1414 Goldschmidt2013 Conference Abstracts

Chromium chemistry in natural Deformation mechanisms in Martian waters, Iceland Shergottites HANNA KAASALAINEN1*, ANDRI STEFÁNSSON1, KACZMAREK M.-A.*12, GRANGE M.1, REDDY S.M.1, INGVI GUNNARSSON2 AND STEFÁN ARNÓRSSON1 AND NEMCHIN A.1 1Institute of Earth Sciences, University of Iceland, Sturlugata 1Department of Applied Geology, The Institute for Geoscience 7, 101 Reykjavik, Iceland, Research, Curtin University of Technology, GPO Box (*correspondence: [email protected]) U1987, Perth, WA 6845, Australia 2Present address: Reykjavik Energy, Bæjarhalsi 1, 110 2Now at University of Lausanne, Institute of Earth Sciences, Reykajvik, Iceland UNIL Mouline, Géopolis, CH-1016 Lausanne, Switzerland Chemistry of Cr and Fe was studied in non-thermal and (*correspondence: [email protected]) geothermal waters in Iceland. Chromium (Cr) is typically present at low concentrations (<1 µg/l) in natural waters, but Nakhla and Zagami are both clinopyroxene-rich basaltic elevated concentrations have been observed in waters with shergottite, with some Fe-rich olivine. The microstructure, the low pH values, e.g. acid mine drainage, and in association preferred orientation of pyroxene using Electron Backscatter with industrial activities. Chromium occurs in two oxidation Diffraction (EBSD) method and the gochemistry are combined states, Cr(III) and (VI), these being characterized by different to study subsamples of both Zagami and Nakhla to decipher (bio)chemical behaviour and solubility. As Cr(VI) is known to deformation processes that have occurred on Mars. be toxic but Cr(III) an essential micronutrient, it is important Nakhla displays a granular texture, essentially composed to determine the two oxidations states. Iron (Fe) is known to of augite, fayalite, plagioclase and magnetite. Our Zagami play an important role in the chemistry of Cr through sample, formed by olivine, plagioclase, and whitlockite is part adsorption on and incorporation in Fe containing minerals, and of the “coarse grained” portion of Normal Zagami texture [1, by affecting the distribution of Cr species. In natural waters, 2] with long prism of clinopyroxene underlying a weak iron is present in two oxidation states (Fe(II) and (III)) and preferrential orientation. Complete maps of both Zagami and understanding its chemistry is complicated by fast oxidation Nakhla samples and detailed maps of clinopyroxene single kinetics, importance of colloidal forms and low solubility in grains were obtained with EBSD. Both samples show a strong the pH range of most natural waters (pH>6). preferred orientation of clinopyroxene and CPOs display Samples were collected from non-thermal surface and several point concentrations on <001> axes within a girdle. spring water, surface geothermal water and geothermal well The relationship between the microstructure and CPOs discharges, and analyzed for their major and trace element inferred the possible activation of (100)[001] and (010)[100] composition. Chromium and Fe speciation was determined in slip systems. Moreover, the several point concentrations on selected samples. The sampled waters showed wide range of clinopyroxene <001> axis might correspond to twinning. composition with temperature, pH and total dissolved solids in Geochemical maps of clinopyroxene single grains the range of 0-184°C, 2.0-9.6, and 35-4030 mg/l, respectively. highlight chemical zoning from augite core to pigeonite rims. The total dissolved Fe and Cr concentrations were between <1 Phases indexation with the EBSD is concordant with the µg/L to 360 mg/L and <0.01 and 660 µg/L, respectively. The geochemistry and highlights no variation in the slip system highest concentrations were associated with steam-heated from cores to rims, suggesting either no variation of acid-sulfate waters with the lowest pH values, whereas the deformation during the evolution of the geochemical system, concentrations in neutral to alkaline waters were low, typically or a late deformation event. Inspection of clinopyroxene single <1 µg/L Cr and <100 µg/L Fe. grains show that Nakhla clinopyroxenes have almost no The main processes controlling Cr chemistry were found internal deformation, rather than Zagami clinopyroxenes to depend on the water pH and rock leaching. At a low pH, showing complicate microtexture with possible activation of Cr(III) becomes released into solution through leaching of Cr- several slip systems. containing minerals contained in basaltic rocks. At neutral to Our results suggest a composite deformation related to alkaline pH, Cr leaching from rock is limited and Cr(III) magmatic deformation (preferred orientation and prismatic concentrations may be further reduced and controlled by clinopyroxene) and to the shock event (single grain internal solubility of Cr(III)-Fe(III) mineral phases. However, Cr(VI) deformation and twinning). mobility is enhanced associated with decreasing importance of mineral surface complexation. Indeed, Cr(VI) was frequently [1] Stolper E. M. et al. 1979. Geochimica Cosmochimica Acta. found to dominate over Cr(III) at pH>6 in concentrations of a 43: 589-602. [2] McCoy T. J. et al. 1992. Geochimica few µg/L. Cosmochimica Acta. 56: 3571-3582.

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Bioavailability of nanoparticulate Determination the step of karst iron derived from atmospheric formation using GPR and Raman mineral dusts Spectroscopy Methods, South East ENIKÖ KADAR1, JONATHAN J. POWELL3 Anatolia, Turkey 2 AND ZONGBO SHI 12 2 SELMA KADIOGLU AND YUSUF KA!AN KADIO!LU 1Plymouth Marine Laboratory, Prospect Place, the Hoe, 1Ankara University Faculty of Engineering Department of Plymouth PL1 3DH, UK email: [email protected] 2 Geopgysical Engineering, Ankara, Turkey School of Geography, Earth and Environmental Sciences, 2 Ankara University Earth Sciences Application and Research University of Birmingham, B15 2TT, U.K email: Center, Ankara, Turkey ([email protected]) [email protected] 3 Biomineral Research Section, Medical Research Council - Ground Penetrating Radar (GPR) is used to identify the Human Nutrition Research, Elsie Widdowson Laboratory, relatively shallow subsurface features at scale from centimeter Fulbourn Road, Cambridge CB1 9NL email: up to meter. In this study dissolution of soluble rocks (Karst) [email protected] including limestone and dolomitic limestone are examined using GPR and Raman spectroscopy methods around We have studied the composition, Fe dissolution/Fe Adiyaman City in East Anatolia Turkey. Karstification led to lability, particle aggregation/size distribution, surface topology form sinkholes, caves, and underground drainage systems. and zeta potential (i.e. colloidal stability) of Fe-rich Rainwater becomes acidic as it comes in contact with carbon nanoparticles (NPs) formed during simulated atmospheric dioxide in the atmosphere and the soil. As it drains into processing of dust in contact with seawater under a range of fractures in the rock, the water begins to dissolve away the environmentally realistic conditions typical in oceanic waters rock creating a network of passages. The step of the karst to shed light on putative relationships between NP structure formation towards the inner parts of the surface of the and water parameters. These laboratory studies showed that: limestone is determined using 250 and 500 Mhz GPR antenna. (i) despite the close resemblance in micromorphology, NPs GPR attribute volumes is sensible and suggests that the formed from mineral dusts have distinct aggregation formation of the cavities along the fracture packets exist over behaviour from ferrihydrite NPs; (ii) the relatively stable and cavity floors elsewhere but that there is also variation in mondosiperse aggregates of NPs formed during simulated fracture intensity and in orientation over the whole system. cloud processing of mineral dust become more polydisperse The matrix consolidation and dissolution of the rocks are and unstable in seawater; (iii) exopolymeric substances (EPS) observed through the processing of the radar data. extracted from phytoplankton seem to "stabilise" the The microscopically examination and Confocal Raman aggregates of dust derived NPs; iv) dissolved Fe concentration spectroscopy determination studies show the degree of the from NPs, is consistently higher in seawater in the presence of dissolution is increased towards the crack and aid to form EPS and is also affected by sunlight; v) EPS-mediated Fe ankerite, siderite, limonite, hydrous carbonate-sulfates, uptake may be responsible for enhanced bioavailability in vermiculite clay minerals with rare amount of albite and phytoplankton. pyrite. To test the hypothesis that nanoparticulate Fe is more bioavailable than the bulk analogue we have grown marine microalgae on synthetic nano-iron substrates. Algal growth was significantly enhanced when the nanomaterials were added in equimolar concentration compared to Fe-EDTA in the optimised algal growth medium (f/2). NP addition influenced cellular fatty acid composition compared to control treatments, but this was significant only in haptophytes. The NP uptake mechanism proposed is via secretion of an extracellular matrix that binds NPs through which Fe is bioavailable via fagocytotic membrane processes and/or NP dissolution. The implications of the use of such engineered nanomaterials as Fe substrate in algal culture are discussed.

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Diamond Bearing Mantle Xenoliths HSE and S-Se-Te fractionation in in Alkaline Basalts: Karacada! components of enstatite chondrites Volcano, South East Anatolia, YOGITA KADLAG1AND HARRY BECKER1 Turkey 1Institut für Geologische Wissenschaften, Freie Universität 12 Berlin, Germany. [email protected], YUSUF KA!AN KADIO!LU [email protected] 1Ankara University. Faculty of Engineering Department of Geological Engineering, Ankara, Turkey and Enstatite chondrites show distinct fractionations of the [email protected] highly siderophile elements (HSE) that may reflect volatility 2Ankara Uni. Earth Sciences Application and Research Center, control or other types of partition processes [1, 2]. To Ankara, Turkey investigate the origin of the fractionation of the HSE, S, Se and Te in enstatite chondrites, we have separated the Small Diamond crystals are determined by Raman components from the unequilibrated enstatite chondrites spectroscopy within the mantle xenoliths from alkali basalts in (EH3) Sahara 97072 and Kota Kota: magnetic, slightly Karacada" Volcanic province South East Turkey. The magnetic and nonmagnetic components in five different grain peridotite mantle xenoliths are in the compositions of dunite size fractions, matrix, chondrules, CAIs (Ca-Al rich and pyroxene bearing dunite and they are ranging from 1 cm inclusions) and dark inclusions. Samples were analyzed up to 30 cm in size. The purpose of this contribution is to following established techniques [2, 3]. review the nature of the latest Cenozoic alkaline magmatism Magnetic components of both meteorites (and the with respect to the geochemistry of mantle xenoliths. Diamond chondrule fraction of Sahara 97072) are enriched in HSE, S, bearing Peridotite xenoliths in basalts of Karacada" provide Se and Te compared to the bulk rocks. Au is more enriched snapshots of the lithospheric mantle beneath particular regions relative to the PGE and Re in the magnetic fractions, at the time of their eruption and hence are crucial direct compared to non-magnetic fractions. In contrast, S, Se and Te evidence of the nature of the mantle beneath regions. The in the magnetic fractions are always depleted compared to the diamond bearing peridotite mantle xenoliths suggests that HSE. The CAI fraction and a dark inclusion from Sahara these diamonds might be cogenetic with old rock provinces in 97072 are depleted in all elements (0.3*bulk) and show a the subcontinental mantle and then erupted with the latest similar abundance pattern as CI chondrites. Magnetic events of the alkaline magmatism. fractions display higher Re/Os (0.08-0.19) than most non- magnetic fractions, which have Re/Os lower than Re/Os of CI chondrites. The relative enrichments, depletions and element fractionation in the components allow some preliminary conclusions: (1) Because metal rich components display strong enrichment of Au and Pd relative to refractory HSE, but depletion of Te-Se-S (with ratios relatively close to CI), the different groups of moderately volatile elements in metal rich components are decoupled. (2) In non-magnetic silicate rich fractions, Se and S are less depleted than HSE and Te, likely reflecting low-pressure metal-silicate-sulfide partitioning [4,5]. Raman Shift value of the diamond crystals within mantle xenolites of Karcada" Basalts [1] Horan, M. et al. (2003) Chem. Geol. 196, 5-20 [2] Fischer- Gödde M. et al. (2010) GCA 74, 356–379. [3] Wang et al. (2013) GCA 108, 21-44. [4] Rose-Weston et al. (2009) GCA 73, 4598-4615. [5] Mann et al. (2012) GCA 84, 593-613.

