 0.00002 and 0.711007 ± 0.00003. These values are in agreement with the average global 87Sr/86Sr composition of seawater, given possible interaction with the insoluble fraction. Therefore, our underlying assumption for the source of the soluble dust fraction is plausible. Initial 234U/238U activity ratios for the soluble fraction increase from 1.178 to 1.229 with depth, suggesting that the daughter excess of 234U correspond to resolvable ages. Surface area and 238U measurements of the insoluble fraction will be presented in the context of the uranium age equation.

[1] Aciego et al. (2011) Quaternary Science Reviews 30, 2389–2397. [2] Suwa et al. (2006) Journal of Geophysical Research 111, D02101. [3] Henderson (2002) Earth and Planetary Science Letters 199, 97–110. [4] Lupker et al. (2010) Earth and Planetary Science Letters 295, 277–286.

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Metamorphic evolution and tectonic The Joy of Making Planets in Disks: implications of carbonate-bearing Dynamical and Chemical Recipes mafic boudins and surrounding MICHAEL R. MEYER1 metasediments of the Tianshan 1Institute for Astronomy, ETH Zurich, [email protected] Mountains (NW China) Cirucmstellar disks are an outcome of the star formation MELANIE MEYER* process, and their physical properties set the initial conditions GeoZentrum Nordbayern, Friedrich-Alexander-Universität of planet formation. Yet the total mass, orbital radius, mean Erlangen-Nürnberg, Schlossgarten 5a, D-91054 Erlangen, density, and composition of planets formed in these disks Germany depends critically on dynamical processes and the (*correspondence: [email protected]) transmutation of the initial ingrediants (gas and dust from the interstellar medium) through chemistry. Here we review some The metamorphic belt in the southern Tianshan Mountains of the key physical and chemical processes in disks that of NW China provides the opportunity to investigate both the dictate the composition of forming planets. In particular we metamorphic evolution of mafic rocks (upper oceanic crust focus on new observational results that constrain theories of with rarely preserved pillows) during subduction and the planet formation. exhumation mechanisms in a subduction channel (mafic rocks as boudins enclosed in metasediments). The (U)HP-LT rocks (blueschists, eclogites and metasediments; as in many (U)HP terranes, voluminous schists enclose rare eclogite lenses and layers [1]) are interpreted to represent part of a tectonic mélange formed along a suture zone between the Yili-central Tianshan and Tarim plates ([2],[3]). This study provides detailed information on the metamorphic evolution of both metasedimentary host rocks and mafic boudins of the (U)HP-LT metamorphic belt. Profiles across different mafic boudins and enclosing metasediments were investigated (whole rock major and trace element geochemistry by XRF and LA-ICP-MS, mineral chemistry by EMPA, thermobarometry, P-T pseudosection modeling using PerpleX) in order to constrain potential protoliths and differences in peak P-T conditions between distinct mafic boudins, and also between metasediments and mafic boudins. Furthermore, metasomatism of the subducted rocks was investigated. This study aims to increase our understanding of the metamorphic evolution of mafic rocks during subduction, the detachment from the subducted slab and the mixing of different materials and metamorphic reactions in the subduction channel during exhumation. All eclogites investigated contain a variable amount of carbonate minerals. Thus, in addition the carbon cycle in subduction zones is addressed in the context of the P-T evolution.

[1] Lü et al. (2012) J. Metamorph. Geol. 30, 907-926. [2] Gao et al. (1999) J. Metamorph. Geol. 17, 621-636. [3] van der Straaten et al. (2008) Chem. Geol. 255, 195-219.

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Deep fast-spread Oceanic Crust - Glaciers and floodplains controls on Fluid Interactions: Petrography and weathering fluxes deciphered from Volatiles from IODP Expedition 345 two glacial-interglacial Nd isotopes Hess Deep Plutonic Crust records on both sides of New Zealand R. MEYER1, R.P. WINTSCH2, T. NOZAKA3, K. M. GILLIS4, LAURE MEYNADIER1, ANTOINE COGEZ1 J.E. SNOW5, AND IODP EXPEDITION 345 SHIPBOARD AND CLAUDE ALLÈGRE1 SCIENTIFIC PARTY 1 Equipe de Géochimie et Cosmochimie, Institut de Physique 1 University of Bergen, Norway; [email protected] du Globe de Paris – Sorbonne Paris Cité, UMR 7154, 2 Indiana University, Bloomington IN, USA Université Paris Diderot 3 Okayama University, Japan 4 University of Victoria, B.C., Canada A wide variety of climatic, tectonic or chemical factors 5 University of Houston, Houston TX, USA can influence weathering intensity and/or fluxes. The interest of studying time series relies on the fact that some of these IODP Expedition 345 returned to the Hess Deep Rift parameters varied through time and other remained constant : almost exactly 20 years after ODP Leg 147. Here we report it is then possible to unravel informations “all other things preliminary results of the recent expedition (Dec. 2012 - Feb. being equal” about controls on weathering mechanisms.

2013) in the Eastern Pacific Ocean. The Hess Deep Rift We studied Nd isotopes (=Nd) in two DSDP sites (593 and exposes a dismembered, but nearly complete lower crustal 594) both in the detrital and authigenic fractions. These sites section of fast-spread East Pacific Rise (EPR) plutonic crust. were collected on the large continental shelf, on both western Recovered core includes high Mg# (79-89) olivine gabbros, and eastern side of New Zealand. The sediment covers the last gabbros, gabbronorites and troctolites. Due to the scarcity of 3 glacial-interglacial cycles (300 kyrs). The interest of this in-situ rocks from these depths alteration processes within area is linked to the rather uniform lithology, and to the such deep parts of the oceanic crust are still ambiguous. contrasts between the western and the eastern sides of NZ, However, such data are essential to better understand global introduced by the Alpin Chain topography. The Main Divide crustal mass balance, tectonics, hydrothermal processes, and of the Alpin Chain separates the eastern side with steep slopes cast light on deep crustal biosphere conditions. Shipboard and high pluviometry, and the western side with small petrography has revealed that high-temperature tremolite- floodplains and lower pluviometry. In addition climatic chlorite replacement of olivine + plagioclase is less abundant forcing factors, such as the glacier extent, did vary through the at deeper levels, in contrast to the dominance of background glacial to interglacial periods.

greenschist/subgreenschist-facies serpentinisation of olivine in Our results show =Nd variations in phase with the climatic addition to prehnite +/- chlorite formation after plagioclase. fluctuations on both cores, but with a much lower amplitudes

Shipboard C, H and S measurements define H2O as major on the western core than on the eastern one. Given the various volatile component (0.95 – 9.57 wt.%) in the sampled plutonic paleoceanographic informations available in the area we are

rocks. Water abundance within these rocks correlates with the able to demonstrate that the =Nd signal can not be explained by degree of alteration, Ni, and modal olivine contents. The variations of the mixing contributions of the different ocean

H2O/MgO ratio of the troctolites (0.31) is consistent with that masses surrounding New Zealand. The =Nd signal has clearly a of serpentine (0.32) and indicates the importance of continental and local origin. serpentinisation within the sampled lowest EPR oceanic crust. Using mixing calculations we show that the weathering Localized low-temperature alteration is possibly due to Cocos- Nd fluxes could have been up to 2 to 3 times higher during Nazca rifting associated with cataclastic deformation. glacials than during interglacials. This result is explained by the control of glacial erosion that deliver higher amount of fine and fresh materials, easily weatherable. Moreover the lower amplitude of the variations on the western site suggests that floodplains play a key role in the chemical maturation of these fresh and fine grounded minerals delivered from the

higher relief. Finally the relationship between our =Nd record and the "18O record suggest a non linear response (hysteresis like relation) of the erosion and weathering processes to climatic forcings.

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Sr-Nd and Pb isotopic portray of the Convergence in chemical Crozet plume compositions between aqueous fluid C. M. MEYZEN1*, A. MARZOLI1, G. BELLIENI1 and silicate melt in the peridotite- AND G. LEVRESSE2 H2O system 1 Università degli Studi di Padova, Via G. Gradenigo, 6, 35131 1 2 KENJI MIBE *, TATSUHIKO KAWAMOTO Padova, Italia (* correspondence: 3 AND SHIGEAKI ONO [email protected], [email protected], [email protected]) 1Earthquake Research Institute, University of Tokyo, Tokyo 2 Centro de Geociencias, Universidad Nacional Autónoma de 113-0032, Japan (*correspondence: [email protected] México (UNAM), Blvd. Juriquilla No. 3001, Querétaro, tokyo.ac.jp) 76230, México ([email protected]) 2Institute for Geothermal Sciences, Graduate School of Science, Kyoto University, Kyoto, 606-8502, Japan New Sr, Nd and Pb isotope data are presented for alkali ([email protected]) basalts of the sub-aerial eruptive stage of East Island. This 3 Institute for Research on Earth Evolution, Japan Agency for landmass is the second largest of the easternmost and oldest Marine-Earth Science and Technology, Kanagawa, Japan. island group of Crozet archipelago. Its lavas are remarkably (sono@ [email protected]) isotopically homogeneous in spanning a narrow range of isotopic variability. They occupy an intermediate position In order to understand the magma genesis and chemical among the isotopic variability spectrum defined by Earth’s differentiation in the Earth's interior, we have been oceanic island basalts. They fall in a mixing triangular shape investigating the stability fields and chemical compositions of formed by the end-member mantle components: a Depleted aqueous fluid, silicate melt, and supercritical fluid magma in Mantle (DM) component, an Enriched Mantle (EM) the peridotite-H2O system. Mibe et al. [1] found that the component and a common component. The mixture second critical endpoint occured at around 3.8 GPa in the domination by a large fraction of the common component system peridotite-H2O. Using the quenched recovered samples suggests an isolation of the East island mantle source from obtained by Mibe et al. [1], we determined the chemical homogenizing effects of convection mixing and recycling composition of aqueous fluid, silicate melt, and supercritical processes for Ga timescales. A possible inter-island source fluid in the vicinity of the second critical endpoint in the heterogeneity, such as those identified in the Pacific and system peridotite-H2O by EPMA analyses. A 10- to 30-um Atlantic oceans, could exist at Crozet islands, as the younger diameter electron beam was used to obtain the composition of western group is more isotopically depleted in Sr-Nd than the quenched materials from aqueous fluid, silicate melt, and eastern one. Overall, lavas from Crozet islands share Pb-Sr-Nd supercritical fluid. isotopic affinities with their Reunion-Mauritius counterparts, In the run at 3.3 GPa, the composition of aqueous fluid but differ from those of Marion-Prince Edward and Kerguelen was high-Mg dacitic, whereas the composition of silicate melt volcanoes. However, we cannot reject the seismic inference was peridotitic. In the run at 3.6 GPa, the composition of that Crozet volcanism is a secondary expression of Kerguelen aqueous fluid was high-Mg andesitic, whereas the hotspot, if its compositional bottom layer is heterogeneous. composition of silicate melt was komatiitic. At 4 GPa (i.e., Finally, the Sr-Nd-Pb isotopic signatures of basalts north of above the second critical endpoint), the composition of the Crozet Bank along the Southwest Indian Ridge show no supercritical fluid magma was basaltic. Our results clearly affinity with those of East island. The seismically ridgeward indicate that the compositions of aqueous fluid and silicate flow identified must thus be composed of isotopically distinct melt converge at around 3.8 GPa, which is consistent with the material from that of feeding East island volcanism. results by Mibe et al. [1].

[1] Mibe et al. (2007) J Geophys Res 112:B03201.

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Concentration and Behavior of CO2 ‘Freiberg Strategy’ for obtaining in MORB and OIB: a reevaluation matrix-matched reference materials PETER J. MICHAEL1* AND DAVID W. GRAHAM2 for resource-related microanalytical 1Dept. of Geosciences, Univ. Tulsa, 800 S. Tucker Dr., Tulsa, methods technology OK, 74104, USA (*correspondence: [email protected]) 1 2 2 2 P.P. MICHALAK , A.D. RENNO ,S. MERCHEL , F. CEOAS, Oregon State Univ., Corvallis, OR, 97331, USA 2 2 3 3 MUNNIK , J. GUTZMER , R. UECKER , Z. GALAZKA , H- ([email protected]) 1 4 4 P. HELLER M. RADTKE AND U. REINHOLZ

1 Estimation of initial magmatic CO2 contents in basalts is TU Bergakademie Freiberg, DE

hindered by degassing and loss of CO2 during magma ascent. ([email protected]) 2 3 4 The most widely accepted estimates of CO2 flux are derived HZDR, Dresden, DE, IKZ, Berlin, DE, BAM, Berlin, DE, from ultra-depleted ([Nb]<1.5ppm) mid-ocean ridge basalts (MORB) and melt inclusions from Siqueiros region of the East Quality assurance of natural raw materials (e.g. ores)

Pacific Rise that did not exsolve CO2 [1], and from highly requires thorough studies on concentration and spatial vesicular Mid-Atlantic Ridge (MAR: 14°N) “popping rocks” distribution patterns of technologically relevant trace elements that did not lose bubbles because they ascended quickly [2,3]. within the mineral matrix at the microscale. Obtaining such a

These data indicated that that CO2/Nb was roughly constant at goal is yet only possible with the use of beam-based

239±46 for MORB and that CO2 behaves incompatibly like microanalytical methods and a proper set of homogeneous, Nb during melting and source enrichment [1]. A correct matrix-matched reference materials (RMs) doped with trace

recalculation of the CO2/Nb in popping rocks from 14°N, and elements relevant to resource technology. new data from popping rocks at 34°N MAR, showed that their Natural minerals usually exhibit chemical heterogeneity at

CO2/Nb is much higher: closer to 576 [4]. These authors µg/g sampling masses and are unsuitable as RMs for in-situ

proposed that the low CO2/Nb values for ultra-depleted chemical microanalysis. On the other hand, available synthetic MORB [1] are unrepresentative of the mantle. Their higher RMs (e.g. glasses, pressed pellets) fail to satisfy matrix-match

CO2/Nb estimate [4] yields higher estimates of CO2 flux from criterion. the mantle, in line with estimates from helium. A collaboration involving several German scientific We have analyzed a larger set of ultra-depleted MORB institutions centered around TU Bergakademie Freiberg glasses from the mid-ocean ridge system. Most erupted proposed a novel strategy for obtaining such RMs through the

undersaturated in CO2, have few or no vesicles, and yield synthesis of multi trace element doped mineral matrices

extremely low CO2 when crushed in vacuo. Their CO2/Nb is subsequently tested for chemical and structural homogeneity 250±50, showing that this ratio [1] is widely applicable to with both microscopic and spectroscopic (RMs-dependent and ultra-depleted mantle. We also compiled published data for absolute) microanalytical methods. enriched submarine basalts including ridge popping rocks [4], Three mineral matrices vital to resource technology and basalts from North Arch, Hawaii. The latter have up to applications – pyrite, tantalite and feldspar – have been 57% vesicles, suggesting two samples lost no bubbles [5]. synthesized using flux method, Czochralski method and

Their CO2/Nb is 1125 and 1216, similar to ratios for some alkoxide-based sol-gel synthesis, respectively and doped with popping rocks from 34°N. For the data set as a whole, various sets of technologically important trace elements at the

CO2/Nb is positively correlated with La/Sm. We propose that concentration range found in corresponding natural minerals.

CO2 is more incompatible than Nb, behaving geochemically Their spatial chemical micro-homogeneity has been

more like Ba or Rb. CO2/Ba is 114±43 for most ultra-depleted investigated using light and electron microscopy as well as through highly enriched MORB. Rb and Ba should be better RMs–dependent (EPMA, LA-ICP-MS) and absolute (PIXE,

proxies for CO2 because, unlike Nb, they are not retained in PIGE) analytical methods. subduction zones during magma genesis. Thus, Rb and Ba Quantitative and qualitative elemental spatial distribution

more closely follow CO2 during subduction and recycling into maps have been obtained for major and trace elements for

deep mantle. A Ba proxy for CO2 suggests a MORB CO2 flux each matrix. Homogeneity of the matrices was evaluated using that is 740% higher than [4] and 73x higher than [1]. petrologically sensitive statistical analysis. Established homogeneity testing protocol will be [1] Saal et al. 2002 Nature 419. [2] Sarda & Graham 1990 employed in the next stages of the project. EPSL 97. [3] Javoy & Pineau 1991 EPSL 107. [4] Cartigny et al. 2008 EPSL 265. [5] Dixon et al. 1997 J. Petrol. 38.

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Biomass combustion – a possible Linking reactive silica with organic source of environmental pollution? matter burial in Mississippi delta M. MICHALIK1*, M. POGRZEBA2, AND W. WILCZY'SKA- sediments MICHALIK 3 P. MICHALOPOULOS * AND K. PARINOS 1Jagiellonian University, Institute of Geological Sciences, Institute of Oceanorgaphy, Hellenic Center for Marine ul. Oleandry 2a, 30-063 Kraków, Poland (*correspondence: Research , Anavyssos, 19013, Greece [email protected]) 2 Institute for Ecology of Industrial Areas, ul. Kossutha 6, Deltaic sediments account for ~40% of organic carbon 40-844 Katowice, Poland ([email protected]) 3 burial in the oceans. Furthermore poorly crystalline Al-Si- Pedagogical University, Institute of Geography, ul. (Fe)-phases precipitate on biosiliceous and clastic particles as ()ych 2, Kraków, Poland Podchor a result of reverse weathering reactions in deltaic sediments ([email protected]) [1]. Amorphous biogenic silica and poorly crystaline Al-Si- (Fe) precipitates are quantified as reactive silica (RSi). This The content of selected elements in biomass (virginia study examines the links between RSi and sedimentary fanpetals; cup plant; switchgrass; eastern cordgrass; organic matter in Mississippi delta sediments and the miscanthus) grown on contaminated experimental field and in low-temperature ash obtained in 475oC was studied. The soil implications for organic matter burial and preservation. is enriched in various elements (e.g. Zn up to 2000 ppm, Pb up Suspended matter and sediment samples from the Mississippi to 430 ppm, Cd up to 19 ppm) and contains numerous river and seven delta stations were analyzed for reactive silica components of anthropogenic origin (spherical dust particles (RSi), total organic carbon (TOC), total nitrogen (TN) and 13 15 from high-temperature industrial processes, fragments of stable isotopes (" C, " >). various types of metallurgical slag, coal ash, etc.). Top (>50cm) and bottom sediments from delta sites close The content of potentially toxic elements determined in to the river mouth have identical "13C, "15> values, indicating biomass is relatively high (e.g. Zn up to 545 ppm, Cd up to 8,5 similar OM sources. In top sediments RSi is not related to ppm, Pb up tp 115 ppm, Hg up to 24 ppb). The content of TOC or TN. Below 50cm, RSi correlates with TOC,TN these elements in low-temperature ash is very high (Zn from suggesting a diagenetic control. Correlations in mid-shelf 4100 to >10 000 ppm, Cd from 30 to 207 ppm, Pb from 380 to stations show that TOC:Si, TN:Si ratios decrease from top to 2870 ppm, Ag from 171 to 1048 ppb, As from 9 to 22.5 ppm, bottom, indicating preferential loss of TOC and TN relative to Hg below 0.5 ppb). RSi. Stronger coupling between RSi and preserved residual Detailed study of dry biomass indicates that high content OM is found in mid-shelf sites where sediments are more of various elements is related partly to dust particles deposited diageneticaly altered. We propose that formation of Al-Si on its surface (e.g. Pb, Cd and Zn sulphides, Zn containing coatings on biosiliceous particles [2-3] may also partially clay minerals, Ca and Ba sulphates, particles rich in Fe, Cr, inhibit the decomposition of diatom-bound OM. During burial, Ni, etc.) and partly to accumulation of various elements (e.g. Zn) in plant tissue. ~34% of residual sedimentary OM appears related to RSi in Results indicate that in the case of biomass cultivated on nearshore and mid-shelf deposits. the polluted sites risk of emission of elements characterized by low values of boiling point during fuel combustion or leaching [1] Michalopoulos et al.(2000) Geology 28:1095-1098 [2] of potentially toxic elements from ash to the environment is Lucaides et al.(2010) Chemical Geology 270:68-79 [3] Presti probable. and Michalopoulos(2008) Cont. Shelf Res. 28:823-838 Study was supported by NCN grant No. 579/B/P01/2011/40.

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Chemical and isotopic features of Crustal evolution of the mafic granulites from Serre massif intracontinental Warburton–Cooper– (Calabria-Italy) Eromanga Basin system, central F. MICHELETTI1*, A. FORNELLI1, A. MUSCHITIELLO1 Australia 1 AND G. PICCARRETA 1 1 1 A. W. MIDDLETON* , I. T. UYSAL AND S. D. GOLDING 1Earth science and geo-environmental Dep., Bari University 1University of Queensland, Queensland 4072, Australia Italy, [email protected] (*correspondence: [email protected])

Different types of mafic granulites characterize the lower The Warburton–Cooper–Eromanga basins host one of the crust of the Serre Massif (Calabria, Southern Italy). They most prospective hot dry-rock geothermal resources (Big Lake consist of: layered metagabbros Suite granite; BLS) that stems from unusual enrichment in (Pl+Opx+Amph±Cpx±Bt±Qtz±Grt) and metric bodies of radiogenic elements (up to 144 ppm Th and 30 ppm U). The meta-monzogabbros (Pl+K-feld+Opx+Cpx+Bt±Qtz±Grt) at overlying Eromanga Basin is also endowed with substantial the base of the lower crust and lenses or layers of metabasites hydrocarbon reserves. Despite these attributes, holistic basin (Pl+Opx+Cpx±Bt±Amph±Qtz±Grt) interleaved with analysis has not been attempted leaving much of central migmatitic metapelites and felsic granulites overlying the Australia’s crustal evolution poorly constrained. By metagabbros. The magmatic protoliths are Neoproterozoic conducting geochemical and geochronological analyses of ('570 Ma), whereas the granulite-amphibolite facies primary, vein-hosted and authigenic phases, this study metamorphism took place in Variscan times [1]. elaborates on its crustal evolution throughout the Palaeozoic Metagabbros and metabasites are sub-alkaline (Na2O+K2O=1- and the influences on basin thermal and fluid flow events. 5%) with K2O<1%, whereas meta-monzogabbros show U–Pb (420 ± 6.7 Ma) and U–Th–total Pb (407 ± 16 Ma) of alkaline character (Na2O+K2O=5-7%) with K2O around 3% granite-hosted primary zircon and uraninite, respectively, reflecting the contents of biotite. provide coincident ages with Sm–Nd of carbonate veins (437 The meta-monzogabbros showing enrichment of ± 17 Ma) of Warburton vein carbonates. Authigenic illite from incompatibile elements are interpreted as derived from small Warburton sediments produce a Rb–Sr isochron age of 323.3 degree of partial melting of enriched mantle, probably as ± 9.4 Ma, consistent with previous U–Pb zircon ages underplating magma in Neoproterozoic times. Subsequent or estimating emplacement of the Big Lake Suite (Marshall et al. incremental mantle partial melting events produced melts with unpublished). Rb–Sr of granite-hosted clay fractions yield ages of 87.4 ± 4.9 Ma and 101.1 ± 6.4 Ma, in agreement with tholeiitic and calc-alkaline affinities forming the protoliths of quartz encapsulated Ar–Ar total-gas ages of the same clay metagabbros and metabasites. separates. Isotopically more robust Sm–Nd dating, however, The isotopic features (Sm-Nd, Rb-Sr) of metabasites produces older ages of 128 ± 16 Ma. Calculated "18O and "D reflect some crust contamination assisted by fluids derived fluid isotopic values are compatible with an influx of meteoric from host metasediments. On the other hand, also the waters in an extensional environment. participation of biotite in the partial melting could account for Multifaceted analysis of primary and secondary phases the variation of Rb-Sr characteristics within the metagabbros produced geologically significant ages attributed to substantial and metabasites (Fig. 1). thermal events throughout basinal evolution. Warburton Basin dates provide evidence of episodic magmatic activity associated with relaxation-related and back-arc extension. Dating of illite from the Cooper–Eromanga constrains intra- cratonic basin formation consistent with episodic rifting of Gondwana and opening of the Tasman Sea along the eastern margin of Australia [1]. Such consistency suggests plate-wide transmission of tensional stress to intra-continental crust weakened by abnormally high geothermal gradients, associated with the BLS, and preceding basinal tectonism [2].

[1] Bryan et al. (2012) Episodes 35, 142–152. [2] Friedmann & Burbank (1995) Basin Res. 7, 109–127.

Fig. 1 Rb-Sr isotopic compositions of mafic granulites.

[1] Fornelli et al. (2011) Mineral Petrol 103, 101-122.

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Potential of uranium removal from Gaussberg leicitites – new data on post-uranium mining heaps by mineralogical and geochemical indigenous bacteria composition S. MIELNICKI1*, L. DREWNIAK 1, M. SZYMKIEWICZ 1, N.A. MIGDISOVA 1*, N.M. SUSHCHEVSKAYA1, B. REWERSKI1 AND A. SKLODOWSKA1. B.V. BELYATSKY2 AND D.V. KUZMIN3 Laboratory of Environmental Pollution Analysis, Faculty of 1Vernadsky Institute for Geochemistry, RAS, Moscow, Russia Biology, University of Warsaw, Warsaw, Poland (*correspondence: [email protected]) (*correspondence: [email protected]) 2IPGG, St.Petersburg, Russia 3Max-Plank Institute fur Chemie, Mainz, Germany In Poland until 1925 there was no information about existence of uranium ore. First uranium mine was established New geochemical data on Quaternary magmatism of the in Kowary in 1948 and after that uranium ore exploitation in Gaussberg volcano (Antarctica) confirms the unique features Poland had lasted to 1967. Nowadays low-grade uranium of ultra-potassium alkaline magmatism developed under heaps exist in Southern Poland posing potential danger to exclusively continental conditions. Volcanic cone is located surrounding environment and human beings. The traditional on the within Gaussberg rift zone possibly being a part of methods of bioremediation are well known but they are costly Lambert fracture zone. The crystallization sequence of and inefficient, moreover they require the use of large Gaussberg volcano lavas is Ol ) Ol + Cpx ) Ol + Cpx + Lc. volumes of acids which can cause irreversible environmental Two different types of clinopyroxene phenocrysts were damages. Alternative environmental friendly methods can be detected: high TiO2, low Al2O3 group (1) and high Al2O3 and developed. Indigenous microorganisms can participate in low TiO2 group (2). Rare element patterns for whole-rocks are pollution mobilisation and the resulting leak can be collected similar to [1]. Rare element distribution for Cpx 1 into the drainage system. Identification of indigenous demonstrates specific signature showing higher LILE values Cpx/Lq microorganisms existing in the environment of piles is the first and appreciably lower D (two orders of magnitude) then step in the assessment whether the process can take place. in [2]. These features can be a result of fluid impact on Five sites containing waste with uranium concentration in magmatic system. Gaussberg volcano mantle source is the range from 112.75 to 2986 mg/L were chosen as a enriched in 207Pb/204Pb and 208Pb/204Pb while it has low potential places for isolation of microorganisms, metagenomic 206Pb/204Pb (717.5) value. High 87Sr/86Sr (70.707-0710) taken DNA and 16S rRNA gene analysis to define microbiological together with low 143Nd/144Nd (70.5119) ratios suggest potential. Bacteria from the genus of Halothiobacillus, LOMU-type of primary mantle source. Sphingomonas, Pseudomonas and Acidithiobacillus were found as dominant. They are well known as microorganisms able to indirect transformation of uranium compounds. After 14 days of incubation, indigenous bacteria in acidic conditions (starting pH 2.5) mobilized 0 - 60% of uranium (depending of the type of waste) in comparison to sterile control in which 0-50% of uranium was mobilized respectively. These preliminary results clearly show that construction of passive bioremediation system is possible and may be efficient.

Figure 1: Isotopic data reveal that Gaussberg volcano melts source was the ancient Gondwana lithosphere but not the Antarctic mantle source (Mesozoic plumes)

[1] Murphy D.T. et al. (2002) J.Petrology, 43, 6, 981-1001. [2] Foley S.F. & Jenner G.A. (2004) Lithos, 75, 19-38. [3] Kamenetsky V. S. et al. (2001) Geology, 29, 3, 243-246.

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Kinetics of arsenic sorption on Copper and lead isotope ratios as aquifer sediment from Bangladesh tracers of soils pollution from the imaged by XRF microprobe in Kombat mining area, Namibia flowing columns MARTIN MIHALJEVIC1*, VOJTECH ETTLER1, BOHDAN 2 3 1 1 1,2 KRIBEK , VLADISLAV CHRASTNY, ALES VANEK I. MIHAJLOV *, B.C. BOSTICK , M. STUTE , 3 3 3 1 AND VIT PENÍZEK I. CHOUDHURY , K.M. AHMED AND A. VAN GEEN 1 1 Institute of Geochemistry, Mineralogy and Mineral Lamont-Doherty Earth Observatory of Columbia University, Resources, Charles University in Prague, Albertov 6, 128 Palisades, NY, USA 43 Prague 2, Czech Republic (*correspondence: [email protected]) 2 (*correspondence: [email protected]) Barnard College, New York, NY, USA 2 3 Czech Geological Survey, Geologicka 6, 152 00 Prague 5, Dhaka University, Dhaka, Bangladesh Czech Republic 3Department of Soil Science and Soil Protection, Czech To avoid groundwater arsenic (As) contamination, much University of Life Sciences Prague, Kamycka 129, 165 21, of the population of Bangladesh depends on deeper wells that Prague 6 – Suchdol, Czech Republic are low in As. Pumping these wells could draw high-As

groundwater into currently As-safe aquifers. This research Copper (Cu) and lead (Pb) concentration, isotopic examines the mechanisms of As adsorption on natural aquifer composition (65Cu/63Cu, 206Pb/207Pb) were studied in sediments that can help retard the migration of As. contaminated and non contaminated luvisols and mollisols Freshly collected sediment from a low-As aquifer in from the Kombat mining area, Namibia. The Cu and Pb Bangladesh was used for sorption kinetics studies in low-O 2 concentrations in the studied soils ranged between 21 mg/kg – batch reactors set up in the field with in situ (unoxidized) 757 mg/kg, and 19 mg/kg – 815 mg/kg respectively. groundwater, as well as in two small columns run under a Concentration of both metals increased with increasing soil synchrotron beam for ~20 hrs. Sorption of As onto column depth. The Pb isotopic signatures (206Pb/207Pb) in soils ranged sediments was monitored by continuous X-ray fluorescence between 1.15 – 1.21. In most of soil samples, surface horizons (XRF) imagery at 2 or 3 µm resolution, and Fe mineralogy exhibited lower 206Pb/207Pb ratio, which originates from the was assessed by XANES at several representative points. slime dust pollution (206Pb/207Pb ~ 1.15) compared to deeper soil horizons, with lithogenic Pb signatures. Isotopic composition of Cu differs on contaminated and uncontaminated sites and cultivated and non-cultivated sites. The "65Cu in the studied soil horizon ranged between –0.373 ‰ and 0.561 ‰. The most pronounced variations occurred in contaminated non cultivated soils (0.529 ‰). The contaminated surface horizons are enriched in isotopically heavier Cu (tailing materials), and "65Cu decreased with depth. Fractionation of Cu isotopes in soils is attributed to mobilization of lighter isotope, and preferential binding of Figure 1: Same-scale and co-located XRF images of As on heavy isotopes on secondary soil components. This study was column sediment at time 0 (A) and after 16 hrs of continuous supported by the Czech Science Foundation flow (B). Warmer colors indicate higher concentrations. (projectP210/12/1413) and IGCP project no. 594.

Results from both batch and beam column experiments consistently indicated that As adsorption proceded at a high initial rate (k~0.5 hr-1) over the first 1-3 hrs, after which it progressively slowed down by 1-2 orders of magnitude. Sites responsible for rapid initial adsorption varied widely in mineralogy and reactivity, while later adsorption rate was more uniform and focused on sites correlated to Fe concentrations. Microscale measurements supplement the macroscopic data and indicate that As transport is kinetically limited by diffusive processes on the grain scale or smaller.

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Ar-Ar and U-Pb isotopic ages of Multiphase inclusions with Early Caledonian granulites from the kokchetavite and K-cymrite in UHP Svyatoy Nos Peninsula calc-silicate rocks from Kokchetav (Transbaikalia) massif E.I. MIKHEEV1, A.G. VLADIMIROV1,2*,3, A.V. TRAVIN1, ANASTASIA O. MIKHNO1* T.B. BAYANOVA4 AND N.I. VOLKOVA1 AND ANDREY V. KORSAKOV1 1IGM SB RAS, Novosibirsk 630090, Russia 1V.S. Sobolev Insitute of Geology and Mineralogy SB RAS, ([email protected], [email protected]) Novosibirsk 630090, Russia 2Novosibirsk State University, Novosibirsk 630090, Russia (*correspondence:[email protected]) (*correspondence: [email protected]) 3Tomsk State University,Tomsk 634050, Russia Ultrahigh pressure (UHP) rocks of the Kokchetav massif 4GIN KSC RAS, Apatity 184209, Russia are of particular interest as they were exhumed from at least ([email protected]) 120 km depth [1] and experienced peak metamorphic conditions of approximately T = 1000-1100 °C and P = 6-7 Metamorphic rocks of Svyatoy Nos Peninsula GPa [2].

(Transbaikalia) are basic granulites, graphitic marbles, Here we present findings of K-cymrite (KAlSi3O8·H2O)

diopside plagioschists and quartzites. The P-T metamorphic and kokchetavite (KAlSi3O8) in association with conditions are estimated to be 815-860°C and 7.9 to 8.3 kbar. muscovite/phengite, lollingite, calcite and (-cristobalite in The granulites are intruded by abundant veins of syntectonic multiphase mineral inclusions in ultrapottasic clinopyroxene granites and granitic pegmatites attributing to Barguzin (K-Cpx) porphyroblasts of calc-silicate rocks (Kokchetav Complex of the Angara-Vitim batholith (280-298 Ma) [1]. The massif, Northern Kazakhstan). These inclusions were U-Pb zircon dating of single grains indicates age of granulite interpreted to be melt at peak metamorphic conditions [3]. metamorphism at 495 ± 5 Ma. Findings of K-cymrite and kokchetavite in polyphase inclusion along with experimental data on K-cymrite calcination [4] proves model of kokchetavite formation through the dehydration of K-cymrite. Presence of K-cymrite in multiphase inclusions in K-Cpx porphyroblasts testifies for

high K2O-content which should be nearly equimolar to H2O- content in melt [5]. Korsakov et al. [6] supposed that gneisses

underwent melting to form K2O-rich melt which migration and further reaction with the carbonate interlayers caused the formation of the calc-silicate rocks with K-Cpx. Neither kokchetavite, nor K-cymrite were reported in gneisses. This fact could imply that melt in gneisses should contain less

Figure: U-Pb dating of single zircon grains from Svyatoy Nos amount of K2O, than that in calc-silicate rocks. Therefore we Peninsula granulites. assume that K-rich melt was formed during the prograde metamorphic stage at low melting degrees and than migrated Syntectonic granosyenite-granites connecting with intense to calc-silicate rocks protholith to form K-Cpx. During peak strike-slip deformations gave ages of 450 ± 5 and 445 ± 5 Ma. metamorphic conditions gneisses underwent extent melting

Ar-Ar ages on amphibole (256 - 245 Ma) probably date a which decreased K2O-content in melt. thermal effect from the Angara-Vitim Batholith. This study was supported by MD-1260.2013.5 and RFBR The sponsorships are the the Earth Sciences Department of grants no.12-05-31431 and no.13-05-00367. SB RAS (IP ONZ-10.3, IP ?77) and Federal Grant Programme of Russia (project ? 2012-1.2.1-12-000-2008- [1] Sobolev & Shatsky (1990) Nature 343, 742-746. [2] 8340). Mikhno & Korsakov (2013) Gondwana Research 23, 920-930. [3] Korsakov & Hermann (2006) EPSL 241, 104-118. [4] [1] Cygankov et al. (2007), Russian Geology and Geophysics Thompson et al. (1998) Contrib.Min.Petrol. 130, 176-186. [5] 48, 156-180. Harlow & Davies (2004) Lithos 77, 647-653. [6] Korsakov et al. (2004) Terra Nova 16, 146-151.