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Transformation of Silver Sulfur and halogen fluxes at mid- Nanoparticles: From the Sewer to the ocean ridges: Estimations based on Fly Ash gas compositions in MORB vesicles R. KAEGI1, A. VOEGELIN1AND B.THALMANN1 T. KAGOSHIMA1*, Y. SANO1, N. TAKAHATA1 2 1 AND B. MARTY Eawag, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, Switzerland (*correspondence: 1AORI, Univ. Tokyo, Chiba, Japan [email protected]) (*correspondence: [email protected]) 2CRPG, CNRS, Nancy, France Silver-nanoparticles (Ag-NP), used in textiles and cosmetics, will eventually be discharged to the municipal Since S and halogens (F and Cl) form various compounds sewer system. We have shown that Ag-NP are efficiently on the Earth’s surface, their geochemical cycles are important transported along the sewer channel without substantial loss to issues in the Earth’s evolution. Though fluxes of S and the biofilm [1]. In the wastewater treatment plant (WWTP), halogens at MORs have been estimated using compositions of partially sulfidized Ag-NP attach to the wastewater biomass chilled margins of MORB glasses characterised as those of and are removed from the wastewater stream. In parallel, the silicate melts derived from the upper mantle, they may be sulfidaton reaction proceeds and the Ag-NP are almost somewhat overestimated [1]. Plausible estimations based on completely sulfidized when leaving the WWTP via the surplus compositions of volcanic gases released as hydrothermal fluids are necessary. We characterised gas and melt sludge [2]. Ag2S is very recalcitrant to oxidation as shown in a recent study where digested sludge was stockpiled for several compositions retained respectively in vesicles and solids of weeks under oxic conditions [3]. MORB glasses and estimated MOR fluxes of S and halogens. In Switzerland sewage sludge is exclusively incinerated, in We analyzed MORB glasses collected at 2 sites on East Germany about 50% with an increasing trend towards thermal Pacific Rise, 2 sites on Mid-Atlantic Ridge and 2 sites on sewage sludge disposal and on a EU level, about one third of Central Indian Ridge. After extractions of gases in vesicles by 3 the sewage sludge is incinerated. In order to allow for later the frozen crushing method [2], concentrations of He were phosphorus (P) recovery, sewage sludge has to be incinerated measured using a VG-5400 and those of S and halogens were in monocombustion facilities. Until an economic and ecologic measured using an ICS-2100. Concentrations of S and process for P recovery from sewage sludge ashes (SSA) has halogens in solids were measured using a NanoSIMS. We 3 3 3 been found, the majority of the SSA are stored in separate calculated relative molar ratios (S/ He, F/ He and Cl/ He) and deposits, although in Germany, a small fraction (5%) of the estimated MOR fluxes of S and halogens calibrating against 3 SSA is directly used as fertilizer. the known He flux (527 mol/yr [3]). 3 3 X-ray fluorescence (XRF) analysis of fly ashes collected For vesicle components, global averages of S/ He, F/ He 3 7 6 from monocombustion (fluid bed) facilities revealed Ag and Cl/ He are (4.2±1.6)#10 , (1.4±0.7)#10 and 7 10 concentrations of ~10 mg/kg. X-ray absorption spectroscopy (2.6±1.0)#10 . For bulk components, they are (0.3–1.2)#10 , 9 9 (XAS) analysis showed that Ag in the fly ash was dominantly (1.6–6.5)#10 and (0.7–3.0)#10 , respectively. Using these 3 Ag S. This result is in contrast to a recent study concluding ratios and the known He flux, MOR fluxes were estimated to 2 10 12 8 12 that Ag S transforms into Ag(0) during the combustion [4], be (2.2#10 –6.6#10 ) mol/yr for S, (7.1#10 –3.4#10 ) 2 10 12 which would possibly have far reaching consequences mol/yr for F and (1.4#10 –1.6#10 ) mol/yr for Cl. Assuming regarding the direct application of SSA in agriculture. The the continuous degassing from the solid Earth, formations of differences are most likely caused by different combustion atmosphere and ocean can not be achieved by the low MOR conditions between the two studies. We will further in- fluxes estimated based on vesicle compositions. The amount vestigate the the fly ash samples using electron microscopy to of S accumulated on the surface are calculated to be 50 times assess whether silver is present in the form of nanoparticles. lower than its surface inventory, and halogens are calculated not to be accumulated because of dominant influxes at [1] Kaegi et al. (2011), ES & T, 49, 3902 – 3908 [2] Kaegi et subduction zones. This implies a possibility that the elements al. (2013), Water Research, doi:10.1016/j.watres.2012.11.060. were significantly degassed in the early Earth.

[3] Lombi et al. (2013), Env.Poll. 176, 193–197. [4] [1] Tajika (1998) GRL 25, 3991-3994. [2] Kagoshima et al. Impellitteri et al. (2013), Water Research , (2012) Geochem. J. 46, e21-e26. [3] Bianchi et al. (2010) doi:10.1016/j.watres.2012.12.041. EPSL 297, 379-386.

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Evaluating possible risks and benefits Characterizing magma migration of nanopesticides application dynamics beneath Mt. Etna using M. KAH1*, S. BEULKE2, K. TIEDE2 AND T. HOFMANN1 combined kinetic and thermodynamic 1Department of Environmental Geosciences, University of (MELTS) modelling Vienna, Austria 1 2 2 MAREN KAHL* , SUMIT CHAKRABORTY , (*correspondence: [email protected]) 3 4 FIDEL COSTA AND MASSIMO POMPILIO 2Food and Environment Research Agency, York, UK 1SEE, The University of Leeds, UK Deliberate application of nanoparticles as plant protection (*correspondence: [email protected]) products within agricultural practices could result in one of the 2GMG, Ruhr-University Bochum, Germany rare intentionally diffuse inputs of engineered nanoparticles ([email protected]) into the environment. The anticipated new or enhanced 3EOS, Nanyang Technological University, Singapore activity of nanopesticides will inevitably result in both new ([email protected]) risks and new benefits to human and environmental health. It 4INGV - Sezione di Pisa, Italy ([email protected]) is unclear whether the current regulatory framework is adequate for the evaluation of these new products. Characterizing the routes of magma migration beneath A literature review [1] was carried out with the objectives active volcanoes is important to understand the dynamic (i) to explore potential applications of nanotechnology within processes in sub-surface magma plumbing systems. We the pesticide formulation sector, (ii) to identify possible present a method that combines kinetic (diffusion) and impacts on environmental fate, and (iii) to analyse the thermodynamic (MELTS) modelling of the chemical suitability of current exposure assessment procedures to stratigraphy preserved in zoned olivine crystals to constrain account for their novel properties within the EU regulatory the nature and dynamics of magma storage and migration context. Nanopesticides encompass a great variety of products beneath Mt. Etna. We used 180 olivine crystals erupted during and cannot be considered as a single category. Nanopesticides several episodes between 1991 and 2008. The compositional can consist of organic ingredients (e.g., active ingredient(s), and zoning record preserved in these crystals reveal five polymers) and/or inorganic ingredients (e.g., metal oxides) in different olivine populations (i.e. Fo79-83, Fo75-78, Fo73-75, Fo70-72 various forms (e.g., particles, micelles). Studies on the and Fo65-69). These can be explained as the result of multistage environmental fate of nanopesticides are scarce. Possible magma mixing and magma exchange between at least four effects of nano-formulations on the fate of the active different magmatic environments (M0 containing olivine of ingredient can be complex and reported results are often Fo79-83; M1with Fo75-78, M2 with Fo70-72 and M3 with Fo65-69). contradictory. Two dominant magma migration routes (M0-M1; M1-M2) have The current level of knowledge does not appear to allow a been identified in the majority of the studied eruption products fair assessment of the advantages and disadvantages that will and thus might represent major pathways for magma transfer. result from the use of some nanopesticides. A great deal of Kinetic modelling of the compositional zoning observed in the work will be required to successfully combine analytical olivines reveal that most of the timescales related to the techniques that can detect, characterize and quantify the active transfer of magma between the environments M0-M1 as well as ingredient and adjuvants emanating from nano-formulations, M1-M2 is less than three months, though a minor population of and also to understand how their characteristics evolve with longer timescales ranging up to 3 years was also found. time, under realistic conditions. Combining these results with thermodynamic modeling using A more robust risk assessments framework for the MELTS thermodynamic database [1], we aim to nanopesticides is urgently needed. In this context, priority for characterize the ambient intensive variables (e.g. P, T, fO2) research are to (i) identify the assumptions currently applied along the two most prominent magma transfer routes (i.e M0- that are not valid in the case of nanopesticides, (ii) evaluate M1; M1-M2). Comparison of the obtained results with the points or situations in which differences may impact compositions of other mineral phases (i.e. Cpx, Plag and Ti- significantly on the exposure assessment outcomes, and (iii) Mt) allows elucidating the P-T-fO2-H2O-time history of the refine or adapt current assessment protocols as required. magmas before eruption.

[1] Kah et al. (2013) Crit. Rev.Environ. Sci.Technol. [1] Ghiroso & Sack (1995), Contrib. Mineral. Petrol. 119, DOI:10.1080/10643389.2012.671750 197-212

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Geochemical and mineralogical Raduzhnoe – epithermal breccia- properties of harzburgite and dunite hosted deposit (Northern Caucasus, in Margı (NE Eskisehir) Area Russia) ASUMAN YILMAZ AND MUSTAFA KU$CU SÜLEYMAN E.N. KAIGORODOVA1 1Aksaray Üniversitesi Mühendislik Fakültesi, Jeoloji 1Institute of Geology of Ore Deposits, Petrography, Mühendisli"i Bölümü ([email protected] Mineralogy and Geochemistry, Russian Academy of 2Demirel Üniversitesi, Mühendislik Fakültesi, Jeoloji Sciences, Staromonetny per., 35, Moscow, Russia Mühendisli"i Bölümü ([email protected])

Study area which located in the Izmir-Ankara suture zone The Raduzhnoe deposit is situated in the central part of is found Tavsanlı zone peridotites. Harzburgites which is a North Caucasian Mountains within Jurassic depression zone, host rock of magnesite have been subject to severe related with extensional-transtentional tectonic regime, serpentinization. Dunite consists of mostly olivine, very few forming horst and graben structures. Intensive tectonic and orthopyroxene and opaque mineral chromite. Harzburgite magmatic activity was associated with the closure of the contains olivine, orthopyroxene, serpentine, talc, opaque Tethys Ocean and the Andean type of subduction. Block mineral magnetite and chromite. Chrysotile, lizardite are movements began in the Early Jurassic (Pliensbachian). common and antigorite is a small amount serpentin mineral Jurassic volcanic formations are represented by Aalenian according to the XRD. Rock has sieve / network-glass clock basalt-rhyolite and Bajocian basalt-porphyry-trachytic texture because of widespread serpentinization. REE (Rare formations. Rhyolites are the most common volcanic rocks at Earth Elements) values oh these rocks have positive La, Nd, this area. Epimagmatic hydrothermal activity related to Eu, Ho, Tm, Lu and negative Pr, Sm, Gd, Er, Yb anomaly by rhyolites led to: broad development of processes of chondrites / normalized distribution and show rather depleted silicification of host rocks, less their kaolinization, according to the chondrite. Can be said that mineral carbonation, sulphidation, baritization, chloritization, the transformation temperature reaches amphibolite facies widespread expression of alkaline metasomatism. according to the mineral association. The ore occurrences are confined to the PZ granite ledge and zones of intense brecciation. Composition of the breccias is quite diverse. Breccias have been changed in a varying degree during gas-hydrothermal activity. Ore minerals which have been identified at Raduzhnoe are native gold, calaverite, dyscrasite, proustite, sulfides. Au content reaches up to 215 g / t, Ag and 4000 g / t. At the deeper levels of the breccias the pyrite content increases and galena, sphalerite and chalcopyrite appear. Polymetallic mineralization is mainly associated with hydrothermally altered basement granites and Pliensbachian sandstones. Gold and silver are being in a finely dispersed state in sulfides. Thus, at the Raduzhnoe there are allocated two types of mineralization: gold-silver (low-sulfidation gold-sylver type) and gold-silver-containing polymetallic (low-sulfidation silver-gold-base metal type) [1]. Probably gold-silver- polymetallic mineralization is earlier process and is associated with developing of the global Jurassic polymetallic belt of the North Caucasus. Gold-silver subtype of mineralization is more recent, local and related to the final (solfatara) stage of volcanism.

[1] Sillitoe R.H., Hedenquist J.W. (2003) Soc. Econ. Geol. !Spec. Publ. 10, 315–343.

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Origin of secondary REE minerals in Addressing the nanoscale complexity grusified Karkonosze granites, SW of mineral-water interfaces in MD Poland simulations: Effects of the substrate BART%OMIEJ KAJDAS1* AND MAREK MICHALIK1 compositional disorder on the 1Institute of Geological Science, Jagiellonian University, properties of surface species Kraków, Poland; (*correspondence: [email protected]) 1 1 ANDREY G. KALINICHEV *, NARASIMHAN L. 1 AND BRICE F. NGOUANA W. , Primary monazite-(Ce), which is one of the most common accesory mineral in Karkonosze granites, is absent in grusified 1Laboratoire SUBATECH (UMR-6457), Ecoles des Mines de granites from G&'bock, Kowary (rednie and Mi&ków. In the Nantes, 4 Rue Alfred Kastler, La Chantrerie, 44307, grusified granites muscovite–thorite or cheralite–xenotime-(Y) Nantes Cedex 3, France (*[email protected]) pseudomorphs after primary monazite-(Ce) are present. Instead of monazite-(Ce) in grusified granites secondary Thermodynamic, structural and transport properties of rhabdophane-(Ce), florencite-(Ce), cerianite-(Ce), hydrated clays and clay-related materials for many rhabdophane-(La) and rhabdophane-(Nd) are present. geochemical, environmental, and technological applications Small (about 5 µm) automorphic crystals of rhabdophane- are routinely studied by computational molecular modeling (Ce) and florencite-(Ce) occur inside sericitised plagioclases techniques. However, simulated system size limitations often often along clevage planes of primary feldspar. Cerianite-(Ce) impose a considerable quasi-periodicity on the distribution of occurs as thin veins or as clusters of crystals impregnating the tetrahedral and octahedral site substitutions in the T-O-T rims of the grains of grus. Rhabdophane-(La) and clay layers. Such quasi-periodicity is then typically propagated rhabdophane-(Nd) crystals are usually small, xenomorphic further even if larger models are later constructed by simply and fill large cracks inside the grains of granitic grus. multiplying the smaller ones, and the effects of this imposed Decomposition of primary monazite-(Ce) might be the structural ordering on the calculated properties of the result of the activity of hydrothermal fluids [1], which could interfaces is not obvious. be also the main factor of the development of microcracks in Here we report the results of molecular dynamics granite that led to the development of grus. REE released from simulations with a new set of larger-scale muscovite and the decomposed monazite-(Ce) crystalized as secondary montmorillonite models which were systematically rhabdophane-(Ce) and florencite-(Ce). Chemical analysis of constructed to introduce as much structural disorder in the primary monazite-(Ce) from Karkonosze granite and distributions of the Al/Si and Mg/Al substitutions as possible. secondary rhabdophane-(Ce) and florencite-(Ce) shows, that The effects of such disorder on the local structural and ratios of REE in primary and secondary REE phosphates are dynamic properties of the interfacial and interlayer water and very similar. hydrated ions are then carefully quantified and analyzed for a Secondary cerianite-(Ce), rhabdophane-(La) and number of typical monovalent and divalent cations. rhabdophane-(Nd) crystallisation could be caused by low The time- and space- averaged properties of the hydrated temperature weathering, oxidizing fluids [2]. interfaces and interlayers, such as atomic density profiles, Decomposition of primary REE minerals and multistage radial distribution functions, and surface diffusion crystalisation of secondary REE minerals in grusified granites coefficients, are observed to be not particualrly sensitive to the indicates that process of grusification sensu stricto was specific details of the substrate disorder. However, local proceded by activity of hydrothermal fluids, which developed effects of the disordered distribution of charge-substituted microcracks in the rock and caused brakedown of primary sites in clay layers can be substantial and can influence the minerals including REE phosphates. Similar observations strength of the ionic and molecular adsorption at a specific were obtained in grusified Tatra granites [3]. surface site, the structure and dynamics of the interfacial hydrogen bonding network around it, and the molecular [1] Berger et al. (2008) Chem. Geol. 254, 238-248. [2] Aubert mechanisms of its local rearrangement. et al. (2001) Geochim. Cosmochim. Acta 6(3), 387-406. [3] Kajdas B & Michalik M (2011) Min. Mag. 75(3), 1135.

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Putting age into the equation: Biogenic or abiogenic hydrocarbon A new look at microbial distribution source of Melekes Depression in subseafloor sediments A.I.KAMALEEVA* AND E.M.GALIMOV JENS KALLMEYER1 Vernadsky Inst. of Geochemistry and Analytical Chemistry 1 RAS, Kosygin 19, Moscow, 119991 Russia Helmholtz Centre Potsdam, GFZ German Research Centre (*correspondence: [email protected]) For Geosciences Telegrafenberg, 14473 Potsdam,

Germany, [email protected] The question of hydrocarbon origin is an important problem in Tatarstan, where some of the geologists suggest At any given depth cell abundance in subseafloor the existence of abiogenic hydrocarbon “inflow” to sediments varies by up to six orders of magnitude between sedimentary oil fields. Core samples for the study of the sites. To a large extend this variability correlates with mean organic matter were taken from Devonian sediments (DS), as sedimentation rate and distance from land. This relationship well as from the rocks of the crystalline basement (CB). The can therefore be used to predict subseafloor cell abundance. oil was taken from the main productive complexes of seven Usually, decrease in subseafloor microbial abundance at fields within the studied areas and from the so-called each site can be described by a logarithmic function. However, "anomalous" boreholes of the Romashkinskoye supergiant at some sites, e.g. IODP Exp. 320, Site U1334 from the field, where the inflow of deep hydrocarbons is possible. The equatorial Pacific Ocean, cell distribution strongly deviates distribution of the isotope ratios of carbon between different from this trend and cannot be described by a simple equation. fractions was studied in oil and extracted bitumoids of rocks In order to better understand why cell distribution at some by the method [1]. sites exhibits such unusual patterns it is necessary to take a In the studied oil the sufficiently common type of carbon closer look at sedimentation rates and therefore sediment ages isotope distribution by fractions was found (Figure). This type as well. The sites that were drilled by IODP Exp. 320 and 321 of oil consists of the sapropelic type of organic matter and recovered a continuous Cenozoic record of the paleoequatorial mixed type, which is formed by a certain percent of humus Pacific by coring above the paleoposition of the highly and aquahumus materials. The "anomalous" oil completely productive equatorial upwelling zone at successive crustal coincides with other samples of oil. So there is no reason to ages on the Pacific plate. Although some of the unusual cell assume for them any other source of hydrocarbons. Bitumoids distribution is caused by strong geochemical gradients and extracted from the organic matter of DS, with a few diagenetic alteration fronts, the significant differences in exceptions, are of the same genetic type as the studied oil. sedimentation rates between within and outside the upwelling zone appear to be a major cause for the strong deviations in cell abundance from the expected logarithmic decline with depth. Subseafloor microbial communities have to subsist without fresh supply of organic matter, which becomes increasingly recalcitrant with increasing age. When assigning ages to cell count data from different oceanic regions, these cells vs. age correlation show less variability between sites than correlations vs. depth. These observations suggest that subseafloor microbial abundance is controlled by organic matter reactivity, which is Bitumoids extracted from the rocks of CB carry traces of largely controlled by sediment age. Using age instead of depth thermal and hydrothermal effects missing in the oil of models might provide important clues about the finer details sedimentary strata [2]. Therefore, they may be the product of of subseafloor cell abundance, especially in areas that have not thermal alteration of sedimentary naphtides but cannot be fitted into previous models. primary with regard to the last one. Thus, the biogenic hydrocarbon source of Melekes Depression is proved.

[1] Galimov (2006) Organc Geochem. 10, 1200-1262. [2] Kamaleeva et al. (2013) Geochemistry Int. 1, 13-22.

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The evolving nature of terrestrial A first-order deep time crust from the Hadean, through the reconstruction of the marine Sr/Ba Archaean, into the Proterozoic ratio from microbial carbonate BALZ S. KAMBER1 BALZ S. KAMBER1, THOMAS F. NAEGLER2, 3 4 1 ELIZABETH C. TURNER , GREGORY E. WEBB Geology Department, Trinity College Dublin, Ireland 5 AND CHLOÉ PRETET The ancient rock and mineral records show that Hadean 1Geology Department, Trinity College Dublin, Ireland crust could persist for 500-700 Ma. Notwithstanding the 2Geological Sciences, University of Bern, Switzerland general longevity of evolved crust, the well-established major 3Earth Sciences, Laurentian University, Sudbury, Canada Precambrian time boundaries remind us that terrestrial 4Earth Sciences, The University of Queensland, Australia geology did not proceed in a uniform manner. The Hadean- 5Earth Sciences, University of Geneva, Switzerland Archaean boundary witnessed the near-complete destruction of the Hadean crust. This crust was chemcially diverse, and at The upper crust is enriched in Sr and Ba where they occur least the zircon bearing magmas formed at relatively low T at a mass ratio of ca. 1.25. The dissolved river load has a and had interacted with the hydrosphere. Opinions diverge as Sr/Ba of ca. 1.8, whereas residual weathering profiles have a to whether these attributes imply plate tectonics. Advocates of Sr/Ba of ca. 0.9, showing that Sr is more easily released. In the existence of Hadean continental lithosphere have yet to our estuarine transects both elements behave conservatively. propose a plausible mechanism by which this lithosphere was Once in the ocean, the fates of Ba and Sr diverge sharply. Sr destroyed. Those who appeal to internal differentiation of has a long residence time and is homogenously distributed largely basaltic crust, aided by volcanic resurfacing, can whereas dissolved Ba concentration in seawater is very low appeal to the episodic collapse of early planetary crustal lids to and varies systematically with depth [1] (very depleted in the explain the disappearance of Hadean crust. shallow ocean and more enriched at depth). The overall Regardless of this unresolved debate, agreement exists that depletion and the depth structure are explained by Ba-removal the entire Archaean record is dominated by greenstone- as biogenic marine barite in organisms and its partial re- granitoid terrains. The much-improved greenstone belt release at depth. Hanor [2] predicted that this type of barite geochronological database demonstrates that most of these formation may not have been constant through time and that edifices grew vertically, by repeated eruptions of new volcanic marine Ba could be a proxy for sulphate concentration. sequences on top of older ones. Although they do not Our data from Holocene microbial carbonate faithfully represent oceanic crust, the existence of subduction and record the very high but variable Sr/Ba (400-1,200) of very subductable oceanic lithosphere can be inferred from a variety shallow seawater. In situ LA-ICP-MS of partly dolomitised of observations, ranging from granitoid geochemistry to samples clearly indicate that dolomitisation greatly increases diamond inclusions. It is thus proposed that the Archaean the Ba content and our deep time reconstruction was represents the era of three types of plates: continental and conducted on best preserved calcite only. The reconstruction oceanic lithosphere as well as prominent oceanic plateaus. shows a very clear first-order Sr/Ba topology. The ratio The Palaeoproterozoic rock record differes in many ways. remained very high (>>200) back to 555 Ma, decreased Greenstone belts have disappeared, platform sediments have rapidly throughout the Proterozoic to 2-5 until the Great become abundant and the first very high-P rocks are preser- Oxygenation Event, before which it was quite constant at 10. ved at the Earth’s surface. These phenomena reflect a change This evolution is interpreted as a three step increase of marine in the mechanical stength of the continents, which increased sulphate levels. A second-order control on the shape of the due to less internal heat production and redistribution of K, Th Sr/Ba topology can be inferred from the absolute Sr and Ba and U. However, the disappearance of komatiites and the concentrations in the microbial carbonate, which, for Sr, was unexpected lack of increase in extent of mantle depletion from much lower for most of the Precambrian but increased strong- 2.7 Ga to 2.0 Ga argue for mantle reorganisation. It is here ly after the Marinoan. This is important as it suggests a much proposed that a mechanical and thermal boundary layer reduced nutrient load to the Precambrian ocean with wide existed in the mantle transition zone until the end of the implications for other deep time studies (e.g. Mo in shale) that Archaean. This led to severe depletion in the upper mantle, assume variable removal but constant supply of metals. promoted build up of heat plumes and prevented recycling of oceanic plates into the deep mantle. Accordingly, the onset of [1] Griffith and Paytan (2012) Sedimentology 59, 1817-1835. deep recycling is dated by the ca. 2 Ga ‘age’ of OIB sources. [2] Hanor (2000) Rev. Min. & Geochem. 40, 193-275.

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PGE-Au potential of sulphide- A two-stage scenario for the saturated melts from the formation of the Earth’s mantle and subcontinental lithosphere core V. S. KAMENETSKY1, R. MAAS2, R.O.C. FONSECA3, E. KAMINSKI1* AND M. JAVOY2 3 3 C. BALLHAUS AND A. HEUSER 1 Institut de physique du globe de Paris, 75005 Paris, France, 1University of Tasmania, Hobart, TAS 7001, Australia; (*correspondence: [email protected]) [email protected] 2Institut de physique du globe de Paris, 75005 Paris, France, 2University of Melbourne, VIC 3010, Australia ([email protected]) 3Universität Bonn, Bonn 53115, Germany Various geophysical constraints on the deep Earth point to The origin of platinum element metal (PGE) enrichment in a chemically heterogeneous mantle. Based on such constraints, large magmatic nickel sulphide deposits is controversial; both Bulk Earth compositions inferred from Enstatite chondrites primary magmatic and hydrothermal processes have been (E-Earth composition) predict that, whereas the Primitive invoked. Irrespective of their exact mode of deposition, the Upper mantle (PUM) had a pyrolitic composition, the ultimate source of such extreme enrichments of these rare Primitive Lower mantle (PLoM) was enriched in Fe and Si metals must be PGE-enriched parental silicate melts capable and depleted in Mg, Ca and Al relative to PUM. We will of reaching sulphide saturation and efficient PGE capture in explain how, in E-Earth formalism, this chemical immiscible sulphide liquids. Direct observation of coexisting heterogeneity can be related to the formation and primary silicate and sulphide melts at the onset of silicate- differentiation of the Early Earth, and mantle Si and Fe sulphide liquid is impossible because of intense magmatic variations reflect variations in the efficiency of Si and FeO processing up until ore deposition. Here we report the dissolution in the metal phase during core formation, through

discovery of Fe-Ni sulphide melt globules highly enriched in the reaction SiO2+2Femetal=Simetal+2FeO which increases

noble metals (Pt, Pd, Os, Ir, Au, Ag; total 150 ppm) within an progressively the fO2 of the silicate. In the simplest and most unusual high-Mg andesitic glass dredged from the southern direct scenario of homogeneous accretion, we calculate by Mid Atlantic Ridge [1]. The composition of this primitive mass balance the composition and the mass fraction of the glass (8.2 wt% MgO, Mg# 67.1 mol%) indicates derivation of metallic extract in equilibrium with a pyrolite. The O, Si and its parental silicate melt from a garnet pyroxenite mantle Ni contents of this metal extract correspond to a silicate-metal source with pronounced ‘continental’ isotopic (Pb, Sr, Nd, Hf, equilibrium at high pressure (50±5 GPa) and high temperature Os, O) signatures [1]. We infer that the chemical properties of (3500±500ºC), in line with a giant impact scenario. The mass

this melt, notably high SiO2 (57.3 wt%) and Ni (310 ppm) of pyrolite produced during that stage is significantly smaller contents, promoted sulphide saturation at low pressures in a than the mass of the Bulk Silicate Earth. Mass balance purely oceanic setting and propose that this unique example, calculations then yield the composition of the proto-core and with its likely origin in the continental lithospheric mantle, the proto-mantle prior to the giant impact. We obtain that the may be a useful analogue for magmatic PGE enrichment and core of the proto-Earth was almost devoid of oxygen, hence incipient Ni-PGE- sulphide melt generation within large Ni- formed under lower pressure and temperature conditions, in PGE magmatic sulphide systems. agreement with an early differentiation of planetesimals in the early solar system. In such a two-stage scenario of Earth’s [1] Kamenetsky, V. S. et al. Geology 29, 243-246 (2001). core formation, no massive silicate differentiation is required to create a pristine mantle heterogeneity. The concentration of lithophile elements in the Primitive Lower mantle, notably Ca, Al, U and Th, can then be constrained using RLE ratios in E- chondrites and in the upper mantle.

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New minerals in the primary, deep- Sampling a natural CO2 reservoir, seated carbonatitic association Green River, Utah FELIX V. KAMINSKY1* AND RICHARD WIRTH2 NIKO KAMPMAN1, MIKE BICKLE1, HAZEL CHAPMAN1, 1 2 3 1 ALEX MASKELL , JIM EVANS AND ANDREAS BUSCH KM Diamond Exploration Ltd., West Vancouver, Canada *correspondence: [email protected] 1Department of Earth Sciences, University of 2GeoForschungsZentrum, Potsdam, Germany Cambridge, Downing Street, Cambridge CB2 3EQ (correspondence: [email protected]) In one of newly studied diamonds from the Juina area, 2Department of Geology, Utah State University, 4505 Old Brazil, several new polymineral inclusions of the carbonatitic Main Hill Logan, UT 84322-4505 16 association were identified. The hosting diamond belongs, like 3Shell Global Solutions International, Kessler Park 1, 2288 GS most of the diamonds from this area, to the Deep Earth. The Rijswijk, The Netherlands composite carbonate-halide-phosphate inclusion consists of magnesite, dolomite and mixed-anion phosphate micrograins We present the initial results from a scientific drilling along with nanograins of eitelite, halite, sylvite, phlogopite, project to recover core and high pressure fluid samples from a

spinel and pentlandite. The inclusion has a ‘negative’ shape, natural CO2 reservoir near Green River, Utah. We use this as

typical for syngenetic inclusions in diamond. The mineral an analogue to investigate fluid-flow and CO2-fluid-mineral assemblage comprising this inclusion belongs to the interactions with caprocks and fault zones likely during carbonate-chloride line of the primary, deep-seated anthropogenic storage of carbon dioxide

carbonatitic association, which has been established among Diamond drilling of drill-hole CO2W55, adjacent to the

inclusions in diamond in our earlier works [1, 2]. Three new CO2-degassing Little Grand normal fault, recovered core from

minerals for this association were identified in this inclusion: two major CO2 reservoirs in the Entrada and Navajo magnesite, eitelite and a mixed-anion phosphate, Sandstones, and from the intervening Carmel Formation

Na4Mg3(PO4)2(P2O7). The presence of magnesite, within this caprock. The well encountered CO2-charged fluids in the basal new mineral association, provides evidence for its stability in sandstones of the Entrada Sandstone, in open fractures in the the diamond stability field, which was earlier questioned; footwall damage zone of the fault penetrating the Carmel magnesite had been suggested to decompose with the Formation, and throughout the Navajo Sandstone. Downhole

formation of ferropericlase and diamond. Eitelite, wireline fluid sampling to recover high-pressure CO2-charged

Na2Mg(CO3)2, has been identified previously in alkaline- fluids during drilling, and analytical methods to measure their

carbonatitic rocks of the Khibini Massif, Kola Peninsula, dissolved CO2 content and pH on-site, are presented and

Russia [3]. The mixed-anion phosphate, Na4Mg3(PO4)2(P2O7), discussed. Measurements of CO2 concentrations, fluid has not previously been observed in the natural environment chemistry and isotope ratios from the drill-hole fluid samples before. This mineral contains an admixture of FeO (up to 6 are used to constrain fluid-fluid mixing, fluid-rock reactions

at.%). In other carbonatitic inclusions, Fe-phosphate and dynamics of CO2 migration within the fault damage zone.