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Transmission electron microscopy of Structure of Amorphous Ferric iron metal in Almahata Sitta ureilite Arsenate from EXAFS Spectroscopy T. MIKOUCHI1*, K. YUBUTA2, K. SUGIYAMA2, and Total X-ray Scattering 1 3 3 Y. AOYAGI , A. YASUHARA , T. MIHIRA , 1 2 4 5 CHRISTIAN MIKUTTA *, F. MARC MICHEL , PETAR M.E. ZOLENSKY AND C.A. GOODRICH 1 1 MANDALIEV AND RUBEN KRETZSCHMAR 1Dept. Earth & Planet. Sci., Univ. of Tokyo, Tokyo 113-0033, 1Institute of Biogeochemistry and Pollutant Dynamics, ETH Japan (*correspondence: [email protected]) Zurich, Switzerland (*[email protected]) 2Inst. for Materials Res., Tohoku Univ., Sendai, Miyagi 980- 2Virginia Tech, Blacksburg, USA 8577, Japan

3JEOL Ltd., Akishima, Tokyo 196-8558, Japan Amorphous ferric arsenate (‘AFA’, FeAsO :nH O) is a 4ARES, NASA-JSC, Houston, TX 77058, USA 4 2 secondary As precipitate frequently encountered in acid mine- 5Planet. Sci. Inst., Tucson, AZ 85719, USA waste environments. Its structure has been proposed to

resemble that of scorodite (FeAsO :2H O) in which isolated Almahata Sitta (AS) is a polymict breccia mainly 4 2 FeO octahedra share corners with four adjacent arsenate composed of various ureilite lithologies with lesser chondritic 6 (AsO ) tetrahedra in a three-dimensional framework lithologies [1]. Fe metal is a common accessory phase in 4 (framework model). Conversely, AFA was postulated to ureilites, but our earlier studies on Fe metals in one of AS consist of single chains of corner-sharing FeO octahedra fragments (#44) revealed unique features never seen in other 6 being bridged by arsenate (chain model). In order to test the ureilites [2,3]. In this abstract we report detailed transmission accuracy of both structural models, we synthesized AFAs and electron microscopy (TEM) on these metal grains to better analyzed their structure by As and Fe K-edge extended X-ray understand the thermal history of ureilites. absorption fine structure (EXAFS) spectroscopy and total X- We prepared FIB sections of AS#44 by JEOL JIB-4000 ray scattering. We found that both As and Fe K-edge EXAFS from the PTS that was well characterized by SEM-EBSD in spectra were most compatible with isolated FeO octahedra our earlier studies [2,3]. The sections were then observed by 6 being bridged by AsO tetrahedra (R = 3.33 ± 0.01 Å). STEM (JEOL JEM-2100F). 4 Fe-As Wavelet-transform analyses of the Fe K-edge EXAFS spectra One of the FIB sections shows a submicron-sized of AFA complemented by shell fitting confirmed Fe atoms at intergrown texture composed of Fe metal (kamacite), Fe an average distance of 5.3 Å, consistent with crystallographic carbide (cohenite), Fe phosphide (schreibersite), and Fe data of scorodite and in disagreement with the chain model. sulfide (troilite). Probably, this eutectic-looking texture was Reduced pair distribution functions, G(r), provided formed by shock re-melting of pre-existing metal + graphite + unequivocal evidence for the absence of single corner-sharing phosphates (phosphide?) + sulfides with various amounts. FeO linkages in AFA. Analyses of radial distribution The other FIB section is mostly composed of 6 functions, R(r), additionally indicated that in AFA each As homogeneous Fe metal (93 wt% Fe, 5 wt% Ni, and 2 wt% Si), atom has on average about four nearest Fe neighbors, in but BF-STEM images exhibited the presence of elongated accordance with the framework model. In summary, our lathy grains (~2 µm long) embedded in an interstitial matrix. findings imply that scorodite formation from AFA in mining The SAED patterns from these lath grains could be indexed by environments proceeds via growth of small clusters with a &-Fe (bcc) while interstitial areas are *-Fe (fcc). The elongated scorodite-type local structure. &-Fe grains show tweed-like structures suggesting martensite

transformation. Such a texture can be formed by rapid cooling from high temperature where *-Fe was stable. Subsequently &- Fe crystallized, but *-Fe remained in the interstitial matrix due to quenching from high temperature. Presence of C may have enhanced its stability. This scenario is consistent with very rapid cooling history of ureilites suggested by silicate mineralogy.

[1] Zolensky et al. (2010) MAPS, 45, 1618-1637. [2] Goodrich et al. (2010) MAPS, 45, A66. [3] Mikouchi et al. (2011) MAPS, 46, Suppl.,5409.

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Unconventional generation of A new calibration of the carbonate hydrocarbons in petroleum basin: the clumped isotope thermometer based role of siderite/water interface on synthetic calcites V. MILESI1*, A. PRINZHOFER2, F. GUYOT1,3, F. BRUNET4, I. MILLÁN*, S. BREITENACH, N. MECKLER, M. ZIEGLER LAURENT RICHARD5, J.DAIROU6 AND S. M. BERNASCONI AND M. BENEDETTI1 ETH Zürich, Geologisches Institut, Sonneggstrasse 5, 8092 1 Univ Paris Diderot, Sorbonne Paris Cité, IPGP, UMR 7154 Zürich, Switzerland. CNRS, Paris, France (*correspondence : [email protected]) (*correspondence: [email protected]) 2 HRT, Av. Atlantica 1130- Copacabana – Rio de Janeiro 3 IMPMC UMR 7590 CNRS, UPMC Previous calibrations of the clumped isotope thermometer 4 ISTerre, Université Joseph Fourrier, Grenoble, France based on synthetic calcites differ in the inferred relationship 5Geoquímics dels Àngels, Carrer dels Àngels 4-2-1, 08001 between isotopic ordering in the carbonate and temperature [1, Barcelona, Spain 2]. The “absolute reference frame” proprosed by Dennis et al. 6 BFA, CNRS EAC 4413, Univ Paris Diderot, Paris, France [3] improved the interlaboratory comparison but did not eliminate the discrepancies between the laboratories. It is clear Hydrocarbons in the petroleum basin of Solimões in that especially for inorganically precipitated carbonates more Northern Brazil show isotopic trends similar to those of experimental data are needed. Here we present a new abiotic hydrocarbons observed in oceanic hydrothermal calibration on synthetic calcites and compile all published systems. calibration data available to date. High concentrations of ferrous iron in the brines indicate a Our new calibration is based on 11 synthetic calcites highly reduced environment. Such redox conditions are precipitated at known temperatures between 4°C and 80ºC.

consistent with the large amount of siderite FeCO3 in the CaCO3 was precipitated inorganically by mixing solutions of sediments. The capacity of siderite-water interactions to NaHCO3 (0.1M) and CaCl2 (0.1M) at the desired generate unconventional hydrocarbons has been tested temperatures. The solutions were kept at known temperatures experimentally. in incubators for 5 days before starting the experiments.

Synthetic FeCO3 and water were reacted in gold containers Analyses were conducted at ETH on small carbonate samples at 500 bars, 200°C and 300°C. Siderite dissolution led to (ca. 170-220 µg) using a Kiel IV Carbonate Device coupled to reducing conditions due to magnetite formation. In addition, at a Thermo Finnigan MAT 253 Mass Spectrometer [4]. The 200°C, TEM showed the precipitation of a nanometric layer of samples were measured multiple times on different days, with

amorphous carbon covering magnetite grains. At 300°C, H2 each measurement consisting of 9-15 analyses of separate

was produced and reacted with CO2 to generate organic aliquots. Data are presented relative to the “absolute reference compounds such as methane and carboxylic acids [1]. The frame” [3]. dissolved organic compounds concentrations are consistent We find a robust linear relationship between %47 and

with a cascade of reduction from CO2 to CH4 [2]. temperature of precipitation. We discuss several issues related % Alternatively, CH4 could form through the hydrogenation to the slope of the linear regression through 47 plotted against of the amorphous carbon coating observed on magnetite solution temperatures and the compilation of previous grains. This latter mechanism is more consistent with the calibrations in the absolute reference frame. isotopic data from the Solimões basin where, in addition,

senile kerogen and H2-rich fluids coexist. Experimental [1] Ghosh et al. 2006. Geochim Cosmochim Ac 70, 1439- validation is currently underway. 1456 [2] Dennis and Schrag, 2010. Geochim Cosmochim Ac 74, 4110-4122 [3] Dennis et al., 2011. Geochimica Et [1] McCollom (2003), Geochim. Cosmochim. acta, 67, 311- Cosmochimica Acta 75, 7117-7131 [4] Schmid and 317. [2] Seewald et al. (2006), Geochim. Cosmochim. acta, Bernasconi, 2010. RCMS 24, 1955-1963. 70, 446-460.

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Hot/cold, wet/dry, big/small, erupt/ Chalcopyrite in the R chondrite PRE stall, juvenile/anatectic? – Multiple 95411 personalities of felsic magmatism K.E. MILLER1*, M.S. THOMPSON1, T.J. ZEGA1 1 1 1 1 AND D.S. LAURETTA C.F. MILLER *, S.M. MCDOWELL , T.L. CARLEY , W.O. FRAZIER1, A.S. PAMUKCU1, A.DEJ. PADILLA1, L.L. 1Lunar and Planetary Laboratory, Dept. of Planetary Sciences, CLAIBORNE1, D.M. FLANAGAN1, G.A.R. GUALDA1, University of Arizona, Tucson, AZ 85721 J.S. MILLER2, J.L. WOODEN3 AND R.W. MAPES4 (*correspondence: [email protected]) 1 Vanderbilt Univ, Earth & Environmental Sciences, Nashville The R chondrites record petrologic grades from 3 to 6, USA, [email protected] (* presenting author) suggesting parent-body histories from unaltered to nearly 3Stanford U, Geol & Env Sci, Stanford USA, equilibrated. However, a growing body of evidence suggests [email protected] 2 the group may have experienced hydrothermal alteration. San Jose State U, Geology, San Jose USA, Reports of amphibole, biotite, and chalcopyrite in the R [email protected] 4 chondrites all support aqueous processes [1-3]. Recent ExxonMobil, Houston TX USA, [email protected] observations of hydrous minerals in a second R chondrite and other indications of aqueous alteration appear to corroborate Felsic magmas are linked by qtz-feldspar-melt equilibria the earlier results [4, 5]. Here we expand on these efforts and that limit their range of major element compositions. Crustal report an investigation of chalcopyrite in a sulfide assemblage processing is thus clearly a common factor in production of all in the R3 chondrite PRE 95411. such magmas, but this does little to resolve – and in fact Electron microprobe analysis indicates the assemblage is obscures – longstanding and recent controversies concerning primarily composed of pyrrhotite with minor pentlandite, sources, generation and emplacement processes, evolution, troilite, and chalcopyrite. Based on previously described and relationships between felsic plutonism and volcanism. methods [6], we used focused ion beam scanning electron Field, geochemical, and geochronological characteristics microscopy (FIB-SEM) to prepare an electron-transparent of similarly silicic rocks from a variety of environments we cross section of the assemblage for transmission electron have investigated* reveal remarkable diversity: • Scales: small (~10-3 km3 - increments in some plutons, microscope (TEM) analysis [7]. Selected-area electron- 3 3 diffraction confirms the presence of chalcopyrite and troilite. small eruptions) to giant (10 km supereruptions) Energy-dispersive X-ray spectrometry shows that the • Initial temperatures: ~700 C to near 1000 C chalcopyrite and troilite grains are bifurcated by an Fe-Ni-O- • Zircon inheritance: negligible to dominant rich vein. The vein center contains a linear domain of Fe-rich, • Entrained crystal fractions: negligible to near lock-up Ni-poor nanocrystalline material. In comparison, the material • Initial water contents: ~dry to wet (<3 to near 10 wt%) • Clear volcano-pluton connections, as well as plutons around the domain is amorphous and relatively Ni-rich and unlikely to have erupted counterparts and eruptions unlikely to Fe-poor. Chemical mapping also reveals that the grain have left appreciable plutonic residue boundary between troilite and the chalcopyrite is enriched in Cu. These microstructural features are reminiscent of those • Isotopically juvenile to ancient crust-dominated associated with a cubanite grain in the Orgueil CI chondrite • Involvement of mafic magma: obvious in some, [8], suggesting hydrothermal alteration. apparently limited in others, absent or occult in yet others These results indicate that the R chondrites experienced Characteristics generally correlate and suggest that (1) volatile-rich conditions. Improved understanding of the cool, wet, crystal-rich magmas, largely anatectic, are doomed distribution of volatiles provides important constraints on the to stall without eruption; (2) very large magma volumes (‘big formation and evolution of the solar system. tanks’) may reflect unusual thermal input, either initially

producing huge volumes or mobilizing stagnant mushes. [1] McCanta et al. (2008) Geochim. Cosmochim. Ac. 72, Intriguing departures from simple relationships warrant further 5757-5780. [2] Schulze et al. (1994) Meteoritics 29, 275-286. consideration – e.g. large variations in T and magma volumes [3] Jackson and Lauretta (2010) Meteorit. Planet. Sci. 45, in closely associated magma systems, isotopically primitive A94. [4] Gross et al. (2013) 44th LPSC, #2212. [5] Ruzicka et granitoids with abundant ancient zircon inheritance, very hot al. (2013) 44th LPSC, #1168. [6] Zega et al. (2007) Meteorit. felsic magmas with no obvious mafic input. Planet. Sci. 42, 1373. [7] Zega and Floss (2013) 44th LPSC, [*Deep-seated to very shallow plutons, convergent and #1287. [8] Berger et al. (2011) Geochim. Cosmochim. Ac. 75, extensional settings, southern Appalachians, SW USA, 3501-3513. Iceland; small to supereruption volcanic deposits, subduction, extension, hot spot settings, Cascades & SW USA, Iceland]

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Significant observed copper isotopic Construction of high-resolution trace abundance variations in biological element time-series in slow growth materials. speleothems by ELA-ICP-MS: KERRI MILLER1*, TYLER COPLEN2 Challenges, new approaches and AND MICHAEL WIESER1 validation strategies 1 Department of Physics and Astronomy, University of 1 NATHAN R. MILLER*AND JAY L.BANNER Calgary, 2500 University Drive NW, Calgary, AB, T2N 1N4, Canada, [email protected] (*presenting author) 1Department of Geological Sciences, The University of Texas 2US Geological Survey, 12201 Sunrise Valley Drive, Reston, at Austin, Austin, TX 78712-1722, USA VA, 20192, USA (*correspondence: [email protected])

Copper is an essential nutrient in both flora and fauna and Speleothems hold important potential to record terrestrial has proven to be critical in maintaining homeostatic balance paleoclimate variations over millennial scales, as increasingly by participating in many metabolic processes. Copper has two supported by monitoring studies of modern karst systems. naturally occuring stable isotopes, 63Cu and 65Cu. The ratio Trace element variations in drip waters and corresponding between the amounts of these two isotopes can be used to plate calcite samples demonstrate the potential for subannual indicate the source of copper to an organism, give insight to resolution in settings having well-expressed seasonality cycling processes as well as metabolic pathways. Natural (rainfall, temperature). The high sensitivity and rapid peak- variations in copper isotopic composition have a measured hopping capabilities of quadrupole ICP-MS, integrated with range of 9 ‰ in geological materials and 3 ‰ in water the superior coupling capacity and high spatial accuracy of samples [1, 2]. Recent evidence has shown that the modern excimer 193 nm laser ablation systems (ELA-ICP-MS assimilation and subsequent use of copper in an organism may line scans), offers an efficient means for constructing high- cause further fractionation. This has been demonstrated in resolution chemical time-series in growth-banded speleothem mice where it was shown that modified gene expression calcite. However, application of the technique becomes caused a shift in isotopic composition of copper in the brain increasingly challenged with decreasing speleothem growth [3]. In a recent study, participants with Parkinson’s disease rates, a factor that has relegated most high-resolution trace demonstrated differences in the metabolism of copper isotopes element studies to growth rates exceeding 100 µm/yr. Slow- [4]. growth speleothem records (< 50 µm/yr) present three In order to explore the copper isotope variability in living significant challenges to ELA-ICP-MS, namely: (1) growth systems, select samples were analyzed: exotic wood samples, banding is often not visible by standard petrographic wild animal hair, and hair and fingernails samples from local techniques, let alone via imaging of the laser ablation system; Calgary residents. Wood samples were analyzed as part of an (2) the crystallographic fabric comprising growth bands ongoing project to determine if isotopic systems can be used develops as successions of rhombohedral overgrowths, the to identify the geographic origins of the wood in an effort to scale and geometry of which can compromise the goal of prevent illegal trading. Hair samples from wildlife in Alberta obtaining unaliased stratigraphic sampling; and (3) achieving were analyzed to determine if copper isotopes can be used to counting statistics capable of resolving subannual chemical identify the dominant source of food. Hair and nail samples signals is more difficult due to the need for small apertures from local Calgary residents were also analyzed and compared (lower signal-to-noise) and because of more limited 65 to the local drinking water. A range in * Cu of over 20 ‰ “dwelling” time within growth band intervals associated with was observed. rapid chemical gradients. Parallel-offset line traverses, a well- established approach for evaluating reproducibility of [1] Larson, P.B., Maher, K., Ramos, F.C., Chang, Z., Gaspar chemical signals, often do not show high correspondence due M., Meinert, L.D. (2003) Chemical Geology 201; 337–350. to such localized sample aliasing – raising the question “We [2] Borrok, D.M., Nimick, D.A., Wanty, R.B., Ridley, W.I. know what we are targeting, but do we know what we are (2008). Geochim Cosmochim Acta 72; 329–344. [3] Büchl, hitting? We reiterate the importance of locating laser ablation A., Hawkesworth, C.J., Ragnarsdottir, K.V., Brown, D.R.; line scans from the informed perspective of oriented growth (2008) Geochem. Trans. 1-7. [4] Larner, F., Sampson, B., band fabric imagery, and developing analytical validation Rehkamper, M., Weiss, D.J., Dainty, J., O'Riordan, S. (2013) strategies that demonstrate the capacity to resolve slow-growth High precision isotope measurements show poorer control of chemical waveforms. copper metabolism in parkinsonism. Metallomics, 5; 125-132.

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Geochemical stratigraphy and Lithium isotopes in surficial waters: correlation within the Faroe Islands examples from rivers and peatlands Basalt Group: Temporal and Spatial ROMAIN MILLOT1*, PHILIPPE NÉGREL1, Evolution of Mantle Sources during ANNE-MARIE DESAULTY1AND AGNÈS BRENOT2 Continental Rupture 1 BRGM, Laboratory Division, Orléans, France (* correspondence : [email protected]) 1 1 1 MILLETT, J. M *., HOLE, M. J ., JOLLEY, D. W . 2 BRGM, Territorial Activities Division, Lyon, France 2 AND PASSEY, S. R. 1Department of Geology & Petroleum Geology, Meston In the present work, we report data for lithium and its Building, Kings College, University of Aberdeen, isotopes in two different hydrosystems in France: the Loire Aberdeen, AB24 3UE UK (*correspondence: River basin and the Sauvetat peatland system within the [email protected]) Massif Central (part of the Loire catchment). 2CASP, West Building, 181A Huntingdon Road, Cambridge Assessing the behaviour of lithium and the distribution of CB3 0DH, UK Li isotopes during weathering is of major importance for studying water/rock interactions at the surface of the Earth. 6 7 The geochemical signatures recorded during periods of This is because lithium ( Li ~ 7.5% and Li ~ 92.5%) is a Large Igneous Province (LIP) volcanism provide important fluid-mobile element and, due to the large relative mass evidence as to mantle sources and magmatic evolution through difference between its two stable isotopes, it is subject to time. Our understanding of the temporal development of these significant low temperature mass fractionation which provides provinces relies on both accurate stratigraphical sampling key information on the nature of weathering processes. The Loire River in central France is approximately 1010 constraints of flood basalt sequences along with the 2 integration of available age-dating methods. In this km long and drains an area of 117 800 km . Lithium contribution we present new major, trace and mineralogical concentrations in river waters of the Loire River main stream element data for the Faroe Islands Basalt Group (FIBG), NE and the main tributaries span a wide range from 3.4 to 46.5 "7 ‰. There is a Atlantic. The FIBG records a near continuous ~6.6km µg/L, whereas Li are between +5.0 and +13.3 clear contrast between the headwaters upstream and rivers composite eruptive succession of the Palaeogene aged North located downstream in the lowlands, with a siginificant Atlantic Igneous Province. All the data is stratigraphically decrease of the "7Li with the distance from the source. In constrained within a GIS database and has been compared to addition, one of the major tributaries in the Massif Central (the biostratigraphic and sedimentary inter-bed geochemical data Allier River) is clearly influenced by inputs from mineralized which allows high resolution inference into the timing of waters resulting of hydrothermal activities having lower "7Li eruption events during continental rupture. Distinct mantle values. source variations occur at a number of intervals through the Concerning the peatland system in the Sauvetat area, we stratigraphy including N-MORB-like and enriched ‘Icelandic’ explore the use of Li and its isotopes as a proxy of ground-to- sources. The integration of the new flow by flow data for the surface water exchanges in a peatland from a mire-lake lower Beinisvør@ and upper Enni Formations helps constrain complex in the French Massif Central, with the aim to the timing and the nature of these transitions. A distinct investigate the capability of Li isotopes as hydrogeological transition from Nb-depleted N-MORB-like to a Nb-enriched tracers. Variations in "7Li values can be used to distinguish ‘Icelandic’ source is recorded in the last few flows of the first between precipitation, groundwater and anthropogenic inputs major phase of FIBG volcanism. This transition immediately (significantly enriched in 7Li) in peat lands, providing a precedes the regional hiatus recorded by the Prestfjall unique perspective on the hydrologic dynamics of the system. Formation before renewed N-MORB-like source volcanism. These two examples reveal important information about The timing of this hiatus, directly after the short lived onset of lithium and its isotopes but, considered together, provide a ‘Icelandic’ source volcanism implies a potential link between more integrated understanding of the factors controling magma plumbing and tectonic reorganisation at the time. lithium isotopic distribution in surficial waters. The Enni Formation at the top of the FIBG encompasses at least two inter-digitating flow fields sourcing separate high- TiO2 enriched sources and a low-TiO2 MORB-like source. The distribution of distinct geochemical lava groups on the Faroe Islands are demonstrated to overlap both in space and time. The present results have important implications to correlation attempts involving lava geochemistry on both the local and regional scale.

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Global silicate weathering: not Experimentally verifying the low always in control of climate, and not oxygen demands of primitive animals required to balance global degassing D.B. MILLS1*, L.M. WARD2, C. JONES1, M. FORTH1, B. 1 1 1 1 1 SWEETEN , A.H. TREUSCH AND D.E. CANFIELD BENJAMIN MILLS , ANDREW J. WATSON AND TIMOTHY M. LENTON2 1Nordic Center for Earth Evolution, Institute of Biology, Univ. 1 of Southern Denmark, 5230 Odense M, DK School of Environmental Sciences, University of East Anglia, (*correspondence: [email protected]) Norwich, NR4 7TJ, U.K. 2 2 Department of Geological and Planetary Sciences, Caltech, College of Life and Environmental Sciences, University of Pasadena, CA 91125, USA ([email protected]) Exeter, Exeter EX4 4PS, UK.

A rise of oxygen in the atmosphere and oceans is one of Silicate weathering and carbonate deposition allows for the most popular explanations for the relatively late and abrupt net transfer of CO from the atmosphere to the crust, and 2 appearance of animal life on Earth [1, 2]. Multiple lines of dependence of the rate on local temperature and CO 2 geochemical evidence support an oxygenation and ventilation concentration stabilizes long term climate [1]. of the Ediacaran ocean (635–542 Ma), corresponding with the However, the operation of this process is considerably diversification of complex life, and supporting oxygen’s role more complex than the simple kinetic relationships employed as the driving environmental factor behind the rise of in current models. Limitation at the global scale via transport metazoans [3, 4, 5, 6]. However, the critical concentration of of cations is possible either under very high temperature/CO , 2 oxygen required for primitive animals remains ambiguous. such as following a snowball Earth event [2], or under very Therefore, in order to evaluate the oxygen-trigger hypothesis low erosion rates, such as during the Mezozoic. In both of for animal origins, the minimum oxygen concentration these cases, climate stability may have been unattainable for supportive of animal life, in general, needs to be long periods. experimentally determined. In the Precambrian, smaller continental area and lack of Our experiments show that modern demosponges, serving biotic soils likely provided harsh limitation of the silicate as analogs for early animals, can survive under low-oxygen weathering flux, requiring the operation of an additional conditions of 0.5-4.0% present atmospheric levels. Given that stabilizing mechanism to counter the higher degassing rates the last common ancestor of metazoans likely exhibited a expected. Seafloor carbonatization appears to be a likely physiology and morphology very similar to those of modern candidate [3], and additional climate regulation via this sponges [7, 8], its oxygen demands may have been met well process decouples the the global silicate flux from CO 2 before the marine redox shifts of the Ediacaran Period. degassing rates. Therefore, while animals certainly require oxygen, their The action of two independent stabilizing mechanisms origination did not necessarily require a contemporaneous rise allows for the global silicate weathering rate to increase in the oxygen content of the atmosphere and oceans. Our permanently in response to biological or tectonic results, overall, suggest that the relatively late origination of enhancements. We suggest that increasing rates of organic animal life on Earth was not due to restrictively low levels of carbon burial over time (leading to planetary oxygenation), as environmental oxygen that were finally lifted during the well as changes in CO dynamics, may be linked to a 2 Neoproterozoic Era. progressive increase in terrestrial chemical weathering rates.

[1] Nursall (1959) Nature 183, 1170-1172. [2] Knoll (1992) [1] Walker, J.C.G., P.B. Hays, and J.F. Kasting (1981), J. Science 256, 622-627. [3] Fike et al. (2006) Nature 444, 744- Geophys. Res. 86, 9776-9782. [2] Mills, B., et al. (2011), 747. [4] Canfield et al. (2007) Science 315, 92-95. [5] Scott et Nature Geosci. 4, 861-864. [3] Caldeira, K. (1995), Am. J. Sci. al. (2008) Nature 452, 456-459. [6] Sahoo et al. (2012) Nature 295, 1077-1114. 459, 546-549. [7] Sperling et al. (2009) Mol. Biol. Evol. 26,

2261-2274. [8] Erwin et al. (2011) Science 334, 1091-1097.

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Fluid flow and redox metal cycling in Biomass residues from different Cayman Trough hydrothermal classes of soil microorganisms are a sediments significant source of soil organic RACHEL A. MILLS1*, WILLIAM B. HOMOKY1 matter AND THE DEEPESTVENTS SHIPBOARD SCIENTIFIC TEAM A. MILTNER*, J. ACHTENHAGEN, C. HOFFMANN- 1Ocean and Earth Science, University of Southampton, JÄNICHE, M. SCHWEIGERT, M. BRAECKEVELT, National Oceanography Centre Southampton, SO14 3ZH, F.-A. HERBST, J. SEIFERT, T. FESTER AND M. KÄSTNER UK (*correspondence: [email protected], UFZ - Helmholtz Centre for Environmental Research, Leipzig, [email protected]) Germany (*correspondence: [email protected])

Metalliferous sediments accumulate adjacent to active Introduction hydrothermal vent sites via mass wasting of mound debris and Cell envelope fragments originating from soil microorga- fall-out of particles from hydrothermal plumes. Continued nisms were demonstrated to contribute significantly to the redox reactions at the limit of oxygen penetration lead to ‘zone formation of soil organic matter (SOM) [1]. This hypothesis refining’ of the sediment pile and metal enrichment around the was supported by chemical and microscopic analyses [1] as active redox front [1]. Diffusive processes and active well as by NMR spectroscopy [2]. Different classes of soil circulation of dilute hydrothermal fluids through the sediments microorganisms have different chemical compositions of their may lead to significant fluxes of some elements into and out of cell envelopes and thus may contribute to SOM formation to a the seafloor, though this is poorly constrained and not different extent. We compared the fate of Escherichia coli included in evaluations of ocean budgets for these elements. (Gram-negative bacterium), Bacillus subtilis (Gram-positive We present dissolved micro-nutrient trace metal pore-fluid bacterium) and Laccaria bicolor (ectomycorrhizal fungus) in data for representative sediments from the Beebe Vent Field soil to estimate their relative contributions to SOM formation. [2]. The Beebe Vent Field fluids are extremely deep (5000 m), Material and Methods high temperature (>400°C) and metal-rich. Fragile sulfide 13C-labeled organisms produced by culturing them on chimneys topple readily to form metalliferous sediments labeled glucose were mixed with soil and incubated for up to which are oxygen depleted within 3-7 mm of the seawater 224 days. Isotopic data of soil and CO released by respiration interface. The deep sedimentary setting precludes significant 2 were used to set up mass balances. Additional information carbonate accumulation at the seafloor and pelagic about the fate of the biomass C was derived from quantitative sedimentation is minimal leaving weathered sulfide exposed to and isotopic analyses of fatty acids and amino acids. Selected seawater. Primary chimney mineral phases which dominate samples were also analysed by scanning electron microscopy. the sediment, break down during seafloor weathering and Results and Discussion there is a flux of reduced metals to the overlying water column For all classes of microorganisms, substantial amounts of associated with this sedimentary reprocessing. Therefore, the label remained in the soil. Fungal biomass was mineralised secondary processing of hydrothermal material during active slower than bacterial biomass, with Gram-negative bacteria weathering of seafloor deposits can lead to enhanced fluxes of being mineralised slightly slower than Gram-positive ones. trace metals to the ocean which are then transported out of the The amount and isotopic composition of the biomolecules benthic boundary layer via plume entrainment and dispersal showed that substantial amounts of the bacterial biomass- over signficant distances. derived C were incorporated into non-living SOM. Proteins

seemed to be particularly prone to stabilision in soil: Highly [1] Severmann, S., et al., (2006) Geochim. Cosmochim. Acta, labeled B. subtilis proteins were detected until the end of the 70, 1677-1694. [2] Connelly, D.P. et al., (2012) Nature experiment. Biomass residues of all types of soil organisms Comms., 3, doi:10.1038/ncomms1636. thus contribute to SOM formation, and proteins seem to be

involved significantly in this process.

[1] Miltner et al. (2012) Biogeochemistry 111, 41-55. [2]

Simpson et al. (2007) Environ Sci Technol 41, 8070-8076.

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Role of zero-valent sulfur in marine Record of bacterial sulfate reduction methane oxidation during 50~210 kyr ago in the J. MILUCKA1* submarine hypersaline Meedee Lake, 1Max Planck Institute for Marine Microbiology, 28359 off Crete Island, Eastern Bremen, Germany (*correspondence: jmilucka@mpi- Mediterranean Sea. bremen.de) 1 1,2 3 H. MINAMI *, K. E. YAMAGUCHI , H. NARAOKA , 4 4 4 Sulfate is the main oxidant for seafloor methane, and the M. MURAYAMA , M. IKEHARA AND H. TOKUYAMA transition zones of methane and sulfate thus play a key role in 1Dept. Chem., Toho Univ. ([email protected]); the biogeochemical carbon cycling in methane-bearing marine 2 3 1 NASA Astrobiology Inst. (NAI); Dept. Earth & Planet. sediments. Our recent results suggest that the impact of Sci, Kyushu Univ. 4Ctr for Adv. Marine Core Res. anaerobic oxidation of methane (AOM) on the marine sulfur (CMCR), Kochi Univ. cycle might be just as important. Using a suite of microbiological and experimental biogeochemical approaches, such as cultivation, stable- and Meedee Lake (2920m deep) is a submarine, hypersaline radio-isotope labelling experiments and single-cell-based lake with its salinity >10 times higher than that of normal techniques, we have investigated microbial sulfur cycling seawater, due to elution of submarine evaporites formed associated with marine methane oxidation in microbial during Messinian Salinity Crisis 5.33 to 6 Ma ago. The enrichment cultures. We could show that during AOM sulfate density-stratified lake water has been kept anoxic due to is only partially reduced to zero-valent sulfur, which is stored consumption of dissolved O2 by decomposition of organic intracellularly as a mixture of cyclo-octasulfur and soluble matter sinking from the overlying water. polysulfides. The release of the produced sulfur from the cells In order to understand changing redox state and microbial provides a local source of zero-valent sulfur in sulphidic activity in the submarine extreme lake environment, sediment marine sediments. Furthermore, we could show that the core was collected from the margin of the lake. The core produced zero-valent sulfur in a form of disulfide can be shows alternation of pyrite-bearing light- and Fe-oxide- further disproportionated to sulfate and sulfide by bacteria bearing dark-colored layers reflecting fluctuating redox during associated with the methane-oxidizing archaea. deposition [1].. The sulfate-rich lake hosted sulfate-reducing Our observations show an unexpectedly diverse metabolic bacteria. potential of the AOM microorganisms and expand the To obtain insight into biogeochemical S cycling in the physiological diversity of known microbial sulfur lake, we measured abundance of S-bearing species by metabolisms. Moreover, our results suggest a solution to the sequential extraction method. Five phases were separately long-standing mystery of a missing intermediate in AOM by quantified: (1) AVS (acid volatile sulfide), (2) pyrite, (3) suggesting a key role of zero-valent sulfur in this process. sulfate, (4) organic-S, and (5) elemental S, by using a method These new insights have important implications for the of [2], a combination of [3, 4, 5]. Isotopic compositions of biogeochemical carbon and sulfur cycling in marine these phases were measured by EA-IRMS at Kyushu sediments. University. Sulfate was found to be the most abundant species, [1] Milucka et al. (2012), Nature 491, 541–546. accounting for 90% in both light and dark layers. The isotopic 34 compositions (" SSO4 vs. VCDT) vary greatly from +16‰ to +32‰. Such large fluctuations are most likely due to variable (a) degrees of sulfate utilization by sulfate-reducing bacteria (SRB) and/or (b) sulfate concentration. When activity of SRB was not enhanced, sulfate utilization by SRB was not complete, and/or sulfate concentration is reasonably high, then 34 the " SSO4 values would not have much changed from their original seawater value (+21‰). Contrary, when activity of SRB was enhanced and sulfate utilization was near complete, 34 then the " SSO4 values would have progressively increased from ~21‰ (i.e., Rayleigh fractionation). Bacteriogenic pyrite would have gone by oxidation due to lowering of lake water level and invasion of oxic seawater, while sulfate minerals would have been preserved. This study demonstrates utility of sulfur isotope compositions of sulfate minerals in sediments to uncover past activity of SRB, even if bacteriogenic pyrite was not well preserved. [1] Izumitani (2010) M.Sc,. Kochi Univ. [2] Kobayashi (2011) Senior Thesis,. Toho Univ. [3] Canfield et al. (1986) Chem, Geol, 54, 189, [4] Buckland & Boman. (2005). Agricul, Food Sci, 14, 70. www.minersoc.org DOI:10.1180/minmag.2013.077.5.13