Fe2Fe5(P2O7)4, and aluminium fluoride AlF3 were identified. Fluid-mineral reactions predicted from fluid geochemistry are They were found in the natural environment for the first time compared to petrological, mineralogical, geochemical and as well. The carbonatitic inclusions most likely originated as a petrophysical measurements from the reservoir and caprock high-density fluid (HDF) micro-inclusions, encapsulated in core, and the implications for reservoir alteration and caprock diamond during its initial growth. Such inclusions are fully performance are discussed. miscible under mantle conditions and subsequently crystallize as polyphase mineral inclusions, during ascent of diamond to the Earth’s surface.

[1] Wirth, Kaminsky, Matsyuk & Schreiber, A. (2009). Earth Planet. Sci. Lett. 286, 292-303. [2] Kaminsky, Wirth, Matsyuk, Schreiber & Thomas (2009) Mineral. Mag. 73, 797- 816. [3] Khomyakov, Sandomirskaya & Malinovskii (1980) Doklady 255, 190-192.

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Cyanide and thiocyanate Petrogenesis and tectonic setting of biogeochemistry in non-polluted the Nasrand granitoid pluton, natural aquatic systems southeast of Ardestan 1 2 3 A. KAMYSHNY JR. *, H. ODURO , Z. F. MANSARAY ALI KANANIAN*, ZAHRA HAMZEHIE, FATEMEH 3 AND J. FARQUHAR SARJOUGHIAN AND JAMSHID AHMADIAN 1Department of Geological and Environmental Sciences, The [email protected] 1 [email protected] Faculty of Natural Sciences, Ben-Gurion University of the [email protected], Negev, P.O. Box 653, Beer Sheva 84105, Israel, [email protected] (*correspondence: [email protected]) 2EAPS, Massachusetts Institute of Technology, E25-639, 77 The Nasrand pluton of Oligo-Miocen age, which is located Massachusetts Avenue, Cambridge, MA 02139-4307, in south-east of Ardestan, intruded into Eocene volcanic rocks USA, [email protected] of the Urumieh-Dokhtar magmatic belt. This pluton consists 3Department of Geology and Earth Systems Science mainly of granite and granodiorite, and has been intruded by a Interdisciplinary Center, University of Maryland, College series diabase dikes. The nasrand plutonic rocks are Park, MD 20742, USA, [email protected], metaluminous, with mineralogical and geochemical [email protected] characteristics of I-type calc-alkaline to high-K calc-alkaline granite. They are characterized by enrichment of LREE and Here, we report on the accumulation of high levels of cyanide LILE, depletion of HREE and HFSE, negative anomalies of as free cyanide, complexed cyanide, iron-cyanide, and Ti, Nb, P, Ba, and positive anomalies of U, K, Th, Rb, Ba, thiocyanate in sediments of the non-polluted Delaware Great associated with high Ba/Nb ratio and interpreted to reflect Marsh (up to 230 µmol kg-1). Free cyanide at concentrations emplacement of the plutonic rocks in an active continental which are toxic to aquatic life (up to 1.92 µmol L-1) were margin. The Nasrand granitic pluton and its diabase dikes detected in sediment pore-waters, and the concentration of were all derived from partial melting of the lower continental total (free and complexed) cyanide in the pore waters was crust, but it seems that the granitic rocks are slightly more found to be as high as 6.94 µmol L-1. The presence of fractionated than diabase dikes and may be modified by hydrogen cyanide in the salt marsh sediments is attributed to assimilation of upper crustal materials. processes associated with decomposition of cord grass Keywords: Ardestan, I type granite, calc-alkaline, diabase Spartina alterniflora roots. The formation of iron-cyanide dikes, active continental margin. complexes and their adsorption onto sedimentary organic matter provide a temporary sink of cyanide, but the ultimate cyanide sink is associated with the formation of thiocyanate by reaction with sulphide oxidation products, principally polysulfides, formed by reaction with by Fe(III) minerals. The formation of thiocyanate by this pathway detoxifies two poisonous compounds, polysulfides and hydrogen cyanide, in the salt marsh sediments [1]. Thiocyanate is stable under anoxic conditions, but diffuses freely through sedimentary pore waters to upper oxic sediment layers, where it may be oxidized by biologically assisted processes either to carbonyl sulfide and ammonia or to cyanate and hydrogen sulfide. Thiocyanate was also detected at concentrations up to 288 nmol L)1 in the water column of Lake Rogoznica (Croatia) [2] and up to 274 nmol L)1 in the water column of Fayetteville Green Lake (NY). Here, thiocyanate appears to be produced in the sediment and diffuse towards the chemocline, where it is consumed by abiotic or biologically enhanced oxidation.

[1] Kamyshny et al. (2013) Aquat Geochem 19, 97-113. [2] Kamyshny et al. (2011) Mar Chem 127, 144-154.

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Mineralogical, petrographical and Role of submicron-sized particles on geochemical investigation of Tefenni- the 134,137Cs migration in Fukushima Burdur chromite occurences M. KANEKO1 , Y. NAKAMATSU1, T. OHNUKI2 , K. NANBA 1 1 1 AND S. UTSUNOMIYA ALEV KAN BOSTANCI , DEMET KIRAN YILDIRIM , MUHITTIN KARAMAN1, ANIL SENA SERT1 1Dept. Chemistry, Kyushu University, Fukuoka 812-8581, AND MURAT BUDAKO!LU1 Japan ([email protected]) 2ASRC, Japan Atomic Energy Agency, Tokai, Japan 1Istanbul Technical University, Department of Geological 3Dept. Environmental Management, Fukushima University Engineering, 34469, Istanbul, TURKEY

In the vicinity of Fukushima Daiichi Nuclear Power Plant The lithological units are consist of Late Jurassic – Early 137 134 (FDNPP), Cs (T1/2 = 30.07 y) and Cs (T1/2 = 2.062 y) have Createaous aged Ye*ilova ophiolites, Upper Cenonian aged great contribution to the radiation dose. Although the initial Kızılcada" ophiolitic melange, Pliyo-Quaternary aged distribution of radionuclides derived from FDNPP accident Niyazlar Formation and Quaternary aged alluvions in the have been reported to date, there are limited knowledge on investigation area. micron- and submicron-scale distribution and migration of Ye*ilova ophiolite consist of tectonites, ultramafic and 134,137Cs in the surface and sub-surface environments. In order mafic cumulates, isotropic gabbros, plagiogranites and basalts to understand the fundamental mechanism of 134,137Cs retention from bottom to top. Ye*ilova ophiolite in which sheeted dike and migration in the contaminated area in Fukushima, Cs complex and pillow lavas are not seen, represents an ophiolite speciation in various environmental samples (soils, aerosol group with missing row character. and groundwater) is investigated, which were collected from In the bottom of the Ye*ilova ophiolite there are tectonics severely contaminated area in Fukushima. ,which is composed of harzburgite, dunite, serpantinized In the soil samples, the vertical profile of 134,137Cs harzburgite and dunite, serpantinite and chromite masses with distribution revealed that >98% of 134,137Cs remained within dunitic envelope. Tectonites are mostly serpantinized in parts top 5 cm. Sequential extraction of the contaminated soils where mafic dikes are dense and along tectonic lines. revealed that most 134,137Cs was strongly bound to high-affinity Tectonites are cut by many mafic dikes. site of clay minerals such as illite and montmorillonite, while According to the metamorphic paragenesis determined in upto 20% of 134,137Cs was present as an ion exchangeable form, the oceanic crust rocks forming Ye*ilova ophiolite, it is suggesting that elution of 134,137Cs from soil minerals would be metamorphised in P/T situations which does not reach the sub minimal in the surface environment in Fukushima. In the size limit of greenschist facies. fractionation experiment, ~78% of 137Cs was distributed in the Upper Cenoniyen aged Kızılcada" ophiolitic melange colloid region (<1 +m) and the concentration was as high as takes place tectonically on Ye*ilova ophiolite. Tectonic ~3,000,000 Bq/kg. The 137Cs radioactivity of airborne particles boundry between these to units is nearly horizontal. collected in Iitate was measured to be 12.2, 15.7, and 11.8 mBq/m3 for the size fractions of <0.4, 0.4-2.5, and >2.5 +m, respectively. 134,137Cs were under the detection limit in the groundwater samples. These results clearly indicate that 134,137Cs have not migrated to the groundwater system until one year after the accident, and the airborne Cs-particles were mainly derived from suspension of the fine fraction of the contaminated soils, namely Cs-bearing clay minerals. The present study strongly suggests that the migration of 134,137Cs in the surface and sub-surface environment is not governed by the adsorption-desorption cycle but by the behavior of Cs-adsorbed submicron-sized particles. Therefore, the unique physico-chemical property of Cs-bearing colloids should be taken into account for predicting the future behavior of 134,137Cs in the surrounding environments in Fukushima.

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Quantification of methanogenic Biomineralization of Strontianite potential in environemtnal samples (SrCO3) by Proteus mirabilis MASANORI KANEKO*1, YOSHINORI TAKANO1, SERKU KANG1, YUMI KIM2, AND YUL ROH3* 2 2 TAKESHI WATANABE , SUSUMU ASAKAWA , 1 Chonnam National University, Gwangju, Korea, SEIGO SHIMA3, NANAKO OGAWA1 1 ([email protected]) AND NAOHIKO OHKOUCHI 2 Chonnam National University, Gwangju, Korea, 1JAMSTEC, Yokosuka, 237-0061 Japan ([email protected])! (*correspondence: [email protected]) 3Chonnam National University, Gwangju, Korea, 2Nagoya Univ. Nagoya, 464-8601 Japan ( *correspondence: [email protected]) 3Max Planck Inst. Marburg, D35043, Germany Microbially induced mineralization of carbonate minerals A Ni porphinoid, coenzyme F430 is the prosthetic group has drawn much attention in recent decades because of its of methyl-coenzyme M reductase, which catalyse a final step practical applications such as atmospheric CO2 fixation of methanogenic reactions in all methanogenic pathways through mineral carbonation and solid phase capture of toxic 90 60 including CO2 resuction, acetate fermentation and radionuclide or metal contaminants (i.e., Sr, Co and Cd). methylotrophic pathyways[1]. F430 is unstable, hence native The objectives of this study were to investigate the potential F430 will not be persisting in sediments through a geologic for microbially induced precipitation of strontianite (SrCO3) time scale. Given its unique structure, functionality and using microorganisms enriched from rhodoliths and to identify lability, F430 can be a robust biomarker for a quantitative mineralogical characteristics of the bio-precipitates. estimation of in situ activities of living methanogens. Carbonate forming microorganism (CFM) was enriched Conventionally F430 was analyzed photometrically using from rhodoliths and aerobically cultured at 25°C in D-1 HPLC or off-line MS [2]. Recently we have developed a high medium containing 30 mM Sr-acetate. The microorganisms sensitive detection of F430 by a HPLC-MS/MS. This were analyzed by 16S rRNA gene DGGE analysis to confirm sensitivity (femto mol level) is 104 to 105 times higher than the microbial diversity. Mineralogical characteristics of the bio- conventional photometric dection and only 102 to 104 precipitates were determined by XRD, TEM/SEM-EDS methanogen cells are required for quantification of F430 in analyses. environmental samples. Our analyses indicated that A 16S rRNA sequence analysis showed the CFM was concentration in paddy field ranges between 9870 and 253 mainly Proteus micrailis [1]. The growth of CFMs gradually fmol/g which is 1-2 orders of magnitude higher than those in increased for 16 days (OD600 = 2.613) and then decreased until marne sediments off Japan, ranging between 100 and 7 fmol/g, 22 days (OD600 = 2.016) of incubation. Medium pH in the and 1910 fmol/g from Peru Margin (68 mbsf). biotic group increased from acidic at first (pH = 5.3) to alkaline condition (pH = 8.6). The pH changes might induce favorable geochemical condition for Sr-carbonate precipitation. In the abiotic group, neither growth of microorganism nor changes in pH were detected. The enriched microorganisms mediated the precipitates in D-1 medium containing 30 mM Sr-acetate. The bio-

precipitates were identified strontianite (SrCO3) by XRD analysis. SEM-EDS analyses showed that the precipitates were round in shape, and around 60 ㎛ in size, and composed of C, O and Sr. TEM-EDS analyses showed that the Sr- carbonate minerals were irregular in shape, 60~70 nm in size, and composed of C, O, and Sr. These results indicate that the CFM induce the Fig. 1. HPLC-MS/MS chromatograms of derivatized F430 from a paddy field and marine sediment. precipitation of strontianite (SrCO3) by biological processes. Therefore, CFM such as Proteus micrailis may play one of [1] Thauer (1998), Microbiology 144, 2377-2406. [2] Takano, important roles in Sr immobilization in Sr-contaminated water Kaneko, Kahnt, Imachi, Shima & Ohkouchi (2013), Org. and CO2 fixation in natural environments. Geochem., in press. [1] Chimetto et al. (2011) Int. J. Syst. Evol. Microbiol. 60(1), 60-64.

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Pb, Sr, Nd, Hf isotope geochemistry Diagnosing the hydroclimate of South Arch lavas: Origin of the influences on soil water " 18O: upstream side Hawaiian arch Precipitation " 18O, evaporation, or volcanism moisture transport? T. KANI1*, B. B. HANAN2, R. KINGSLEY3 LISA KANNER1*, NIKOLAUS BUENNING1, 3 1 2 AND J.-G. SCHILLING LOWELL STOTT , AXEL TIMMERMAN , DAVID NOONE 4 1 AND LISA SLOAN Kumamoto University, Kumamoto 860-8555, Japan (*correspondence: [email protected]) 1University of Southern California, Los Angeles, CA, USA 2San Diego State University, San Diego, CA, USA [email protected], [email protected], [email protected] ([email protected]) (*presenting author) 3GSO, University of Rhode Island, RI, USA 2University of Hawaii, Honolulu, HI, USA, [email protected] 3University of Colorado, Boulder, CO, USA, South Arch volcanic field is located on the crest of a [email protected] broad swell surrounding the Hawaiian Islands, 200 km south 4University of California - Santa Cruz, Santa Cruz, CA, USA, of Kilauea, along the peripheral edge of the radially dispersing [email protected] mantle plume stream, diverted to the NW by the migrating Pacific lithospheric plate. The stable oxygen isotopic composition of soil water that Pb, Sr, Nd and Hf isotope compositions of 14 alkali is incorporated into paleoclimate proxies is often assumed to basalts collected at water depths > 4 km by JAMSTEC Kaiko be the same as precipitation !18O in order to obtain and Shinkai dives (K217 and S697), distinguish these magmas information about past hydroclimate variations. For example, from shield tholeiites, rejuvenated stage, and North Arch the !18O of soil water, when taken up by tree roots, is lavas. Pb isotope compositions of South Arch lavas are more transferred to the !18O of xylem water and eventually radiogenic compared to North Arch and rejuvenated lavas, but incorporated into the tree cellulose. Thus, implicit in the use of similar to Kea lavas, confirming plume compositional cellulose !18O as a proxy for precipitation !18O is that influence on the upstream plume periphery is stronger than evaporative influences on soil water !18O do not overprint the downstream. In Pb-Sr-Nd multi-isotope binary plots the data precipitation !18O signal. clusters, with little variation, and no apparent correlation. The In this study, we use an isotope-enabled land surface 87 86 Sr/ Sr is lower and the !Nd higher than Hawaiian shield model (IsoLSM) to diagnose environmental influences on soil 18 tholeiites indicative of a depleted source. Plots of !Hf against water ! O across seasonal to interannual timescales. An 87 86 206 204 !Nd, Sr/ Sr or Pb/ Pb define trends oblique to the mantle unpeturbed control simulation from 1979-2004 reveals that in

array. The variation is in !Hf essentially at constant !Nd, many semi-arid regions, such as the southwest United States, 87Sr/86Sr or 206Pb/204Pb. These relationships cannot be the !18O of xylem water is only partially related to the !18O of explained by seawater or sediment contamination, but could precipitation. At these locations, both evaporation and upward result from metasomatism. The results suggest that the South moisture fluxes in the soil water column contribute to Arch basalt source consists of metasomatised oceanic variations in xylem water !18O. For typical soil water profiles lithosphere and plume components. The isotope characteristics that are more depleted at depth, soil water tagging simulations of the South Arch lavas could be interpreted to represent reveal that in years with lower precipitation, an upward flux of metasomatised Pacific lithosphere, residue of a MORB-related deep soil moisture can lead to isotopically depleted xylem melting event at ~100 Ma, modified by plume fluids and water. Consequently, this depleted cellulose !18O signal may melts. Alternatively, the South Arch mantle source may be be misinterpreted as reflecting more istopically depleted ancient recycled oceanic lithosphere, part of the Hawaiian precipitation or enhanced rainfall due to an inferred “amount plume. effect”. Thus, where these soil moisture transport processes are dominant, there is a positive correlation between xylem water !18O and relative humidity, even though a decrease in relative humidity would be expected to enrich surface water !18O. Furthermore, sensitivity experiments demonstrate that for these semi-arid regions, the seasonal cycle in xylem water !18O is not driven by the isotopic composition of precipitation but instead by ground evaporation.

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Crystal structures of two oxygen- Estimates of atmospheric CO2 in the deficient calcium aluminum silicate Neoarchean-Paleoproterozoic perovskites from NMR and powder YOSHIKI KANZAKI* AND TAKASHI MURAKAMI X-ray diffraction Department of Earth and Planetary Science, the University of Tokyo, Tokyo 113-0033, Japan M. KANZAKI1*, X. XUE1, Y. WU2 AND S. NIE2 (*Correspondence: [email protected]) 1Institute for Study of the Earth’s Interior, Okayama Univ., Misasa, Tottori 682-0193 Japan The weak luminosity of the younger Sun requires the early (*Correspondence: [email protected]) Earth to have more greenhouse effects than those today. The 2 School Earth and Space Sciences, Peking Univ., China candidates for such greenhouse effect gases are CO2 and CH4 in the Neoarchean and the Paleoproterozoic. The

Several high-pressure phases along the Ca2Si2O6-Ca2Al2O5 quantification of CO2 and CH4 levels in the Neoarchean- join have been reported to occur with oxygen-deficit Paleoproterozoic is a crucial issue, because the multiple perovskite structures [1], but their detailed crystal structures glaciation events at ~2.9 Ga and ~2.4-2.2 Ga are considered to

remained undetermined. We have successfully determined the have been caused by the transitions of CO2 and CH4 levels.

crystal structures for two of these phases: a Ca2AlSiO5.5 phase Paleosols record vestiges of weathering by CO2 and

synthesized at 7 GPa and 1500 °C, and a Ca2Al0.8Si1.2O5.6 therefore have given estimates of atmospheric CO2 levels.

phase synthesized at 11 GPa and 1500°C, both in a multi-anvil However, the CO2 levels estimated from paleosols are less

press. Here we report these results. than those estimated by the climate model. Therefore, CH4 is 29Si MAS NMR and 27Al 3Q MAS NMR revealed one considered to have had a significant role as greenhouse effect

tetrahedral Si peak and one octahedral Al peak for the gas. Because the CO2 levels have been usually discussed

Ca2AlSiO5.5 phase, and two Si (one tetrahedral and one indicating the contemporary CH4 levels and vice versa, it is

octahedral) peaks and one octahedral Al peak for the important to validate or assess the CO2 levels extracted from Ca2Al0.8Si1.2O5.6 phase. paleosols so far. In this study, another method was developed

The crystal structures were solved with an ab initio to re-evaluate CO2 levels from paleosols.

structural determination technique (using the program FOX) The new method estimates CO2 levels operating in from synchrotron powder X-ray diffraction data (measured at weathering profiles in 3 steps: (1) estimation of cation BL19B2, SPring-8) using information from NMR as concentrations in porewater at the time of weathering from the constraints, and were further refined using the Rietveld loss amounts of cations in paleosol profiles, (2) estimation of method (RIETAN-FP). The space groups for both phases were pH in porewater at the time of weathering from likely found to be C2/c. The crystal structure of the Ca2AlSiO5.5 secondary minerals in paleosols (kaolinite and smectite with

phase consists of double-layers of perovskite-like AlO6 no carbonates), and (3) CO2 estimation from a charge-balance

octahedra and double-layers of SiO4 tetrahedra, stacked equation in porewater for dissolved CO2 species (carbonic alternatively in the [111] direction of cubic perovskite, acid, bicarbonate ion and carbonate ion) and cations, using the forming an 8-fold superstructure. That of the Ca2Al0.8Si1.2O5.6 estimated cation concentrations and pH. Application of the phase is made of triple-layers of perovskite-like AlO6-SiO6- new method to modern weathering profiles has revealed that

AlO6 octahedra and double-layers of SiO4 tetrahedra, also the new method reproduces modern soil CO2 levels stacked alternatively in the [111] direction, forming a 10-fold reasonabley well, confirming the validaty of the method. superstructure. The double-layers of SiO4 in both phases are Applyng the new method to the Neoarchean-

similar, having deficient oxygens at the middle with one Paleoproterozoic paleosols, the CO2 levels were calculated to terminal oxygen (not bonded to other Si/Al) for each SiO4 be > 100 PAL at ~2.8-2.4 Ga and < 100 PAL at ~2.3-1.8 Ga.

tetrahedron. These structures are related to the merwinite The calculated levels of CO2 throughout the above eras were (Ca3MgSi2O8) structure, which consists of alternating single sufficient to keep the average surface temperature of the Earth layers of MgO6 octahedra and double-layers of SiO4 more than the freezing point of water. These results indicate

tetrahedra. This series of oxygen-deficit peroviskites provide (i) the general decreasing trend of CO2 throughout the additional insights into the local structural environments of Neoarchean-Paleoproterozoic and (ii) that it would have been 3+ Al- and Fe -containing CaSiO3 perovskite. more difficult to make the Earth a Snowball than previously thought. [1] Bläß, UW et al. (2007) Phys. Chem. Mineral., 34, 363- 376.

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Delineation of recharge patterns and SHRIMP U–Pb zircon dating, nitrate contamination using stable geochemical and petrographical isotopes of water, 3H-3He, and CFCs characteristics of calc-alkaline Early in an agricultural basin Miocene "apçı volcanics around DUGIN KAOWN1*, DONG-CHAN KOH2, YOON-YEOL Balıkesir (W Turkey) 2 1 3 YOON , HEEJUNG KIM , JIN-YONG LEE 1 1 2 1 D. KAPLAN , Z. ASLAN * AND B.CHEN AND KANG-KUN LEE 1 1School of Earth and Environmental Sciences, Seoul National Balıkesir Univ., Dept. Geol. Engn., Balıkesir,Turkey (*correspondence: [email protected]) University, Seoul 151-747, Korea (*correspondence: 2 [email protected]) Peking Univ., Dept. Geol. Engn., Beijing 100871, Peoples R 2Korea Institute of Geoscience and Mineral Resources, China ([email protected]) Groundwater Resources Group, 30 Gajeong-dong, Yuseong-gu, Daejeon 305-350, Korea Tertiary volcanic rocks are widespread in the Biga ([email protected]) Peninsula of western Anatolian region (Turkey), and related to 3Department of Geology, Kangwon National University, a collision tectonics in origin [1]. One of them, the $apçı Chuncheon 200-701, Korea ([email protected]) volcanics crop out in the northwest of Balıkesir. The volcanics consist of tuffs and lava flows in andesite and trachyandesite Haean basin in Yanggu (Korea) shows a bowl-shaped compositions. The rocks show microlitic, hyalo-microlitic, topography and the drainage system shows a simple dendritic microlitic-porphyritic and fluidal textures. Modal minerals of pattern. Stable isotopes of groundwater, 3H-3He, and the rocks are plagioclase (An 30-49), hornblende, biotite, Fe-Ti chlorofluorocarbon (CFCs) combined with hydrogeochemical oxide and accessory apatite and zircon. data were applied to delineate groundwater residence time, The SHRIMP U–Pb zircon dating from the lava yielded recharge patterns and nitrate contamination of groundwater in ages between 22.72 ± 0.19 and 22.97 ± 0.23 Ma, which are the agricultural basin. The study area is consisted of forests regarded as the crystallization age. The $apçı volcanics have a (58.0%), vegetable fields (27.6%), rice paddy fields (11.4%) composition of 60.09-66.45 % SiO2, 0.47-0.60 % TiO2, 14.64- and fruit fields (0.5%). Thus, most of residents in the study 16.38 % Al2O3 and 2.75-4.00 % K2O. Petrochemically, they have high-K calc-alkaline characteristics, and exhibit similar area practice agriculture. The concentration of NO3-N in groundwater showed 0.2 ~ 15.2 mg/L in June, 2012 and 0.4 ~ features of volcanic arc setting. Besides, the trace element 14.8 mg/L in September, 2012. Nitrate concentrations were compositions are indicative of subduction-related volcanism. higher in the downgradient area than in the upgradient area The volcanics have high large ion lithophile elements (LILEs) due to the land use pattern and topography. The values of ,18O contents and low high field strength elements (HFSEs) and ,D showed that groundwater is derived mainly from contents compared to N-type Mid-Ocean Ridge Basalt summer precipitation and the evidence of evaporation was (MORB), and have a high ratio of La/Yb, Zr/Nb. Chondrite observed in some wells in the paddy fields. The apparent normalized rare earth element (REE) patterns are concave groundwater ages using 3H-3He and CFCs are ranged from 7 upwards with (La/Lu)CN = 6.72–21.84, indicating significant to 10 years in the upgradient area and from 15 to 30 years in fractional crystallization during the evolution of the volcanics. the downgradient area. The apparent groundwater age Furthermore, some trace element ratios indicate that the role corresponds to the different nitrate concentrations in the of a subduction component and/or crustal contamination in the upgradient and downgradient area. The NO3-N concentration genesis of the $apçı volcanics. in recently recharged groundwater showed 3-15 mg/L while the NO3-N concentration in 30 years old groundwater showed [1] Altunkaynak, & Genç (2008) Lithos 102, 316-340. less than 3 mg/L. The reconstructed 3H input and initial 3H were used to estimate groundwater mixing. A conceptual model of groundwater flow using measured apparent 3H-3He and CFCs age will be developed to understand the hydrological processes of the study area.