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Geochemical map of 87Sr/86Sr ratios Tectonic and geothermal significance using stream sediments is useful for of thermal springs of Sicily Isl. detection of food-producing areas (southern Italy) and human migration? ANGELO MINISSALE1, SALVATORE GIAMMANCO2, 3 4 1 2 3 DOMENICO MONTANARI , SALVATORE MONTELEONE M. MINAMI *, Y. JOMORI AND A. OHTA AND MARCO DOVERI3 1Center for Chronological Research, Nagoya University, 1 Institute of Geosciences & Earth Resources, Italian Research Nagoya 464-8602, Japan Council (CNR), Via La Pira 4, 50121 Florence (Italy), e- (*correspondence: [email protected]) mail: [email protected] 2Graduate School of Environmental Studies, 2 Italian National Institute for Geophysics and Volcanology, Nagoya University, Nagoya 464-8601, Japan 3 Piazza Roma 1, 95125 Catania (Italy), e-mail: Geological Survey of Japan, AIST, Ibaraki 305-8567, Japan [email protected] 3 87 86 Institute of Geosciences and Earth Resources, National Geochemical map of Sr/ Sr ratios is needed for multiple Research Council of Italy (CNR), Via Moruzzi 1, 56124 purposes of detection of food-producing areas, tracing of Pisa (Italy), e-mail: [email protected]; patterns of ancient human migration, and culture change in [email protected] earlier times, as well as environmental applications. We have 4 87 86 Deparment of Geology, University of Palermo, Via Archirafi started a nationwide geochemical mapping of Sr/ Sr ratios 20, 90100 Palermo (Italy), [email protected] using catchment outlet stream sediments (<180 µm) in Japan. 87 86 The Sr/ Sr spatial distribution in Shikoku Island and the Kii 87 86 Rough morphology, thick (>5km ) buried, trusted Peninsula in Japan largely reflected underlying Sr/ Sr sequences of Mesozoic platform limestone and active faulting, bedrock distribution [1]. The result shows that 87Sr/86Sr map in a very dynamic context at the boundary between the using stream sediments is useful for investigating the African and Eurasia plates, make Sicily a perfect place for the geochemical and geological features of bedrocks. Meanswhile, emergence of deep circulating waters as thermal springs. Most 87Sr/86Sr values of stream sediments might not be indicative of 87 86 of them are located in its western sector (west Sicily biological Sr/ Sr values of vegetation and fauna. In this 87 86 springs=WSS); a few are related to the presence of the Etna study, therefore, we investigated relationship between Sr/ Sr and Iblei Mts Quaternary volcanics in eastern Sicily (ESS). ratios in biological samples and in stream sediments collected Most of WSS are located along the seashore, or anyhow near around the sampling points. The samples used are rice-plants, the coast; others emerge inland at relatively higher elevations, animal bones, paddy water and soil, and stream water and but always at the edges of outcrops of the limestone sediments collected from an area distributing of granite sequences. The chemistry of springs suggests that the main bedrocks in Toyota, Japan. For soil and stream sediments, circuit of WSS is inside the Mesozoic limestone, and the bulk Sr and ammonium acetate extractable Sr (exchangeable relative composition is: i) Ca-SO (HCO ) for those located Sr) fractions were both analyzed. 87Sr/86Sr ratios were 4 3 inland, ii) markedly Na-Cl for those emerging along the sea, measured with thermal ionization mass spectrometer (TIMS; respectively. The "18O and "D composition of most of them VG Sector 54) at Nagoya University. suggests meteoric origin, with average recharge elevations at The bulk Sr fractions in soil and stream sediments showed 87 86 700 m. Among WSS, the springs from Sciacca are the most larger Sr/ Sr ratios than the exchangeable Sr fractions and 87 86 promising for geothermal prospecting, since they seem to be a biological samples. The Sr/ Sr ratios of exchangeable Sr mixing between meteoric water and high temperature oxygen- fractions were in agreement with the 87Sr/86Sr ratios in shifted Mediterranean seawater. Moreover, they also have a biological samples within analytical errors. The results 87 86 CO dominated associated gas phase suggesting the presence suggest that the Sr/ Sr ratio of biological samples is 2 of a degassing hydrothermal system in the deep reservoir. constrained by the 87Sr/86Sr ratio of catchment outlet stream Excluding the Sciacca springs in southern Sicily and some sediments, that is, underlying bedrocks upstream of the 87 86 mud volcanoes at the foot of the Etna Mt., strongly CO - sampling points, and that the Sr/ Sr map using stream 2 dominated and high in 3He/4He ratio, suggesting the presence sediments can be an important database for identifying food- of a mantle gas component, the gas phase associated to the producing areas and ancient human migration in archaeology. carbonate WSS is N -dominated, reflecting the atmospheric 2 recharge areas more than any deep hydrothermal systems. [1] Jomori et al. (2013) Geochem. J. 47, 321-335

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Interaction of ions at the surface of Textural control over electron soil components transfer and reaction with Li+ of BABAK MINOFAR1,2 biomineralized Fe-oxides 1Institute of Nanobiology and Structural Biology of J. MIOT1,2,3,4*, N. RECHAM1,4, D. LARCHER1,4, F. Academy of Sciences of the Czech Republic GUYOT2,5 AND J.M. TARASCON1,4 2 Faculty of Science, University of South Bohemia 1LRCS/CNRS, Univ. Picardie J.Verne, 80039 Amiens, France Branisovska 31Ceske Budejovice, [email protected] 2IMPMC/CNRS, UPMC, 75252 Paris, France 3LMCM/MNHN, 75005 Paris, France (*correspondence : Complex structure of soil makes it interesting for both [email protected]) experimental and theoretical studies. One of most important 4RS2E, CNRS 3459, France components of soil, which has strong effect and play 5Univ. Denis Diderot, Sorbonne Paris Cité, IPGP/CNRS, important role in the process of adsorption of different 9Paris, France elements to the plants and complex formation process of many metal ions in the environment is natural organic matter The capacity of biominerals, in particular Fe-bearing (NOM). minerals, to conduct electrons is increasingly studied with the Solvation structure and dynamics of building blocks of aim of understanding the mechanisms by which bacteria can NOMs in aqueous solution studied and surface propensity to retrieve electrons from minerals [1,2] and designing electricity the air/aqueous interface observed and decrease of surface providing [3] or energy-storing devices [4]. Here, we present a tension measured1 which is supported by surface sensitive 2 two-step biomineralization pathway using the anaerobic Fe- (VSFG) spectroscopy . oxidizing bacteria Acidovorax sp. strain BoFeN1 leading to Also we have used the Temple-Northeastern- Birmingham & 3 the formation of -Fe2O3 that was used in Li-ion batteries. (TNB) model of humic acid which was proposed by Sein et Biomineralization of *-FeOOH within the 40-nm thick cell al. for complex formation with different ions such as wall of the bacteria [5], followed by a short heat treatment carbonate and iodate ions. We have observed that strong provided an alveolar material consisting of hollow rod-type interactions between carboxylate groups of model humic acid shells made of an assemblage of nanometric and oriented &- take place both in protonated and not protonated hucmic acids. Fe2O3 particles (Fig. 1A, B). This material exhibited enhanced Moreover, hydrogen bonding and complex formation are two electrochemical properties compared to abiotic controls, which main factors which influencing the aggregation of model relies on its specific texture at the µm- and nm-scales allowing humic acid in aqueous solutions. Moreover, we studied the increased electronic transfer and sustained reaction with Li+ surface propensity and interaction of TNB with different ions. These results have implications for energy storage and organic contaminants such pesticides by classical molecular for understanding the mechanisms of electron/ion transfer dynamics (MD) simulations and revealed that the hydrophbic through biominerals. interaction between organic contaminants and hydrophobic parts of humic acid is one of the most important factor for interactions and surface propensity to the air/aqueous solution interface.

[1] Minofar, B.; Jungwirth, P.; Das, M. R.; Kunz, W.; Mahiuddin, S.: Jungwirth, P.:. Journal of Physical Chemistry C, 111 (2007) 8242. [2] Yi Rao, Mahamud Subir, Eric A. Figure 1:Texture of &-Fe2O3 bacteriomorphs biomineralized McArthur, Nicholas J. Turro, Kenneth B. Eisenthal,Chemical by BoFeN1 observed by SEM (A) and TEM in thin section Physics Letters 477 (2009) 241–244 [3] Sein LN, Varnum JM, (B). Electrochemical capacity-power (vs. Li0) for textured and Jansen SA. Conformational modeling of new building block of untextured materials (C). humic acid: approaches to the lowest energy conformer. Environ Sci Technol 1999;33:546–52. [1] Kato et al. (2012) PNAS 109, 10042-46. [2] Pfeffer et al. (2012) Nature 491, 218-221. [3] Lovley (2011) Env. Microb. Reports 3, 27-35. [4] Miot et al. (submitted) En. & Envir. Science. [5] Miot et al. (2011) Geobiology 9, 459-470.

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The effect of light elements on Reconstruction of Holocene climate metal/silicate partitioning variability using stalagmites from the FRANCESCA MIROLO1, EKATERINA S. KISEEVA1, JON Herbstlabyrinth, central Germany 1 1 WADE *AND BERNARD J. WOOD 1 1 2 SIMON MISCHEL *, DENIS SCHOLZ , CHRISTOPH SPÖTL 1University of Oxford (*correspondence: AND KLAUS PETER JOCHUM3 [email protected], [email protected], 1 Institute for Geosciences, University of Mainz, J.-J.- [email protected], [email protected]) Becherweg 21, 55099 Mainz, (*correspondence:

[email protected]) The accretion of the Earth was marked by the high- 2 Quaternary Research Group, Innrain 52a, A-6020 Innsbruck, pressure segregation of most of its core, accompanied by [email protected] dissolution of about 10% of one or more “light” elements into 3 Max Planck Institute for Chemistry, Hahn-Meitner-Weg 1, the metallic phase. Various light elements have been proposed 55128 Mainz, [email protected] including S, Si, C and O, with each having an effect on the partitioning behaviour of the trace elements. Metallurgical The Herbstlaybrinth cave system lies at an elevation of data indicate that dissolution of even small amounts of light 435 m asl in a small limestone area in Central Germany. The elements in liquid Fe can have profound effects on the cave has a length of about 7 km and is well decorated with activities of some trace components. For instance, significant speleothems. partitioning of Si into the core of the growing Earth should The chronology of two Holocene stalagmites is have affected the observed Mo1 content of the mantle. established by precise 230Th/U dating using a NU Plasma MC- Here, we use the epsilion model of non-ideal interactions ICPMS at the Max Planck Institute for Chemistry, Mainz. The in Fe liquids (=)2. We present interaction parameters (=), age model is constructed using StalAge [1]. Trace element derived from 1.5GPa, 1650oC metal-silicate equilibration concentrations and stable isotope ratios have been analysed at experiments, for W, Ni, Co and Mo in liquid Fe alloyed with a temporal resolution of ~50 years. C, S and Si. In order to support the interpretation of the proxies in At oxygen fugacities above IW-3, we can safely assume a terms of past climate variability, we set up an extensive cave 6+ valence for W and 4+ for Mo3. In the system Fe-S we can monitoring program to understand the processes occurring in then derive Ni, Co, W and Mo interaction parameters. For S the cave system. example, our W interaction parameter (e W) is 8.4(±1), as 4 In both stalagmites, P, Ba and U are positively correlated opposed to the literature value of 6.1 . This means that at 13 with each other and negatively correlated with " C. This fixed oxygen fugacity, W becomes less siderophile with suggests that these proxies reflect the productivity of the increasing metallic S content. However, for Mo in the same vegetation above the cave. In contrast, Mg, which is system we derive =S to be 0.5 (±1.7); the partitioning Mo interpreted as a proxy for effective precipitation above the behaviour of Mo is therefore significantly less sensitive to the cave [2], is negatively correlated with P, Ba and U. This S content of the metallic phase. In contrast to W, the metal- indicates that the vegetation is more productive during more silicate partitioning of Ni and Co are relatively insensitive to humid phases. both S and C contents of the metal. Mars is proposed to posses 18 The " O values of precipitation in the research area show a sulphur rich core, which would imply the primitive martian a strong positive correlation to the winter North Atlantic mantle possesses a higher W/Mo ratio than Earth’s if the Oscillation (NAO) index [3]. Due to strong evapotranspiration core’s S content is taken into account. during summer months, summer precipitation does not

contribute to the recharge of the cave system. Thus, the "18O [1] Ono-Nakazato et al. (2007) ISIJ Int 47, 365-369 (2007). values of the dripwater and speleothem calcite reflect winter [2] Wagner. Thermodynamics of Alloys (1962). [3] Wade et al. 18 precipitation. Therefore, the " O values recorded in the (2012) Chem Geol 335, 189-193. [4] Steelmaking, J. S. f. t. P. speleothems from Herbstlabyrinth may give us the opportunity o. S. a. t. t. C. o. Steelmaking Data Sourcebook (1988). to reconstruct the NAO, with more positive values reflecting NAO+-conditions and vice versa.

[1] Scholz & Hoffmann (2011), Quaternary Geochronology 6, 369-382 [2] Fairchild & Treble (2009), Quaternary Science Reviews 28, 449-468 [3] Baldini, McDermott, Foley & Baldini (2008), Geophysical Research Letters 35, L04709

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Multiple sulfur isotope geochemistry Determination of U, Cs and Sr of Dharwar Supergroup, Southern isotopes and their distribution India: Late Archean record of coefficients in soil affected by changing atmosphere Fukushima daiichi nuclear power KAORU MISHIMA1*, RIE YAMAZAKI2, M. SATISH- plant accident 3 4 1, 5 KUMAR , TOMOKAZU HOKADA , AND YUICHIRO UENO 1,2 1 1 3 S. MISHRA , A. TAKAMASA , H. ARAE , W. MIETELSKI , 1Department of Earth & Planetary Sciences, Tokyo Institute of Y. WATANABE1, S. YOSHIDA1 Technology, Tokyo, Japan. [email protected] AND S.K.SAHOO1 ! 2 Institute of Geosciences, Shizuoka University, Shizuoka, 1 National Institute of Radiological Sciences, 4-9-1 Anagawa, Japan Inage-ku, Chiba 263-8555, Japan 3Department of Geology, Faculty of Science, Niigata 2Bhabha Atomic Research Centre, Mumbai – 400 085, India University, Niigata, Japan 3 4 The Henryk Niewodniczanski Institute of Nuclear Physics, National Institute of Polar Research, Tachikawa, Tokyo, Polish Academy of Sciences, Krakow, Radzikowskiego 152, Japan Poland ([email protected]) 5 Earth-Life Science Institute, Tokyo Institute of Technology, Meguro, Tokyo, 152-8551, Japan Isotopic determination of U (238U, 235U and 234U), Cs (137Cs

and 134Cs) and Sr (90Sr) were carried out in soil samples Sulfur isotope mass-independent fractionations (S-MIF) in around Fukushima daiichi nuclear power plant (FDNPP) to sedimentary sulfides and sulfate provide strong constraints on find out source and extent of contamination due to fallout the evolution of the early Earth’s atmosphere. In the late activity resulted as a consequense of the nuclear accident Archean, the S-MIF signature changed dramatically: minimum 137 caused due to a severe earthquake followed by tsunami. Cs %33S at around 2.9 Ga, subsequent large %33S variation activity was found to vary from 930±20 Bq/Kg to 62,200±900 culminated at 2.5 Ga and its sudden drop at the end of 33 36 Bq/Kg which is much higher than the global fallout in Japan. Archean. Moreover, % S-% S relation shows characteristic 134 137 Cs/ Cs activity ratio was found to vary from 0.84-0.87, slope of around -0.9 in the Archean period [1]. The change of 90 33 36 comparable with other reported values. Sr activity found to % S/% S slope may reflect perturbation of atmospheric 33 vary from 8.4 ± 1.5 Bq/Kg to 21.2 ± 2.6 Bq/Kg. Distribution chemistry, though the mechanisms of the large % S 33 36 coefficients (K ) were measured using laboratory batch variations and the % S-% S relation is still a matter of debate. d method to establish transfer of radionuclides. K values for U, We report multiple sulfur isotope data for sedimentary pyrite d Cs and Sr were found to be logU-K 73 > logCs-K 72 > logSr- derived from the Dharwar Supergroup in the Western Dharwar d d K 71-2 (Fig.1). Chemical characterization with respect to craton, southern India. The lower unit (post-3.0 Ga) of the d different soil parameters like particle size distribution, pH, Dharwar Supergroup consists of basal conglomerate, organic content, cation exchange capacity, CaCO , elemental stromatolitic carbonate, silici-clastics with diamictite, 3 and oxide composition of soil has been carried out to chert/BIF and pillow basalt in assending order. The upper unit understand the geochemical behavior of these radionuclides. A unconformably overlies the pillow lava, and consists of good correlation was observed for U-K with Fe and organic conglomerate/sandstone with ~ 2.6 Ga detrital zircons, d content of soil. Similarly Cs-K and Sr-K show good komatiite lava, BIF and silici-clastic sequence with mafic d d correlation with cation exchange capacity and fine particle volcanics. Sulfur isotope analysis of extracted sulfide of these concentration respectively. sedimentary rocks display clear MIF record of high %33S Site specific K values can be used for contaminant transport values up to +3.9‰. The %33S/%36S slope changes from -1.52 d model to predict the radionuclide migration and also the to -0.96 in accending stratigraphic order. The lowest slope relationship between soil parameters and sorption behavior of value of -1.52 from Bababudan Group is stratigraphically just radionuclides will be helpful for soil remediation and dose below the Talya diamictite, implying the link between shift of assessment. atmospheric chemistry and climatic system. On the other

hand, carbonate rocks from Bababudan Group show very large 33 variation "34S values up to +19.4‰ with negative % S,

whereas other sedimentary rocks show near 0‰ "34S value.

The observed lithologic control possibly reflect geographical

heterogeniety of S-MIF and sulfate reducing activity in the

late Archean ocean.

[1] Farquhar (2000) Science, 289, 756-758.

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Glass forming ability of sub-alkaline Lithium Isotope History of Cenozoic silicate melts Seawater: Changes in Silicate VALERIA MISITI1, FRANCESCO VETERE2-3, GIANLUCA Weathering and Reverse Weathering 1-2 3 3 IEZZI , HARALD BEHRENS , FRANCOIS HOLTZ , GUIDO 1, 1 1 3 SAMBUDDHA MISRA * VENTURA , ANDREA CAVALLO , MARCEL DIETRICH 2 AND PHILIP N. FROELICH AND SILVIO MOLLO1. 1Department of Earth Sciences, University of Cambridge, CB2 1Istituto Nazionale di Geofisica e Vulcanologia, Via di Vigna 3EQ, UK, *correspondence: [email protected] Murata 605 00143 Rome, Italy 2 Froelich Education Services, 3402 Cameron Chase Dr., 2Dipartimento di Ingegneria & Geologia, Università G. Tallahassee, FL, 32309. USA. d’Annunzio, Via dei vestini 30, 66100 Chieti, Italy

3Institute for Mineralogy, Leibniz University of Hannover, Weathering of uplifted continental rocks plays a central role Callinstr. 3, Hannover, D-30167, Germany in controlling both climate and seawater chemistry by

consuming CO and releasing cations to the ocean. Lithium The glass forming ability (GFA) of six sub-alkaline 2 isotopes provide a unique record of these changes because Li, silicate melts is quantified via the experimental determination of their critical cooling rate Rc (the minimum rate at which a unlike other tracers of ocean chemistry change, is hosted liquid can be frozen to a solid with crystals < 2 vol.%). entirely in silicates. The isotopic composition of dissolved Li The 7 in seawater (" LiSW ~31.0‰) reflects a balance between river selected compositions vary from basalt (B) to rhyolite (R) 7 dissolved Li inputs (" LiRiv ~23‰), hydrothermal Li input (B100, B80R20, B60R40, B40R60, B20R80 and R100). 7 For each composition, six cooling rates (150, 30, 3, 1, (" LiHT ~8.4‰) and large fractionation (%SW–SED ~15‰) during 0.116 and 0.0167 °C/min) are investigated between 1300 °C seawater-Li removal into marine authigenic clays via reverse 7 7 (liquidus region) and 800 °C (quenching temperature). weathering (" LiSED ~16‰). A geologic record of " LiSW The crystallized phases and their contents are determined change is sensitive to the very large Li-isotope fractionation by image analysis on backscattered SEM pictures and include factors and to changes in silicate sources and sinks on time

glass, pyroxene, spinel, plagioclase and, occasionally, olivine scales of the Li residence time in seawater (+Li ~1.5 Ma). From 7 and melilite. the Paleocene (60 Ma) to the Present " LiSW rose 9‰, The estimated Rc values are 0.02, 0.12, 10, 50 130 and requiring large changes in continental forward weathering and 160 °C/min for R100, B20R80, B40R60, B60R40 B80R20, and B100 seafloor reverse weathering consistent with pulsed tectonic respectively. uplift, more rapid continental denudation, increasingly Rc increases by 4 order of magnitude from R to B and 100 100 incongruent continental weathering and more rapid CO2 can be related to the NBO/T (non bridging oxygen per drawdown. tetrahedron) parameter as shown by the following figure:

´ Our results on the crystallization kinetics of the most abundant and common silicate melts in nature can be applied to retrieve solidification conditions of volcanic rocks as well as to design glass-ceramics with inexpensive starting materials.

Figure: Li-, Sr-, and Os-isotope records over the past 68 Ma [1]. [1] Misra and Froelich, Science, 2012

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Analysis of anion adsorption and its Coupled µ-XAFS-FISH technique for effects on alumina nanoparticles direct observation of the microbe- stability metal-mineral interaction TIZIANA MISSANA, ANA BENEDICTO, NATALIA S. MITSUNOBU1* AND F. SHIRAISHI2 MAYORDOMO AND URSULA ALONSO 1 Institute for Environmental Sciences, University of Shizuoka, 1CIEMAT, Avenida Complutense, 40. C.P 28040 Madrid Shizuoka 422-8526, Japan (*corrspondence: mitunobu@u- (Spain) shizuoka-ken.ac.jp) 2Department of Earth and Planetary Systems Science, Nanoparticles may enhance contaminant transport in Hiroshima University, Hiroshima 739-8526, Japan groundwater provided the contaminant is irreversibly adsorbed ([email protected]) onto their surface and they are stable and mobile. Colloid- driven contaminant transport is an issue of concern associated Many geochemical important redox reactions are largely to hazardous waste repositories, because many uncertainties associated with microbial activity and are energy sources for still exists. microorganisms. For instance, recent studies suggest a The chemistry of the groundwater mainly determines the significant relationship between Fe(II)-oxidizing bacteria and ancient Banded Iron Formation, one of the large geochemical size and charge of the particles and has a large impact on events [1]. However, the detailed mechanisms of environmental particles stability and mobility but the colloidal properties can biogenic reactions are largely unknown, because there are few also be affected by the contaminant adsorption itself. This is a adequate analytical techniques to observe it in high spatial point potentially very relevant on the overall colloid-driven resolution. transport, but scarcely considered. Here, we directly coupled synchrotron microprobe (µ- The stability of colloidal systems is generally evaluated by XAFS) with in situ phylogenetic analysis, fluorescence in situ studying the aggregation kinetic after the change of a specific hybridization (FISH), to determine simultaniously the chemical chemical condition, generally pH or ionic strength of the species and distributions of microbial community at micrometer aqueous solution. Often, the effects of divalent cations, scale (Fig. 1), which leads to better understanding the microbial µ especially Ca2+, are evaluated. On the other hand, the effect of reaction in the environment. We applied the coupled -XAFS- FISH to one of the most ubiquitous environmental anion adsorption on colloid stability is mostly neglected. biomineralizations, Fe mineral deposition by Fe(II)-oxidizing In this work, the effects of Se(IV) (selenite) adsorption on bacteria (FeOB). alumina (Al2O3) nanoparticles were analysed. Selenite In situ visualization of microbes by FISH revealed that adsorption was studied in a wide range of pH (2-12) and ionic -4 -1 Betaproteobacteria (presumably revealed to FeOB, Gallionella strengths (5·10 - 1·10 M in NaClO4) and the effect of the spp.) were localized within 10 µm of the Fe mat surface. adsorption on the main properties of the colloids (size and µ 2- Furthermore, in situ mineralogical characterization by -XAFS charge) were analysed. Similarly, the effects of SO4 suggested that Fe local structure at the FeOB accumulating parts competitive adsorption were studied. was dominantly composed of secondary short-ordered Fe-O6 Adsorption on Al2O3 was almost independent of the ionic linkage, which is normally not observed in synthetic Fe strength and decreased with increasing pH, as expected for oxyhydroxides [2]. The present study indicates that the coupled anions. The set of adsorption data was successfully fit by XAFS-FISH technique could be a potential technique to provide surface complexation modeling. direct information on specific biogenic reaction mediated by It was clearly shown that the anion adsorption (at medium- specific microbe. high surface occupancies) affected alumina nanoparticle stability. A clear shift of the isoelectric point towards more acid pH and enhancement of colloid aggregation, even at low ionic strength, were observed. The presence of anions in the chemical composition of natural water, frequently not accounted for in stability studies, will be discussed, as well as the implications on possible colloid-driven contaminant transport in the environment.

ACKNOWLEDMENT: The work has been partially supported by the project NANOBAG (CTM2011-27975).

Fig. 1 Schematic figure showing coupled µ-XAFS-FISH technique.

[1] Kappler et al. (2005) Geology 33, 865. [2] Mitsunobu et al. (2012) Environ. Sci. Technol. 46, 3304.

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Similarities between discordant Discovery of coesite and stishovite chromitites from northern Oman from eucrite ophiolite and chromitite xenoliths M. MIYAHARA1, E. OHTANI1, A. YAMAGUCHI2, S. from Takashima alkali basalt, OZAWA2, T. SAKAI3 AND N. HIRAO4 southwest Japan arc 1 Graduate School of Sci., Tohoku Univ., Sendai 980-8578, Japan. [email protected] 1 1 2 MAKOTO MIURA , SHOJI ARAI , MARIE PYTHON AND 2 NIPR, Tokyo 190-8518, Japan. 1 AKIHIRO TAMURA 3 GRC, Ehime Univ., Matsuyama 790-8577, Japan. 4 1Dept. Earth Sci., Kanazawa Univ., Kanazawa 920-1192, JASRI, 1-1-1 Kouto Sayo, Hyogo 679-5198, Japan. Japan (*correspondence: [email protected] u.ac.jp) The existence of a high-pressure polymorph in a meteorite 2Dept. Natural History Sci., Hokkaido Univ., N10W8, is a critical evidence for a dynamic event occurred on its Sapporo 060-0810, Japan parent-body. It is expected that HEDs meteorites originate from an asteroid, 4 Vesta. Although recent Dawn mission We examined some discordant podiform chromitites in the clarified that 4 Vesta suffered from heavy meteorite mantle section of northern Oman ophiolite along Wadi Hilti, bombardments, a high-pressure polymorph has not been found Fizh and Rajmi, to consider their origin. They are clearly in HEDs meteorites so far. We got one of eucrite samples, discordant to the foliation of the surrounding mantle Béréba. Béréba sample studied here has several shock-melt harzburgite. In outcrops, they show various texture (layered, veins, implying that it was heavily shocked. We investigated massive, schlieren, anti-nodular and rarely nodular texture). Béréba using a laser micro-Raman spectroscopy, FEG-SEM Chromian spinels from all chromitites examined are full of and FIB-TEM techniques to clarify a record of a dynamic minute orbicular inclusions of hydrous (pargasite and Na- event and its possible parent-body. phlogopite) and anhydrous (pyroxenes) silicates. They usually We focused our interests on a silica phase of Béréba in show a concentric distribution indicating a primary origin. this study. Raman spectroscopy analyses showed that silica Their chromian spinels in all discordant chromitites show grains in the host-rock of Béréba are quartz and minor a relatively high Cr# (=Cr/(Cr+Al) atomic ratio), 0.7 to 0.8, cristobalite. Most quartz grains entrained in the shock-melt veins transform to coesite. Some silica grains entrained in or and a low TiO2 content, 0.15 to 0.2 wt%. The Oman discordant chromitites are comparable in chemical adjacent to the shock-melt veins have network-like and/or characteristics of chromian spinel with some arc-related lamellae-like textures. Raman spectroscopy and TEM plutonic rocks [1]. observation indicate that such silica grains include coesite, Their chromitite xenoliths from Takashima alkali basalt, stishovite and silica glass along with quartz. This is the first southwest Japan arc, are similar to the Oman chromitites in report of a high-pressure polymorph in HEDs meteorites. spinel chemistry and texture [2]. In addition, we found laurite, The existence of stishovite indicates that pressure one of platinum-group minerals, in the Takashima chromitite. condition recoded in Béréba should be ~8 GPa at least based The Takashima laurite is included in the compositional range on a phase diagram obtained from static high-pressure and of laurites in Oman chromitite [3]. Chondrite-normalized PGE high-temperature synthetic experiments. U-Pb radio-isotope pattern of the Takashima chromitite shows a slightly negative age of apatite entrainned in the shock-melt vein is ca 4.2 Ga slope from Ru to Pt, which is also analogous to that of some [1], which is relatively younger than bulk-rock Pb-Pb radio- chromitites from Oman. isotope age (ca 4.5 Ga) [2]. The young U-Pb radio-isotope age These similarities between the Oman discordant chromitite of apatite would be due to disturbance by a thermal event such and Takashima chromitite xenoliths, strongly suggest that as a dynamic event. When a high-pressure polymorph is some ophiolitic podiform chromitites are of sub-arc origin. heated under ambient condition, it vitrifies easily. Accordinglly, a dynamic event formed coesite and stishovite [1]Arai et al. (2011) Island Arc 20, 125-137. [2]Arai and Abe in Béréba occurred at least after ca 4.2 Ga ago.

(1994) Mineral Deposita 29, 434-438. [3]Ahmed and Arai nd (2002) Contrib Mineral Petrol 143, 263-278. [1] Zhou Q. et al., 42 LPSC., 2575pdf (2011). [2] Carlson R.W., et al., 19th LPSC., 166-167 (1988).

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Evaluation on reactivities of metal Progress of serpentinization reactions ions with hard ligands having oxygen triggered by silica addition: donor Petrological evidence from A. MIYAJI* AND Y. TAKAHASHI Iwanai-dake ultramafic body, Hiroshima University, Higashi-Hiroshima 739-8526, Japan Hokkaido, Japan (*correspondence: [email protected]) 1 A. MIYOSHI AND T. KOGISO

Complexation of metal cations by ligands such as 1Graduate School of Human and Environmental Studies, hydroxide ion, carbonate ion, carboxylate ion, and phosphate Kyoto University, Kyoto 606-8501, Japan. ion is one of the most important factors to control behavior of [email protected] metal ions in natural environment. Previous study showed that these ligands were classified as intermediate hard ligands Transformation of peridotite into serpentinite in the mantle having oxygen donor, which favors to form the ionic bond [1]. wedge is one of the key processes that influence geodynamic However, it was found that the reactivity of each ligand regimes of subduction zones, because serpentinization changes greatly depends on ionic radius and that there is a great the physical properties of peridotite, such as density, magnetic difference of the reactivity between hydroxide ion and other susceptibility, electric conductivity and rheology. Recent ligand such as carbonate and carboxylate. For example, among petrologic studies have proposed that serpentinization the divalent alkaline earth metal ions, Mg2+ mainly precipitates 2+ reactions proceed via a two-stage process involving the early as hydroxide (brucite), while Ca prefer to form carbonate (calcite) or phosphate (apatite) minerals than hydroxide. formation of serpentine + brucite and subsequent magnetite However, quantitative discussion on the selectivity of metal formation. Magnetite, which is the key mineral controlling cations is not quantitatively performed. magnetic properties, electrical conductivity and density of In this study, we evaluated the standard Gibbs free energy peridotite as well as the efficiency of hydrogen generation, is thought to be formed by the second-stage reaction, but there ( ), enthalpies ( ) and entropy ( ) for the has been little consensus among researchers regarding what complex formation of hydrated metal cations with these factor promotes the formation of magnetite during ligands based on a critical thermodynamic database including serpentinization. We investigated successive changes in


and . As a result, we found that the mineralogical textures associated with the progress of entropic contribution to the free energy was large in the case serpentinization observed in serpentinized harzburgite and of hydroxide complex of small radius cation. In contrast, the dunite samples from Iwanai-dake ultramafic body (Hokkaido, entropic contribution to the free energy was small in the case Japan), which probably derived from a mantle wedge. Two of hydroxide complex of large radius cation and other kinds of mesh rim types were observed in the serpentine mesh complex. In addition, the enthalpy contribution was not texture of serpentinized harzburgite: a rim consisting of both significant in the reaction. In the aqueous complexation serpentine and brucite (type-A rim) and a rim consisting solely reaction,
was controlled by the number of water of serpentine (type-B rim), which are always accompanied by brucite-magnetite veins. The formation of type-B rims and molecules replaced by the ligand, suggesting that hydroxide brucite-magnetite veins appears to have occurred concurrently complex for large cation was not stable due to the small effect with the serpentinization of orthopyroxene, suggesting that of dehydration.


serpentinization reactions of harzburgite took place in two stages, with magnetite being formed by the second-stage [1] D. Turner et al. (1981) Geoshim. Cosmochim. Acta 45 reactions, which were triggered by a supply of silica 855-881 component from serpentinization of orthopyroxene. In the case of serpentinized dunite, type-A rim was predominant and the fraction of magnetite does not increase with the progress of serpentinization. These observations suggest that silica supply is the trigger for the second-stage serpentinization reactions, in which magnetite and hydrogen are generated.

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Effect of grid resolution and Reconstructing past organic matter permeability anisotropy on mineral fluxes from !15N records trapping for CO2 disposal in the J. MÖBIUS*, B. GAYE, N. LAHAJNAR AND K.-C. EMEIS saline aquifer of Subei Basin, China Center for Earth System Research and Sustainability (CEN), 1 1 2 1, University of Hamburg, Bundesstrasse 55, S.X. MO , F. ZHENG , S.M. JIANG , X.Q. SHI *, 1 1 D-20146 Hamburg, Germany L. ZHAO AND Y. CHEN (*correspondence: [email protected]) 1School of Earth Sciences and Engineering, Nanjing University, China Organic matter fluxes from mixed layer to sea floor are 2 Department of Hydraulic Engineering, Tongji University, hard to quantify from sediment records. Remineralization in Shanghai 200092, China the water column and in the sediment extinguishes the (*correspondence: [email protected]) primarily produced signal to different degrees. As the reliability of biogenic barium as a proxy for primary A vertical 2-D numerical model is built to study the production turned out questionable during the past decade, the interactions between water and minerals after supercritical quantification of organic matter fluxes is open again. In a

CO2 is injected into the saline aquifer of Yancheng Formation recent study, we demonstrate that in certain settings stable in Subei Basin, China using the parallel reactive transport isotopes of nitrogen (*15N) may provide a tool to reconstruct modelling code TOUGHREACT-MP. The result shows that past organic matter fluxes. the carbonate minerals (e.g., calcite, siderite and dawsonite) Stable isotope ratios of nitrogen are indicative for N significantly precipitated due to the dissolution of epidote, sources, availability and cycling in the water column. The * chlorite and albite. The total amount of CO2 mineral trapping 15N signal can be transferred to the sea floor by sinking was as high as 34.0% after 5000a. The results of sensitivity particulate organic matter and further archived in the analysis show that the volume of epidote significantly affects sediments. Interpretation of sedimentary *15N records is

the CO2 storage capacity. Three scenarios for the same usually complicated by an early diagenetic isotopic conceptual model with different grid resolution are carried on enrichment that mainly occurs during particle sinking and at to analysis the effects of numerical resolution. The results the sediment water interface. However, we discovered that show that grid resolution has little impact on the reaction path isotopic enrichment proceeds systematically due to organic of minerals dissolution and precipitation, however, the total matter remineralization and follows Rayleigh type

amount of CO2 mineral trapping using coarser grid is fractionation logics. Accordingly, if isotopic enrichment is overestimated comparing to that with finer grid. The known, we can recalculate the amount of organic N that has influence of the ratio of permeability anisotropy is also been remineralized. compared using another three scenarios corresponding to Our study has been carried out on Eastern Mediterranean large, moderate and small vertical permeability, respectively. Sea sediments from Holocene to Pleistocene sapropels and The results indicate that reduction of the vertical permeability their remnants after post-depositional remineralization. The results in more solubility and mineral trapping for a short data set further comprises recent to subrecent sediments as

period of time (e.g., 1000 a). However, more CO2 is stored in well as sediment trap samples. Reconstructed N fluxes from minerals for the model with a moderate vertical permeability recent and past sediment samples match fluxes reported in after 1000a, which implies that convective mixing process sediment traps and seem to validate our approach. Similar may significantly enhance mineral trapping. coincidence has been obtained for Arabian Sea core record and sediment traps. Hence, the new application of *15N Acknowledgement: This research was supported by the possibly is appropriable in a wider range of marine settings. Natural Science Foundation of Jiangsu Province (BK2012313) and NSFC No. 41172206.

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New tool for the direct isotopic dating Barium stable isotope fractionation of PGM (190Pt-4He method): new during diffusion through silica constructions on the timing of Pt hydrogel: Experimental mineralization in Kondyor and determination of kinetic isotope Galmoenan massifs, Russian Far East effects at low temperatures MOCHALOV A.G.1, YAKUBOVICH O.V. 1,2, BRAUNS M.3 K. MOELLER1*, T.F. NÄGLER1, M. DIETZEL2 AND SHUKOLYUKOV YU.A. 1,2,* AND M.E. BÖTTCHER3 1 IPGG RAS, Makarova nab., 2, Saint-Petersburg, Russia 1Institute of Geological Sciences, University of Bern, Bern, [correspondence: [email protected]] Switzerland 2 Saint-Petersburg State University, Saint-Petersburg, Russia (*correspondence: [email protected]) 3 Institute of archaeometry, Mannheim, Germany 2Institute of Applied Geosciences, Graz University of * deceased Technology, Graz, Austria 3Leibniz-Institute for Baltic Sea Research, Warnemünde, 190 4 New Pt- He method of isotope geochronology for the Germany native minerals of platinum is based on the +-decay of 190Pt isotope. Radiogenic helium in crystal structures of native Only very few studies have so far focussed on barium (Ba) metals tends to form atomic clusters that appear as nanoscale stable isotope fractionation in nature. Many questions thus still 190 4 “bubbles”. Therefore the stability of Pt- He isotope system remain regarding the direction and extent of isotope in native minerals of platinum is rather high [1]. fractionation in physical and (bio)geochemical reactions. To By the novel 190Pt-4He method we have determinated age date, experimental studies of Ba isotope fractionation are of Pt>Ir fluid-metamorphogenic, Pt>Os magmatogenic-fluid- limited to precipitation of Ba-carbonates and -sulphates [1,2] metasomatic, and Pt magmatogenic-fluid-metasomatic types and adsorption of Ba onto Mn-oxides and clay minerals [3]. of platinum mineralization of alkaline-ultramafic massifs Here, we investigated Ba isotope fractionation during Kondyor (Aldanian Shield, Russia) and gabbro-dunite- diffusion of Ba through a silica hydrogel. The gel was pyroxenite Galmoenan massif (Koryak-Kamchatka belt, prepared in 15 cm long glass U-tubes. A concentration Russia). gradient was established by applying a BaCl solution (0.1 and Obtained age of isoferroplatinum for Pt>Ir fluid- 2 1.0 mol/l, respectively) on one side of the gel and deionised metamorphogenic, and Pt>Os magmatogenic-fluid- water on the other side. Diffusion experiments were run at two metasomatic types of platinum mineralization of Galmoenan massif is 63 ± 3 Ma (average from 10 samples). The data are different temperatures (10 and 25°C) over 2, 6, 12, 20 and 27 in good agreement with relevant geological observations. days, respectively. Obtained age of isoferroplatinum for Pt>Ir fluid- The rates of Ba diffusion through the silica hydrogel metamorphogenic, and Pt magmatogenic-fluid-metasomatic correlate positively with initial BaCl2 concentration and types of platinum mineralization of Kondyor massif is 123 ± 6 temperature. Ba isotope fractionation, however, appears to be Ma (average from 20 samples). The data are also in excellent independent from both boundary conditions. Initially, diffused agreement with relevant geological observations and other Ba was found to be fractionated by as much as -2.2 ‰ in 137/134 existing geochronological determinations. Noteworthy that the " Ba relative to the BaCl2 stock solution. With continuing age of Pt>Ir fluid-metamorphogenic and Pt>Os duration of the experiments, the "137/134Ba values increased magmatogenic-fluid-metasomatic types of platinum rapidly to about -0.6 ‰ after 27 days. We hypothesise that mineralization doesn’t have any significant discrepancy. initial kinetic isotope fractionation caused by Ba diffusion 190 4 Conducted Pt- He dating experiments also let us to switched to a later control via adsorption of Ba onto the silica separate a new young type of Pt mineralization on the 190 4 hydrogel. Our experiments thus show that fractionation of Ba Kondyor massif. Pt- He ages for fine cubic crystals of isotopes of more than 2 ‰ in "137/134Ba (~0.7 ‰/amu) are isoferroplatinum turned out to be around 8 Ma. The same possible under experimental conditions and that the light Ba young age for these crystals was also obtained by the isotopes are favoured substantially during Ba diffusion independent 190Pt-186Os method. These data may indicate through an aqueous medium. formation of these Pt minerals under surface conditions. [1] von Allmen et al. (2010) Chem Geol 277, 70-77. [2] [1] Shukolyukov (2012) Petrology, 20.6., 491-505 Böttcher et al. (2012) Isot En Health Stud 48, 457-463. [3] Böttcher et al. (2012) Mineral Mag 76, 1495.

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Geochemistry and petrogenesis of Comparing MSW landfill sites of Hassan Salaran granitoid complex in Ottawa (capital of Canada) and SE Saqqez, western Iran Mashhad (the 2nd biggest city of Iran) FAKHRADDIN MOHAMMAD ABDULLAH1*, ALI A. HOSSEIN MOHAMMADZADEH SEPAHI2 AND SHELER. S. AHMAD1 Groundwater research center (GRC), Faculty of science, 1 University of Garmian, Kalar, Kurdistan Region, Iraq, Ferdowsi University of Mashhad, Iran, P.O.B, 91775-1436 (*correspondence: [email protected]) ([email protected]) 2 Bu Ali Sina University, Hamadan, Iran ([email protected]) Waste disposal is an important issue in almost all cities The Hassan Salarn granitoid complex is located 20km to and landfilling of municipal solid waste (MSW) is the most southeast of Saqqez city in Kurdistan Province, western Iran. widely used disposal method in all over the world. In big cities It is composed of two distinct granitic rock suites that have like Mashhad (cultural capital of Iran) and Ottawa (capital of various petological and geochemical characteristics. They also Canada), in spite of waste composting and recycling, have different origins and petrogenesis. G1 granitoids considerable amount of MSW is disposed in landfill sites. In comprise alkali feldspar granite, syenogranite and quartz alkali this study, the Mashhad municipal landfill (ML) and Ottawa feldspar syenite, whereas G2 granitoids are composed of municipal landfill (OL) sites which are owned and operated by monzogranite, granodiorite and tonalite. Geochemically, G1 the Cities of Mashhad (Iran) and Ottawa (Canada), granitoids are peralkaline, A-type and acmite-normative but respectively, have been investigated. The ML and OL sites G2 granitoids are subalkaline (calc-alkaline), metaluminous, I- were compared by looking at 1) site characterization of ML type and diopside-normative. G1 granitoids are also ferroan and OL; 2) waste composition and the geochemical alkali and ferroan alkali-calcic whereas G2 granitoids are composition of leachate in both ML and OL sites; and 3) the magnesian and calcic. environmental impacts of both sites. According to tectonic discrimination diagrams [1], G1 Landfilling in OL and ML sites began in 1960s and 1975, granitoids plot in the field of the within plate granites whereas respectively. Both sites accept residential, industrial, G2 granitoids plot in the field of volcanic arc granites. commercial/institutional, and construction/demolition MSW Considering the method for classification of granites setting material. However, ML is receiving about 584000 tons MSW [2], G1 granitoids plot in the post-orogenic field but G2 annually (with dial average of 1600 tons), which is much more granitoids plot in the field of mantle fractionated rocks. G1 than that of OL landfill (355070 tons annually). At Ottawa granitoids contain higher concentrations of alkalies, Zr, Rb, landfill site, both the shallow and deep aquifers have been Nb, Y, Th, Ce, high FeO/MgO ratios and lower concentrations impacted by the landfill leachate infiltrating from the unlined of Mg, Ca and Sr, resembling post-orogenic A-type granites. It portions of the landfill site. The presence of methane, DIC and is possible that heat from a mantle-derived magma which the enriched d13C-DIC values at some monitoring wells, in intruded into the lower crust, and/or rapid crustal extension comparison with pristine groundwater, provide evidence for have been essential generation of approriate melts producing leachate impact on groundwater at OL site [1, 2]. The detailed G1 granitoids. Thus we can conclude that G1 granitoids were description of sampling procedures, analytical techniques, generated from a mixed mantle-crust source. Negative Nb leachate composition, and leachate impact on the environment anomalies and low contents of Ti and P probably indicate a is given by Mohammadzadeh and Clark [3]. The ML site, with subduction-related origin for protolith of G2 granitoids. an elevation of 1080 a.s.l., is located on an igneous bedrock Negative Nb anomalies and enrichment in Ce relative to its covered with alluvial deposit. Since the covered soil is not that adjacent elements can be related to involvement of continental much thick and there is fractured network in granitoeid crust in magmatic processes. G2 granitoids are also enriched in bedrock, it is suspected that ML leachate have had an impact Rb, Ba, K, Th, Ce and depleted in Nb, Zr and Y, indicating on groundwater resources. that they have had interacted with crust. G2 granitoids may result from contamination of mantle-derived magmas by [1] Mohammadzadeh, H., I.D. Clark, M. Marschner, and G. continental crust during an subduction event. St-Jean. (2005). Compound specific isotopic analysis (CSIA) of landfill leachate DOC Components. Chemical Geology [1] Pearce et al. (1984) Journal of Petrology 25, 956-983. 218: 3-13. [2] Mohammadzadeh, H., and I.D. Clark. (2008). [2] Batchelor & Bowden (1985) Chem. Geol. 84, 43-55. Degradation pathways of dissolved carbon in landfill leachate traced with compound-specific 13C analysis of DOC. Isotopes in Environmental and Health Studies 44: 267-294. [3] Mohammadzadeh, H., and Clark, I.D. (2011). Bioattenuation in a groundwater impacted by landfill leachate traced with d13C, Ground Water, 49 (3).

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Evolution of neodymium isotopic Water quality and human helth in signature of seawater during the Late relation to aquatic environment Cretaceous: new insights on oceanic polutiom by metals circulation changes T.I. MOISEENKO1, N.A. GASHKINA1 2 1 1 2 AND V.V. MIGORSKY M. MOIROUD *, E. PUCÉAT , Y. DONNADIEU , G. BAYON3 AND J.-F. DECONINCK1 1 V.I.Vernadsky Institute of Geochemistry and Analytical 1 Chemistry, RAS, Kosygin 19, Moscow 119991, Russia UMR CNRS, Université de Bourgogne, 21000, Dijon, France (*correspondence: [email protected]) (*correspondence: [email protected]) 2 Institute of the North Eco-Industrail Problems, Kola Science 2UMR CEA/CNRS, Laboratoire des Sciences du Climat et de Center of RAS, Fersman 14, Apatity 184200, Russia l’Environnement , 91191, Gif sur Yvette Cedex, France

([email protected]) The assessment of the ecological consequences of element 3Département Géosciences Marines, Ifremer, 29280 Plouzané, geochemical cycle changes due to the impact of mining and France ([email protected]) the metallurgical industry is of great importance for the health of the environment. This study collates published data Changes in oceanic circulation during the Late Cretaceous concerning surface water contamination by metals, have been inferred from the neodymium isotopic composition bioaccumulation and health of humans and fish within the (! ) of fish remains, which reflects the signature of past Nd Euro-arctic region of Russia (Murmansk region), in order to seawater [1, 2]. However the nature of these changes remains investigate their relationship. The results of metal controversial, mainly due to insufficient temporal and spatial concentration analysis of water from the sites of surface water coverage of Nd isotope data. Data from continental margins in intake for five cities and towns, as well as from pipe systems particular remain scarce for the Cretaceous [3, 4]. supplying drinking water to the public, show that industrial This work aims at reconstructing the signature of neritic water treatment fails to remove toxic metals from the water. and oceanic water ! during the Late Cretaceous/Early Nd Fish were used as a biological indicator to show the impact of Paleogene in potential areas of deep water sinking and the pollution on living organisms. Renal disorders prevailed seaways linking different oceans. For this purpose, samples of among the observed diseases within human populations. fish remains, foraminifera and detrital fraction have been Statistical analysis demonstrated that human populations in recovered in Late Cretaceous to Paleocene sediments from those cities which are located in close proximity to smelters both oceanic (DSDP/ODP sites 152, 258, 323, 690 and 700) show the highest incidence of disease. The highest and neritic (Wyoming, Texas, New Jersey, Chile, Seymour accumulation of metals within the kidney and liver were Island, Egypt and HokkaidA) sites. recorded in inhabitants of Monchegorsk, where the The results primarily point out a decreasing trend after the concentrations of many metals, especially, nickel, copper, Cenomanian-Turonian interval, previously observed in the chromium, cadmium, and lead, are 2–10-fold higher compared Atlantic and the Indian sector of the Southern Ocean [5, 6] and the normal. The highest concentrations within the kidney a general increasing trend during the Maastrichtian and the tissue were recorded for chromium and cadmium. Kidney Paleocene, but also document the first Cretaceous ! data for Nd pathologies are abundant within the population using the the Southern Pacific, the continental margins of North contaminated water supply for drinking water. The correlation America and Japan, and the Panama and Drake passages. between the content of this chemical element in water and Nevertheless, further comparisons with ! data available in Nd pathology of kidney and liver of those patients who were the literature and climate modelling are required to tentatively examined postmortem was significant. Statistical analysis explain the oceanic circulation during the Late Cretaceous. demonstrated that human populations in those cities which are

located in close proximity to smelters show the highest [1] Robinson et al. (2010) Geol. Soc. of Am. 38 (10), 871-874. incidence of disease. The highest content of toxic metals, [2] MacLeod et al. (2011) Nat. Geosci. 4, 779-782. [3] Pucéat especially cadmium, was found in the liver and kidney organs. et al. (2005) EPSL 236, 705-720. [4] Soudry et al. (2006) The burden of evidence of the disorders observed in fish and Earth-Sci. Rev. 78, 27-57. [5] Murphy et al. (2012) in human populations indicates that there is a high probability Paleoceanography 27, PA1211. [6] Robinson & Vance (2012) of prolonged water contamination having a negative influence Paleoceanography 27, PA1102. on the health of human populations.

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New U-Pb ages for syn-orogenic Water on the primordial Earth magmatism in the SW sector of the S.J. MOJZSIS1*, A. MORBIDELLI2, K. PAHLEVAN3 AND Ossa Morena Zone (Portugal) E.A. FRANK1 1 1 2 2 3 Geological Sciences, CLOE, University of Colorado, USA P. MOITA *, J.F. SANTOS , M.M. COSTA AND F. CORFU 2 Observatoire de la Cote d’Azur, CNRS, Nice, France 1Centro de Geofísica de Évora, Universidade de Évora, 3 Geology and Geophysics, Yale University, USA Portugal, [email protected] (*[email protected]) 2Geobiotec, Dep. Geociências, Universidade de Aveiro, Portugal Water is the medium for life; it facilitates the long-term 3Geology Department, Oslo University, Norway carbon cycle and aids in plate tectonics by modulating key geophysical parameters such as the mechanical strength of -4 The Ossa-Morena Zone (OMZ) is a major geotectonic unit crust. Earth’s surface hydrosphere totals 2.8,10 M-, and the -3 within the Iberian Massif (which constitutes an important mantle may contain 2.7(±1.3),10 M- of water [1], segment of the European Variscan Belt) and one of its approximately its storage capacity [2]. Ancient rocks show the distinguishing features is the presence of a noteworthy hydrosphere existed in the first 700 Myr, and Hadean zircons compositional diversity of plutonic rocks. In the SW sector of extend this to about 180 Myr after solar system formation [3]. the OMZ, the tonalitic Hospitais intrusion (located to the W of Earth has retained its volatiles since primary accretion [4], but Montemor-o-Novo) is considered a typical example of syn- H- and N-isotopic compositions are chondritic rather than orogenic magmatism, taking into account that both the long cometary [5]. As such, water may have arrived late in the axis of the plutonic body and its mesoscopic foliation are accretion epoch viz. the Grand Tack model [GT; 6] or even oriented parallel to the Variscan WNW-ESE orientation. later via a Late Veneer [LV; 7]. The Late Heavy Bombardment Another relevant feature of the Hospitais intrusion is the [LHB] was not significant: it delivered too little (0.1% of the -3 occurrence of mafic microgranular enclaves within the main LV’s mass), too late. Whether the LV mass (~5,10 M-) was tonalite. In previous works (Moita et al., 2005; Moita, 2007), brought in by many small undifferentiated planetesimals or a it was proposed that: (1) the Hospitais intrusion is part of a small number of large differentiated bodies is still an open calc-alkaline suite, represented by a large number of intrusions issue, and we discuss advantages and disadvantages of both in this sector of the OMZ, ranging from gabbros to granites; options. Such a mass was insufficient to deliver all the water (2) the enclaves are co-genetic to the host tonalite in the even assuming CI composition. Earth-Moon O-isotopes Hospitais pluton. exclude a CM, CI, or OC composition for the LV; EC In this study, zircon populations from one sample of the composition would be possible but they are so water poor that main tonalite (MM-17) and one sample of the associated they cannot explain Earth’s water abundance whatever the LV enclave (MM-17E) were analysed by ID-TIMS for U-Pb mass. Volatiles were delivered towards the end of Earth geochronology. In each sample, three fractions of nice glassy, accretion rather than via an LHB, LV, or Moon-forming event. euhedral, long prismatic and inclusion free crystals were This view is consistent with the latest dynamical models analysed. The results from the three fractions of MM-17 provided that Moon formation was fortuitously late [8]. yielded a weighted average 206Pb/238U age of 337.0 ± 2.0 Ma. Similarly, for the enclave MM-17E a weighted average [1] Hirschmann & Dasgupta (2009); [2] Smyth & Jacobsen 206Pb/238U zircon age of 336.5 ± 0.47 Ma was obtained. These (2006); [3] Harrison (2009); [4] Albarède et al. (2013); [5] identical ages, within error, are in agreement with a common Marty (2011); [6] Walsh et al. (2011); [7] Albarède (2009); parental magma for the tonalite and mafic granular enclaves. [8] Halliday (2013). Similar U-Pb ages have been reported in previous works for plutonic and metamorphic events in this region (e.g.: Pereira et al., 2009; Antunes et al., 2011). Furthermore, also in the SW sector of the OMZ, palaeontological studies (Pereira et al., 2006; Machado & Hladil, 2010) carried out in Carboniferous sedimentary basins containing intercalated calc- alkaline volcanics (Santos et al., 1987; Chichorro, 2006) have shown that they are mainly of Visean age. Therefore, magmatism displaying features typical of continental arc setting seems to have been active in this part of the OMZ during the Lower Carboniferous times.

Funding: FCT through projects Petrochron (PTDC/CTE- GIX/112561/2009) CGE PEst-OE/CTE/UI0078/2011and Geobiotec (PEst-C/CTE/UI4035/2011).

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The geochemical evolution of Lithospheric mantle connection of clinopyroxene in the Roman clinopyroxene inclusions in chromites Province: A window on from the Archean Nuasahi decarbonation from wall-rocks to ultramafic-mafic complex (India) magma SISIR K. MONDAL1*, SHOJI ARAI2, BETCHAIDA D. 2 2 1. 2 PAYOT AND AKIHIRO TAMURA S. MOLLO AND A. VONA 1 1 Department of Geological Sciences, Jadavpur University, Istituto Nazionale di Geofisica e Vulcanologia, Via di Vigna Kolkata-700032, India Murata 605 00143 Rome, Italy (*correspondance: (*correspondence: [email protected]) [email protected]) 2 2 Department of Earth Sciences, Kanazawa University, Dipartimento di Scienze, Universita` degli Studi Roma Tre, Kanazawa 920-1192, Japan L.go San leonardo Murialdo 1 00146 Rome, Italy

The 3.1Ga Nuasahi igneous complex in India is a sill-like We present results from atmospheric pressure experiments layered intrusion within the early Archean greenstone belt of conducted at 1140, 1160 and 1180 °C under the buffering the Singhbhum craton. The igneous complex consists of a conditions of air, MH and NNO. The starting materials were a lower ultramafic unit (~ 400m thick) containing three shoshonite and a phonotephrite from the Roman Province. chromitite ore bodies and an upper gabbroic unit containing These natural samples were doped with variable amounts of magnetite bands. In between the lower ultramafic unit and the CaO and CaO+MgO whose stoichiometric proportions upper gabbro a PGE-rich discordant breccia zone is present. reproduced the assimilation by magmas of calcite and The main rocks of the lower ultramafic unit are dolomite, respectively. orthopyroxenite, harzburgite, dunite and chromitite. Chromites Results underline that, during magma-carbonate from the massive chromitites contain numerous independent interaction, the oxygen fugacity exerts a primary control on clinopyroxene (cpx) inclusions (> 95% of total inclusion clinopyroxene composition. With increasing fO , the content 2 populations) along with tiny phlogopite (<1%). The cpx of Tschermak molecules, i.e., CaAlAlSiO , CaFeAlSiO , and 6 6 inclusions are of variable sizes and shapes (rounded, elliptical CaTiAlSiO , in clinopyroxene significantly increases at the 6 and euhedral crystals), and in places they mimic the shape of expenses of hedenbergite and enstatite components. the host chromite grain, and appear as the seed and negative The compositional variation of clinopyroxene described crystals. In addition, few opx and olivine grains are identified by our experiments is compared with the chemical analyses of in net-textured chromitites. Major element analysis by EPMA natural crystals found in skarns and lavas at the Roman confirms that the cpx inclusions are Cr-diopside in Province. This comparison provides that the simple ingestion composition which suggest a lithospheric mantle origin of the of carbonate by magmas cannot explain the geochemical inclusions. Phlogopites are K-rich and compositionally similar evolution of clinopyroxene in the Roman Province. At the to mantle phlogopite. In situ trace element analyses by laser periphery of magma chamber, the decarbonation reaction ablation ICP-MS show that the chondrite-normalized REE proceeds with the highest efficiency producing high CO 2 patterns for the cumulus cpx in the upper gabbro and the cpx emissions. This causes extreme oxidizing conditions that, in inclusions in chromites from the massive chromitites from the turn, control the geochemical evolution of clinopyroxene in Nuasahi complex are different. Previous studies showed that skarns. However, the oxidative capacity of CO fluxing 2 the chromitite-bearing sill-like ultramafic-mafic complex in progressively decreases from the skarn shell to the interior of Nuasahi was formed from a boninitic parental magma in a the magma. Consequently, the chemical analyses of supra-subduction setting. Previous Os isotopic study of the clinopyroxenes found in lavas testify to laterally variable unaltered chromites indicated melt extraction as early as 3.7Ga lower redox conditions in the magma chamber. from a subchondritic Os isotopic source implying derivation

from a subcontinental lithospheric mantle. The high-Mg parental magma of the Nuasahi igneous complex may have originated in the deeper parts of the metasomatized lithospheric mantle wedge from where the cpx xenocrysts (along with phlogopite) were collected and transported to the crustal magma chamber where it had been entrapped by the growing chromite crystals.

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Natural uranium ores host iron- Towards Understanding Magnetite reducing and iron-oxidizing bacteria Biomineralisation: The Effect of as demonstrated by high throughput Short Chain Peptides on the {100} sequencing and cultural approaches. and {111} Magnetite Surfaces L. MONDANI1, K. BENZERARA2, M. CARRIERE3, R. AMY E. MONNINGTON* AND DAVID J. COOKE CHRISTEN4, L. FEVRIER5, W. ACHOUAK6, P. NARDOUX7, Department of Chemical & Biological Sciences, University of C. BERTHOMIEU1 AND V. CHAPON1*, Huddersfield, Queensgate, Huddersfield, HD1 3DH, 1LIPM, UMR 7265/CEA/CNRS/Aix –Marseille Univ., Saint- (*correspondence: [email protected], Paul-lez-Durance, France. [email protected]) (*correspondence: [email protected]) 2IMPMC, CNRS UMR 7590, Univ. Curie, Paris, France. Biomineralisation is the process by which living 3LLAN, CEA, Grenoble, France. organisms form minerals. The earliest known example of 4Univ. Nice Sophia-Antipolis/CNRS, UMR 6543, Nice, biomineralisation is that of the biosynthesis of magnetite [1]. France. A major step forward in understanding the principles of 5IRSN, SERIS, L2BT, Saint-Paul-lez-Durance, France. magnetite biomineralisation occurred with the discovery of 6LEMIRE, UMR 7265/CEA/CNRS/Aix –Marseille Univ., Magnetotactic bacteria (MTB) [2]. Despite this, much of the Saint-Paul-lez-Durance, France. detailed atomistic mechanism by which the process occurs is 7SEPA, AREVA NC, Bessines-sur-Gartempe, France. unknown. Numerous commercial applications for bacterial MNPs We investigated the influence of uranium on the have been suggested, including the removal of radionuclides indigenous bacterial communities in natural uranium ores by and heavy metals from waste water, MRI contrast agents, conducting an in-depth analysis of soil samples collected in magnetic antibodies and drug and gene delivery. However, the region of Bessines, one of the most important natural such applications are not commercially viable at present. In uranium deposits in France. Soil samples exhibiting 1.5 to order to produce MNPs more economically the 25.5% U in mass were compared with nearby control soils biomineralisation processes need to be further understood. containing trace uranium. EXAFS and XRD analyses of soils Therefore, we are developing an atomistic model for the revealed the presence of U(VI) and uranium-phosphate system, in an attempt to understand the processes involved. mineral phases, identified as sabugalite and meta-autunite. Magnetite formation within Magnetospirillum A comparative analysis of bacterial diversity using DGGE magneticum AMB-1 occurs under the influence of the Mms6 [1] and high throughput pyrosequencing of 16S rRNA genes protein. It was previously discovered that the Mms6 protein revealed the presence of complex populations in both control was linked to the control of the morphology and size of the and uranium-rich samples. Among the 232.000 reads analyzed magnetite crystals within the M.magneticum AMB-1 [3]. The by pyrosequencing, 23 bacterial phyla were detected with acidic C-terminal region of this sequence is of particular Proteobacteria, Acidobacteria and Chloroflexi being interest due to its potential linkage to iron binding. It is predominant. Statistical analyses of the DGGE fingerprints hypothesised that if key iron binding sites within the C- and pyrosequencing data showed that bacterial communities of terminus of the Mms6 protein are substituted for alanine, the uranium-rich samples differ from that of controls. An protein’s overall iron binding ability is diminished. enrichment of sequences related to iron- and uranium-reducing In this study, an atomistic model of Mms6-driven bacteria as well as iron-oxidizing species in uranium-rich magnetite formation was developed, using molecular samples was evidenced by both methods. Several iron- dynamics (based on classical atomistic potentials), to study the reducing anaerobic isolates related to Pelosinus, Clostridium attachment of a series amino acid repeats (alanine-alanine, and Enterobacter were cultured from the uranium-rich soil alanine-glutamic acid & glutamic acid-glutamic acid) to the samples and characterized. {100} & {111} magnetite surfaces and investigate the effect Taken together, these results demonstrate that uranium on iron binding ability. shapes bacterial diversity and suggest the existence of an iron and/or uranium redox cycle mediated by bacteria in the soil. [1] J.W. Schopf et al. , Science, 1965, 149, 1365, [2] R. Blakemore, Science, 1975, 190, 377, [3] A. Arakaki et al., J. [1]Mondani et al. (2011) PLoS ONE 6(10): e25771. Colloid Interface Sci., 2010, 343, 65. doi:10.1371/journal.pone.0025771

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Time scales of mingling in shallow Do amino acids inhibit calcite reservoirs. growth? C. P. MONTAGNA1, P. PAPALE2AND A. LONGO3 G. MONTANARI*, N. BOVET, AND S. L. S. STIPP 1Istituto Nazionale di Geofisica e Vulcanologia, via della Nano-Science Center, Department of Chemistry, University of Faggiola 32, 56127 Pisa, Italy; [email protected] Copenhagen, Denmark (*[email protected]) 2Istituto Nazionale di Geofisica e Vulcanologia, via della Faggiola 32, 56127 Pisa, Italy; [email protected] The organic matrix that regulates growth of biogenic 3Istituto Nazionale di Geofisica e Vulcanologia, via della calcium carbonate contains high concentrations of acidic Faggiola 32, 56127 Pisa, Italy; [email protected] amino acids. They can form long macromolecules, which bind to surface sites and inhibit growth of the mineral. In this study, Arrival of magma from depth into shallow reservoirs has we investigated the effect of single amino acid units on calcite been documented as one of the possible processes leading to crystal growth, to determine how their structure is related to eruption, e.g. for the recent eruption of Eyjafjallajkull [1], or inhibition. We tested glycine (Gly), the smallest amino acid, for most eruptions at Campi Flegrei [2]. Magma intruding and and aspartic acid (Asp), with concentration range from 8*10-6 rising to the surface interacts with the already emplaced, to 4*10-4 M. Both have an amino group but they differ in the degassed magmas residing at shallower depths, rejuvenating number of carboxylic groups. To quantify their impact on them and causing intense mixing and mingling. These crystal growth rates, we undertook calcite precipitation processes can cause pressure variations in the reservoirs and experiments, using the constant composition method [1]. XPS eventually lead to eruptions. The chemical signatures of such (X-ray photoelectron spectroscopy) of calcite exposed to processes are often identifiable in eruptive products. amino acid bearing solutions revealed that both molecules We performed two-dimensional numerical simulations of adsorbed. Calcite morphology was observed with SEM the arrival of gas-rich magmas into shallow reservoirs. We (scanning electron microscopy); rough corners and step edges solve the fluid dynamics for the two interacting magmas indicate blocking of surface sites (Figure 1). evaluating the space-time dependent evolution of the physical properties of the mixture, including density and viscosity. Volatile exsolution is computed self-consistently as well. Our results show that patterns of convection and mingling develop quickly into the chamber and feeding conduit/dike, leading on longer time scales to a density stratification whereas the lighter, gas-richer magma, mixed with different proportions of the resident magma, rises to the top of the chamber due to buoyancy. Over time scales of hours, the magmas in the reservoir appear to have mingled throughout, and convective patterns become harder to identify. Our simulations have been performed changing the geometry of the shallow reservoir, and the gas contents of the initial end-member magmas. Both parameters play an Figure 1: SEM image of calcite crystal exposed to Aspartic important role in determining the efficiency of the mixing acid. Rounded and roughened corners and serrated edges are processes. Horizontally elongated magma chambers favour clearly visible. mixing, while vertically elongate, dike-like reservoirs inhibit efficient convection. Higher density contrasts between the two Asp is a better inhibiting agent than Gly, which is active magmas cause faster ascent velocities and increase mixing only for the highest concentrations investigated. The extra efficiency as well. carboxylic group and the particular conformation of Asp can Petrological evidence suggests for Campi Flegrei be the main factors promoting the interaction with surface residence and mixing times of few days, from the arrival of sites. These results shed light on the parameters to take into fresh magmas to eruption, supporting our findings [3]. account to predict or design a good scale inhibiting molecule.

[1] Moune et al. (2012) J. Geophys. Res. 117, B00C07. [2] [1] Lakshtanov et al. (2011) GCA 75, 3945-3955. Arienzo et al., (2010) Chem. Geol. 270, 135-147. [3] Perugini et al. (2010) Bull. Volc. 72, 431-447.

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Highly siderophile and chalcophile New insights on the nucleation and element systematics of crust-derived growth of chrysotile, magnesite, Ligurian garnet pyroxenites goethite and calcite ALESSANDRA MONTANINI1*, AMBRE LUGUET2, STEPHAN G. MONTES-HERNANDEZ1 2 3 KÖNIG AND RICCARDO TRIBUZIO 1 ISTERRE, University of Grenoble I and CNRS, BP 53, 11 Dip. Fisica e Scienza della Terra, Università di Parma, Italy 38041 Grenoble Cedex 9, France ([email protected]). [email protected] 2 Steinmann Institut, Universität Bonn, Poppelsdorfer Schloss, 53115 Bonn, Germany Chrysotile, magnesite, goethite and calcite are widespread 3 Dip. Scienze della Terra e dell’Ambiente, Università di minerals in Earth systems and other telluric planets. These Pavia, Italy minerals play an important role on the fate and transport of several trace elements (including the so-called strategic There is growing evidence from major, trace elements and elements or rare-Earth elements of economic interest) and isotopic systematics (e.g. Nd, 187Os, 186Os) that pyroxenites organic molecules at the mineral-fluid interfaces. Particularly, are significant constituents of OIB and MORB sources. carbonate minerals plays also a crucial role on the global Although pyroxenites probably play an important role in the carbon cycle. In general, their formation and textural recycling of crustal 187Os and 186Os signatures within the properties have already been investigated in the past. mantle, their highly siderophile and chalcophile element However, various questions still remain unanswered signatures are not well contrained. Here, we present platinum concerning their formation in natural systems as well as their group elements (PGE: Os, Ir, Ru, Pt, Pd), Re, Se, Te and production at laboratory and industrial scales. In this way, 187Os compositions of nine garnet pyroxenites and two various new results on the nucleation and growth processes of peridotites from the External Ligurian ophiolites (Italy). On these minerals from macroscopic to nanoscopic scales are the basis of their mineralogical, geochemical and Nd-Hf summarized in this meeting contribution. In last six years, isotopic features, the pyroxenites (HREE-depleted Type A, independent semi-continuous or batch experiments under HREE-enriched Type-B and retrogressed) were correlated specific physicochemical conditions were carried out to with partial melting of an eclogite source derived from precipitate chrysotile nanotubes via dissolution of so-called gabbroic protoliths [1]. Whereas the host peridotites exhibit proto-serpentine precursor [1], micro-crystals of magnesite via typical mantle-like concentrations and a relatively flat CI- simultaneous dehydration and carbonation of brucitic layer of chondrite-normalised HSE patterns, the pyroxenites show dypingite precursor [2], acicular nanocrystals (in width) of large concentration ranges, reaching up to 46 ppb Pd, 538 ppb goethite from ferric hydroxide gel [3] and nanosized calcite Se and 81 ppb Te. Their HSE patterns display a positive slope via aqueous or gas-solid carbonation of portlandite [4-5]. I from Os to Re, but with significant differences between the note that the nucleation and growth mechanism routes of these pyroxenites. Type-A pyroxenites show lower Os, Ir, higher Pt, common minerals are still debated, for example, the role of so- Pd concentrations and flatter Pd-Re segments than Type-B called precursor formation and/or pre-nucleation existence pyroxenites. The retrogressed pyroxenites show mixed addressed in the recent years are not clear at the present time, signatures with Os-Ir contents similar to Type-B pyroxenites opening a broad spectrum of experimental and modeling but Pt, Pd concentrations as well as Pd-Re segments similar to possibilities to decipher this fundamental scientific obstacle. Type-A. Selenium and Te are significantly enriched in all the pyroxenites but independently of the pyroxenite groups. The [1] R. Lafay, G. Montes-Hernandez et al. Chemistry – A 187Os/188Os ratios vary from unradiogenic in the peridotites European Journal (2013) DOI: 10.1002/chem.201204105 (0.1257) to highly radiogenic in the pyroxenites (0.2649- [2] G. Montes-Hernandez et al. Crystal Growth & Design 12 2.4748). Here we show that crust-derived mantle pyroxenites (2012) 5233-5240. [3] G. Montes-Hernandez et al. Crystal show a large range of highly siderophile and chalcophile Growth & Design 11 (2011) 2264-2272. [4] G. Montes- elements signatures, which could likely contribute to Hernandez et al. Chemical Geology 290 (2011) 109-120. geochemical and isotopic heterogeneities of the Earth’s [5] G. Montes-Hernandez et al. Crystal Growth & Design 10 mantle. (2010) 4823-4830.

[1] Montanini et al. (2012) EPSL 351-352, 171-181.