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Simulating Precambrian banded iron The platinum group and precious formation diagenesis metals contents of Mu!la-Ortaca A. KAPPLER1*, N. R. POSTH2, I. KÖHLER1, Area Chromites 1 1 1 E. SWANNER , C. SCHRÖDER , E. WELLMANN , 1 1 1 3 4 SALIH BURAK KARABEL , LOKMAN GUMUS , DEMET B. BINDER , K.O. KONHAUSER , U. NEUMANN , 1 1 4 4 5 KIRAN YILDIRIM , SERENA UZASCI SULTANYAN , C. BERTHOLD , M. NOWAK AND D. PAPINEAU 1 1 MURAT BUDAKO!LU AND MUSTAFA KUMRAL 1Geomicrobiology, Center for Applied Geoscience, University 1Istanbul Technical University, Department of Geological of TuebingenTuebingen, Germany (*correspondence: Engineering, 34469, Istanbul, TURKEY [email protected])

2Nordic Center for Earth Evolution (NordCEE), Institute for The study area is located in Mente*e Region, which is Biology, University of Southern Denmark, Odense, called Taurus belt, Southwest of Turkey. Structural units in Denmark the area are Menderes Massive, Western Taurus Nappes, 3Department of Earth and Atmospheric Sciences, University of Beyda"ları Autochthonous and Antalya Nappes. Alberta, Edmonton, Alberta, Canada. In general, region consists of from bottom to top 4Mineralogy & Geodynamics, Department of Geosciences, allochthonous units, peridotite nappe and alluvium. University of Tuebingen, Tuebingen, Germany Allochthonous units, include Jura aged limestone interlayered 5Geophysical Lab, Carnegie Institution of Washington, with calciturbidite. The Upper Cretaceous aged complex Washington DC, USA consist of limestone with micritic texture and marn which is

formed intermediate layers. Sedimentary rocks as old as 3.8 billion years, such as The peridotitic unit is composed of serpentinite, Precambrian banded iron formations (BIFs), offer a unique serpentinized dunite, dunite and harzburjite and it is archive of key past chemical and biological processes. Yet, Cretaceous aged. Also Quaternary alluvium is located at the post-depositional alterations such as diagenesis can alter these top of the peridotites. sediments and make accurate interpretation of primary In this study, in order to determine the geochemical and processes challenging. Fe(II)-oxidizing bacteria have been petrographic characteristics (ore and rock) major, trace and proposed as key contributors to BIF deposition. One main rare earth elements were analyzed around Mu"la-Ortaca. challenge to this proposition is to understand how The distribution of platinum group elements for temperature/pressure diagenesis transforms biogenic Zimparalik shows according to geochemical analyses that Pt Fe(III)(hydr)oxides formed by these bacteria. content is between 10 ppb and 147 ppb, Pd content is between We present diagenetic experiments of the transformation 6 ppb and 54 ppb and Ir content is between 12 ppb and 131 of precursor Fe(III) minerals associated with microbial ppb. In additon, Au content is between 24 ppb and 135 ppb in biomass. Mixtures of ferrihydrite (biogenic ferric this area. oxyhydroxide mineral proxy) and glucose (microbial biomass The samples from Yemislik show that Pt content changes proxy) were incubated in gold capsules at 1.2 kbar and 170ºC. between 30 ppb and 138 ppb, Pd content is approximately 8 Key BIF minerals are produced by electron transfer from ppb, Ir content changes from 10 ppb to 100 ppb and also Au organic carbon to Fe(III) minerals during this diagenesis. content reaches to 205 ppb. Ferrihydrite transforms to hematite, magnetite, and siderite. Silica-coated ferrihydrite mixed with glucose yields hematite and siderite. Spheroidal siderite, a structure found in IF, forms depending on the Fe(III):C ratio of primary ferrihydrite- biomass sediment. Our results thus suggest that post- depositional BIF mineralogy does not directly archive the oceanic or atmospheric conditions during their lithification. Furthermore, we argue that spherical to rhombohedral siderite structures in deep-water Fe-oxide IF can be used as a biosignature for photoferrotrophy, whereas massive siderites reflect high cyanobacterial biomass loading in highly productive shallow-waters.

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Geophysical constraints on the water Four types of olivine from orangeites content in the lunar mantle and its of Kostomuksha-Lentiiro area implications for the origin of the (Russia, Finland) Moon A.V. KARGIN, A.A. NOSOVA AND E.V. KOVALCHUK SHUN-ICHIRO KARATO113 Institute of Geology of Ore Deposits, Petrography, Mineralogy and Geochemistry of the Russian Academy of Sciences, 1Yale University, Department of Geology & Geophysics, New Russia, Moscow, [email protected] Haven, CT, USA

Mineral characteristics of alkaline ultramafic rocks of the Although the Moon was considered to be “dry”, recent Kostomuksha-Lentiiro area suggest their orangeitic rather than measurements of hydrogen content in some of the lunar lamproitic nature. The orangeites are divided into three types samples showed a substantial amount of water comparable to by their macrocryst assemblages: Ol-Phl-Cpx, Ol-Phl and Phl- the water content in the Earth's asthenosphere. However, the Carb. The Ol-Phl-Cpx orangeites of Lentiiro contain four interpretation of these observations in terms of the distribution generations of unaltered olivine that vary in composition and of water in the lunar interior is difficult because the origin. composition of these rocks reflects a complicated history Olivine I is large (3-2 mm) typically rounded zoned involving melting and crystallization. In this study, I analyze macrocrysts. Core composition is Fo 92 with the highest geophysically inferred properties to obtain constraints on the content of NiO (0.33-0.37 wt. %) and the lowest -./ (0.03- distribution of water (and temperature) in the lunar interior. 0.04 wt. %). This olivine is interpreted as a xenocryst derived The electrical conductivity inferred from electromagnetic from depleted mantle peridotite. induction observations and the geodetically or geophysically Olivine IIa is represented by euhedral and subhedral inferred Q are interpreted in terms of laboratory data and the phenocrysts (commonly 0.15-0.3 mm). Olivine IIa and rims of theoretical models on the influence of water (hydrogen) on olivine I and III have the same composition - Fo 88-89 with these properties. Both electrical conductivity and Q are high content of -./ (0.10-0.42 wt. %), and moderate contents controlled by defect-related processes that are sensitive to the of NiO (0.14-0.35 wt. %) and MnO (up to 0.07-0.21 wt. %), water (hydrogen) content and temperature but less sensitive to which is consistent with fractional crystallization trend of the major element chemistry. After a correction for the olivine from orangeites. This olivine crystallized from influence of the major element chemistry constrained by orangeitic melt at 950-960°C (content of Ca and Al [1]). geophysical observations and geochemical considerations, I Olivine IIb is observed as microphenocryst in a estimate the temperature-water content combinations that are groundmass (< 0.1 mm). It is Fo 86-87 with the highest consistent with the geophysically inferred electrical content of -./ (1.19-1.40 wt. %). This olivine is the product conductivity and Q. I conclude that the lunar interior is cooler of late-stage crystallization of evolved kimberlitic melt. than Earth (at the same depth) but the water content of the Olivine III forms medium size (commonly 1.0-1.5 mm) lunar mantle is similar to that of Earth's asthenosphere. A rounded zoned "tablet"-shaped crystals [2]. Core of olivine III possible model is presented to explain the not-so-dry Moon is Fo 82-83 with the lower content of -./ (0.03-0.05 wt. %), where a small degree of water loss during the Moon formation NiO (0.12-0.17 wt. %) and high MnO (up to 0.40 wt. %). This is attributed to the role of liquid phases that play an important generation is interpreted to represent either early stage role in the Moon forming environment. crystallization of megacryst assemblage [3] or a product of metasomatic interaction between mantle peridotite and protokimberlitic melt [2].

[1] De Hoog J.C.M., Gall L., Cornell D.H. Trace-element geochemistry of mantle olivine and application to mantle petrogenesis and geothermobarometry // Chem. Geol. 2010. V. 270. P. 196–215. [2] Arndt N.T., Guitreau M., Boullier A.M., et al. Olivine and the origin of kimberlite // J. of Petrology. 2010. V.51. P. 573-602. [3] Moore A.E. The case for a cognate, polybaric origin for kimberlitic olivines // Lithos. 2012. Vol. 128-131. P. 1-10.

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Calcium and magnesium isotopes Tungsten species in natural reveal Earth system response in the ferromanganese oxdies related to its aftermath of a Cryogenian glaciation different behavior from molybdenum S.A. KASEMANN*1, P. POGGE VON STRANDMANN2, in oxic ocean 3 4 5 A.R. PRAVE , A.E. FALLICK , T. ELLIOTT 1 2 TERUHIKO KASHIWABARA AND YOSHIO TAKAHASHI AND K.-H. HOFFMANN6 1Japan Agency for Marine-Earth Science and Technology 1Department of Geosciences Univ. Bremen, 28334 Bremen, (JAMSTEC), [email protected]* Germany (*correspondence: [email protected]) 2 Hiroshima University, [email protected] 2Dept. of Earth Sciences, University of Oxford, Oxford OX1 3AN, UK ([email protected]) Different concentrations of Mo and W in oxic ocean 3Earth Sciences, University of St Andrews, St Andrews KY16 attribute to their different distributions at the 9AL, UK ([email protected]) seawater/ferromagnanese oxide interface. Recent studies also 4Scottish Universities Environmental Research Centre, East revealed large isotopic fractionation of Mo on ferromagnanese Kilbride G75 OQF, UK ([email protected]) oxides, which leads to the utility of Mo isotope systems as a 5Department of Earth Sciences, University of Bristol, Bristol paleoredox proxy. In contrast to extensive attentions on Mo, BS8 1RJ, UK ([email protected]) chemistry of W at the solid/water interface is pooly 6Geological Survey of Namibia, P.O. Box 2168, Windhoek, understood. The aim of this study is to reveal the W species in Namibia ([email protected]) natural ferromanganese oxide, which affects its different

behaviors from Mo in modern oxic ocean. Neoproterozoic response to, and recovery from, a Conventionally, it has been difficult to obtain high quality postulated greenhouse state following global glaciation fluorescence XAFS spectra of trace amount of W because of represents an acute test of feedbacks within the Earth system interferences of intense scattering and/or fluorescence from to maintain an equable environment. One explanation for the other predominant elements, such as Fe, Mn, Ni, Cu, and Zn. severe environmental change predicts progressive build-up of Here, we applied wavelength dispersive XAFS method, where pCO during extreme glaciation, and rapid melt back and 2 Bent Crystal Laue Analyzer was used in front of detector to influx of atmospheric CO into the ocean [1]. A boron isotope 2 selectively extract fluorescence X-rays of W [1]. study of post-glacial carbonates from Namibia identified a We revealed that the W species are in distorted Oh temporary ocean acidification (pH ~7), potentially linked to symmetry in natural ferromanganese oxides. The host phase oceanic uptake of carbon dioxide [2]. ,44Ca (0.4 to 1.3‰) and of W is suggested to be Mn oxides. We also found that the W ,26Mg (-2.1 to -1.4‰) excursions in Neoproterozoic carbonate forms inner-sphere complexes in hexavalent state and profiles elucidate the recovery of the Earth System from such distorted Oh symmetry on both synthetic ferrihydrite and "- an ocean acidification event and elevated greenhouse gas MnO2. It is known that Mo forms a distorted Oh inner-sphere concentrations in the glacial aftermath. Both isotope patterns complex on #n oxides and a Td outer-sphere complex on indicate an enhanced weathering influx following the ferrihydrite, and the host phase of Mo in natural glaciation demise, and increase in global temperature and ferromanganese oxides is "-MnO2 [2]. Therefore, the different precipitation in the greenhouse aftermath. This enabled the behaviors of W and Mo at the seawater/ferromanganese oxide ocean to return to normal pH after climatic amelioration. interface can be caused by (i) the stability of inner-sphere Differences in time-development of the Ca and Mg isotope complexes on the Mn oxides and (ii) mode of attachment patterns reflect a change from carbonate- to silicate-dominated (inner- or outer-sphere) on Fe oxyhydroxides. In addition, weathering flux and suggest primary dolomite formation preferential adsorption of lighter W isotopes is expected based during “cap dolostone” sedimentation. Differences in the on the molecular symmetry of the adsorbed species, implying magnitude of both isotope patterns across the the potential significance of the W isotope systems as paleo palaeocontinental margin of the Congo Craton suggest a local redox proxy similar to Mo [3]. influence potentially overprinting and amplifying the global pattern. Thus, extreme regional signals can lead to an [1] Kashiwabara et al. (2011) Geochim. Cosmochim. Acta. 75, overestimate of the global chemical weathering flux. 5762-5784. [2] Kashiwabara et al. (2010) Chem. Lett. 39, 870-

871. [3] Kashiwabara et al. (2013) Geochim. Cosmochim. [1] Hoffman et al. (1998) Science 281, 1342–1346. [2] Acta. 106, 364-378. Kasemann et al. (2010) Geology 38, 775-778.