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Peering into the Cradle of Life: THEREDA – Thermodynamic Multiple sulfur isotopes reveal Reference Database insights into environmental HELGE C. MOOG1 AND FRANK BOK2 conditions and early sulfur 1Gesellschaft für Anlagen- und Reaktorsicherheit (GRS) mbH, metabolism some 3.5 Ga Theodor-Heuss-Straße 4, 38122 Braunschweig, Germany, [email protected] A. MONTINARO1*, H. STRAUSS1, P. MASON2 2Helmholtz-Zentrum Dresden-Rossendorf e.V., Institute of AND A. GALIB2 Resource Ecology, Surface Processes Division (FWOG), 1Westfälische Wilhelms-Universität Münster, Münster, Bautzner Landstraße 400, 01328 Dresden (Germany), Germany (*correspondance:[email protected]) f.bok@hzdr.de 2Utrecht University, Utrecht, The Netherlands THEREDA was founded by five institutions in Germany Multiple sulfur isotopes have been used successfully for and Switzerland. Our main ojectives are • constraining Earth’s early sulfur cycle, prevailing overall To ensure that equilibrium calculations for nuclear environmental and redox conditions in particular, as well as disposal issues are consistent among different institutions • for tracing life on Earth. ICDP project “Peering into the Cradle To save basic thermodynamic data in a way which renders of Life” aims at investigating the environmental conditions them usable on a long term • that existed when life emerged and evolved on our planet. To have a technical platform which facilitates the Samples stem from the Barberton Greenstone Belt in South decentralized editing of data • Africa (3.55–3.23 Ga), one of the oldest well preserved rock To provide users with ready-to-use parameter files for the successions from the earliest part of Earth history. This study most widely used geochemical codes • centers on core BARB5, comprising carbonaceous shale, To make sure that each datum can be traced back to its interbedded sandstone and conglomerate and volcanoclastic original source • rocks from the middle Mapepe Formation of the Fig Tree To classify the entered day in order to inform the user Group. Total sulfur abundance ranges between 0.01 and 3.03 about the quality of the data and hence his calculations wt.% and total carbon abundances between 0.15 and 10.29 wt.%. The carbonaceous shale displays "34S values between - Following these objectives THEREDA has evolved into a 0.99 and 3.33‰; volcanoclastic rocks between -6.57 and web-based platform for a common thermodynamic database. 2.32‰; sandstone and conglomerate between 0.37 and 3.44‰. The main focus lies on providing a database for high-saline Similar to the "34S values, 133S values are different for each systems. However, some efforts have been made to design lithofacies. Samples from the carbonaceous shale yielded a THEREDA as flexible as possible for future demands, as range between 0.41 and 2.33‰; volcanoclastic rocks between necessity arises, namely: other models for the aqueous -0.32 and 0.20‰; sandstone and conglomerate between 0.14 solution, non ideal gas and solid phases, etc. and 0.61‰. Some preliminary conclusions can be drawn. Each Backbone of the whole database is a Pitzer-consistent set lithofacies is characterized by a different isotopic composition. of phase constituents along with equilibrium constants and Clearly, 133S values in carbonaceous shale reflect mass- Pitzer coefficients for the basic hexary system Na-K-Mg-Ca- independent isotope fractionation, hence an atmospheric Cl-SO4-H2O. The set is at present being extended to be valid signature. In contrast, volcanoclastic rocks display rather small for temperatures between 120 and 200°C, depending on the 133S values but substantial variability in "34S, that could particular system. At the same time data are added to extend the database for polythermal, in parts even polybaric equilibria reflect solely mass-dependent isotopic fractionation, hence a - terrestrial signature. However, alternatives have been with HCO3 /CO2(g). proposed. Consistently to the above mentioned backbone, other joint members of THEREDA collaborate to extend the database for actinides, activation- and fission products, and heavy metals. Another string of endeavour is targed towards geothermal applications. The THEREDA team welcomes colleagues from other database projects to discuss or collaborate on specific subjects of common interest.

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Reactive transport of common Melt inclusion constraints on the hydrological tracers in porous media origin of the Peridote Mesa – an experimental study phonotephrite, San Carlos, Arizona PRATHAP MOOLA1, BERGUR SIGFÚSSON2 G. MOORE AND A. STEFÁNSSON1 Department of Earth and Environmental Sciences, University 1Institute of Earth Sciences, University of Iceland, Sturlugata of Michigan, Ann Arbor, MI, 48107, USA 7, 101 Reykjavík, Iceland ([email protected]) (*correspondence: [email protected]) 2Reykjavík Energy, Baejarhálsi 1, 110 Reykjavík, Iceland The Peridote Mesa vent in San Carlos, Arizona, USA, is Groundwater flow is commonly studied by means of tracer known for its striking array of upper mantle xenoliths, and the tests. The tracers commonly used involve inorganic salts and gem quality peridot that is mined from them. While many organic compounds. The results of such tests in porous rocks studies have been conducted on the xenoliths, suprisingly little are based on the assumption that the tracers are inert, i.e. do is known regarding their host magma. Our previous not react with the solutions and/or minerals of the groundwater petrographic, analytical, and experimental work [1, 2] showed system. that the Peridot Mesa lava is not a basanite as previously In this study the chemistry of commonly used organic thought [3], but an evolved phonotephrite, and that the hydrological tracers were studied experimentally upon flow in phenocrysts are consistent with crystallization of anhydrous porous rocks. The tracers studied included Fluorescein, magma during rapid ascent. Phase equilibrium experiments on Rhodamine B, Sodium Naphthionate, Pyranine, Amino the lava composition failed to reproduce the observed Rhodamine G and Amino G in solutions of pH 3, 6 and 9 with phenocryst assemblage however, regardless of a variety of three types of porous sand, quartz, rhyolitic and basaltic sand. pressures, temperatures, and volatile contents [2]. The experiments were conducted using a Teflon flow-through Given the energetic magmatic environment required to reactor packed with the sand of interest. Experimental entrain and erupt such large (up to 50 cm dia) mantle xenoliths solutions with and without the tracers were alternatively on the surface, one hypothesis for the inability of phase pumped at fixed flow rates through the reactor and the tracer equilibrium experiments to crystallize the observed concentration at the outlet of the reactor continuously assemblage is that the erupted lava is the final product of monitored spectrophotometrically. The major chemistry of mixing of two or more magmas that had different the outflow solution was further studied. The experimental crystallization paths. This possibility is supported by the results were supported by 1-D reactive transport simulations observation that there are several older occurences of conducted with the aid of the PHREEQC program. In the eruptions with similar characteristics in the area [4], indicating simulations, dissolution of the solids and formation of a well-developed pathway for such magmas. secondary minerals was taken into account as well as possible As this mixing hypothesis must be ruled out before further sorption processes. According to the experimental results and phase equilbrium experiments are considered, an effort has the reactive transport simulations the primary rocks alter to been undertaken to identify and measure the composition of form secondary minerals and solutes that are partially melt inclusions in the phenocrystic phases found in rapidly transported out of them column (system). Some of the quenched scoria. Preliminary results from the electron hydrological tracers studied were observed to be non-reactive, microprobe on the bulk composition of the melt inclusions however, others seem to be affected by processes like show that, similar to the residual glass, there is not significant adsorption and desorption. The results imply that simulation variation in the liquid composition, suggesting that magma of groundwater flow in porous rocks based on tracer tests may mixing and/or assimilation of xenolithic material is not an not be valid in some cases without considering reactive important process, or is extremely rapid and efficient, transport and incorporating sorption reactions of the tracer resulting in a homogeneous magma. used. [1] Gullikson et al. (2010) AGU Fall Meeting Abstracts, 2263. [2] Gullikson et al. (2012) Mineralogical Magazine 76, 1790. [3] Frey & Prinz (1978) E.P.S.L. 38, 129–176. [4] Wrucke et al., (2004) Geological Investigation Series, U.S.G.S., I-2780.

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Detection of non-stoichiometric Recent Changes in Coastal Aquifers: silicate mineral dissolution in rivers Local effects expressed globally 44/40 draining alpine glaciers using " Ca WILLARD S. MOORE1 J. MOORE1,2, A. D. JACOBSON2, C. HOLMDEN2 1Department of Earth and Ocean Sciences, University of South AND D. CRAW3 Carolina, Columbia, SC USA, [email protected] 1 Department of Physics, Astronomy, & Geosciences, Towson Coastal populations are increasing rapidly, while potable University, Towson, MD 21252 USA (*correspondence: water supplies are decreasing due to over-pumping and sea [email protected]) 2 water intrusion into coastal aquifers. This problem has Department of Earth and Planetary Sciences, Northwestern affected almost all coastlines during the past century. Here I University, Evanston, IL 60208 USA focus on biogeochemical consequences of sea water intrusion ([email protected]) 3 into coastal aquifers, systems we call subterranean estuaries. Saskatchewan Isotope Laboratory, Department of Geological Oxygen is the most powerful oxidizing agent in most Sciences, University of Saskatchewan, Saskatoon, Canada waters. However, its oxidizing capacity is limited by solubility SK S7N 5E2 ([email protected]) 4 (maximum ~0.28 mmol/L). Once dissolved oxygen is Geology Department, University of Otago, Dunedin, New depleted, sulfate ion (~29 mmol/L in seawater) becomes the Zealand ([email protected]) electron acceptor of choice to facilitate carbon oxidation. Thus seawater has a great deal more oxidizing capacity than fresh Rivers draining glaciers frequently have high Ca water. The reaction products of sulfate oxidation of organic concentrations, which have been attributed to the dissolution matter include both inorganic and organic forms of dissolved of carbonate minerals, even in predominantly silicate N, P, and C as well as sulfide. Additionally, reducing watersheds. Apportioning riverine Ca between silicate and conditions in the aquifer lead to reduction of iron and carbonate weathering is typically done with the “Ca/Na manganese oxides. This increases concentrations of Fe2+ and method,” which assumes that plagioclase is the dominant Mn2+ as well as other metals, plus ions that were absorbed source of silicate Ca and that Ca and Na are released in onto the oxides. As this chemically-altered seawater stoichiometric proportions. Here, we tested whether high- 44/40 exchanges into coastal waters as submarine groundwater precision Ca isotope measurements (" Ca by MC-TIMS, discharge, it carries high nutrient, carbon, metal, and sulfide 2! =±0.07‰) could track Ca sources to non-glacial and SD concentrations. glacial rivers draining the Southern Alps of New Zealand. The Continued seawater intrusion will lead to greater inland mountain range consists of schist and greywacke containing expansions of subterranean estuaries. This expansion may trace hydrothermal calcite (1-3%). Hydrothermal calcite and produce greater total SGD fluxes of nutrients, carbon, and silicate rocks are isotopically distinct. The Ca isotope metals because the biogeochemical reactions that affect their composition of rivers is consistent with mixing between concentrations will operate over larger spatial scales and affect calcite and silicate sources. Glacial rivers are statistically portions of aquifers that have not been in contact with different than non-glacial rivers (p < 0.001) and have more 44/40 seawater for thousands of years. negative " Ca values. The glacial rivers plot closer to the silicate end-member. We observe no evidence for isotopic fractionation as a factor controlling the variability in stream water "44/40Ca values. For non-glacial rivers, carbonate weathering provides ~50 – 90% of the riverine Ca, and more importantly, the Ca/Na and Ca-isotope source apportionment methods yield the same results within 2%. However, for glacial rivers, the Ca-isotope method yields 25% more Ca from silicate weathering compared to the Ca/Na method. Taken together, the data point to the enhanced release of silicate Ca in glacial watersheds. We attribute the effect to non-stoichiometric release of Ca from silicate mineral surfaces damaged by glacial grinding. One implication is that alpine

glacial watersheds may consume atmospheric CO2 at higher rates than previously realized.

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Insights into glacial weathering from Dust direct radiative forcing and the a new hydrochemical database from complex refractive index of hematite 95 glaciated catchments H. MOOSMÜLLER* AND J. P. ENGELBRECHT NILS MOOSDORF1, JENS HARTMANN1 Desert Research Institute, Nevada System of Higher AND JOSHUA A. WEST2 Education (NSHE), Reno, NV 89512, USA 1 (*correspondence: [email protected]) University of Hamburg, KlimaCampus, Bundesstraße 55,

20146 Hamburg, Germany ([email protected]) 2 Ambient light absorption of entrained mineral dust in the University of Southern California, Department of Earth visible and near-visible spectral region is generally dominated Sciences, Los Angeles, CA 90089, USA by iron oxides, in particular by hematite ((-Fe O ) [1, 2]. 2 3 Therefore, sign and magnitude of mineral dust direct radiative Chemical rock weathering in glaciated areas is involved in forcing are critically dependent on the complex refractive several feedback loops in the earth system. The fluxes and index spectrum of hematite, especially its imaginary part. geochemical characteristics of glacial weathering have been Here, we discuss the sensitivity of mineral dust shortwave assessed at many single locations, but only a few studies have radiative forcing on the imaginary part of the hematite compared multiple sites [e.g. 1] to draw broader conclusions. refractive index. Here we present a new database compiled from 95 Spectra of the imaginary part of the hematite refractive glaciated catchments, published by 46 sources. This database index have been reported in more than 15 publications. allows to analyze general patterns associated with the effect of Unfortunately, these literature values vary greatly, between glaciers on chemical weathering. one and nearly five orders of magnitude for different parts of

the spectrum (Fig. 1). In addition, virtually all of these publications fail to give an error estimate for their results. Here, we review these published values together with the respective methods of determination. attempting to give a recommendation for values and errors that should be used. Furthermore, we estimate the error in dust radiative forcing originating from the uncertainty in hematite refractive index.

Figure 1: Precipitation corrected cation concentrations against glacial cover. Each point represents one catchment.

The first analysis of the database shows that cation concentrations decrease with increasing glacial cover (Figure Figure 2: Imaginary part of the hematite refractive index as 1). Mean concentrations are below the global average of 875 function of wavelength as obtained from 15 different µMol/L [2], but cation denudation rates are on average 21.4 t publications. km-2 a-1, above the global average of 10 t km-2 a-1 [3]. [1] Lafon et al. (2006) J. Geophys. Res., 111, The database will be analyzed in depth to identify doi:10.1029/2005JD007016. [2] Moosmüller et al. (2012) J. relations between ion concentrations, weathering rates, Geophys. Res., 117, doi:10.1029/2011JD016909. stochiometry and seasonality with potential influencing factors

(e.g. dominating lithology).

[1] Anderson et al. (1997) Geology 25, 399-402. [2] Livingstone (1963) In: Fleischer (Ed.), Data of Geochemistry, Sixth Edition. USGS Professional Papers, pp. 1-61. [3] Hartmann et al. (in prep).

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Composition of the Earth’s core from Origin of noble gases on Earth: a density measurements of liquid iron mixture of Solar, solar wind alloys at megabar pressure implantation and phase Q G.MORARD1,*, D.ANTONANGELI1, J.SIEBERT1, MOREIRA MANUEL1 AND CLAIRE ROUBINET2 2 3 1,5 D. ANDRAULT , N.GUIGNOT , F.GUYOT 1 4 [email protected] AND G.GARBARINO 2 [email protected] 1Institut de Minéralogie et de Physique des Milieux Condensés, Univ. Pierre et Marie Curie, Paris, France The origin of noble gases on Earth is debated since more *correspondence: [email protected] than 70 years and the observation that the noble gas elemental 2Laboratoire Magmas et Volcans, Clermont-Ferrand, France relative abundances are not solar [1]. Mantle and atmospheric 3Synchrotron SOLEIL, Gif-sur-Yvette, France noble gas isotopic compositions are neither chondritic nor 4European Synchrotron Radiation Facility, Grenoble, France solar, at the exception of the neon isotopic ratio that shows a 5 Institut de Physique du Globe de Paris, France value intermediate between the chondritic components and the solar value, wlode to the neon B value. Since the works of The liquid core of the Earth extends between 2900 km and Cafee et al. [2] and Holland et al. [3], the question of the 5150 km depth accounting for 18% of the total planetary terrestrial primordial isotopic composition of the Kr and Xe is volume. Although mostly composed of iron, it contains discussed. They show that the primordial mantle might have impurities that lower its density and its melting temperature been chondritic instead of atmospheric. In addition to that, with respect to pure Fe. Knowledge of the nature and content Pujol et al. [4] have shown that the archean atmosphere might in light elements (O, S, Si, C) in the core has major have been chondritic, suggesting a xenon loss fractionation implications for establishing the bulk composition of the Earth accompanied with mass fractionation. A major implication of and for building models of Earth’s differentiation. these observations is the massive subduction of atmospheric Angle dispersive X-ray diffraction experiments in double- xenon in the whole mantle. sided laser heated diamond anvil cell (LH-DAC) were We show in this study that the Ne and Ar were added to performed at ID27 beamline at the European Synchrotron the parent bodies of the Earth by solar wind implantation. Radiation Facility (ESRF) in Grenoble. In situ investigations Atmospheric Kr isotopes, on contrary, suggest a late veneer of enable determination of melting temperature and structural cometary material with a solar composition added to the and density properties of the Fe-based alloys. Experiments chondritic krypton degassed from the mantle. The primordial were performed on an Fe-Ni-S alloy up to 94 GPa and 2800 K noble gas compositions on Earth are therefore a mixture and on an Fe-Ni-Si alloy up to 91 GPa and 3200 K. New between the chondritic, solar, and implanted solar wind. An results on Fe-O and Fe-C liquid alloys will be also presented. unknown isotopic fractionation has modified the isotopic The appearance of a diffuse X-ray scattering signal at composition of the xenon of the atmosphere, without affecting wavevectors of about 30 nm-1 was used to determine the onset the other noble gases. Subduction of atmospheric Kr and Xe of melting. Extrapolations of measured melting curve up to the into the whole mantle is required in such a model. core–mantle boundary pressure yielded values of 3,600–3,750 K for the freezing temperature of plausible outer core [1] Brown, H. (1949). In The Atmospheres of the Earth and compositions. We extracted densities and compressibilities Planets. E. G. Kuiper. Chicago, University of Chicago Press: from the diffuse X-ray signal scattered by the liquid up to 258-266. [2] Cafee, M. W., G. P. Hudson, et al. (1999). megabar conditions, using a method developed for diamond Science 285: 2115-2118. [3] Holland, G. and C. J. Ballentine anvil cells by Eggert and collaborators [1]. The obtained (2006). Nature 441: 186-191. Holland, G., M. Cassidy, et al. equations of state parameters indicate that sulfur, and not (2009). Science 326: 1522-1525. [4] Pujol, M., B. Marty, et silicon, can more easily account for the differences in density al. (2011). Earth and Planetary Science Letters 308: 298-306. and bulk modulus between pure iron and a reference Earth seismic model. This challenges traditional Earth’s accretion and differentiation models, that do not foresee S as major light element in the core. These results thus rather argue for strong disequilibrium Earth formation mechanisms.

[1] Eggert, Weck, Loubeyre and Mezouar (2002), Phys RevB, 2002, 65, 174105

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Nd and Sr isotope geochemistry of Speciation study in the sediments and associated biota from sulfamethoxazole-copper-pH-soil Tagus and Sado estuaries (Portugal) system: Implications for antibiotic S. MOREIRA1*, M.C. FREITAS1, J. MUNHÁ1, C. retention prediction in soils ANDRADE1 AND C. TASSINARI2 M.-C. MOREL, L. SPADINI*, K. BRIMO 1Universidade de Lisboa, Fac. Ciências, Departamento de AND J.M.F. MARTINS Geologia, Centro de Geologia. 1749-016 Lisboa, LTHE Laboratory., UMR5564 CNRS, University of Grenoble Portugal. (*correspondence: [email protected]) 1, BP 53, 38041 Grenoble Cedex 09, France 2Universidade de São Paulo, Centro de Pesquisas (*correspondence [email protected]) Geocronológicas. CEP 05508-080 - São Paulo, Brasil. ([email protected], jean.martins@ujf-

grenoble.fr) This study reports on Nd and Sr isotopes and elemental

geochemistry of sediments and associated biota (Spartina Most antibiotic substances are acid-base reactive and maritima; Scrobicularia plana) collected in the intertidal metal complexing. These characteristics determine specific domain of Sado and Tagus estuaries. Sediments display UCC chemical relationships for the prediction of their retention in type REE patterns, but variable 143Nd/144Nd (0.512171– soils, aquifers, and suspended matters. The results for 0.512325) and 87Sr/86Sr (0.715367–0.725351) isotopic ratios, Sulfamethoxazole (SMX), a persistent sulfonamide antibiotic which tend to decrease with increasing Ca/Al and Si/Al commonly found in natural waters, is presented. The values. The observed variations of isotopic ratios suggest that + speciation of the SMX - Cu(II) - H system in solution and the Nd and Sr in the Tagus and Sado estuarine sediments were combined sorption of these components on a natural vineyard mainly derived from an heterogeneous UCC source (e.g., old whole soil were investigated by acid base titrimetry and recycled CIZ shales + juvenile IPB volcanics) with variable Infrared Spectroscopy. Cu(II) is considered to represent a inputs from relatively unradiogenic, Ca, Si – rich, marine 2+ +2 strongly complexing trace element cation (such as Cd , Zn , components. S.maritima and S.plana tissues have 143Nd/144Nd Pb+2, Ni+2, etc.) in comparison to major but more weakly isotopic ratios (0.512272–0.512330 and 0.512197–0.512204, ++ ++ binding cations (such as Ca and Mg ). The analysis showed respectively), which are similar to those of their host that SMX is a medium to weak copper complexing agent and sediments; however, 87Sr/86Sr values (0.709193–0.709408 and it also qualifies as a weak to medium soil sorbate at pH 6. 0.709321–0.710204, respectively; excepting visceras of However, the sorption of SMX in soil increases strongly in the S.plana bearing lithic particles = 0.712855) are much lower presence of copper. This strongly supports the hypothetical then those of their sedimentary substrate. These results formation of ternary SMX-Cu-soil complexes, especially indicate that Sr and REE in S.maritima and S.plana tissues had when considering the almost quantitative sorption of the distinct sources; metabolic Sr was mostly derived from strongly sorbing copper. The data were successfully modelled seawater, whereas REE were bio-processed from sources with the assumption of the existence of binary and ternary identical to those of the estuarine sediments. surface complexes in equilibrium with aqueous Cu, SMX and

Cu-SMX complexes. It is thought that other strongly Speciation study in the complexing cations such as Cd(II), Ni(II), Zn(II), Pb(II), sulfamethoxazole-copper-pH-soil Fe(II/III), Mn(II/IV) and Al(III) present on the surface of reactive organic and mineral soil phases affect the system: implications for antibiotic solid/solution partitioning of SMX, and that the sorption retention prediction in soils strength may be estimated from existing sorption constant relationships. This study thus suggests that the state of M.-C. MOREL, L. SPADINI*, K. BRIMO AND surface-adsorbed cations significantly affects the sorption J.M.F. MARTINS strength of SMX, and that the interactions may be predicted by combining equilibrium analysis and modeling studies.

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Arsenic-chloride exchange in the Cyclic subduction of the Aeolian Arc: Pecora River Valley (Southern Evidence from Salina. Tuscany, Italy) MORETTI, H.C.1*GOTTSMANN, J.C., 1BLUNDY, J.M. 1 2 1 1,2 3 AND G. MORELLI *, M.GASPARON P.COSTAGLIOLA , V. SULPIZIO, R. 3 3 3 RIMONDI , M.BENVENUTI , F.DI BENEDETTO , 1*Department of Earth Sciences, University of Bristol, BS8 3 3 P.LATTANZI , AND M.PAOLIERI 1RJ, [email protected] ( [email protected]), ([email protected]) 1School of Earth Sciences, The University of Queensland, 2Universitá di Bari A. M., 70125, ([email protected]) Brisbane, Qld, 4072, Australia (*[email protected]) 2 National Centre for Groundwater Research and Training, The island of Salina is part of the Aeolian Arc of Italy, Australia 2 located in the southern Tyrrhenian Sea. It occupies a central Dipartimento di Scienze della Terra, Università degli Studi di position at the junction of a sub-arcuate chain of seamounts Firenze, Florence, Italy and volcanic islands with a linear belt of volcanic islands High concentrations of As have been documented in large defined by the Tindari-Letojanni fault and is related to a aquifers (e.g. Bangladesh, China, India -West Bengal [1]) and steeply dipping Beniof zone. Volcanic activity on Salina has coastal Holocene/Quaternary alluvial plains where fresh stretched from 430ka to 13ka, initially consisting of mafic groundwater mixes with intruding seawater [2]. Very high As lavas and concluding with more evolved, mingled, basaltic concentrations have been measured in the alluvial sediments andesite and rhyolite explosive eruptions. (As>500mg/kg) of the Pecora River (Southern Tuscany, Italy; Geochemical evidence from basalts across the Aeolian [3]). As concentrations exceeding 10 ,gL-1 [4] have been Arc suggests that whilst Panarea, Salina and Lipari have a recorded in some of the groundwaters potentially exposed to strong signature of fluid metasomatism from a subducting seawater intrusion caused by aquifer overexploitation. To slab, the outlying islands of Alicudi and Stromboli have a quantify how the ionic exchange between As oxianions more complex genesis with evidence of slab sediment melting, (adsorbed on minerals’ surfaces) and seawater Cl- may inflowing mantle and crustal assimilation [1]. contribute to the release of As in groundwater, desorption A temporal trace element analysis for Salina shows the kinetic experiments were carried out on three samples from amount of Barium, for example, varies across eruptions; some this alluvial deposit. After 24 hours, desorption experiments more evolved eruptions have significantly higher barium for using four aqueous solution with different salinity extracted similar levels of silca and suggest a marked cyclicity that may between 20 and 80 ,gL-1 of As, with the highest levels not be driven by fractionation alone. The variations are extracted by seawater. For longer desorption periods (~20 examined to determine the degree to which they are driven by days), the samples were saturated with the same solutions to changes in subduction fluid metasomatism as opposed to constrain the timing of the As-Cl reaction. The solutions with increased assimilation of crustal materials or changes in the Cl-<2000 mgL-1 extracted <20 ,gL-1 of As after at least 8 style of fractionation. days, while the extracted As using seawater varied between 20 and 60 ,gL-1 Compared to other experimental studies [5], the percentage of extracted As is much lower (< 0.04% of the total) because the mobile (and thus potentially bioavailable) As is only 9-11% of the total As, which is mainly associated with relatively stable Fe-oxides and sulphides. This study deomostrates the importance of a rigorous mineralogical characterization for a prediction of potential As release from coastal aquifers following seawater intrusion.

[1] Smedley and Kinniburgh (2002) App. Gechem 17, 517– 568. [2] Liu et al. (2003) Sc.Tot.Envir. 313, 77–89. [3] Costagliola et al. (2008) App. Gechem. 23, 1241– 1259. [4]

Rossato and Tanelli (2009), Rendiconti Online Soc. Geol. It., [1] Francalanci et al., in Beccaluva, Bianchini and Wilson, 6, 404-405. [5] Goh and Lim (2005) App. Gechem. 20, 229– Cenozoic volcanism in the Mediterranean Area, p235-264, 239. (2007).

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Pathways of redox state and sulfur Bend-Faulting, Serpentinization, and release track the shift from low- Mantle Recarbonation at Trenches energy to highly-explosive basaltic JASON P. MORGAN1 eruptions at Mt. Etna 1Earth Science Department, Royal Holloway Univ. London, 1,2 3 3 6 Runnymede, Surrey, TW20 0EX MORETTI R. , MÉTRICH N. , ALLARD P. , AIUPPA A. , 2 1 ([email protected]) ARIENZO I. AND DI RENZO V.

1 DICDEA, Seconda Università degli Studi di Napoli, Aversa It is well known that mid-ocean ridges are a key site for (CE), Italy chemical interactions between oceanic crust and the 2 INGV, sezione Osservatorio Vesuviano, Napoli, Italy hydrosphere, and that these interactions modulate the 3 IPGP, Sorbonne-Paris Cité, Univ. Paris Diderot, UMR 7154 chemistry of the oceans. Subduction forearcs are also key CNRS, Paris France sites of chemical fluid-rock exchanges. These fields are likely 4 DiSTeM, Università di Palermo, Palermo, Italy to still have many surprises to reveal, but are relatively mature. However, it is becoming increasingly evident that the Basaltic magmas can transport and release large amounts oceanic lithosphere may also strongly interact with the of volatiles into the atmosphere, especially in subduction hydrosphere during plate subduction, as it bends — by bend- zones, where slab-derived fluids enrich the mantle wedge. Mt. faulting — when it enters a trench. I briefly review recent Etna in Sicily, is one typical basaltic volcano where the seismic evidence collected by the SFB574 and others that volatile control on variable activity (effusive to Plinian) can be suggests that bend-faulting is associated with ~10-20% investigated. Based on a melt inclusion study of sulfur in serpentinization in a layer extending at least 5km below the products from Strombolian or lava-fountain activity to Plinian Moho. If this serpentine forms with a 1% carbonate fraction eruptions, here we show that different eruptive styles (note that at least this degree of carbonitization occurs during correspond to distinct sulfur degassing paths. Depending on mid-ocean-ridge serpentinization processes), then bend- their initial water content, oxidation state, and extent of CO2- faulting-linked serpentinization will consume an atmosphere’s

fluxing, Etnean magma batches can soon reach the limit of worth of CO2 every 40,000 years, and it is likely that the sulfide saturation or get rid of sulfur on degassing only. Melt carbonate storage in serpentinized subducting lithosphere inclusion data indicate that the magma involved in the exceeds that in overlying oceanic crust and sediments. This 6+ powerful 122 BC Plinian eruption is richer in sulfate (S /Stot > poorly-understood geological process clearly merits further 0.65) than the magmas erupted during less energetic explosive study, with significant potential implications for the global February 1999 and Strombolian effusive 1997-98 eruptions. carbon cycle, for the geochemical evolution of the mantle, and We propose a direct relationship between the high sulfate for human exploitation for potential carbon sequestration at 2- (SO4 ) content in melts and hence high oxidation state of the oceanic trenches. CO2-rich fluids released by melts and the magnitude of an eruption. Highly oxidized deserpentinization reactions may even play a role in 6+ conditions ([S /Stot]melt and SO2,gas/[H2S+SO2]gas > 0.6 ) in ‘lubricating’ the subduction channel, and in the volatilization Etnean magma batches enhance the probability of violent of the forearc. While bend-faulted Moho lies within the explosive eruptions, such as the 122 BC Plinian event. The potential drilling window for the Chikyu marine drilling different patterns of sulfur release (oxidized vs reduced) of platform, it may prove to be much easier to gain constraints on Etnean magmas are discussed and modeled. bend-fault-related serpentinization from observations on Alpine serpentinites. Another critical observation to begin to document this interaction would be to find and study an active site of bend-fault fluid venting at the seafloor — with candidate sites evident in swath-mapping and deep-bottom photos offshore Central America.

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Potassium stable isotopic Diffusion of Helium in the mantle: an compositions measured by high- explanation for MORB-OIB patterns resolution MC-ICP-MS of 3He/4He ratios L.E. MORGAN1, N. LLOYD2, R. ELLAM1, J. I. SIMON3, W. JASON MORGAN1, AND JASON P. MORGAN2 4 AND M. TAPPA 1 Earth Science Department, Harvard Univ., Cambridge, MA, 1Scottish Universities Environmental Research Centre, USA ([email protected]) Rankine Ave., East Kilbride, G75 0QF, UK 1Earth Science Department, Royal Holloway Univ. London, (*correspondence: [email protected]) Runnymede, Surrey, UK ([email protected]) 2ThermoFisher Scientific, Hanna-Kunath Str. 11, 28199 Bremen, Germany OIBs have a wide range of 3He/4He ratios, MORBs have 3Center for Isotope Cosmochemistry and Geochronology, a much narrower range peaked at 3He/4He 7 8 Ra. In addition, ARES, NASA JSC, Houston, TX 77058, USA the ratio of 3He/20Ne (both stable isotopes) is significantly 4JE-23 ESCG/Jacobs Technology, Houston, TX 77258, USA higher in MORB than in OIB, likewise the ratio of 4He/21Ne (both daughter isotopes produced by U and Th decay) are Potassium stable isotopic (41K/39K) compositions are similarly higher in MORB than OIB. (Stable 3He/36Ar and notoriously difficult to measure. TIMS measurements are radiogenic 4He/40Ar have the same pattern as the He/Ne hindered by variable fractionation patterns and too few plots, only with more scatter.) [See Honda and Patterson, isotopes to apply an internal spike method for instrumental GCA 63, 1999.] To explain this, we assume that rising mantle mass fractionation corrections. Internal corrections via the plumes are ‘lumpy’; a mixture that includes lumps of 40K/39K ratio can provide precise values and are appropriate in primordial mantle (which will be rich in 3He, 20Ne, 22Ne, some cases (e.g. identifying excess 41K [1]) but not others 36Ar, etc.) as well as lumps containing the EM1, EM2, HIMU (e.g., determining fractionation effects and metrologically- components, all in a general matrix of relatively-barren, traceable isotopic abundances). SIMS analyses have yielded previously-melted 'harzburgite'. When the rising lumps results with 0.25‰ precisions [2]. Previous studies have not (plums) melt, the He, Ne, Ar, and most of the other resolved isotopic variation in terrestrial materials. incompatible elements will go into the melts that are known as We measured 41K/39K ratios on NIST K standards with < OIB. But not all of the lumps melt (near the cooler edge, some 0.07‰ precisions (1!) on the Thermo Scientific NEPTUNE don't rise shallow enough to pressure-release melt); those that Plus MC-ICP-MS. 39K and 41K were sufficiently resolved from don’t melt go into the asthenosphere, flowing horizontally the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma away from the rising column. At a spreading center, this and high-resolution mode. Measurements were made on asthenosphere contributes the ‘plums’ left over from OIB narrow but flat, interference-free, plateaus (ca. 50 ppm by partial melt-extraction but also some of the more barren matrix mass width for 41K). Although ICP-MS does not yield accurate that the plums are embedded in becomes part of the melt 41K/39K values due to significant instrumental mass because of the higher extents of partial melting that occur fractionation (ca. 6%), this bias is sufficiently stable that when making MORB. What is the effect of diffusion? If the relative 41K/39K values can be precisely determined via helium, because of its small size, can diffuse a distance of 100 sample-standard bracketing. Measurement tolerances on m or 1000 m in a billion-plus years (the ‘age’ of a lump) matrix effects that are amplified by the cold plasma were whereas neon or argon diffuse only decimeters or centimeters tested; the use of clean samples and standards is critical. in this time because of their larger radii (i.e., not much more On the Thermo Scientific TRITON TIMS, using a co- than non-noble incompatible elements like K, Rb, or U can loaded Rb standard to normalize for fractionation, accurate but diffuse), then the 3He and 4He (and H) can diffuse far out into less precise 41K/39K ratios have been measured. Differences in the 'barren harzburgite' matrix. Thus when the lumps in a 41K/39K between NIST K standards identified via MC-ICP-MS plume melt there will be a shortage of 3He and 4He relative to are also apparent in the TIMS data. Combined, these the 20Ne, 21Ne, or argon. With the extensive melting that approaches yield more reliable K isotopic measurements than occurs to make MORB, fluxing causes some of the barren were previously possible and may allow for the identification matrix to contribute its 3He and 4He to the MORB melt which for the first time of sub-permil terrestrial variations in 41K/39K. results in an excess of helium relative to neon and argon. This extraction of helium from the longtime-diffused-into barren [1] Wielandt and Bizzarro, 2011. [2] Humayun and Clayton, matrix also can explain the uniformity of the 3/4 ratio in 1995. MORB as opposed to the variability of 3/4 in OIB.

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Structure and reactivity of Light hydrocarbons and dissolved nanocrystalline iron oxides in the organic carbon in shallow aquifers of environment the St. Lawrence Lowlands: 13 GUILLAUME MORIN1, FABIEN MAILLOT1, AREEJ ADRA1, Concentrations and " C signatures 1 1 MARC BLANCHARD , GEORGES ONA-NGUEMA , 1 2 1 1 ANJA MORITZ , JEAN-FRANCOIS HELIE , DANIELE YUHENG WANG , NICOLAS MENGUY 2 2 2 2 PINTI , MARIE LAROCQUE , DIOGO BARNETCHE AND GORDON E. BROWN JR . 1 AND YVES GELINAS 1 Institut de Minéralogie et de Physique des Milieux Condensés 1 Concordia University, 7141 Sherbrooke West, Montreal, QC, (IMPMC), Environmental Mineralogy, UMR 7590 CNRS H4B 1R6, Canada – UPMC – IRD. 4 place Jussieu, 75252 Paris cedex 05, [email protected], [email protected] France 2 UQAM, 405 rue Sainte-Catherine East, Montreal, QC, H2L 2Department of Geological & Environmental Sciences, 2C4, Canada Stanford University, Stanford, CA 94305-2115, USA [email protected], [email protected],

[email protected], [email protected] Iron (oxyhydr)oxides are widespread minerals in Earth’s surface environments. They exhibit a large variety of polymorphic structures that can be used as tracers of Recent field studies identified a new source of natural gas physicochemical conditions of formation, especially redox and in Quebec: shale gas. These gases are mainly found in the pH. Moreover, structural defects and inorganic and organic Utica Shale and result from kerogen cracking. Gases formed impurities are also potential indicators of formation pathways, from kerogen cracking are referred to as thermogenic gases either biotic or abiotic. When formed at ambient temperature, and are mainly composed of methane, ethane and propane. iron oxide minerals usually have sub-micron size, which Due to the presence of natural faults in the bedrock above the enhances their surface reactivity. Although the properties and Utica Shale, these gases can migrate and contaminate the occurences of iron oxide minerals have been studied for shallow aquifers that are exploited for human consumption. several decades, recent advances have been made in Contamination of the aquifers can also be caused by the understanding the structures of nanocrystalline iron migration of biogenic gases formed by methanogenic bacteria oxyhydroxides as well as their surface reactivity. in surface wetlands and lake sediments. As part of an effort In the present communication, we will review recent initiated by the Québec Commission d’étude environnementale spectroscopic investigations of ferrihydrite [1], stratégique on shale gases, the project consists in the schwertmannite [2], and nanomagnetite [3] that play a key role development and implementation of the methods and the in iron and trace element cycling in the environment and in analysis of the concentration and the isotopic signature of water treatment technologies. Local structures of these mineral these light hydrocarbons and dissolved organic carbon (DOC) phases, including the status of sorbed or coprecipitated in groundwater samples. The stable isotope analyses will help impurities, will be discussed based on Extended X-ray determine the origin of the gas and DOC in these samples, Absorption Fine Structure (EXAFS) analyses. Implications for including the discrimination between Utica shale gas and the remediation of arsenic contaminated waters in mining conventional gas. Water samples have been collected from environments will be especially adressed. In addition, we will >100 wells in the St. Lawrence Lowlands (Québec, Canada). present specific properties of nanomagnetites for scavenging pollutants such as arsenic via precipitation, sorption, and redox reactions. Spectroscopic results will be interpreted in light of theoretical calculation for arsenic sorption onto the surface of the reference mineral, hematite.