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Future calamity of Arsenic poisoning Role of aggregates formed during in the groundwater of Thoubal and process stabilization in a production Bishnupur districts of Manipur of methane in biogas reactors (India) M. KASINA1,2*, A. KLEYBÖCKER1, M. MICHALIK2, 1 1 2 M. LIEBRICH AND H. WÜRDEMANN A. K. CHANDRASHEKHAR *; S. H. FAROOQ ; D. CHANDRASEKHARAM1 AND P. THAMBIDURAI1 1Helmholtz Centre Potsdam, GFZ German Research Centre 1 for Geosciences, 14473 Potsdam, Germany Department of Earth Sciences, IIT Bombay, Mumbai - ([email protected]) 400076. (*correspondance: [email protected]) 2Institute of Geological Science, Jagiellonian University, 2School of Earth, Ocean and Climate Sciences, Indian Institute Kraków, Poland; of Technology Bhubaneswar, Bhubaneswar-751013,

([email protected]) To optimise the co-digestion of sewage sluge and rape

seed oil a fast increase in the organic loading rate and the Above 10 µg/L (WHO 2001) concentration of arsenic in addition of CaO was tested in an experimental setup. The the drinking water lead to carcinogenic, cardiovascular process stability was increased by aggregate formation. Theses disease, neurotoxicity and diabetes in the human. Arsenic aggregates were extracted and subjected to detailed poisoning in the groundwater is growing threat to a very large characterization using SEM-EDS, XRD, FTIR and optical portion of Indian population. Along with the West Bengal, microscopy. The aim of this study is to describe the aggregates many areas of Uttar Pradesh, Jharkhand, Bihar, Chhattisgarh in terms of their morphology and mineral composition, as well and Assam have been reported with higher concentrations of as to find the answer about the role of microorganisms in their arsenic in the groundwater. To know the extent of arsenic formation. The relationship between Calcium and organics poisoning in parts of Manipur a study has been carried out and components like long-chain fatty acids (LCFA), 26 groundwater and samples were collected for analysis. More polysaccharides and proteins and microorganims was than 57% samples recorded arsenic > 10µg/L while this investigated to get a more detailed inside into biofilm concentration in the surface waters samples is negligible. The formation that is known to favour syntropic acetate oxidation highest concentration of arsenic (535 µg/L) was registered and methane formation. from Ngangkha Lawai Mamang Leikai area of Bishnupur The aggregates differed in size (from 0.5 mm up to 0.5 district which is fifty fold of the (WHO 10 µg/L) limit for cm), shape (usually rounded) and porous inner structure arsenic and tenfold of Indian permissible limit (50 µg/L). (different pore size) and showed a bipartite structure. In each In previous study the highest concentration of arsenic 200 part organic material containing calcium was the main µg/L[2] was reported in the same area of Bhishnupur district. component (LCFA-Ca). Whereas in present study the highest concentration of arsenic Adsorption effects as well as precipitation of insoluble is (535 µg/L) which is nearly three fold of previous study. salts of LCFA and Ca formed an outer cover of aggregates and This study shows that the arsenic concentration in offered interfaces within the aggregate as well. The aggregates groundwater is increasing with time. If situation continues, the formation was stimulated by CaO addition and had a positive groundwater may become higly pollutted with arsenic and impact on growths of synthrophic consortia. Due to the high may become a major cause of concern to the population of this concentrations of short-chain organic acids phosphate region. accumulating bacteria (PAO) took up acids like acetate and In this study the presence of arsenic free water on the propionate and released phosphate which precipitated with surface and contaminated groundwater at subsurface levels cations present in the sludge. Iron and aluminium phosphates indicates the existence and functioning of arsenic release were more common than calcium phosphates. Therefore we mechanism within the aquifer sediments [3]. assume that calcium added during experiments mainly

precipiated with LCFA as a strengthening material for [1] WHO 2001.[2] Jayalakshmi et al. (2010) Environ Earth aggregates. It was noted that precipitation of LCFA decreased Sci 62:1183–1195 [3] Farooq et al., (2012) Applied their toxicity and obviousloy, activity of PAO and syntrophic Geochemistry., 27, 292-303. consortia increased the pH inside the aggreagates and created favourable conditions for methan production. Therefore, an stable biogas production was observed although the pH and

the H2 concentration in the liquid phase of the sludge were below optimum.

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Experimental study of mineral- What caused the rise microbial interaction to investigate of atmospheric O2? the effects of CO2 storage JAMES F. KASTING MONIKA KASINA1*, DARIA MOROZOVA1, Dept. of Geosciences, 443 Deike, Penn State University, LINDA PELLIZZARI1, ANDREA KASSAHUN2 University Park, PA 16802 ([email protected]) AND HILKE WÜRDEMANN1 Oxygenic photosynthesis appears to have evolved well 1Helmholtz Centre Potsdam, GFZ German Research Centre before O levels increased in the atmosphere, at around 2.4 for Geosciences, 14473 Potsdam, Germany, 2 Ga. This has led to numerous suggestions as to what may have ([email protected]) kept O suppressed and then eventually allowed it to rise. 2Dresden Groundwater Research Centre e.V., 01217 Dresden, 2 These suggestions include changes in the recycling of carbon Germany and sulfur relative to water (or hydrogen), a switch from dominantly submarine to dominantly subaerial volcanism, The influence of biological processes on the composition gradual oxidation of the continents and a concomitant of reservoir sandstones the interactions between fluids and decrease in reduced metamorphic gases, a decline in minerals are monitored during exposure to CO2 in long-term deposition of banded iron-formations, a decline in nickel experiments. Samples from the core deposit were incubated availability, and various proposals to increase the efficiency of with fresh reservoir fluids as inoculum for indigenous photosynthesis. Several of these different mechanisms could microorganisms in a N2/CH4/H2-atmosphere at a temperature have contributed to the rise of O , although not all of them are o 2 of 80 C and a pressure of 40 bars for half a year. Afterwards equally effective. To be considered successful, any proposed the samples were exposed to supercritical CO2. Incubation was mechanism must make predictions that are consistent with the performed under lower temperature than in situ conditions to carbon isotope record in marine carbonates, which shows create more favourable growth conditions for microorganisms. relatively little change with time, apart from short-lived (but Analyses of the downhole fluids taken from a reservoir occasionally spectacular) excursions. The reasons for this well using genetic fingerprinting methods (PCR SSCP and constancy are explored here, but are not fully resolved. In the DGGE) revealed different DNA sequences indicating the process of making these comparisons, a self-consistent redox presence of H2-oxidising, biocorrosive thermophilic bacteria, balance framework is developed which will hopefully prove thiosulfate-oxidising bacteria as well as some microorganisms useful to others who may work on this problem and to similar to representatives from other deep environments, astronomers who may one day try to decipher spectral which have not been cultivated previously. Given a high signatures of oxygen on Earth-like exoplanets. temperature (120 – 127°C) and high salinity (up to 420 g/l) of fluids, the cells were difficult to detect because of very low numbers. The analysis of rock and fluid material from the long-term experiment after 11 and 31 months of incubation

with CO2 indicated the dissolution of major minerals and cements present in the sandstones, and secondary precipitation of new mineral phases such as quartz, albite, gypsum, halite, iron oxides and clay minerals. Changes in organic acid concentration and the release of organic components might indicate a metabolic activity of microorganisms or a

mobilisation due to CO2 exposure. Slight indication of microbial activity like EPS formation was detected: Calcofluor white staining of carbohydrates indicates the presence of biofilms. We assume that changes

observed in the samples until now were related mainly to CO2 exposure and fluid-rock interaction. In the next steps, samples

will be fed with H2 to enhance microbial growth and molecular biological analyses will be used to characterise the

changes in the biocenosis due to CO2 and H2 exposure.

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Melting of FeO-SiO2 system at high Experimental studies of partial pressure and the fate of subducted melting at the contact between banded iron formations limestone and pelitic gneiss CHIE KATO1*, RYUICHI NOMURA1 AND KEI HIROSE1,2,3 M. KATO1*, Y. HIROI2 AND M. ARIMA3 1Department of Earth and Planetary Sciences, Tokyo Institute 1Chiba University, Chiba 263-8522, Japan (*correspondence: of Technology, Tokyo, Japan (*Correspondence: [email protected]) [email protected]) 2Chiba University, Chiba 263-8522, Japan 2Earth-Life Science Institute, Tokyo Institute of Technology, 3Yokohama National University, Yokohama 240-8501, Japan Tokyo, Japan 3Institute for Research on Earth Evolution, Japan Agency for Continental crust is much more diverse than oceanic crust Marine-Earth Science and Technology, Yokosuka, Japan in composition. To evaluate the significance of partial melting for interaction between such diverse lithologies during high- Large amount of banded iron formations (BIFs) is thought grade metamorphism, we performed high-pressure to have subducted into the deep mantle. Because of their high experiments of partial melting at the contact between density, BIFs may have fallen down toward the core mantle limestone and pelitic gneiss, which are characteristic boundary (CMB) region and might cause the ultra-low lithologies in Gondwana fragments such as the Highland velocity zones (ULVZs) [1]. BIFs would be composed of FeO Complex of Sri Lanka and the Lützow-Holm Complex (LHC)

and SiO2 in the mantle because its oxidation state is close to of East Antarctica [1].

iron-wustite. FeO and SiO2 form a simple binary eutectic The rock fragments of limestone from Japan were loaded system above 16 GPa [2]. Its eutectic temperature must be in a sealed Pt capsule with powdered garnet-sillimanite gneiss

lower than the melting temperature of FeO, which is estimated from the LHC. H2O or NaCl aqueous solution were also added to be about 3,500 K at the CMB pressure [3]. Since to the capsule. Experiments were performed at 900 °C, 800 temperature at the CMB is most likely over 3,500 K, MPa, and 100 hours with a piston-cylinder, high-pressure subducted BIFs may have melted there. In order to understand apparatus at the Yokohama National University. the fate of the subducted BIFs, we have conducted high- At the contacts between limestone and partially molten

pressure melting experiments on FeO-SiO2 binary system, garnet-sillimanite gneiss (garnet + spinel + peraluminous using laser-heated diamond-anvil cell techniques. Results at liquid), different mineral assemblages are formed depending 47 GPa demonstrate that eutectic composition is extremely on the composition of solution as follows.

FeO-rich only with < 3 wt% SiO2. Dense FeO-rich melt H2O: Wollastonite, clinopyroxene, plagioclase, biotite, and

should have segregated downward, while buoyant SiO2- subaluminous to peraluminous liquid. dominant solid residue may have recycled upward. Such FeO NaCl aqueous solution: Clinopyroxene, plagioclase, melt accumulating between the core and mantle could have scapolite, and metaluminous liquid. formed Fe-rich lowermost mantle and O-rich topmost core. The results show that clinopyroxene, scapolite, plagioclase, and metaluminous liquid could be formed by the [1] Dobson & Brodholt (2005) Nature, 434, 731-734. [2] Kato melting reaction between limestone and garnet-sillimanite et al. (1984) J. Phys. Earth, 32, 97-111. [3] Boehler (1992) gneiss when NaCl aqueous solutions are involved. We attempt EPSL, 111, 217-227. to disuss the origin of clinopyroxene-scapolite-bearing calc- silicate granulites that have been reported from many high- grade metamorphic terrains including Antarctica [2], Sri Lanka [3], southern India [4] based on our experimental results.

[1] Shiraishi et al. (1994) Jour. Geol 102, 47-65. [2] Satish- Kumar et al. (2006) Polar Geoscience, 19, 37–61. [3] Mathavan and Fernando (2001) Lithos 59, 217-232. [4] Satish-Kumar and Harley (1998) Lithos 44, 83-99.

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Mineralization rates of organic Highly sensitive and precise analysis carbon in freshwater vs marine of stable chlorine isotope ratio by environments and implications for continuous-flow isotope ratio mass carbor burial efficiencies spectrometry SERGEI KATSEV1 , SEAN A. CROWE2, SHINSUKE KAWAGUCCI AND UTA KONNO MATTHEW KISTNER1AND JIYING LI1 Subsurface Geobiology Advanced Research Project 1Large Lakes Observatory, University of Minnesota Duluth, (SUGAR), Japan Agency for Marine-Earth Science and ([email protected]) Technology (JAMSTEC), 2-15 Natsushima-cho, 2NordCEE, University of South Denmark, Yokosuka 237-0061, Japan, ([email protected]) ([email protected]) Recent advancements in continuous-flow isotope ratio The mineralization and burial rates of organic carbon in mass spectrometry (CF-IRMS) enable us to determine stable aquatic sediments influence the global carbon cycle and over isotope ratios with only subnanomolar quantities. However,

geological time scales determine the atmospheric CO2 and the current CF-IRMS methods for stable chlorine isotope 37 oxygen levels. As organic matter descends through the water ratios (, Cl) of CH3Cl had required more than several

and then sediment columns, its reactivity towards hundreds nano-mole CH3Cl. We thus develope a CF-IRMS mineralization decreases. In marine environments, the system for the ,37Cl analysis that combines a sample decrease in organic carbon reactivity was described as a processing procedure largely based on the highly sensitive 13 power-law function of carbon age, sometimes referred to as method for the , C analysis of CH3Cl with the IRMS setting 37 Middelburg power law. The relationship extends over time for the , Cl analysis of CH3Cl. scales spanning eight orders of magnitude and is largely The newly developed system successfully reduces sample

independent of temperature, exposure to oxygen, requirements (>0.6 nmol-CH3Cl) to less than one hundredth of concentration of sulfate, and other factors that have been that required by the previous CF-IRMS systems while suggested to affect carbon mineralization rates. In contrast, no maintaining comparable precision in the ,37Cl determination relationship of this kind was suggested in freshwater where (±0.1 ‰, 10). This system is also able to determine carbon

conditions are typically more variable. Using a compilation of isotope ratio for CH3Cl with comparable precision (±0.3 ‰, 37 data from large lakes, we show that the reactivity of 10, >0.3 nmol-CH3Cl) to the previous study. , Cl-SMOC and 13 autochthonous organic carbon in fresh water decreases with , C-VPDB values of CH3Cl in commercial tank were time according to a similar power-law. The similarity suggests determined to be -6.8 ± 0.1 ‰ and -46.9 ± 0.3 ‰, that mineralization rates of organic carbon are determined respectively. primarily by intrinsic factors rather than the characteristics of The gas emitted from the leaves of Myrica rubra was the enviroment. It also suggests that carbon mineralization by collected near a harbor of Tokyo Bay (35°19.1’N, 139°39.0’E) sulfate reduction is not fundamentally faster than by using the vial method reported previously. On a dry weight

methanogenesis, with a particular implication that carbon basis, Myrica rubra was found to emit CH3Cl with a flux of

mineralization rates in oceanic sediments 0.5Ga ago, when 3.1)3.9 ng-CH3Cl/g-leaves/hour, whereas no CH3Cl was 37 13 sulfate concentrations were low, were not particularly detected in the empty vials. The , ClSMOC and , CVPDB values

different from today. Our results indicate that carbon reactivity of the leaf-emitted CH3Cl ranged from -4.9‰ to -2.9‰ (n=4) is higher in presence of oxygen, consistent with the enhanced and from -112.7‰ to -108.0‰ (n=4), respectively. The newly preservation of carbon in anoxic sediments. Using the developed system is applicable not only to atmospheric

obtained relationships for oxic and anoxic mineralization CH3Cl, but also to any chlorine in liquid and solid samples rates, we calculate the theoretical burial efficiencies as a when appropriate treatment such as silver chloride function of oxygen exposure time, which match the previously precipitation and its methylation is combined. reported observational trends. In contrast to the effect of oxygen, the effect of temperature on specific (per carbon atom) carbon mineralization rates appears to be minor, suggesting that climate-related warming of lake sediments may not lead to increases in specific rates of carbon mineralization.