[1] Maillot et al. 2011 GCA 75, 2708-2720. ; [2] Maillot et al. 2013 GCA 104, 310-329 ; [3] Wang et al. 2011 ES&T 45, 7258-7266 ; [4] Blanchard et al. 2012 GCA 86, 182-195

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Seasonal distributions of archaeal Technological challenges for the membrane lipids and TEX86 advanced study of subseafloor life thermometry in the modern shallow YUKI MORONO1*, TAKESHI TERADA2, MOTOO ITO1 coastal ocean TATSUHIKO HOSHINO1 AND FUMIO INAGAKI1 1 1 2 3 Kochi Institute for Core Sample Research, Japan Agency for MORIYA, K.* , KUWAE, M. , YAMAMOTO, M. , 4 2 5 2 Marine-Earth Science and Technology (JAMSTEC), KUHINIRO, T. , ONISHI, H. , HAMAOKA, H. , SAITO, M. , 2 6 2 2 Monobe B200, Kochi 783-8502, Japan. (*correspondence: SAGAWA, T. , FUJII, N. , YOSHIE, N. , OMORI, K. AND 2 [email protected]) TAKEOKA, H. 2 Marine Works Japan Ltd., Oppamahigashi 3-54-1, Yokosuka 1 Fac. of Natural System, Kanazawa Univ., Japan. 237-0063, Japan. (*correspondence: [email protected]) 2 Center for Marine Environ. Studies, Ehime Univ., Japan. During the past decades, scientific ocean drilling has 3 Div. Earth System Science, Hokkaido Univ., Japan. explored the subseafloor biosphere at some representative 4 Royal Netherlands Inst. for Sea Res., Yerseke, Netherlands. drilling sites: on the ocean margins, organic-rich anaerobic 5 National Res. Inst. of Fisheries and Environ. of Inland Sea, sedimentary habitats (e.g., Shimokita coalbeds) harbor sizable Fisheries Research Agency, Japan. numbers of microbial cells over 1,000 meters below the 6 Inst. Lowland and Marine Rese., Saga Univ., Japan. seafloor whereas microbial populations in ultra-oligotrophic aerobic sedimentary habitats of the oceanic gyre (e.g., South While a large number of studies have documented rapid Pacific Gyre) are several orders of magnitude lower. increase in the annual sea surface temperature (SST) and Molecular analysis at the community level demonstrates the global mean sea level rising, global warming effect on occurrence of subseafloor microbial ecosystems that consist of enclosed coastal seas, such as Seto Inland Sea or Chesapeake phylogenetically diverse microbes; however, metabolic Bay, is less understood. For understanding historical SST functions of individual microbial components and strategies records in these shallow basins, we need to utilize a certain for long-term survival under the energetically and SST proxy preserved in sediments. However, paleo- geophysically severe condition have remained largely thermometry in the shallow coastal basin is rather difficult unknown. To address these issues, analytical developments because carbonate microfossils typically used for customized for subseafloor life are of our essential challenges paleotemperature proxies are practically absent in the shallow for the advanced microbiological and biogeochemical ocean. On the hand, it is expected that organic compound analyses. based paleo-temperature proxies, such as TEX86, can be One of the most fundamentally significant techniques is utilized even in the shallow coastal sea. However, since TEX86 the precise detection and enumeration of indigenous thermometry has rarely been used for such shallow marine subseafloor life. Recently, we have standardized an improved sediments, applicability of TEX86 in the coastal ocean is still cell separation method, which effectively detached the cells uncertain. from mineral grains of the sedimentary habitat, by applying Here we test potential ability of TEX86 paleothermometry multiple density gradient layers. Based on the cell-derived in shallow coastal anoxic basin. We collected particulate fluorescent wavelength pattern [1], the detached cells can be organic matters from the water column of Beppu Bay (Seto precisely enumerated using an automated fluorescent Inland Sea) (~70m deep) at every 10 m. The vertical depth microscopic system [2] and/or a flow cytometry. The profile of glycerol dialkyl glycerol tetraethers (GTGTs) combined use of this technique with a cell sorter allows us to distribution within the anoxic and oxygen-enriched water separate the cells for single cell genomics and mass columns was determined. We also calculated TEX86 values, spectrometry (e.g., NanoSIMS) analyses. The systematic H L TEX86 and TEX86 temperatures which were compared with analytical scheme currently applies to some representative the in situ measurements of water temperatures. deep-biosphere samples such as the South Pacific Gyre and Comparing total GDGTs in the anoxic water mass to those Shimokita coalbeds (i.e., IODP Expedition 329 and 329, of the oxygen-eiriched water mass, those are significantly respectively), from which results may open a new window to H/L abundant in the anoxic bottom water. TEX86 derived the study of subseafloor life. temperatures correlate with the in situ measurements of water temperatures. Therefore it is expected that temperatures [1] Morono et al. (2009) ISME J. 3, 503-511. [2] Morono et H/L delived from TEX86 represent in situ water temperatures in al. (2010) Sci. Drilling 9, 32-36. Beppu Bay.

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Characterization of the deep Crystal-chemical analyses of soil and microbial life at different CCS sites drilled rock in Gale crater, Mars DARIA MOROZOVA1*, DOMINIK NEUMANN1, MICHAEL S.M. MORRISON1*, R.T. DOWNS1, D.F. BLAKE2, ZETTLITZER2 AND HILKE WÜRDEMANN1 D.L. BISH3, D.W. MING4, R.V. MORRIS4, A.S. YEN5, 7 6 7 1 S.J. CHIPERA , A.H. TREIMAN , D.T. VANIMAN , Helmholtz Centre Potsdam GFZ, International Centre for R. GELLERT8, C.N. ACHILLES4, E.B. RAMPE4, Geothermal Research, Hermannswerder 15, 14473 T.F. BRISTOW2, J.A. CRISP5, P.C. SARRAZIN9, Potsdam, Germany. *Correspondence: J.M. MOROOKIAN5 AND THE MSL TEAM [email protected] 2 RWE Dea AG, Laboratory Wietze, Industriestraße 2, 29323 1 U. Arizona, Tucson, AZ 85721, USA (*correspondence: Wietze, Germany [email protected]) 2 NASA ARC, Moffett Field, CA 94035, USA Deep subsurface formations like subsurface saline aquifers 3Indiana U., Bloomington, IN 47405, USA or depleted gas reservoirs are candidate sites for the carbon 4NASA JSC, Houston, TX 77058, USA capture and storage (CCS) technology. Since the Earth 5JPL-Caltech, Pasadena, CA 91109, USA subsurface is known to be a major habitat for a high number of 6LPI, Houston, TX 77058, USA different groups of microorganisms, our working group aims 7PSI, Tucson, AZ 85719, USA at microbial monitoring at different CCS-sites in Germany (a 8U. Guelph, Guelph, ON N1G 2W1, Canada 650m-deep saline aquifer and a 3.5km-deep depleted gas 9SETI Institute, Mountain View, CA 94043 reservoir). Both sites are characterized by high salinity (325 g/l and up to 420 g/l) and relatively high TOC content (up to The CheMin instrument on the Mars Science Laboratory 150 mg/l and up to 300 mg/l). In order to characterize the Rover Curiosity performed X-ray diffraction analyses in Gale microbial life in extreme habitats we aim to localize and crater on both martian soil at Rocknest [1] and drilled rock at identify microbes including their metabolism influencing John Klein. Crystalline phases were identified and their mineral creation and dissolution. The ability of abundances and unit-cell parameters were refined with the microorganisms to speed up dissolution and formation of Rietveld method [2]. Crystal-chemical systematics, using data minerals might result in changes of the local permeability and from the literature, were developed for the observed phases

the long-term safety of CO2 storage. Genetic fingerprinting and were used to estimate the chemical compositions of the (PCR SSCP, DGGE), qPCR and FISH are applied for martian minerals. identification and quantification of changes in deep microbial Estimated Rocknest soil mineral compositions:

community caused by the injection of supercritical CO2. olivine: (Mg0.63(3)Fe0.37)2SiO4

Although saline aquifers could be characterized as an plagioclase: (Ca0.57(13)Na0.43)(Al1.57Si2.43)O8

extreme habitat for microorganisms due to high pressure and augite: [Mg0.87(10)Fe0.40Ca0.73(4)]Si2O6

salinity, a high number of diverse groups of microorganisms pigeonite: [Mg1.13(9)Fe0.70(10)Ca0.17]Si2O6 were observed with molecular biological methods in downhole In addition to the crystalline component, there is also an samples from the injection and observation wells at a depth of amorphous component. Subtracting the weighted chemistry of about 650m depth. Of great importance was the identification the crystalline component from the bulk composition, of the sulfate reducing bacteria, which are known to be determined by APXS [3], provides an estimate of the amount involved in corrosion processes. Microbial monitoring during and chemical composition of the amorphous component.

CO2 injection has shown that both quantity and diversity of Currently, the analysis of the John Klein drilled rock

microbial communities were strongly influenced by the CO2 sample continues. Preliminary data indicate the presence of injection. smectite(s), sulfates, and igneous minerals similar to those First results of the sequence analyses from a 3,5km-deep, found in Rocknest soil, representing the mineralogy of a

120-130°C hot reservoir indicate the presence of several H2- potentially habitable environment. These data facilitate oxidizing bacteria, thiosulfate-oxidizing bacteria and determination of comparable crystal–chemical systematics and biocorrosive thermophilic microorganisms. Due to the comparisons with Rocknest soil. hypersaline and hyperthermophilic reservoir conditions, and therefore low cell numbers, the quantification of those [1] Blake et al. (2013) LPS XLIV, Abstract. [2] Bish et al. microorganisms was not yet possible. (2013) LPS XLIV, Abstract. [3] Yen et al. (2013) LPS XLIV, Abstract.

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Atomic Views of Martian Evolution Effect of the isotopic composition of D.E. MOSER1*, D. A. REINHARD2, D. OLSON2, P. H. nitrite on the enrichment factor CLIFTON2, D. J. LARSON2, J.R. DARLING3, K.T. TAIT4, M. during benthic denitrification BUGNET5, B. GAULT5 AND I.R. BARKER1 1 1 1 AURELIE MOTHET *, MATHIEU SEBILO , ANNIET M. Univ. of Western Ontario, London, Ont., CAN N6A 5B7 2 1 2 LAVERMAN , VERONIQUE VAURY (*correspondence: [email protected]); CAMECA, 1 AND ANDRE MARIOTTI Madison, WI 53711, USA; 3University of Portsmouth, 4 1 UK; Royal Ontario Museum, Toronto, Ont. CAN M5S UPMC Univ Paris 06, UMR Bioemco, 4 place Jussieu, 2C6; 5CCEM, McMaster University, Hamilton, Ont. CAN 75252 Paris Cedex 05, France, [email protected] (*presenting author) 2 The extremely sluggish volume diffusion rates of U and UPMC Univ Paris 06, UMR Sisyphe, 4 place Jussieu, Pb in minerals such as baddeleyite and zircon, together with 75252 Paris Cedex 05, France their resistance to breakdown during shock metamorphism, Mediated by denitrifying bacteria under anoxic conditions, make them ideal recorders of inner Solar System evolution. In denitrification plays an important role reducing nitrate the case of highly shocked basaltic shergottite NWA5298, our pollution in surface and groundwater. Denitrification can be discovery of igneous (187±33 Ma) micro-baddeleyite, with traced by isotopic biogeochemistry; the isotopic enrichment micron-wide reaction rims of much younger launch-generated factor associated with denitrification may vary significantly zircon, promises further information on young Mars evolution (i.e. for nitrogen, ! vary from -30 to 0‰). This large range if afforded high spatial resolution techniques. might be due to the presence of nitrite, an intermediate during Here we present the first atomic resolution STEM denitrification, not accounted for in the enrichment factor. The (HAADF detector) imaging of baddeleyite and zircon presence of nitrite, either transient or continuous, during microstructure, and our progress toward their combination denitrification is regularly observed. Variations in nitrite 15 with atom probe tomography (CAMECA LEAP®) results for concentrations (production and/or reduction), depleted in N 18 extraterrestrial phases. Conventional EBSD analysis indicates and O could modify the enrichment factor for nitrate, when the isotopic composition of nitrite and nitrate are measured that euhedral baddeleyite CL zones are now amorphous at 50 together. nm length-scales, whereas high resolution STEM results Therefore, the objective of this study was to determine the reveal a mosaic of slightly misoriented nanocrystalline nitrogen and oxygen isotopic fractionation (=15N, =18O) domains overgrown by unshocked zircon in single orientation. associated with both nitrate and nitrite during denitrification Rare dislocation trains in zircon are perhaps due to thermal by environmental benthic denitrifying communities. stress on transit to outer space and Earth. Atom probe results Denitrification rates were determined in sediments from four for terrestrial reference zircon BR266 reveal a generally different locations in the Seine bassin (France). Nitrate homogeneous distribution of radiogenic Pb2+. The goal of reduction rates as well as nitrite production and reduction rates 15 18 LEAP analyses is to map Pb and trace element distribution in were determined and the N and O of both compounds were martian ejectic zircon rims, the age of which is constrained to analysed. As expected, our results show that the isotopic 15 18 lie between the youngest shocked baddeleyite date of 22±2 Ma composition of nitrite ( N and O) is depleted. With a maximum nitrite concentration of about 1% of the initial [1] and the cosmic ray exposure ages of ~3 Ma for similar nitrate concentration, the isotopic enrichment factor shows a shergottites [2]. These techniques open the door to direct significant isotopic shift (-2‰ for nitrogen and oxygen). This analysis of atom-scale mineral records of the evolution of indicates the importance of considering a correction of the Mars and the interplanetary travel of martian crust. enrichment factor for denitrification taking into account nitrite. [1] D.E. Moser et al. (2012) Microstructure and U-Pb dates of martian baddeleyite rimmed by zircon indicate a ‘young’ igneous and metamorphic history for shergottite NWA 5298. Lunar Planet Sci Conf. XLIII Abs. 2173. [2] O. Eugster et al. (1997) Ejection Times of Martian Meteorites. Geochim.Cosmochim. Acta. 61, 2749–2757.

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Calculating rates of ductile thrusting Geochemistry of Nowdouz potassic MOTTRAM, C.M1*, PARRISH, R.R2, WARREN, C.J1, volcanic rocks‚ the sample for early HARRIS, N.B.W1 AND ARGLES, T.W1 cenozoic potassic magmatism in 1 Dept. of Environment, Earth and Ecosystems, The Open NW Iran University, Walton Hall, Milton Keynes, MK76AA, U.K. 2 NERC Isotope Geosciences Laboratory, British Geological SEYED ZAHED MOUSAVI1 Survey, Keyworth, Nottingham NG12 5GG, United 1Basic science department‚ Meshkinshahr branch‚ Islamic Kingdom Azad University, Meshkinshahr‚ Iran‚ *correspondence: [email protected] ([email protected]) The ductile interiors of mountain belts, key to our understanding of orogenic processes, are often exhumed from The studied area is situated at 47°16´. 47°23´East and mid-crustal levels by ductile shearing. The Sikkim Himalaya 38°20´. 38°23´North between Meshkinshahr and Ahar cities‚ presents some of the best exposures of a ductile shear zone in NW Iran. Despite the importance of the potassic volcanic in the world. The Main Central Thrust (MCT) is a major geology of Iran and good studies done on it‚ yet there is no Himalayan structure that has accommodated a large amount of clear information from the history of the this volcano rocks. In movement during India-Asia convergence. In Sikkim, a this article we will attempt a review of past research results‚ duplex beneath the thrust has folded the MCT into a dome. new data (field‚ petrography and geochemical). In addition by This structural configuration allows a novel method for using the geo-chemical data‚ we discuss the origin and determining rates of processes by exploiting the late-stage tectonic position. This area is part of Azarbaijan structural folding of the MCT (figure 1). zone. High intensity alteration systems have effected on this rocks that argilice and silica zones are importance of them. Geochemical characterization and magma series show that composition on Nowdouz volcanic rocks are basalt‚ leucitite‚ tephrites and phonolitic tephrites. Many samples are in alkalic range. A general trend are observed toward increasing

alkalinity with decreasing of SiO2.Main oxides and rare earth element characterization confirm the fractionation of assemblage of olivine‚ pyroxin‚ plagioclases based on the

decreasing of MgO‚CaO‚ FeOt and MnO with decreasing of

SiO2 and increasing of Rb/K ‚ Sr and also decline of Sc with

increasing of SiO2. Fairly regular linear trends in major and

trace elements in SiO2 represent the same magma reservoir for rocks of this area. Although there is a enrichment of Large Ion Lithophile Elements and depletion in High Field Strength Elements. However with survey of geodynamical models for

potassic magmatism ‚ it seems that this area‚ based on idea of Figure 1. Illustrates a schematic cross-section before (a) Arabian plate sub ducting under Iranian plat in late cretaceous and after (b) folding of the MCT. Both the two marker and geochemical feature‚ are comparable with postcollosion locations (1 and 2) are currently at the surface (b), prior to related magmatism patterns. folding location 2 lay at depth (a). Therefore the age of peak metamorphism at 2 is likely to be younger than at 1, assuming metamorphism is contemporaneous with thrusting. The age difference between samples taken from locations 1 and 2 can be used to calculate a rate of thrusting. The timing of metamorphism of rocks formed at equivalent metamorphic grades across the MCT (1 and 2 on figure 1) has been determined from U-Th-Pb monazite geochronology. The data show significant differences in the timing of metamorphism in the northern and southern exposures of the MCT in Sikkim, consistent with the figure 1 model. Rates of thrusting from initial calculations (~1cm/yr ) appear slower than reported in earlier studies. This approach is the first to exploit folding of a major fault to calculate rates of ductile thrusting at a mid-crustal level.

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Archaean granites: classification, Applications of Absorption origin and tectonic implications Spectroscopy for Water Isotopic JEAN-FRANÇOIS MOYEN12 Measurements in Cold Clouds 1Université Jean-Monnet, Saint-Etienne, France. ELISABETH MOYER1*, LASZLO SARKOZY1, [email protected] KARA LAMB1*, BEN CLOUSER1, ERIC STUTZ1, 2CNRS UMR6524 BENJAMIN KÜHNREICH2, JANEK LANDSBERG3, JAN HABIG4, NARUKI HIRANUMA4, STEVEN WAGNER2, The Archaean continental crust is dominated by VOLKER EBERT5, ERIK KERSTEL3, OTTMAR MÖHLER4 granitoids, covering a large range of compositions and rock AND HARALD SAATHOFF4 types. While several classification schemes exist for modern 1Department of the Geophysical Sciences, University of granitoids, there is relatively little application to Archaean Chicago, Chicago, IL, USA (*correspondence: rocks and a comprehensive terminology is lacking. [email protected]) Similar to modern granitoids, Archaean rocks fall under 2Center of Smart Interfaces, Technische Universität three main groups: peralkaline granites; metaluminous Darmstadt, Darmstadt, Germany granites and related rocks (granite to diorite); and 3 Laboratoire Interdisciplinaire de Physique, J. Fourier metaluminous to peraluminous granites. Archaean peralkaline University of Grenoble, Grenoble, France granites, although superficially similar to their modern 4 Institute for Meterology and Climate Research, KIT, counterparts, are mostly magnesian and lack the enrichments Karlsruhe, Germany in trace elements that reflect, in the modern Earth, an origin 5Physikalisch-Technische Bundesanstalt, Braunschweig, related to fractionation of mafic melts derived from enriched Germany mantle sources. Metaluminous granites (including sanukitoids)

are, in some respect, similar to modern arc granites; but are no While mass spectrometry has been the measurement technique exact match to modern rocks, most likely pointing to different of choice for environmental water isotopic studies, absorption mantle enrichment processes in Archaean “subduction” spectroscopy is becoming increasingly competitive for many environments. Metaluminous to peraluminous granites are applications. Advances in instrument sensitivity allow formed by dehydration melting of mafic hydrous silicates and extending the use of isotopic measurements beyond tracing include potassic rocks, very similar to modern rocks and large-scale water transport, an application with relatively loose similarly generated by biotite dehydration melting; as well as measurement requirements, to microphysics studies in cirrus sodic rocks (TTGs and low-pressure sodic granitoids), related and convective clouds in the dry upper troposphere. We to breakdown of amphibole (or of an equivalent eclogitic outline measurement requirements for science applications in assemblage). Sodic granitoids can further be subdivided in cold cirrus clouds, describe the development of isotopic low-pressure rocks (similar to rare, oceanic-plateau related instrumentation for microphysics studies at the AIDA aerosol granites, with the same apparent “arc” signature); medium- and cloud chamber, and present isotopic measurements from pressure TTGs; and high-pressure TTGs, that do not have a the 2012-2013 ISOCLOUD campaign. ISOCLOUD adiabiatic modern counterpart, suggesting some uniquely Archaean expansion experiments from 233-190 K produced the first petrogenetic process, involving deep (> 15—20 kbar) melting direct measurements of isotopic fractionation factors at of metamafic rocks. temperatures applicable to cirrus clouds and suggest the The differences between Archaean and modern granitoids feasibility of field studies using water isotopologues as reflects similar differences observed in mafic rocks: Archaean microphysical tracers. mafics lack the clear dichotomy observed in the modern record between arc and non-arc samples; and do not show any evidence for strongly depleted or enriched mantle sources. Likewise, Archaean granites reveal a tectonic system with a near-primitive mantle; more common melting of oceanic plateaus; some continental collision; deep melting of mafic rocks, with no modern equivalent; and lacking modern-style subductions (with water fluxed melting of the mantle wedge), although some rocks record melting of a mantle enriched by buried surface matter.

www.minersoc.org DOI:10.1180/minmag.2013.077.5.13

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Heterogeneous distribution of Zn Cd mobility in anoxic Fe-mineral-rich stable isotopes in mice environments – potential use of FREDERIC MOYNIER1, TOSHIYUKII FUJII2, Fe(III)-reducing bacteria for soil ANDREY S SHAW3 AND MARIE LE BORGNE3 remediation 1 Department of Earth and Planetary Science and McDonnell 1 1 E. MARIE MUEHE *, IRINI J. ADAKTYLOU , MARTIN Center for Space Sciences, Washington University in St 2 1 1 OBST , CHRISTIAN SCHRÖDER , SEBASTIAN BEHRENS , Louis. [email protected] 3 4 2 ADAM P. HITCHCOCK , TOLEK TYLSIZCZAK , Research Reactor Institute, Kyoto University, 2-1010 5 1 UTE KRÄMER AND ANDREAS KAPPLER Asashiro Nishi, Kumatori, Sennan, Osaka 590-0494, Japan. [email protected] 1Geomicrobiology, University of Tuebingen, Germany, eva- 3 Department of Pathology and Immunology and Howard [email protected] (* presenting author) Hughes Medical Institute, Washington University School 2Environ. Analy. Microscopy, University of Tuebingen, of Medicine in St Louis. [email protected]; Germany [email protected] 3Chemistry and Chemical Biology, McMaster University Hamilton, Canada Zinc is required for the function of more than 300 4ALS, Lawrence Berkeley National Laboratory, Berkeley enzymes involved in many metabolic pathways, and is a vital 5Plant Physiology, University of Bochum, Germany micronutrient for living organisms. To investigate if Zn isotopes could be used to better understand metal homeostasis, Agricultural soils worldwide are increasingly burdened as well as a biomarker for diseases, we assessed the with heavy metals such as Cd from industrial sources and distribution of natural Zn isotopes in various mouse tissues. impure fertilizers. Metal contaminants potentially enter the We found that, with respect to Zn isotopes, most mouse food chain via plant uptake from soil and may affect human organs are isotopically distinct and that the total range of and environmental health negatively. New remediation variation within one mouse encompasses the variations approaches are needed to diminish soil metal contents, but in observed in the Earth's crust. Therefore, biological activity order to apply them it is necessary to understand how soil must have a major impact on the distribution of Zn isotopes in microbes and minerals interact with these toxic metals. inorganic materials. The most striking aspect of the data is that Here, we show that microbial Fe(III) reduction leads to Cd red blood cells and bones are enriched by ~0.5 per mil in 66Zn immobilization in Cd-bearing anoxic soils. To understand how relative to 64Zn when compared to serum, and up to ~1 per mil microbial Fe(III) reduction influences Cd mobility, we isolated a new when compared to the brain and liver. This fractionation is Cd-tolerant, Fe(III)-reducing Geobacter sp. strain Cd1 from a heavily well explained by the equilibrium distribution of isotopes Cd-contaminated soil in Germany. In lab experiments, this Geobacter between different bonding environments of Zn in different strain first mobilized Cd from Cd-loaded Fe(III) (oxyhydr)oxides organs. Differences in gender and genetic background did not followed by precipitation of Cd-bearing mineral phases. Using appear to affect the isotopic distribution of Zn. Together, these Mössbauer spectroscopy and Scanning Electron Microscopy, the results suggest that potential use of Zn isotopes as a tracer for original and newly formed Cd-containing Fe(II) and Fe(III) mineral dietary Zn, and for detecting disturbances in Zn metabolism phases, including Cd-Fe-carbonates, Fe-phosphates and Fe- due to pathological conditions. (oxyhydr)oxides, were identified and characterized. Using Energy Dispersive X-ray spectroscopy and Synchrotron-based Scanning Transmission X-ray Microscopy, Cd was mapped in the Fe(II) mineral

aggregates formed during microbial Fe(III) reduction. Microbial Fe(III) reduction mobilizes Cd prior to precipitation of the Cd as Cd-bearing mineral phases. On the one hand, the mobilized Cd could potentially be taken up by phytoremediating plants, resulting in a net removal of Cd from contaminated sites. On the other hand, Cd precipitation could immobilize Cd more strongly and reduce Cd bioavailability in the environment, causing less toxic effects to crops and soil microbiota. However, the stability and therefore bioavailability of these newly-formed Fe-Cd mineral phases needs to be assessed thoroughly. Whether phytoremediation or immobilization of Cd in a mineral with reduced Cd bioavailability are feasible mechanisms to reduce the toxic effects of Cd in the environment still remains to be determined.

www.minersoc.org DOI:10.1180/minmag.2013.077.5.13

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Sequestration of labile organic Unraveling cooling histories using Fe- carbon in Alaskan permafrost soils Mg zoning of exsolution lamellae in a MUELLER CARSTEN W.1; KAO-KNIFFIN JENNY2; garnet pyroxenite from the RETHEMEYER JANET3; LÖPPMANN SEBASTIAN1; HINKEL Granulitgebirge, Saxony, Germany AND KENNETH4; BOCKHEIM JAMES5 1 2 1 THOMAS MUELLER ,HANS-JOACHIM MASSONNE Lehrstuhl für Bodenkunde, TU München, Freising- 2 AND ARNE P. WILLNER Weihenstephan, 85356 Germany, [email protected] 1Institut für Geologie, Mineralogie und Geophysik; Ruhr- 2Cornell University, Department of Horticulture, Ithaca, NY Universität Bochum; D-44801 Bochum; Germany; 14853, USA, [email protected] [email protected] 3University of Cologne, Institute of Geology and Mineralogy, 2Institut für Mineralogie und Kristallchemie; Universität Cologne, 50674, Germany, janet.rethemeyer@uni- Stuttgart; D-70174 Stuttgart, Germany koeln.de 4University of Cincinnati, Department of Geography, The exchange of elements such as Fe-Mg between co- Cincinnati, Ohio, 45221, USA, [email protected] existing ferromagnesian minerals is a consequence of 5University of Wisconsin-Madison, Department of Soil changing external (intensive) variables, such as temperature Science, Madison, WI 53706, USA, [email protected] and/or pressure and proceeds via a series of kinetically controlled processes. Compositional zoning patterns of co- Permafrost affected soils of the Northern circumpolar existing mineral pairs can thus be used to model the region represent 50% of the terrestrial soil organic carbon incomplete diffusive equilibration process if diffusive (SOC) reservoir and are most strongly affected by climatic parameters and the partition coefficient are known as a change. Although a large number of studies revealed the function of P and T. Unraveling such zoning patterns is the overall C cycles in this region, there is only scarce knowledge key tool to decipher the nature of measured temperatures using about the quantitative and qualitative properties of organic geothermobarometry and are thus potential recorders of matter compartments and their potential stability. To unravel cooling and exhumation processes on various timescales. chemical and physical properties of SOC in permafrost soils The studied sample is a garnet pyroxenite from the we combined the physical soil fractionation with the Granulitgebirge, Germany. The rock contains remarkable evaluation of the chemical composition using nuclear exsolution textures from former megacrysts that produced up magnetic resonance spectroscopy (NMR) and microscopic to mm-wide, alternating lamellae of garnet (grt) and techniques as nano-scale secondary ion mass spectrometry clinopyroxene (cpx). Compositional profiles of Fe and Mg (NanoSIMS). measured with the electron microprobe perpendicular to the Approximately 50-75% of Alaska’s Arctic Coastal Plain is grt-cpx interfaces reveal almost flat, but often slightly zoned covered with thaw lakes and drained thaw lakes that follow a patterns with increasing Fe from the grt center towards the 5,000 yr cycle of development (between creation and final interface and decreasing Fe (from core to rim) in the adjacent drainage), thus forming a natural soil chronosequence. The cpx. drained thaw lakes offer the possibility to study SOM We present data from a numerical finite difference scheme dynamics affected by permafrost processes over millennial that simulates diffusive exchange between grt and cpx along a timescales. In April 2010 we sampled 16 soil cores reaching virtual cooling path. The model assumes local equilibrium at from young drained lakes (0-50 years since drainage) to the interface and diffusive fluxes are constraint by mass ancient drained lakes (3000-5500 years since drainage). balance. Preliminary modeling results suggest very efficient We can show that up to over 25 kg SOC per square meter compositonal resetting even for very fast cooling rates at were stored as mostly labile organic matter particles rich in temperatures above 1000 °C, so that no record of the growth carbohydrates. In contrast only 9.7 ± 2.3 kg OC per square of the lamellae is preserved. Nevertheless, the presence of meter were sequestered as presumably more stable mineral slight chemial zoning can successfully be used to estimate P-T associated OC dominated by aliphatic compounds. The conditions of lamellae formation as well as cooling / formation of soil aggregates, comparable to soil aggregation in exhumation rates in the temperature range between 700 – 1000 temperate soils, was proved by physical fractionation and °C. Finally, modeling results indicate fast cooling rates of >> microscopic evidence. Here we show that significant amounts 100 °C/Ma in agreement with published estimates for the of labile SOC are stored in permafrost soil layers which soon crystalline complex of the Granulitgebirge based on could be degraded due to the deepening of the active layer geochronology. resulting from climatic change.

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Dating deposition and low-grade An EBSD study of textural evolution metamorphism by in situ U-Pb across a shear zone in the Bergen geochronology of titanite Arcs, Western Norway J.R. MUHLING1,2*, B. RASMUSSEN2 AND I.R. FLETCHER2 HIROKI MUKAI1*, HÅKON AUSTRHEIM2 1 1 AND ANDREW PUTNIS CMCA, The University of Western Australia, Stirling Highway, Crawley, WA 6009, Australia 1 Institute for Mineralogy, University of Münster, Münster, (*correspondence: [email protected]) Germany (*correspondence: hmukai001@uni- 2Dept of Applied Geology, Curtin University, Kent Street, muenster.de) Bentley, WA 6102, Australia 2 Physics of Geological Processes, University of Oslo, 0316 Oslo, Norway

Titanite (CaTiSiO5) is a widespread accessory mineral, composed of major rock-forming elements, that incorporates The interaction between fluid infiltration, mineral sufficient U into its structure for U–Pb geochronology. It reactions and rock deformation has been the subject of much occurs in felsic to imtermediate igneous rocks, in very low to debate and raises fundamental issues such as the mechanism high-grade metamorphic rocks, in sedimentary rocks and in of fluid transport in nominally impermeable rocks. hydrothermal ore deposits. Because titanite can form at Localisation of deformation in shear zones provides an temperatures below 700°C, its closure temperature for the opportunity to study the textural and mineralogical evolution diffusion of Pb, it can provide ages for a wide range of low- to from relatively undeformed wall rocks through to the highly moderate temperature geological processes. Although titanite strained shear zone and to evaluate the various mechanical and forms detrital and authigenic grains in sedimentary rocks, it chemical processes which result in rock weakening. Rock has rarely been used to date deposition, diagenesis or low- strength or rheology is a critical parameter in geodynamic grade metamorphism. models for collision and subduction zones. Two generations of titanite are preserved in tuffaceous The present study was carried out from cross sections rocks of the Paleoproterozoic Timeball Hill Formation, through an amphibolite facies shear zone associated with the southern Africa: euhedral, brown crystals with apatite Caledonian Orogeny (~420Ma) that transects older inclusions, and colorless, pore-filling cement. The brown anorthositic granulite facies rocks (~930Ma) in the Bergen titanite has elevated U, Th and Fe and low Al, consistent with Arcs, western Norway. In this region, it is possible to study a magmatic origin, whereas the colorless titanite has high Al the textural and chemical changes from the relatively and F and low Fe contents, suggestive of a diagenetitc or unaltered granulites which retain the high grade mineralogy metamorphic paragenesis. In situ SHRIMP geochronology of and texture, through to highly strained and hydrated minerals brown titanite from a tuff bed gives a weighted mean within the shear zones. 207Pb/206Pb age of ~2275 Ma and is interpreted to provide a Our SEM observations of the cross sections showed that

reliable estimate for depositional age. the granulite facies rock is composed of plagioclase (An50), Authigenic titanite has been reported as pore-filling garnet and an Al-rich clinopyroxene, with minor scapolite. cement in a number of sandstone units worldwide but has not Closer to the shear zone, the original granulitic plagioclase is previously been dated. Fe contents vary widely, and some replaced by a 2-phase feldspar intergrowth composed of an examples have elevated amounts of high-field-strength Na-rich and Ca-rich network where the Na-rich domains

elements. The compositions may reflect local metamorphic or (composition ~An24) are surrounded by thinner "veins" of Ca-

hydrothermal fluid compositions. In situ U–Pb dating of rich plagioclase (An64). At the same time the garnet grains intergranular titanite from a tuffaceous sandstone in the develop Fe-richer rims of variable width and involve the Timeball Hill Formation yields an age of ~2145 Ma, which production of amphibole crystals at the boundary with the corresponds with previous estimates for a low-grade plagioclase. Lastly, in the shear zone, polygonal plagioclase tectonothermal event in southern Africa. retaining the 2-phase structure and foliated amphibole crystals Our results demonstrate that titanite is a versatile were observed. chronometer that can be used to constrain depositional ages, In the present study, we investigated in detail the evolution and those of diagenesis and low-grade metamorphism. It has of the microtextures by electron back scattered diffraction the potential to increase the number of sedimentary rock units (EBSD). Especially, we focused on their crystal preferred that can be dated, and to elucidate the histories of low- orientations (CPOs) which can be related to the deformation temperature geological processes in depositional basins. mechanisms.

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Relationship Between Volatiles and The results of metal mercury Noble Gases in Icelandic Lavas: solubility in water study Evidence for Crustal Recycling RENATA V. MUKHAMADIYAROVA 1* 1 AND YURY V. ALEKHIN S. B. MUKASA1, L. C. LOUDIN1, M. PETERSON2 AND E. T. DIXON3 1 Geochemistry Department, Faculty of Geology, Lomonosov 1 Moscow State University, 119991 Moscow, Russia Department of Earth Sciences, University of New Hampshire, (*correspondence: [email protected]) Durham, NH 03824, USA 2 Department of Geological Sciences, Brown University, Correctly determine of the metal mercury solubility in the Providence, RI 02912, USA 3 form of Hgº(aq) results [1,2] have set us the task to adjust the US Department of Energy, 1000 Independence Ave, SW, Henry’s constants for a wide range of temperatures and in Washington, DC 20585-0420, USA accordance with our published data. It is well known that the The anomalously high volume of magma erupted on process of dissolution for inert and unhydratable gases in Iceland relative to elsewhere along the Mid-Atlantic Ridge water temperature dependence of the Henry’s coefficients has historically has been attributed to an unusually hot mantle. an extreme [3]. For Hgº temperature dependence of the Henry’s constant More recently, compositional gradients in the underlying has a distinct, but little extreme at the temperature range 120- mantle, established during much earlier melting events, have 130 ºC, which is close to the position of extrema in systems also been invoked. We propose a third alternative, namely, with inert gases (Ar, Kr). We considered our new results, data significant quantities of volatiles in the melt source. of Sorokin et al. [4] for Hgº and to compare - data for such Olivine-hosted melt inclusions from Mi@fell in Iceland’s hydratable gases like CO2 and H2S [3]. Western Volcanic Zone have major oxide compositions that Thus, we see that the dissolution of elemental mercury place them among the most primitive lavas (highest MgO and vapor in water has an extreme by temperature, and, obviously, lowest SiO2) on the island. Trace-element-abundance patterns their interaction with water is very similar to that of the inert for these inclusions define two end-member compositions – gases, but at lower equilibrium partial pressure of the vapor. depleted and enriched mantle sources –suggesting intimate This fact provides a virtually constant value of Henry's law spatial association between the two. These end-member constant in the range log KH = -2,40 ÷ -2,43 in a wide compositions are observed even between melt inclusions from temperature range. the same individual hand sample, indicative of the survival of The obtained values of the Henry’s constants for Hgº show mantle heterogeneity within an incompletely mixed magma that these values are close to the values characteristic of weak chamber. hydratable gases as Ar, CH , CO, H , N , O , etc. [3]. Although degassing is common among the inclusions, 4 2 2 2 Obviously, the data presented in [4] characterize Henry's Law some have exceptionally high H O concentrations of up to 3.0 2 constant, calculated based on the total concentrations of wt. %, by far the highest water concentrations ever reported in mercury, including the dominant to 100-150 ºC oxidized basalts from an ocean island. A subset of the olivine separates forms. from Mi@fell and Eldborg, previously analysed for Ne and He

isotopic compositions, have melt inclusions which show that [1] Alekhin, Zagrtdenov, Mukhamadiyarova (2011) Mos. when 20Ne/CCNe and 3He/4He R/R in the host olivine are a Univ. Geol. Bul., 66(6), pp. 439-441. [2] Alekhin, Zagrtdenov, relatively low (10.39 and 18 R/R , respectively), the H O, CO a 2 2 Mukhamadiyarova (2011) Goldschmidt Conf. Abst., p. 421. F, S and Cl concentrations are all elevated. In contrast, when [3] Naumov, Rygenko, Khodakovsky (1971) Thermodynam. 20Ne/CCNe and 3He/4He are high – 11.10 and 29 R/R , a database directory. – 240 p. (in Russ.) [4] Sorokhin, respectively – the concentrations of the five volatiles are low. Pokrovsky, Dadze (1988) Physicochemical conditions of This suggests that crustal recycling was an important process mercury-antimony mineralization formation. - 144 p. (in in mantle melting beneath Iceland. Russ.). Exceptionally high-water concentrations in some of the

melt inclusions suggest that part of the uniqueness of Iceland’s The research has realized by supporting of RFFI (-11-05- geochemistry and eruptive nature is due to a hydrated source 93107-CNRS-D; -12-05-31155). rather than solely the presence of a large thermal anomaly. This has important implications for the concentration of water in mantle materials, and thus the geophysical properties that govern the nature of flow in the mantle and the magma generation that produces ocean islands.

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Trace-element fingerprints of A Mesoarchean Paleosol from eastern chromites and sulfides from the India—the second oldest paleosol on Archean Nuggihalli greenstone belt, Earth western Dharwar craton, India JOYDIP MUKHOPADHYAY1#, QUENTIN CROWLEY2, 1 1 1,2 1 GAUTAM GHOSH , SAMPA GHOSH , RIA MUKHERJEE *, SISIR K. MONDAL , 1 1 2 2 KALYAN CHAKRABARTI , B. MISRA JOSÉ M. GONZÁLEZ-JIMÉNEZ , WILLIAM L. GRIFFIN , 1 2 2 AND SANKAR BOSE NORMAN J. PEARSON AND SUZANNE Y. O’REILLY 1 1 Department Of Geology, Presidency University, Kolkata, Department of Geological Sciences, Jadavpur University, India, E-Mail: [email protected] India (*correspondence: [email protected]) 2 2 Department Of Geology, School Of Natural Sciences, Trinity ARC Centre of Excellence for Core to Crust Fluid Systems College, Dublin, Ireland (CCFS) and GEMOC, Macquarie University, Australia

The Keonjhar paleosol, in the southern part of the The Nuggihalli greenstone belt hosts discontinuous lens- Singhbhum craton has long been identified [1] but its age has shaped bodies of 3.1Ga plutonic ultramafic-mafic rocks not previously been well constrained. The paleosol occurs (chromitite-bearing serpentinite and tremolite-chlorite- between the Singhbhum Granite and supracrustal siliciclastics actinolite schist, pyroxenite, anorthosite, magnetite-bearing unconformably overlying the granite, along the western gabbro), that are conformably surrounded by a margin of the pluton. The paleosol is locally mined for contemporaneous unit of metavolcanic schists (komatiite- pyrophyllite. Recently, the paleosol has been classified as a komatiitic basalt), encompassed within the tonalite- vertisol [2]. The Singhbhum Granite on which the paleosol has trondhjemite-granodiorite suite of rocks. Trace-element been developed has been dated at ca. 3.33 Ga (U-Pb zircon compositions analyzed by laser ablation ICP-MS on unaltered LA-ICPMS) [3]. Here we report detrital zircon U-Pb LA- chromites (Cr# [100Cr /(Cr+Al)] = 79-87, Mg# [100Mg 2+ ICPMS ages from overlying sandstones covering a wide /(Mg+Fe ) = 45-55) show enriched values for Ti (1766-3277 geographic locality from Pal Lahara in the west to Mahagiri ppm), Mn (2037-2615 ppm), Zn (382-763 ppm), Co (197-257 hills in the east. U-Pb detrital zircon ages from four samples ppm) and lower values of Ga (21-27 ppm), Ni (660-1202 and more than 120 concordant or near concordant analyses ppm), V (475-682 ppm) and Sc (3.99-7.14 ppm) relative to indicate that the youngest grains cluster between 3.0 and 3.3 MORB. In chromite/MORB multi-element plots the trace- Ga, and none of the zircons are younger than 3.0 Ga. Our data element patterns of the unaltered chromites resemble Archean suggest that the depositional age of the sandstones is ca. 3.0 chromites from Ni-sulfide unmineralized komatiitic rocks. Ga and thus constrain the age of formation of the paleosol Compositionally zoned chromites have modified core (Cr# = 3+ 3+ 3+ between 3.0 Ga and 3.3 Ga. The Keonjhar paleosol is 65-73, Mg# = 7-15, Fe # [100Fe /(Cr+Al+Fe )] = 5-12, Ga therefore the second oldest known paleosol on Earth, after the = 10-29 ppm, Ti = 839-1680 ppm, Zn = 7098-9188 ppm, Sc = Pilbara paleosol (ca. 3.4 Ga) [4] and provides an excellent 2-7 ppm, Mn = 1701-5554 ppm, Ni = 113-570 ppm, V = 538- opportunity to study the Earth’s Mesoarchean atmosphere 893 ppm, Co = 520-866 ppm) with rims of ferritchromit and 3+ directly from the rock record. rare magnetite (Cr# = 72-99, Mg# = 2-32, Fe # = 23-77, Ga =

1.5-43 ppm, Ti = 544-8929 ppm, Zn = 578-13039 ppm, Sc = [1] Saha (1994), Geol. Soc. Ind. Mem. 27, 341p. [2] 0.62-30.69 ppm, Mn = 1284-25176 ppm, Ni = 200-3584 ppm, Bandopadhyay et al. (2010) Precamb. Res.177, 277-290. [3] V = 157-2837 ppm, Co = 112-2255 ppm). The altered Tait et al. (2011), Geol. Mag., 148, 340-347. [4] Johnson et al. chromites show inter-sample, intra-sample, and intra-grain (2009), Goldschmidt Conference Abstract, A601. heterogeneity in trace-element distribution owing to hydrothermal alteration. Minor sulfides represented by millerite and niccolite (~2 modal%, 20-40 µm) occur in the interstitial spaces within massive chromitites. Disseminations (5-8 modal%, 20-50 µm) of chalcopyrite, pyrite and Ni-Co bearing sulfides occur in magnetite in the interstices and as inclusions. The platinum group elements are below the detection limits of laser ablation ICP-MS for all the sulfide occurrences in the Nuggihalli greenstone belt.

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Probing the Hadean world with noble Of ancient reservoirs and recycled gases noble gases SUJOY MUKHOPADHYAY1 S. MUKHOPADHYAY, R. PARAI, J. M. TUCKER 1 1 AND M. K PETE Dept. of Earth and Planetary Sciences, Harvard University, Cambridge, MA 02138, USA; [email protected] 1Dept. of Earth & Planetary Sciences, Harvard University, Cambridge, MA 02138, USA; [email protected] Earth’s violent accretion likely generated multiple magma oceans. In particular, the Moon-forming giant impact is often The noble gases provide important constraints on thought to have produced a whole mantle magma ocean, planetary volatile cycling and our understanding of mantle which would have homogenized any pre-existing chemical structure and dynamics. For example, OIBs have 129Xe/130Xe heterogeneity within the mantle. The ratio of primordial 3He to ratios closer to the atmospheric ratio than MORBs, which primordial 22Ne in the mantle preserves a record of magma could either reflect a higher proportion of recycled Xe in the oceans on the early Earth. Importantly, the 3He/22Ne ratio of OIB source or the sampling of an ancient, less-degassed the Earth’s shallow depleted mantle is significantly higher reservoir (>4.45 Ga, since 129I, which produces 129Xe, is extinct than the deep mantle. To explain this observation, I propose after ~100 Ma). However, measurements of mantle-derived that at least two giant impact-induced atmospheric blow-off noble gases indicate that OIB sources do not have a higher and magma ocean degassing episodes are required and that the proportion of recycled atmospheric Xe relative to MORB last giant impact did not generate a whole mantle magma sources. The observation that the differences in the Xe ocean. Accordingly, if plumes are derived from Large Low isotopic composition of MORBs and OIBs cannot be Shear Wave Velocity Provinces (LLSVPs) at the base of the attributed solely to recycling requires that OIBs sample a mantle, then LLSVPs (i) are not remnants of crystallization of reservoir that evolved with a lower I/Xe ratio than the MORB a global magma ocean associated with the last giant impact; source. Thus, differences in the degree of outgassing between and (ii) are not dense cumulate piles that crystallized from the the MORB and OIB sources must have been established by last magma ocean at shallow depths and were subsequently 4.45 Ga and subsequent mixing between the two reservoirs gravitationally overturned to the core-mantle boundary, as must have been limited. As a result, if OIBs are derived from shallow cumulates would be the most degassed (with the the large low shear wave velocity provinces (LLSVPs) at the highest 3He/22Ne ratios). LLSVPs either correspond to base of the mantle, then the Xe data require these features to crystallization products from an earlier magma ocean or are be at least as old as 4.45 Ga. produced through a mechanism not associated with magma Although the differences in MORB and OIB Xe isotopic oceans. composition cannot be solely due to recycling, new high- Mantle Xe isotopic constraints indicate that the final precision Xe measurements in MORBs and OIBs indicate that mantle outgassing and atmospheric blow-off events inferred ~80-90% of the Xe in the MORB and OIB sources could be from 3He/22Ne ratios were accomplished between ~30 to 65 attributed to recycled atmospheric Xe. Thus, recycling of Myrs after the start of the Solar System. Therefore, atmospheric noble gases is a process important to mantle catastrophic outgassing associated with giant impacts, volatile budgets. Our ability to constrain mantle source including the Moon-forming impact, must have occurred 129Xe/130Xe and 40Ar/36Ar ratios through multiple step crushing within this time window. Previous calculations of impact- experiments now reveals significant heterogeneities in these induced atmospheric erosion have, however, found that it is ratios among mantle sources. For example, along 500 km of difficult to completely remove the atmosphere from a body as the Southwest Indian Ridge, in a region removed from any large as Earth by a giant impact. The need for atmospheric known plume influence, we observe ~50% and ~80% of the loss inferred from the noble gas data can be reconciled with total mantle variation in 40Ar/36Ar and 129Xe/130Xe, the dynamics of giant impacts by considering the new high- respectively. Such large variations indicate a MORB source spin Moon formation hypothesis. I will discuss the origin of that has experienced heterogeneous recycling and mixing of Earth’s early atmosphere in light of the new high-spin model material metasomatized by subduction zone fluids carrying for Moon formation and new noble gas data from mantle- recycled atmospheric Ar and Xe. Thus, a more complex derived rocks. I propose that major differences in the noble picture emerges from new high-precision noble gas data, of a gas signatures of terrestrial planetary atmospheres reflect the planetary interior that has both retained broad ancient diverse outcomes of late impact events on each planet. degassing features and developed fine-scale heterogeneity from a chaotic, integrated history of volatile cycling.

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Nitrogen and oxygen isotopic Anoxic geothermal fields and the composition of atmospheric nitrate early life 1,2 3 near the highways ARMEN Y. MULKIDJANIAN , ANDREW YU. BYCHKOV , 1,2 4 DARIA V. DIBROVA , MICHAEL Y. GALPERIN ARATA MUKOTAKA*, SAKAE TOYODA AND EUGENE V. KOONIN4 AND NAOHIRO YOSHIDA 1University of Osnabrück, Germany ([email protected]), Tokyo Institute of Technology, Japan 2School of Bioengineering and Bioinformatics, and 3School of (*correspondence: [email protected]) Geology, Moscow State University, Russia 4 15 National Center for Biotechnology Information, NLM, NIH, Nitrogen isotope ratio (" N) and conventional oxygen Bethesda, Maryland 20894, USA isotope ratio ("18O) in atmospheric nitrate has been used to

estimate the NOX sources and its oxidation pathways. 17 17 17 18 We have reconstructed the ‘hatcheries’ of the first cells by Recently, O-excess (% O . " O - 0.52 / " O) is known to combining geochemical analysis with phylogenomic scrutiny be more robust indicator of atmosperic nitrate formation 18 15 18 17 of the inorganic ion requirements of universal components of pathways than " O value. Although the " N, " O and % O modern cells [1]. These ubiquitous, and by inference values in atmospheric nitrate have been studied in various primordial, proteins and functional systems show affinity to regions [e.g. ref.1 and references therein], only a few and functional requirement for K+, Zn2+, Mn2+, and phosphate. observations of the oxygen isotope ratios in urban area have Thus, protocells must have evolved in habitats with a high been reported. In this study, we collected precipitation and K+/Na+ ratio and relatively high concentrations of Zn, Mn and atmospheric particles near the highways located in Yokohama, phosphorous compounds. Geochemical reconstruction shows Japan from Janualy 2012 to December 2012, and measured 15 18 17 that the ionic composition conducive to the origin of cells " N, " O and % O values in nitrate. could not have existed in marine settings but is compatible Precipitation samples were collected using a funnel and with emissions of vapor-dominated zones of inland plastic bottle. The atmospheric particle samples were collected geothermal systems. Under anoxic, CO -dominated on quartz filters using high-volume air sampler. The filters 2 atmosphere, the elementary composition of pools of were replaced every week. The stable isotope ratios of nitrate condensed vapor at anoxic geothermal fields would resemble were measuerd by GC-IRMS after converting nitrate to N2O. 15 18 15 the internal milieu of modern cells. The " N and " O values in precipitation, and the " N The scientists who address the origin of life problem from values in particle showed a temporal variation similar to the 15 a purely chemical viewpoint argue that specific formation of previously reported values (-2.2‰ < " N < 13.6‰ and 52.6‰ 18 18 activated, cyclic ribonucleotides with a potential for < " O < 83.4‰) [2, 3]. The variation of " O values in polymerization could take place in formamide-rich solutions, particulate nitrate was similar to that of precipitation, but particularly under the action of UV light and in the presence of extremely low values (26.2‰ to 39.7‰) were observed from 18 borate and phosphorous compounds [2, 3]. the end of August to the end of November. The low " O The exhalations of even modern geothermal fields contain values cannot be explained by typical nitrate formation high amounts of ammonia, phosphate, borate and processes that involve ozone, and imply that isotopically light 18 hydrocarbons, so that the anoxic geothermal fields should oxygen, such as O (" O = 23.5‰) played a key role in NO 2 X have been conducive for formation of simple amides and oxidation prosess in the period [4, 5]. Implication from %17O nitrogen-containing organic molecules, including activated data will be also discussed. nucleotides.

Hence, the anoxic geothermal fields, which we identified [1] Savarino et al., (2013) Proc. Natl. Acad. Sci. USA., doi: as tentative cradles of life by using the top-down approach and 10.1073/pnas.1216639110. [2] Kaiser et al. (2007) Anal. phylogenomic analysis, could provide exactly those Chem., 79, 599-607. [3] Michalski et al. (2003) Geophys. Res. geochemical conditions that were suggested as most Lett., 30(16), 1870. [4] Kroopnick and Craig (1972) Science, conducive for the emergence of life by the chemists who 175, 54-55. [5] Proemse et al. (2012) Atmospheric pursued the complementary bottom-up strategy. Environment, 60, 555-563.

[1] A.Y. Mulkidjanian, A.Y. Bychkov, D.V. Dibrova, M.Y. Galperin, E.V. Koonin (2012) Origin of first cells at terrestrial, anoxic geothermal fields, Proc Natl Acad Sci U S A, 109: E821-830. [2] S.A. Benner, H.J. Kim, M.A. Carrigan (2012) Asphalt, water, and the prebiotic synthesis of ribose, ribonucleosides, and RNA, J. Am- Chem. Sci. 45: 2025-34. [3] R. Saladino, G. Botta, S. Pino, G. Costanzo, E. Di Mauro (2012) Genetics first or metabolism first? The formamide clue, Chem Soc Rev, 41: 5526-5565.

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Mantle compositional gradients in a Multiple sulphur isotope analyses of hot subduction setting, the Garibaldi sulphate deposits from the Sargur Volcanic Belt, northern Cascade Arc Group, Dharwar Craton, India. EMILY K. MULLEN* AND D. WEIS E. MULLER1, P. PHILIPPOT1, C. ROLLION-BARD2 AND D. S. SARMA3 PCIGR, University of British Columbia, Vancouver, Canada (*correspondence: [email protected]) 1Institut de Physique du Globe, Paris, France, [email protected] 2CRPG-CNRS, Vandoeuvre-les-Nancy, France Hot subduction zones challenge the dehydration melting 3CSIR-NGRI, Hyderabad - 500 007, India model for primary arc basalt generation, as hot slabs may liberate water at depths too shallow to trigger mantle melting. Sulphides from sedimentary rocks older than 2.45 Gyr old The Garibaldi Volcanic Belt (GVB), the northernmost define a positive "34S-F33S correlation called the “Archean segment of the Cascade Arc, extends from Glacier Peak in the Array”. In contrast, Archean sulphates were deposited during south to Bridge River Cones in the north and is one of the short periods of times between 3.5 and 3.2 Gyr ago and define hottest subduction zones globally [1, 2]. The age of the a narrow isotopic range that is not correlated with the subducting plate decreases from ~10 Ma in the south to ~5 Ma Archaean Array. Sulphide associated with the sulphate in the north at the trench [3], resulting in a northerly increase deposits form a specific isotopic domains characterized by 34S- in slab temperature beneath the arc axis [1]. Together with a depleted values with both positive and negative F33S. These decrease in magmatic productivity, basalts grade progressively sulphides were interpreted to reflect a combination of UV- from typical calc-alkaline arc basalts in the south to alkalic photochemical processes in optically-thick volcanic plumes basalts in the north, reflecting reduced melt fractions due to combined with terrestrial processes of biologic and/or non low slab input [4]. Both basalt varieties occur at Mt. Garibaldi. biologic origin. Here we present S isotope systematics of the 87 86 Gradual northerly decreases in La/Nb, Sr/ Sr (0.70318 to 3.2 Ga sulfate deposit of the Sargur Group near 0.70298) and Pb isotope ratios are consistent with the Ghattihosahalli (Dharwar Craton, India). hypothesis of decreasing slab input. In addition, decoupling of The rocks investigated consist of a meter-scale layer of =Hf from =Nd indicates sediment input as a fluid. The most barite interbedded within different types of quartzites and alkaline basalts record minimal slab input, with Pb isotope micaschists grading towards the west into Cr-micaschists, ratios lower than in other Cascade Arc basalts and similar to ultramafic volcanics and felsic gneiss. Bulk and in situ S- 208 206 Explorer MORB. However, Zr/Nb, Pb*/ Pb*, =Nd (+8.9 to isotope analyses were measured with IRMS in dual-inlet mode +7.1) and =Hf (+13.3 to +8.5) decrease to the north, indicating at IPGP and ims 1280 HR2 at CRPG, respectively, both with a an arc-parallel gradient in mantle source enrichment that is reproductibility better than 0.2 ‰ (2!) in "34S and 0.1 ‰ in unrelated to slab input. The alkaline basalts tap a mantle 133S. source more incompatible element enriched and isotopically S-isotope compositions of barites ("34S = 3.19 to 4.35 ‰ distinct from the depleted mantle that produces calc-alkaline and F33S = -0.49 to -0.47 ‰) fall within the range of other basalts. The enriched mantle is also hotter (~1500°C) than the Archaean sulphates. Pyrites in sulphates and other rock types sub-arc mantle wedge (max ~1350°C) [2], consistent with show a narrow range of %33S values between -0.70 and +0.37 upwelling asthenosphere, possibly at the slab edge [5]. Arc- ‰ but a larger range of "34S values between -12.21 and +0.27 parallel mantle flow may draw the upwelling mantle into the ‰ in barite, -4.12 and +0.63 ‰ in micashists and quartzites, - arc, generating a compositional gradient upon which slab input 6.96 and -2.43 ‰ in Cr-micaschists, and 1.83 and 5.99 ‰ in is superimposed. The influx of this upwelling mantle may surrounding gneisses. These results are consistent with 208 206 have far-reaching effects, as the Pb*/ Pb* trend begins as previous data obtained in other Archaean sulphate deposits far south as Mt. Adams and continues to the end of the GVB. from the Pilbara Craton and Barberton Greenstone Belt, thus arguing for a common origin. Different from other deposits, [1] Harry & Green (1999) Chem. Geol. 160, 309-333. [2] however, is the relative small range of both "34S and %33S Syracuse et al. (2010) Phys. Earth Planet. Interiors 183, 73- values, which suggests that the isotopic imprint inherited from 90. [3] Wilson (2002) USGS Open-File 02-328. [4] Green atmospheric and microbial/hydrothermal processes have been (2006) Lithos 87, 23-49. [5] Long & Silver (2008) Science reequilibrated in part during greenschist/amphibolite facies 319, 315-318. metamorphism and pervasive ductile deformation.

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Vibrational spectroscopic study of Nano-particulate pressed powder Np(V) sorption on mineral oxides tablets for LA-ICP-MS KATHARINA MÜLLER, JULIA BERGER, MAXENCE S. MÜLLER1 AND D. GARBE-SCHÖNBERG1* CORDIEZ, ANNETT GRÖSCHEL, 1 CAU Kiel, Institut für Geowissenschaften, 24098 Kiel, AND HARALD FOERSTENDORF (*correspondence: [email protected]) Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Dresden, Germany The accurate determination of ultra-trace elements in (*correspondence: [email protected]) geological samples containing refractory minerals - e.g., zircon in plutonic rocks and sediments, spinel in ultramafic Mineral oxides play a decisive role in regulating the rocks and eclogites - is a challenge. While standard table-top mobility of contaminants in the environment because of their or microwave-assisted digestion protocols fail in completely widespread occurrence in rocks and soils, their tendency to dissolving these minerals, alternative procedures also show form coatings on mineral surfaces and their wide-ranging shortcomings: (i) pressurized bomb digestion yields accurate technical applications [1]. results but is time-consuming; (ii) preparation of fused glasses Due to its long half-life and its toxicity, Np-237 is with, and without, addition of a flux for subsequent analysis considered as a major contaminant of the ecosystem in the by either LA-ICP-MS or after re-dissolution with ICP-MS long-term safety assessment of nuclear waste repositories. The suffers from contamination from heterogeneously distributed pentavalent state is environmentally most relevant [2]. impurities in lithiummetaborate, and strong memory for Li, B; For the first time, in-situ Np(V) sorption is comparatively (iii) shock melting using a strip-heater produces glasses studied on the oxyhydroxides of Fe, Mn, Si and Ti by ATR contaminated with strip material. Ultrabasic or evolved rocks FT-IR spectroscopy under a variety of environmentally cannot be melted without matrix modification. All fusion relevant sorption conditions. From the results, the formation of techniques bear the risk of volatile losses, and glass beads binary inner-sphere complexes on oxides of Si, Mn, Fe and Ti typically show significant inhomogeneity of trace elements if can be derived [3]. In case of ferrihydrite, the formation of an not thoroughly homogenized during melting. additional ternary Np-carbonato surface species is assumed. In Pressed powder tablets have repeatedly reported as a addition, time resolved spectra provide kinetic information on means for the direct analysis of solids by laser ablation. the surface reactions. Analytical results, however, were not convincing in terms of detection limits, accuracy, and precision if compared to results obtainable with solution analysis or homogeneous glasses. Here we show that undiluted pressed powder tablets can be successfully used for ultra-trace element analysis of granitoid, gabbroic, and ultrabasic rocks from the Oman ophiolite (Wadi Gideah reference profile) after pulverisation to nano-particle grain size. More than 40 trace elements have been analysed in a series of rock CRMs with average RSDs of 1-3% and excellent accuracy for most elements incl. HFSE. Detection limits are in the low ppb range.

Fig. 1: IR spectra of an aq. Np(V) solution and of the sorption complexes formed onto several mineral oxides (50 µM Np(V), 0.1 M NaCl, pH 7, 60 min sorption, 0.1 mg mineral 2 oxide/cm , N2).

[1] Dixon J. B. et al.(1989) Minerals in soil environments. Madison, Wisc.: Soil Science Soc. of America. 1244. [2] Kaszuba J. P. et al. (1999) Env. Sci. & Techn. 33(24), 4427- 4433. [3] Müller K. et al. (2009) Env. Sci. & Techn. 43(20): p. 7665-7670

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Downhole Fluid Analysis coupled A secular solution to a diabolical with Asphaltene Nanoscience for problem: Porphyry vs. iron oxide- Reservoir Evaluation copper-gold deposits OLIVER C. MULLINS A. HAMID MUMIN1 AND JEREMY P. RICHARDS2 [email protected] 1Dept. Geology, Brandon University, Brandon, Manitoba, Canada, R7A 6A9, [email protected] For condensates, the most important compositional 2Dept. EAS, University of Alberta, Edmonton, Alberta, variation is GOR, and the cubic equation of state (EoS) Canada, T6G 2E3 [email protected] treatment of GOR variations is well developed and successful. Consequently, key reservoir attributes such as vertical and Porphyry Cu±Mo±Au (porphyry) and magmatic- lateral connectivity, extrapolating gradients to obtain contacts hydrothermal iron oxide-copper-gold deposits (IOCG) are for reserves estimation, and properties of the produced fluids distinct in being dominated by Fe±Cu-sulfide minerals in the are addressed by Downhole Fluid Analysis (DFA) on the former and Fe-oxides in the latter. Most of the largest IOCG MDT measuring GOR and light end compositional variations. deposits formed in the Precambrian, whereas porphyry In contrast, black oils are generally defined as having low deposits occur most commonly in late Phanerozoic rocks and GOR; while black oils can exhibit GOR variations, the most are rare in the Precambrian. Despite these major differences, important compositional variation of black oil and heavy is the they share many similarities: associated magma composition asphaltene concentration. However, there had been no (calc-alkaline to mildly alkaline); tectonic setting (orogenic to predictive equation of state for asphaltene gradients because post-orogenic), depth of formation ($5 km from surface), the (colloidal) size of asphaltene particles in crude oils had major metal inventory (Cu, Au), and hydrothermal alteration been unknown. Consequently, the gravity term was unknown. styles (albeit with wider development of high-T near-neutral Without knowing the gravity term, modeling of reservoir alteration, and more restricted development of low-T fluids is precluded. hydrolitic alteration in IOCG deposits). In recent years, the molecular and colloidal size of We conclude that fundamentally similar tectonomagmatic asphaltenes in crude oils – from condensates to mobile heavy and hydrothermal processes give rise to these two distinct oil – has been resolved and codified in the Yen-Mullins deposit types. We link the key differences in mineralization model. These scientific advances have led to the first style (Fe-sulfide vs. Fe-oxide) and temporal prevalence to predictive equation of state (EoS) for asphaltene gradients, the oxidation of the deep oceans during the Neoproterozoic Flory-Huggins-Zuo EoS. By coupling this new science of the Oxidation Event. Following this event, sulfate concentrations FHZ EoS with the new technology of DFA, a powerful new in deep ocean waters, seafloor sediments, and seawater-altered method of reservoir evaluation has been developed leading to oceanic crust increased dramatically, and for the first time in myriad applications. Establishing thermodynamic geological history abundant sulfur and sulfate were introduced equilibration of asphaltenes strongly implies reservoir into subduction zones and arc magmas. Phanerozoic arc connectivity as proven in published case studies involving magmas were thereafter significantly richer in S than in the light condensates to mobile heavy oil. Huge asphaltene and Precambrian (Prouteau & Scaillet, 2013) and, combined with viscosity gradients are obtained in mobile heavy oil columns their relatively high oxidation state, were ideal transportation around the world in agreement with simple application of the agents for Cu and Au into upper crustal magmatic- FHZ EoS, and where conventional modeling fails miserably. hydrothermal systems. Two mechanisms of tar mat formation are seen to be a natural In contrast, S-poor Precambrian arc and derivative process readily accounted for by the FHZ EoS and resolving a magmas formed S-poor IOCG deposits in orogenic, and post- long standing enigma in the oil industry. Disequilibrium has orogenic settings, while S-rich conditions were relatively rare become much easier to identify using DFA & the FHZ EoS in (leading to a dearth of porphyry-type deposits). Higher conjunction with the cubic EoS. Methods for production geothermal gradients in the Precambrian, combined with the optimization and risk management are identified. lower acid-generating potential of S-poor hydrothermal fluids The confluence of advanced asphaltene science with the may explain the greater extent of high-T near-neutral pH third generation of DFA tools, the IFA, enables a powerful alteration in IOCG deposits compared to porphyries. new approach to address many complexities in reservoir dynamics. [1] Prouteau & Scaillet, 2013: J. Petrology, v. 54, p. 183–213.

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The role of mesoscale ocean eddies in Lithospheric mantle heterogeneities the glacial cycle of atmospheric pCO2 beneath Southern Patagonia DAVID R. MUNDAY*1, HELEN L. JOHNSON2 A. MUNDL1*, T. NTAFLOS1, E.A. BJERG2, AND DAVID P. MARSHALL1 L. ACKERMAN3 AND C.A. HAUZENBERGER4 1Department of Physics, University of Oxford, Oxford, UK 1Department of Lithospheric Sciences, University of Vienna, (*correspondence: [email protected]) Austria (*correspondence: [email protected]) 2Department of Earth Sciences, University of Oxford, Oxford, 2CONICET-Universidad Nacional del Sur, Departamento de UK Geologia, Bahia Blanca, Argentina 3Institute of Geology v.v.i., Academy of Sciences of the Czech The close relationship between Antarctic temperature and Republic, 165 00 Praha 6, Czech Republic 4 atmopsheric pCO2 suggests an important role for the Southern Institute for Earth Sciences, University of Graz, Austria Ocean in glacial cycles. Recent high-resolution model results indicate that the sensitivity of Southern Ocean upwelling and Thirty samples from Pali Aike Volcanic Field (PAVF) and global stratification to changes in Southern Ocean wind stress Tres Lagos in Southern Patagonia comprise Sp-lherzolites, Sp- may be low [1]. This may limit the sensitivity of the climate harzburgites, Sp-Gt-lherzolites and Sp-Gt-harzburgites. system as a whole to changes in Southern Ocean wind stress, According to Cpx REE and other trace element patterns, by limiting the change in ventilation of abyssal carbon the samples can be divided in 3 Groups within Sp-peridotites reseroirs. and 3 within Sp-Gt-peridotites. Group I Sp-peridotites show a We use MITgcm in an idealised configuration to depletion in LREE reflecting different degrees of partial investigate the changes in circulation that occur at both coarse melting. Group II shows flat REE patterns from HREE to (climate model) resolutions and higher, eddy-permitting, MREE with an enrichment in LREE indicating metasomatic resolutions as the applied wind stress is changed. At coarse overprint. Group III samples show an enrichment in MREE resolutions, the mesoscale eddy field is represented by the over LREE and HREE suggesting basaltic melt percolation. Gent & McWilliams parameterisation. However, at eddy- While Group I Sp-Gt-peridotites represents slightly depleted permitting resolutions, large geostrophic eddies are well samples with typical REE patterns of Cpx in equilibrium with represented by the model. By coupling these physical Gt, Group II Cpx REE patterns show LREE enrichments circulations to MITgcm’s simple biogeochemistry package, reflecting metasomatic event(s). The garnets in this group we are able to elucidate the effect that changes in the exhibit wide kelyphitic rims that have been formed according mesoscale eddy field, and/or its representation, have on to the reaction of Gt+Ol to Sp+Cpx+Opx. Primary Sp

atmospheric pCO2. inclusions in Gts of Group I and II indicate transitions from We find that the use of an eddy-permitting ocean model spinel to garnet stability field. Group III of Sp-Gt-peridotites

reduces the sensitivity of atmospheric pCO2 to both increasing is represented by highly depleted samples showing REE and decreasing wind stress. A carbon pump decomposition patterns otherwise typical for Cpx coexisting with Gt. indicates that the 4 main reservoirs of carbon in the ocean However, an entire abscense of Gt suggests that all Gt has (saturation state, disequilibrim, soft tissue carbon, and hard been consumed during partial melting event(s). tissue carbon) vary quite differently when the model is Re-Os analyses of unmetasomatized Sp-peridotites reveal

eddying, as opposed to the eddy field being parameterised. highly variable TRD. While TRD at Tres Lagos range from 1 to 1.6 Ga, samples from PAVF yield ages from 0.3 to 2.3 Ga. A [1] Munday, D. R., H. L. Johnson, and D. P. Marshall, 2013: depletion in Pt, Pd and Re reflects different degrees of partial Eddy saturation of equilibrated circumpolar currents. J. Phys. melting. Depleted Os compared to other IPGEs (Ir, Ru) can be Oceanogr., 43, 507–532. connected to sulfide breakdown upon eruption, while a general depletion in IPGEs in comparison to PM is suggested to be due to melt percolation processes. Trace element patterns, samples showing highly different degrees of partial melting, as well as transition reactions from spinel to garnet stability field reflecing a multi-stage thermal history, suggest a very heterogeneous SCLM beneath S- Patagonia.

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Mantle-crust fractionation of the An extraterrestrial cause for the platinum-group elements Silicate Earth’s Nb paradox? JAMES E MUNGALL1 AND JAMES M BRENAN1 C. MÜNKER1, R..O.C. FONSECA2,AND T. SCHULZ3 1Department of Earth Sciences, University of Toronto, 1Institut für Geologie und Mineralogie, Universität zu Köln, Toronto ON; [email protected]; Germany, [email protected] [email protected] 2Steinmann Institut, Universität Bonn, Germany 3Dept. für Lithosphärenforschung, Universität Wien, Austria We use new sulfide melt/silicate melt partition coefficients ~ 106 to develop a fully constrained model of PGE behavior Although both elements are considered lithophile, the during melting to predict the abundances of PGE in mantle- silicate Earth exhibits a marked Nb deficit relative to its derived magmas and their restites, including mid-ocean ridge geochemical twin Ta, when compared to chondrites [1]. This basalts, continental picrites, and the parental magmas of the feature is commonly referred to as “terretrial Nb paradox”. Bushveld Complex of South Africa. Our model constrains Many explanations for this paradox that favour the presence of mid-ocean ridge basalt (MORB) to be the products of pooled hidden silicate reservoirs cannot explain the observation that low and high degree fractional melts. A significant control on the Early Archean silicate Earth was already depleted in Nb. PGE fractionation in mantle-derived magmas is exerted by This would leave core formation at high pressures in a reduced residual alloy or platinum group minerals in their source. early Earth as the only viable explanation for the terrestrial Nb Within-plate picrites are pooled products of larger degrees of paradox [2]. fractional melting in columnar melting regimes. At low In a combined geochemical and experimental study, we pressures (e.g., MORB genesis) the mantle residual to partial investigated, whether low pressure metal segregation on small melting retains primitive mantle inter-element ratios and planetesimal precursors can also account for the Nb deficit. abundances of PGE until sulfide has been completely We performed high precision measurements of HFSE dissolved but then evolves to extremely high Pt/Pd and low concentrations employing isotope dilution and ion exchange Pd/Ir because Pt and Ir alloys form in the restite. During separation on representative groups of iron meteorites, their melting at high pressure to form picrites or komatiites Ir alloy sulfide inclusions and achondrites. This protocol avoids continues to appear as a restite phase but Pt alloy is no longer molecular interferences on many HFSE, in particular for iron stable due to the large effect of pressure on fS2, which causes meteorites and sulfides rich in transition metals. Our results large increases in alloy solubility. Magmas parental to the indicate that reduced achondrites exhibit strongly Bushveld Complex of South Africa appear to be partial melts subchondritic Nb/Ta (as low as 1), whereas more oxidised of mantle that has previously been melted to the point of total achondrites (e.g., eucrites) exhibit near chondritic Nb/Ta. As sulfide exhaustion at low pressure, closely resembling mantle expected, iron meteorites exhibit extremely low Nb-Ta xenoliths of the Kaapvaal craton. Using the new extremely concentrations (<1 ppb), whereas Nb can be strongly enriched sul large D PGE the the Merensky Reef and UG2 Pt deposits of relative to other HFSEs in sulfides (to ppm levels). the Bushveld Complex can be modeled as the result of sulfide To simulate metal-sulfide segregation on small saturation due to mixing of magmas with unremarkable PGE planetesimals, we performed experiments at ~1300ºC and 10 contents, obviating the need to postulate anomalously PGE- kbar using a piston cylinder apparatus. Measured sulfide- rich parent magmas or hydrothermal inputs to the deposits. silicate partition coefficients for Nb are ca. 2 orders of

magnitude higher than for Ta. At fO2 lower than IW-3, Nb becomes chalcophile while Ta remains lithophile, and the silicate melt is thus depleted in Nb, as found in our study for more reduced achondrites. Collectively, our results reveal that Nb may be sequestered

into planetesimal cores at low pressures and low fO2, provided that immiscibile sulfide and metal liquids were segregated. Therefore, the silicate Earth’s Nb deficit may be a feature inherited from differentiated planetesimals that did not fully equilibrate with the proto-Earth upon their accretion.

[1]Münker et al. (2003) Science 301, 84-87 [2] Wade & Wood (2001) Nature 409, 75-78.

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Pb, Zn and Cd dynamics in mining Structure and thermal property of areas under Mediterranean climate dense silicate glasses under high- and carbonated geologic context: pressure northern Tunisia example MOTOHIKO MURAKAMI1 MUNOZ MARGUERITE1 AND GHORBEL MANEL2 1Department of Earth and Planetary Materials Science, 1 Tohoku University, 6-3 Aoba, Sendai, Miyagi 989-8578, GET, Observatoire Midi Pyrénées, Université de Toulouse, Japan [email protected] CNRS, IRD, 14 avenue E. Belin, F-31400 Toulouse,

France. [email protected] 2 The current structure of Earth’s interior is believed to have RME, Faculté de Sciences de Tunis el Manar, 2092 Tunis, formed through dynamic differentiation from a global magma Tunisia. [email protected] ocean in the early Earth. Elucidation of the structural changes and heat transport properties of silicate melts in the deep Earth Maghreb countries, particularly Tunisia contain large is fundamental to understanding the evolution and structure of amounts of mining wastes richs in metals such as Pb, Cd and Earth’s interior. The possible presence of dense, Zn. Wastes are located in active or abandoned mining sites. gravitationally stable, silicate melts at the bottom of the Metals can diffuse to all environment compartments: water, air current mantle as a remnant of a deep magma ocean has been and soil. proposed to explain observations of anomalously low seismic In wastes, due to carbonated geology, calcite is dominant velocities above the core-mantle boundary. However, the and metals are mainly associated with carbonates (cerussite, nature of silicate melts under such extreme pressures is poorly smithsonite and hydrozincite), in addition to silicates understood. Direct measurements of structural changes or (hemimorphite and willemite) and sulphides (galena and thermal properties on silicate melts under ultrahigh-pressure sphalerite). Cd substitutes Zn in zinc-carbonates, silicates and conditions remain a great challenge and are currently beyond sphalerite where it can reach 0.98wt%. experimental capabilities. Silicate glasses have alternatively In this carbonated context, drainage water display a basic been extensively studied as analogues for quenched silicate pH and metals are fixed by precipitation of stable minerals melts, to simulate the high-pressure behavior of silicate melts. under oxidizing conditions (cerussite, hydrozincite, Previous experimental works on silicate glasses have, smithsonite and hemimorphite). Equilibrium between water however, been still limited to lower pressure condition, which and secondary minerals in mining drainage controls is far below the pressure condition of the bottom of the concentrations of metals at low values. mantle. Ore treatment wastes are fine grained (silt and clay). Their To address this issue, we have conducted several series of cohesion is variable (15 and 124 kPa) and their permeability is ultrahigh-pressure experiments on silicate glasses with low (10-6-10-9 m/s) and limits infiltration process. These chemical compositions ranging from pure silica to more features, under Mediterranean climate, promote mechanical complex system up to ~200 GPa using combined erosion of wastes during brief and intense rainfall events. spectroscopic techniques including Brillouin scattering, However, the low density of water runoff makes the impact of optical absorption (from visible to near-infrared) and particulate transport often limited, but highly concentrated, in synchrotron Mössbauer measurements in the energy domain. soils around the waste dumps. Thus, maximum concentrations The results based on sound velocity data reveal the possible in soils have been measured up 2% Pb, 3% Zn and 200 mg.kg- densification mechanism of silicate glasses above ~100 GPa 1 Cd. that is likely associated with the onset of a change in Si-O This climate, also characterized by a long dry season, coordination number to higher than sixfold. Optical and allows contaminated dust emissions from dumps especially in synchrotron Mössbauer data show a significant change in the summer. Maximum emission flux of dust was estimated to absorption coefficients of the iron-bearing silicate glasses with 88.2 g/s of PM10. Resulting concentrations of airborne Pb and pressure, most likely due to their gradual electronic structural Cd exceeded WHO guidelines for air quality, up to 1km from changes. Based on the present results, we will discuss the the source in the dominant wind direction (Ghorbel, 2012). possible implications for the densification mechanisms and Remediation is intended to support natural processes using heat transport property of the silicate melts at the base of the phytostabilisation of wastes by covering them with native mantle. metal-resistant plants.

[1] Ghorbel, M (2012). Contamination métallique issue des déchets de l’ancien site minier de Jebel Ressas : modélisation des mécanismes de transfert et conception de cartes d’aléa post-mine dans un contexte carbonaté et sous un climat semi-aride. Evaluation du risque pour la santé humaine. PhD thesis of Toulouse and Tunis El Manar Universities. 231p.

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Reconstruction of the accident- Heterogeneous melt involved in derived I-131 deposition in formation of a thick Moho transition Fukushima through the analysis of I- zone in northern Oman ophiolite: 129 in soil. implications for MORB evolution YASUYUKI MURAMATSU1*, HIROYUKI MATSUZAKI2, R. MUROI1*, S. ARAI1, H. NEGISHI1 AND A. TAMURA1 1 1 TAKESHI OHNO , NAOYA INAGAWA 1 Dept. Earth Sci., Kanazawa Univ., Kanazawa 920-1192, AND CHIAKI TOYAMA1 Japan 1 Department of Chemistry, Gakushuin University, Mejiro, (*Correspondence: [email protected]) Tokyo, Japan, 171-8588; *Corespondence:[email protected] The evolution process of MORB from depleted melts in 2 Department of Nuclear Engineering and Management, The equilibrium with abyssal peridotites has been left unclear. University of Tokyo, Tokyo, Japan, 113-8656. Here a melt with gentle REE pattern like the ordinary MORB is referred to “Melt 1”, and a melt with steeply LREE-depleted Large quantities of radionuclides were released durring the pattern like ultra-depleted MORB [1] to “Melt 2”. CPXs accident at Fukushima Daiichi Nuclear Power Plant which (clinopyroxenes) in dunites and wehrlites in the Moho occurred during March of 2011. We have carried out intensive transition zone of Oman ophiolite were generally in studies on the distribution and behaviour of radioiodine and equilibrium with Melt 1 [2]. We found dunites-wehrlites radiocesium in the environment following the accident. containing CPXs in eqiulibrium with Melt 2 in predominant Special attention was paid to I-131 (half-life: 8 days) because Melt-1 related dunites-wehrlites from a thick Moho transition of its affinity to thyroid glands and because, at the time of the zone of Wadi Thuqbah, northern Oman ophiolite [3]. Some of Chernobyl accident, an increase of thyroid cancer for infants the Melt-2 related dunites-wehrlites contain relic OPX and children was observed as a result. Although the amount of (orthopyroxeen) partially replaced with olivine: other Melt-1 I-131 released from the Fukushima accident is about one tenth related ones are free of OPX, and occasionally contain sulfides of that released from the Chernobyl accident, it is necessary to [3]. The Fo content of olivine is higher in the Melt-2 related obtain information on the deposition density of this nuclide in rocks (around 91) than in the Melt-1 related ones (88-90). The

different locations surrounding the nuclear power plant at the Cr2O3 content in CPX is higher in the former (1.1-1.3 wt%) time of the accident. However, most of it decayed away after than in the latter (0.9-1.1 wt%). The OPX in the former is some months due to its short half-life and there were not simar in chemistry to that in the mantle harzburgite enough data to construct a deposition map for I-131. downsection. In order to estimate the deposition of I-131, we focused on These features possibly indicate chemical evolution of I-129 (half-life: 15.7 million years) which was also co- Melt 1 from Melt 2 through reaction with the mantle peridotite released during the accident and deposited in soils across the (consumption of OPX combined with olivine production). The region. Surface soil samples collected from different places in Moho transition zone dunites and wehrlites are cumulates Fukushima Prefecture were analyzed for I-129 by AMS from melts enriched with olivine crystals (crustal mush) [3]. (accelerator mass spectrometry) after the chemical separation. The Mlet-2 related rocks sometimes with OPX were formed Soil samples that had been determined for I-131 were used to from an incomplete melt-peridotite reaction product, and the estimate I-131/I-129 ratio. A good correlation was found Melt-1 related rocks, from a melt-peridotite reaction product, between the concentration of I-131 and that of I-129 in soil. where OPX digestion was completed. This suggest a possibly This finding suggests the possibility to estimate the I-131 imprtant role of the Melt 2-peridotite reaction in formation of deposition through the analysis of I-129 in soil. We also ordinary MORB (Melt 1) in the upper mantle [cf.4,5]. analyzed soil samples collected from different locations of Fukushima Prefecture within a project organaized by MEXT [1] Sobolev & Shimizu (1993) Nature 363, 151-154. [2] (Ministry of Education, Culture, Sports, Science, and Akizawa et al. (2012) Contrib. Mineral. Petrol. 164, 601-625. Technology, Japan) for reconstracting the deposition density [3] Negishi et al. (2013) Lithos 164-167, 22-35. [4] Kelemen of I-131. et al. (1995) Nature 375, 747-753. [5] Arai & Matsukage (1996) Proc. ODP, Sci. Results 147, 135-155.

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The coupling of particle acidity and Fractionation of 238U/235U by gas phase ammonia in the biosphere- reduction during low T uranium atmosphere system mineralisation processes JENNIFER MURPHY1 AND ALEXANDRA TEVLIN1 MELISSA J. MURPHY1*, CLAUDINE H. STIRLING2, 2 1 1 ANGELA KALTENBACH , SIMON P. TURNER Department of Chemistry, University of Toronto, Toronto AND BRUCE F. SCHAEFER2 ON, Canada 1GEMOC, Department of Earth and Planetary Sciences, Ammonia is the most important gas phase base in the Macquarie University, Australia (*Correspondence: atmosphere and is known to influence the formation and [email protected]) growth of atmospheric particles. While the magnitude and 2 Centre for Trace Element Analysis and Department of trends of ammonia emissions are highly uncertain, it is likely Chemistry, University of Otago, New Zealand that a legacy of synthetic fertilizer application has led to an increased potential for ammonia emissions from many Investigations of ‘stable’ uranium isotope fractionation ecosystems. We have obtained observational evidence for the during low temperature, redox transformations may provide bi-directional exchange of ammonia between the surface and new insights into the usefulness of the 238U/235U isotope the atmosphere, and the coupling of this process to gas- system as a tracer of palaeoredox processes. Sandstone-hosted particle partitioning. From intensive field campaigns in urban uranium deposits accumulate at an oxidation/reduction and rural environments, simultaneous measurements of interface within an aquifer from the low temperature reduction particle composition and gas phase ammonia permit the of soluble U(VI) complexes in groundwaters, forming calculation of particle acidity, which affects gas-particle insoluble U(IV) minerals. This setting provides an ideal partitioning of ionizable species and may influence toxicity environment in which to investigate the effects of redox and secondary organic aerosol formation. In a complementary transformations on 238U/235U fractionation. Here we present analysis, we use long-term measurements (1990-2010) of coupled measurements of 238U/235U isotopic compositions and particle composition from Canada’s Chemistry and U concentrations for groundwaters and mineralised sediment Precipitation Monitoring Network (CAPMoN) to calculate samples collected in the vicinity of the high-grade Pepegoona trends in strong acidity and infer trends in gas phase ammonia. sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios, spanning a 5 ‰ range. The groundwaters show a greater than 2 ‰ variation in their 238U/235U ratios, and exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during the precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. Previous studies on the same groundwaters have shown significant disequilibrium between 234U and 238U. 238U/235U ratios however, show a poor correlation with (234U/238U) activity ratios, which suggests that mineral leaching during weathering is unlikely to control the observed uranium 238U/235U isotopic variability within this low temperature, redox-controlled mineralised system. Rather, the results imply that 238U/235U fractionation may be controlled by the nuclear field shift effect during the reduction of U(VI) to U(IV) during mineralisation processes. The findings of this study support the use of the 238U/235U isotopic system as a palaeoredox tracer to constrain the nature and timing of palaeoredox conditions.

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Stabilising a craton: The 3.1 Ga Zinc Melanterite Formation from Mpuluzi batholith (Swaziland / RSA) Acid Mine Drainage in Pan de R.C. MURPHY1*, W.L. GRIFFIN1, N.J. PEARSON1 Azúcar Mine (Zn-Pb-Ag), Northwest AND SUZANNE Y. O’REILLY1 Argentina 1 GEMOC/CCFS, Earth and Planetary Sciences, Macquarie 1 2 JESICA MURRAY ALICIA KIRSCHBAUM University, NSW 2109 Australia 3 AND BERNHARD DOLD (*correspondence: [email protected]) 1,2 IBIGEO-CONICET [email protected]; 3 The Barberton Greenstone Belt and Ancient Gneiss [email protected] ; Bernhard Dold Sustainable Complex in Swaziland and adjacent South Africa are some of Mining Research & Consult (SUMIRCO), the most-studied Early- to Mid-Archean (3.6 to 3.2 Ga) crustal [email protected] remnants. The granite-greenstone belt is surrounded and overlain by several large granitoid bodies (Mpuluzi, Piggs Melanterite formation in Pan de Azucar Mine: Peak, and Nelspruit batholiths), all emplaced ~3.1 Ga, and Evaporation of acid mine waters formed by oxidation of marking the end of TTG magmatism and regional sulfide rich tailings in Pan de Azúcar Mine (Zn-Pb-Ag) favors metamorphism in the area. the formation of soluble sulfates as Melanterite 2+ The granitoids were emplaced as extensive, km-thick (Fe SO4·7H2O), which is one of the most common ferrous sheets and extend over more than 10,000 km2. Zircon U-Pb sulfates in nature and one of the first phases to precipitate ages range from ~3.08 to ~3.15 Ga; emplacement may have from evaporation of acid mine drainage. One of the most occurred over as much as 70 Ma. Some samples also have a important characteristic of these phases is their ability to store minor inherited population at ~3.5 Ga, implying the metals as Ni(II), Cu (II), Zn (II) [1] Zn-Melanterite: Acid mine 2- involvement of older crustal material. Zircon Hf-isotope data drainage (139 g/L SO4 ; 8960 mg/L Zn; 99,7 mg/L Cd; 47 show a range of up to 15 epsilon units within each sample, but mg/L Fe (total); 44 mg/L As; 10 mg/L Cu; 1,4 mg/L Pb) seeps little variation between samples. Average model ages of the from one of the tailings impoundments during dry season. 3.1-Ga zircons are ~3.5 Ga, corresponding to the age of the High evaporation rates and high concentration of sulfate and inherited population. These older grains commonly have iron favors the precipitation of melanterite at pH=2.1. Some model ages back to 4 Ga. preliminary SEM-EDS studies show high Zn concentrations in Whole-rock Sr and Nd isotopic data yield isochron ages of melanterite crystals, which indicates its ability to capture this 3.022 Ga for both systems, and the initial ratios yield model metal in their structure instead of Cu or Ni, probably due to age of 3.11 Ga for each system, perfectly consistent with the the Zn excess in the acid water. XRD and field observation U-Pb data. The tight isochrons for both systems (r2 for Sr = suggests that during the dry season, melanterite dehydrates 2+ 0.9974, Nd = 0.9615) strongly suggest that the whole mass and changes to rozenite (Fe SO4·4H2O) as has been formed and cooled together, and the small time gap between described by Nordstrom [1, 2]. In the following rainy season the isochron and model ages suggests rapid cooling. that phases dissolves and metals are again available to the These 3.1 Ga granitoids therefore represent the final stage hydrological cycle. This process has an important influence in the cratonisation of the region; this could represent the on temporal variation of metals in surface waters. “draining” of fusible material from the lower crust, increasing its rigidity and limiting further tectonism. The unusual [1] Sulfate Minerals, Cristallography, Geochemistry and emplacement style, the large volume of magmas involved and Environmental Significance (2000). Reviews in Mineralogy the apparently short timescale of emplacement raise several and Geochemistry, V 40. [2] Nordstrom (1982). Acid Sulfate important questions about the processes involved in the Weathering: Soil Science Society of America Spec. 10, 37-56 stabilisation of the eastern Kaapvaal Craton in particular and ancient crust in general: (1) What was the heat source for the magmas, and what was the source material? (2) How were these volumes of magma extracted from the deep crust? (3) What controlled the emplacement style as sheets rather than deep-rooted batholiths? These problems will now be addressed by dynamic and thermodynamic modeling.

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Application of Clumped Isotopes to Helium isotope compositions of the Dolomite Problem geothermal fluids and alkaline MURRAY, SEAN T. 1, PETER K. SWART 2 volcanics in Turkey: A comparative AND MONICA M. ARIENZO 3 assessment for crust-mantle dynamics 1,2,3 4600 Rickenbacker Causeway, Miami FL 33149 1 2 3 1 HALIM MUTLU , ERCAN ALDANMAZ ,FIN M. STUART , [email protected] 1 4 5 DURU ARAL ,NILGÜN GÜLEÇ AND DAVID R. HILTON [email protected] [email protected] 1Eski5ehir Osmangazi Univ., 26480, Eski5ehir, Turkey (*correspondence: [email protected]) The measurement of clumped isotopes has been applied to 2Kocaeli University, 41380, Izmit, Turkey Miocene to late Pliocene dolomites from San Salvador, 3SUERC, Glasgow, G75 0QF, Scotland Bahamas. These dolomites formed as recently as 500 ky BP, 4Middle East Technical Univ., 06531, Ankara, Turkey yet are texturally mature and display near perfect 5Scripps Inst. of Oceanography, CA, 92093, USA

stoichiometry (46-48% MgCO3). They were proposed to have formed at low temperatures (20-28°C) and from normal to As a part of the Alpine-Himalayan orogenic belt, the slightly evaporated sea water1. Given the well constrained Anatolian land has experienced a series of volcanism, environmental conditions, these dolomites offer the plutonism and active tectonism since the Neogene. This opportunity to test the application and accuracy of the various unique geologic disposition facilitated occurrence of vast

calibrations for relating F47 and temperature. Accurate number of fossil and modern geothermal systems which are temperatures of formation can than be used to determine closely associated with Neogene-Quaternary volcanism in which of the multitude of formulas for determining the areas of seismic unrest. He-CO2 systematics of geothermal fractionation of #18O between the dolomite and the fluid is fluids in Anatolia has been the subject of several studies over most accurate. the last decade. He-isotope compositions, reported as R/Ra

The dolomites returned F47 values from 0.64‰ to 0.68‰. values, vary over a wide range from 0.27 to 7.76 (Nemrut Based on the analysis of these samples and the application of caldera-eastern Anatolia). The mantle-derived helium

the various formulas for relating F47 to temperature, we component, which is likely transferred to the crust beneath propose a modified Dennis et al. (2011)2 method which takes Turkey by recent magmatism, constitutes up to 96% of the 3 into account the temperature difference between the total He composition in fluids. CO2/ He ratios varying from theoretical calibrations for dolomite and calcite proposed in 2.4x105 to 26x1013 encompass the range of island arcs Guo et al. (2009)3. This method produced temperatures (~2.0:1010) and continental fluids (>1011). Additionally, in this ranging from 23.3°C to 41.5°C. All other methods proposed in work new helium isotope data are presented for mantle- the literature produced temperatures that were considered too derived xenolith-bearing basaltic lavas from the Thrace basin high considering the well constrained depositional and in NW Turkey as well as olivine-bearing volcanic rocks from diagenetic setting of these samples. western and southern Anatolian regions. The peridotite Using the modified Dennis et al. (2011)2 method, it has xenoliths from the Thrace alkaline volcanic suite are 18 been concluded that the # Odolomite-fluid fractionation equation composed of spinel-harzburgites and dunites. Homogenous of Sheppard and Schwarcz (1970)4 produces the most 3He/4He ratios (6.7-7.1 Ra) of harzburgites are very close to 18 reasonable water # Owater values considering our interpretation that of MORB-type mantle. One dunite sample from the same of the temperatures. region is represented by a lower helium isotope composition (3.0 Ra). Alkaline basalts from Kula (western Anatolia) and [1]Swart, Ruiz, & Holmes(1987), Geology 5, 262-265. Osmaniye (southern Anatolia) areas have 3He/4He ratios of 7.9 [2]Dennis, Affek, Passey, Schrag, & Eiler (2011), Geochimica Ra which is coincident with values typical of upper mantle. et Cosmochimica Acta 75, 7117-7131. [3] Guo, Mosenfelder, Olivine in basalt sample from the Söke area in western Goddard III, & Eiler (2009), Geochimica et Cosmochimica Anatolia yielded lower helium composition (1.9 Ra). Our Acta 73, 7203-7225. [4] Sheppard & Schwarcz (1970), Contr. ongoing survey on isotope compositions of noble gases in Mineral and Petrol. 26, 161-198. Turkish volcanics, will lead to a better understanding of these apparent anomalies in regard to temporal changes in crust- mantle dynamics in the eastern Mediterranean.

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A bond valence approach to surface Gold in sulfide wastes - peat system energy and crystal morphology I.N. MYAGKAYA*, E.V. LAZAREVA, M.A. GUSTAYTIS 1 2 AND S.M. ZHMODIK. ANDREAS MUTTER AND MARTIN T. DOVE 1 Institute of Geology and Mineralogy SB RAS, Pr. Koptug, 3, Department of Earth Sciences, Univeristy of Cambridge, Novosibirsk, 630090, Russia (*[email protected]) Downing Street, Cambridge CB2 3EQ, UK.

[email protected] 2 Carbonaceous matter is an effective concentrator of School of Physiks and Astronomy, Queen Mary University of precious metals. We study gold partitioning between sulfide London, Mile End Road, London E1 4 NS, UK. material and peat in a halo around the Ursk tailing pit [email protected] (Kemerovo region, Russia) with ore cyaniding wastes. The wastes of processed primary ore and ore from the oxide zone The aim of our research is to provide a methodology, are piled up in two 10-12 m piles. Being not fastened, the which can be applied to investigate the interaction and the material has been washed out by floods and rainfalls for more reactivity of mineral interfaces with the environment. The than 50 years. The swampy area downstream of the tailings is underlying principle of our approach is to define the burnt by acid mine drainage (AMD) and covered by shed interaction between internal structural parameters and surface material, with remains of peat mounds rising above. parameters in order to obtain an ideal abstract crystal The shed wastes and peat have been sampled in test pits to morphology. This abstract crystal morphology can then be 20 cm deep. The gold contents are 0.1 to 3.8 ppm (mean 0.6 used as a references morphology to different growth ppm) in all wastes, and 1.2 ppb in AMD nearby. morphologies or crystal morphologies predicted by other Gold in peat varies broadly, from 0.18 to 155 ppm, mostly atomistic simulations. 0.18 to 19 ppm. The mean and median values are different (5 The internal parameters choosen on behalf of our model and 2 ppm). There are three Au zones in the Ursk halo peat: are the number of atoms per surface area (reticular density) (1) near the piles and mainstream AMD where the primary and the lattice density. The surface parameters are the number and oxide zone ore wastes interlayer (max. 40 ppm); (2) same of dangling bonds (bond valence deficiency) per surface area as (1) but farther from the piles and with higher gold (max. 60 or their corresponding surface energy. The internal parameters ppm); (3) a perennially wet zone 200 m far from the oxide are determinate by the crystal structure type and therefore are zone wastes with extremely high gold (40 to 155 ppm). invariable. In contrast, the surface parameters are variable due Peat along the oxide zone wastes bears secondary to differences in the chemical compositions of different minerals, namely concentric aggregates of Fe(III) compounds, minerals, even though they may agree in their crystal structure gypsum, Na-jarosite, framboidal pyrites; barite druses and type. globules; zinc sulfide; euhedral Hg selenides and sulfides: In order to obtain the surface energies of different crystal timmanite (HgSe), onofrite (Hg(S,Se)), cinnabar (HgS). interfaces, our model uses the bond valence approach of [1] Gold is high (80 ppm) in material rich in Hg sulfides with Brown . First we calculate the surface specific bond valence Cu, Ag, I, and Se impurities. Submicron and nanoparticles of deficiency, then we asign to each bond via its bond length a gold largely cover organic detritus and locally form sheaths certain bond energy, which then in its sumation over the over bacterial cells. Native Au particles (to 1.5 µm in diamter, surface area gives us the surface energy. The main advantage purity 947-1000 ‰), at Cu impurity of 7.5-53 ‰, occur in of this approach is, compared to other atomistic simulations, material cemented with secondary Fe(III) compounds. Cu- that it does not demand for charged neutral surfaces to obtain gold formation may be mediated directly by bacteria. This the surface energy. Therfore, naturally charged and charged process in peat was reproduced in laboratory [1]. Formation of neutral surfaces can be compared likewise, which is a major secondary Au in the presence of sulfides is mediated first by advantage while comparing different growth morphologies in iron- and sulfur-oxidizing bacteria and then by thiosulfate variably composed solutions. oxidizers and sulfate reducers [2]. This performance of our model, its combined approach of The study was supported by Grant 11-05-01020 from internal and interfacial parameters, not only gives results RFBR and an 2012-2013 OPTEC grant for young scientists, which are in good agreement with literature data, but also and was run as part of SB RAS Integration Project #94 enables us to discuss the importance and the occurrence of

naturally polar surfaces on behalf of the crystal morphology. [1] Kuimova et. al. (2011). Lithosphere. 4. 131-136.

(Published in Russian). [2] Southam et. al. (2009). Elements. [1] Brown, I.D. (2002), The chemical bond in inorganic 5(5). 303-307. chemistry. Oxford Science publications.

www.minersoc.org DOI:10.1180/minmag.2013.077.5.13

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Structures of weakly binding anions Strontium Isotope Anomalies and at the interfaces of Fe-polymers and 26Al-26Mg Chronology in CAIs from Fe-oxides: Evidence from X-ray and CV Chondrites infrared spectroscopic studies K. MYOJO1, T. YOKOYAMA1,Y. SANO2, N. TAKAHATA2, N. 3 1 1 1 SUGIURA , H. IWAMORI AND M. UNO , SATISH C. B. MYNENI AND NYSSA CROMPTON 1Department of Earth and Planetary Sciences, Tokyo Tech, 1Departments of Geosciences and Chemistry, Princeton [email protected] University, Princeton, NJ 08544, USA. 2Atmosphere and Ocean Research Institute, Univ. of Tokyo [email protected] 3 Department of Earth and Planetary Science, Univ. of Tokyo 2- - Halides and oxoanions (e.g. CO3 , NO3 ) are common in Many nucleosynthetic isotope anomalies have been! all aquatic systems, and play an important role on the documented in calcium and aluminum rich inclusions (CAIs). interfacial reactions of both cations and anions. Several of Recently, Moynier et al. [1] found positive 84Sr/86Sr anomalies - - - 2- these ions (e.g. Cl , Br , NO3 , SO4 ) are considered to interact in Allende CAIs, suggesting excess of the p-process weakly at the mineral-water interfaces, and thus are used as component or deficit of the r-process component in the CAIs. inert-electrolytes in aqueous geochemical studies for decades. In contrast, Brennecka et al. [2] measured Ba, Nd and Sm However, our X-ray and infrared spectroscopic data suggest isotopic compositions in Allende CAIs and discovered that the that these ions form strong complexes at the interfaces of Fe- CAIs have r-process excesses only for Ba isotopes. If these oxides, and play an important role in Fe-oxide anomalies in CAIs were caused by the injection of refractory transformations. materials via a nearby supernova, isotopic anomalies could - - 2- 4- We examined the reactions of Cl , NO3 , SO4 , and SiO4 r76ku7have variation due to difference in time and/or location. with soluble Fe-polymers, and freshly prepared Fe- To reveal the timing of injection toward the early solar system oxyhydroxides. The coordination environments of several of or processes that caused excesses of nucleosynthetic isotope these ligands are highly disputed, and experimental evidence anomalies in CAIs, we first measured Al-Mg ages in type B CAIs from Allende and NWA 2364 and type C CAI from was presented for the formation of both inner- and outer- Allende, then we measured Sr isotopic anomalies in the same sphere complexes using different macroscale and molecular CAI. For Al-Mg ages, we used NanoSIMS at the AORI, the methods. We examined the coordination environments of Univ. of Tokyo, and for Sr isotopic analysis, we used TIMS, these ions using the X-ray and vibrational spectroscopy Triton plus at Tokyo Tech. techniques. We found that these ions exhibit a variety of Al-Mg internal isochrones of type B CAIs yielded initial complexes at the Fe-oxide-water interfaces; however, H- 26Al/27Al ratio which are consistent with the canonical value of bonded complexes are identified as the predominant 5.11/10-5 [3]. Two Allende CAIs show 84Sr/86Sr anomalies of complexes for these ligands at the Fe-oxide-water interfaces. 187 ppm (type B) and 46 ppm (type C) higher than terrestrial Differences in the molecular structures of these ions at the standard, whereas the CAI from NWA 2364 has no anomalies. Fe-oxide-water interfaces are attributed to the rates at which In addition, we also measured "88Sr/86Sr ratio to trace the freshly prepared Fe-oxides transformed to goethite. Our degree of mass dependent isotope fractionation. Allende type studies indicate that goethite appeared first in freshly  2- - B CAI has 0.3 higher and other two CAIs have values precipitated Fe-oxides in the presence of SO4 and NO3 , when - lower than terrestrial standard. These results suggest that Sr compared to that of Cl . However, the rate at which the isotope signatures in individual CAIs inherited isotope concentration of goethite increased was much lower in the 2- signatires of their formation locations. The excesses of a p- presence of SO4 . In addition, the crystallinity of goethite was process nuclide (84Sr) in CAIs are most likely caused by affected significantly in the presence of these ligands irradiation from the proto-sun, and their heterogeneous isotope indicating that these weakly coordinating ligands play a signature is attributed to the distance from proto-sun to central role on the stability and crystallinity of Fe-oxides. formation region of individual CAIs. Details of these interactions will be presented.

[1] Moynier et al. (2012) Astrophysical Journal, 758:45, [2] Brennecka et al. (2011) LPSC Abstract #1302 [3] Jacobsen et al. (2008) EPSL 272, 353-364.

www.minersoc.org DOI:10.1180/minmag.2013.077.5.13

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Impact of crustal elements on global atmospheric deposition of Nitrogen STELIOS MYRIOKEFALITAKIS1, NIKOS DASKALAKIS1 AND MARIA KANAKIDOU1 1 Environmental Chemistry Processes Laboratory, Department of Chemistry, University of Crete, P.O. Box 2208, 71003 Heraklion, Greece; [email protected]; [email protected]; [email protected]

Nitrogen (N) deposition plays a significant role in ecosystem functioning and particularly in ocean productivity. Reactive nitrogen also impacts on tropospheric chemistry driving tropospheric ozone production, and on atmospheric acidity. A large number of compounds consist the reactive N pool, like nitrogen oxides, ammonia, nitric acid, organic nitrates, amines, amino-acids etc. Chemical transformations occurring in all phases present in the atmosphere, affect the solubility of reactive nitrogen pool and thus of N-deposition. A significant fraction of N-deposition occurs in the form of particulate matter (PM) deposition. Atmospheric PM is composed of water, inorganic salts, crustal material, organics and trace metals. Important contributors to the dry fine PM are + inorganic compounds like ammonium (NH4 ), and nitrate - + = - (NO3 ), sodium (Na ), sulfate (SO4 ) and bisulfate (HSO4 ). Crustal species like Ca2+, K+, Mg2+ are major components of dust and can neutralize part of the acidity of the atmosphere - = (e.g. NO3 , SO4 ). Their presence is thus affecting the - = + partitioning of NO3 , SO4 and NH4 on atmospheric PM as well as N-solubility and deposition, especially in areas where dust comprises a significant portion of total PM such as the Mediterranean region. The effect of crustal material on N-containing species deposition is here investigated using the global TM4-ECPL global chemistry-transport model (Myriokefalitakis et al., ACP, 2011; Kanakidou et al., GBC, 2012 and references therein). The model is able to simulate oxidant chemistry, accounting for non-methane volatile organic compounds and all major aerosol components, including secondary aerosols like sulfate, nitrate and secondary organic aerosols. It also accounts for multiphase chemistry in clouds and aerosol water. Gas-particle partitioning of inorganic and crustal components is solved using the ISORROPIA II aerosol thermodynamics model (Fountoukis and Nenes, ACP, 2007). Global simulations have been performed considering and neglecting crustal material for the partitioning of HNO3/NO3- and H2SO4/SO4=. Differences between the N-deposition amounts and their solubility are presented and thoroughly discussed.

www.minersoc.org DOI:10.1180/minmag.2013.077.5.13

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