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Reconstruction of pH and PCO2 by Supercontinent cycle and 2nd boron isotopes of unaltered continents ammonoids & nautiloids and the KENJI KAWAI1,2 HIROKI ICHIKAWA13 expected high alkalinity during the SHINJI YAMAMOTO4 TAKU TSUCHIYA3 AND SHIGENORI MARUYAMA1 Cretaceous 1Earth-Life Science Institute, Tokyo Institute of Technology 1, 1 2 KAWAHATA, H. , FUKUSHIMA, A. , MORIYA, K. , ([email protected]) 3 4 SUZUKI, A. AND ISHIKAWA, T. 2Department of Earth and Planetary Sciences, Tokyo Insitute 1Atmosphere and Ocean Research Institute, The University of of Technology 3Geodynamics Research Center, Ehime University Tokyo, [email protected] 4 2Waseda, University Graduate School of Arts and Sciences, The University of 3AIST, [email protected] Tokyo 4JAMSTEC, [email protected] It has been thought that granitic crust, having been formed The reconstruction of pCO2 during the geological time is on the surface, must have survived through the Earth’s required in order to predict the future environments. Boron evolution because of its buoyancy. Recent geological studies isotopic ratio is an excellent proxy for pH and the relevant have suggested that a significant amount of crustal material partial pressure of carbon dioxide in the seawater (PCO2). By has been lost from the surface due to delamination, continental using P-TIMS method, we conducted the high precision collision, and subduction at oceanic–continental convergent analysis of delta 11B (+/- 0.1 per mil reproducibility) of margins (von Huene and Scholl 1991; Yamamoto et al. 2009; unaltered aragonite shells of ammonoids and nautiloids mainly Ichikawa et al. 2013a). If so, then the subducted crustal in the Cretaceous and in Jurassic (70-162 Ma), which were materials are expected to be trapped in the mid-mantle due to expected to be much warmer due to higher PCO2. So far, the density difference from peridotitic materials induced by difficulty of fresh biogenic carbonate during these periods has the phase transition from coesite to stishovite (Kawai et al. produced no reliable reconstruction data using foraminiferal 2013). In order to study the effect of the subducted granitic delta 11B before Cenozoic era. Our careful assessment of materials floating around the mantle transition zone, we secondary alteration was conducted by 1) Determination by X- conducted two-dimensional numerical experiments of mantle ray diffraction (XRD), 2) Observation of microstructures of convection incorporating a continental drift with a heat source the nacreous layers by SEM, and 3) Measurement of trace placed around the bottom of the mantle transition zone. We element contents. Positive correlation between delta 11B and found that the addition of heat source in the mantle transition delta 18O (temperature) of biogenic aragonites in 80 and 86 zone considerably enhances the onset of upwelling plumes in Ma revealed that relatively deeper dwellers within the surface the upper mantle, which further reduces the time scale of ocean showed lower delta 11B values, which corresponded to continental drift. The heat source also causes massive lower pH. It is observed in the modern vertical water column. mechanical mixing, especially in the upper mantle. The results The reconstructed maximum PCO2 levels at late Cretaceous suggest that the heat source floating around the mantle (80 Ma and 86 Ma) are 1,750 and 1,540 ppm, respectively. transition zone can be a possible candidate for inducing the This is moderately high, coinciding with the suggestion by supercontinent cycle (Ichikawa et al. 2013b). Breecker et al. (2010). Abundant deposition of biogenic carbonate during the Cretaceous requires the enhancement of alkalinity, which could be raised by 20% relative to modern value. This is indirectly supported by seawater-rock interaction in Oman ophiolite around 100Ma. Both terrestrial and ocean environments have strong buffering mechanism for pH and PCO2 levels in moderate time scale.

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A molecular view of the reductive Contrasting behaviour of monazite dehalogenase-homologous gene in and zircon during partial melting and subseafloor sediments fluid infiltration: An example from MIKIHIKO KAWAI12*, TAIKI FUTAGAMI13, the Ryoke metamorphic belt, Japan 4 2 ATSUSHI TOYODA , YOSHIHIRO TAKAKI , 1 TETSUO KAWAKAMI IKUO UCHIYAMA5, ASAO FUJIYAMA4, TAKEHIKO ITOH6, 1 FUMIO INAGAKI1 AND HIDETO TAKAMI2 Department of Geology and Mineralogy, Kyoto University, 1 Japan, [email protected] Kochi Institute for Core Sample Research, Japan Agency for Marine-Earth Science and Technology (JAMSTEC), Behaviour of monazite and zirocn in the pelitic and Monobe B200, Nankoku, Kochi 783-8502, Japan. psammitic migmatites are investigated in the low P/T type (*correspondence: [email protected]) Ryoke metamorphic belt at the Aoyama area, Japan where 2Inst. Biogeosciences, JAMSTEC, Yokosuka 237-0061, Japan. regional metamorphic terrane is thermally overprinted by later 3Kyushu University, Fukuoka 812-8581, Japan. granite intrusions. 4Natl. Inst. Genetics, Mishima 411-8540, Japan. Monazite grains in migmatites yield a CHIME age of 5Natl. Inst. Basic Biology, Okazaki 444-8585, Japan. 96.5±1.9 Ma mainly in the core, and rims and patchy domains 6Tokyo Inst. Technology, Tokyo 152-8550, Japan. yeild 83.5±2.4 Ma. The age of ~97 Ma is interpretd to

represent the timing of monazite growth during prograde Recent molecular analysis of microbial communities in regional metamorphism. Some monaizte includes PbO-rich subseafloor sediment indicates that phylogenetically diverse phases at the core/rim boundary where sharp chemical and age bacteria utilize organohalides as the electron acceptor: e.g., zonings are observed, suggesting the contribution of interface- diverse 16S rRNA and reductive dehalogenase-homologous coupled dissolusion-precipitation mechamism. Patchy young (rdhA) genes related to the member of Dehalococcoides have domains could represent the result of fluid-related Pb loss been detected by PCR from organic-rich deep subseafloor through mircocracks. Therefore, ~80 Ma overprint on sediments (Futagami et al., 2009, 2013). Incubation migmatites represents the wide and combined effect of experiments also demonstrated the biological degradation of thermal input and fluid activity on the monazite grains caused organohalides (e.g., trichloroethene), indicating that by the ~80 Ma granite intrusions [1]. organohalides support anaerobic microbial respiration in On the other hand, zircon in the same area records sedimentary habitats that are generally poor in bio-available 90.3±2.2 Ma alone except for inherited ages at the core. electron acceptors. Between inherited core and the metamorphic rim, a thin, dark- To gain molecular insight into the largely unknown CL annulus containing <2 µm melt (glass) and nano-granite subseafloor reductive dehalogenation processes, we studied inclusions is commonly developed, suggesting the presence of metagenomic pools obtained from five sediment core samples melt during the rim growth. In diatexites, the annulus is (i.e., 0.7, 5, 18, 48, 107 m in depth) at Site C9001 off the further truncated by the brighter-CL overgrowth, suggesting Shimokita Peninsula of Japan during the Chikyu Shakedown the resorption and regrowth of the zircon after peak Cruise CK06-06 in 2006. From all samples examined, we metamorphism. This kind of zircon rim probably crystallized detected phylogenetically remarkably diverse rdhA- during the solidification of the melt in migmatites, and yeilds homologous genes that affiliate to novel specific clusters, 90.3±2.2 Ma. Therefore, zircon records the timing of partial indicating that molecular characteristics of subseafloor rdhA- melting event but not the fluid infiltration event during the homologous genes are evolutionary and functionary more ~80 Ma contact metamorphism [2]. diverse than those previously expected from the modern Using the difference of growth timing of monazite and surface biosphere (e.g., anthropogenic habitats). Consistently, zircon, the duration of metamorphism higher than the the frequency of rdhA-homologous genes in the subseafloor amphibolite facies grade is estimated to be ca. 6 Myr [2], metagenomic pools was found to be statistically high as similar to ~5 Ma estimated by [3]. This duration of high- compared to those in genomic sequences of over 1,800 temperature metamorphism is difficult to be attained by the isolated species. Interstingly, however, no or very little intrusion of a single granite sill (3 km thick), and requires differences in phylogenetic distribution of rdhA-homologous additional granite intrusions [4] or alternative heat source. genes were observed between five pools, suggesting that the

genes are spatially evenly distributed in sediment regardless of [1] Kawakami & Suzuki, (2011), Island Arc, 20, 439-453. [2] the formation age ranging from modern to Pleistocene. Kawakami et al, (2013), CMP, 165, 575–591. [3] Suzuki et al, (1994), EPSL, 128, 391-405. [4] Okudaira, (1994), Earth Monthly, 16, 486-489. (in Japanese)

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Synchrotron radiation X-Ray Difficulty of the self-replication of fluorescence analysis of aqueous prebiotic RNA molecules fluids and high-Mg Andesite melt K. KAWAMURA1*, Y. MARUOKA1, K. HAMAHIGA1 under high-temperature and high- AND N. KONAGAYA2 pressure conditions 1Department of Human Environmental Studies, Hiroshima Shudo University, Hiroshima, Japan (*correspondence: 1 2 TATSUHIKO KAWAMOTO , KENJI MIBE , [email protected]) 1 3 KEN-ICHI KUROIWA AND TESTU KOGISO 2Department of Nutritional Sciences, Yasuda Women’s 1Institute for Geothermal Sciences, Graduate School of University, Hiroshima, Japan Science, Kyoto University, Kyoto 606-8502, Japan; [email protected] Difficulties of RNA formation 2Earthquake Research Institute, The University of Tokyo, The RNA world hypothesis is supported by the discovery Tokyo 113-0032, Japan; [email protected] of ribozyme, the simulations of RNA formation under the 3Graduate School of Human and Environmental Studies, primitive earth environments, and in vitro selection of a Kyoto University, Kyoto 606-8501, Japan; variety of functional RNA molecules. However, there are [email protected] several drawbacks regarding the formation and replication of entirely prebiotic RNA molecules. First, the efficient pathway Chemical fractionation of slab-derived supercritical fluids of formation of RNA monomers under the primitive earth can play an important role in elemental transfer from conditions is not yet clarified. Second, the cylization of short subducting slab to the mantle wedge and arc magmatism [1]. oligonucleotides [1], such as dinucleotides and trinucleotides, Synchrotron radiation X-ray fluorescence (XRF) analysis is inhibits the accumulation of long RNA. This was partially conducted to know elemental partition between aqueous fluids solved by addition of intercalators [2]. Third, although it is and high magnesian andesite melt with Kawai-type large- true that RNA molecules preserve genetic information and volume press at BL04B1, SPring-8, Japan. Incident X-ray is a enzymatic function in vivo, these functions are not yet white beam with energy ranging from 20 keV to 150 keV. elucidated for the RNA molecules formed entirely prebiotic During heating at a given pressure, synchrotron XRF spectra conditions. It is known that the template-directed synthesis of are collected from the melt and the aqueous fluid with help of oligoguanylate from activated nucleotide monomers proceeds X-ray radiography under HT-HP [2]. The spectra show on a polycytidylic template [3]. However, other combinations characteristic X-ray peaks of the doped elements (Cs, Ba, Rare of activated nucleotide monomers on a complementary Earth Elements (REE)) superimposed on a continuous X-ray polynucleotide template proceed with very low efficeincy. background. A series of experiments has been carried out to obtain partition coefficients between them at 1000-1200 °C Results and Discussion and 0.5 - 2.2 GPa. The results suggest that (Na, K)Cl in We have attempted screening to enhance the efficency of aqueous fluids have large effects on the partition as previous the template-directed formation of oligonucleotides. The studies [3]. Two slab-derived components: a melt and a fluid screening was carried out in the presence of intercalator, component are suggested to explain trace element polypeptides, metal ions, and naturally-occuring minerals. In characteristics of basalts and basaltic andesites in the Mariana addition, the template-directed reaction was carried out at arc [4]. Both components are characterized by enrichment of temperature below 0 ºC. Although the efficieny of the alkali and alkali earth elements. In addiiton to these, the melt template-directed reaction was slightly enhanced in the component has immobile elements such as REE [4]. Such presence of intercalator, that was generally reduced in the features can be explained if the fluid component is a Cl-rich presence of polypepetides, metal ions, and minerals. aqueous fluid [3]. We suggest that slab-derived components Furthermore, the influence of very low temperatures was not have compositional features consistent with a Cl-rich aqueous also deteceted. These results imply the fact that the replication fluid and a melt, which can be formed through a separation of of RNA moleculs consisting of entirely prebiotic materials a slab-derived supercritical fluid [1]. would be very difficult.

[1] Kawamoto et al (2012), Proc Nat Acad Sci USA 109, [1] Kawamura & Ferris (1999) OLEB 29, 563-591. [2] 18695 [2] Mibe et al (2004) Geochim Cosmochim Acta 68, Horowitz et al. (2010) PNAS 107, 5288-5293. [3] Inoue 5189 [3] Keppler, (1996) Nature 380, 237 [4] Pearce et al. (1983) Science 219, 859-862. [4] Sawai & Wada (2000) OLEB (2005) Geochem Geophys Geosys 6, Q07006 30, 503-511.

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Reactive transport modelling of Hydrogen isotope exchange between mineral trapping of CO2, revised by insoluble organic matter and water in water sampling data at Nagaoka CO2 chondrite parent bodies storage site Y. KEBUKAWA12* AND G. D. CODY1 YUKO KAWATA*, ZIQIU XUE AND SAEKO MITO 1Geophysical Laboratory, Carnegie Institution of Washington, Washington DC, 20015, USA (*[email protected]) Research Institute of Innovative Technology for the Earth 2Department of Natural History Sciences, Hokkaido (RITE), 9-2 Kizugawadai, Kizugawa-shi, Kyoto 619- University, Sapporo 060-0810, Japan 0292, Japan (*correspondence: [email protected])

The high deuterium enrichment in insoluble organic Carbon dioxide capture and storage (CCS) in saline matter (IOM) in chondrites has largely been attributed to small aquifer is one of the global warming countermeasure molecule chemistry prior to IOM, specifically ion-molecule technologies. A part of injected CO will be stored by reacting 2 reactions at low temperature interstellar medium (ISM) [1]. with formation water and reservoir rock forming minerals over The hydrogen isotope (D/H) ratio of IOM tends to decrease as many years, which is more stable for CO trapping. 2 alteration proceeds [2]. While water in carbonaceous Conducting reactive transport simulation is needed to evaluate chondrites is more depleted in D [3]. Thus, the decrease in CO mineralization. However, some geochemical input data 2 D/H ratio of IOM could be attributed to the hydrogen isotope for kinetic mineral dissolution/precipitaion calculation has exchange between D-enriched IOM precursor and D-depleted high uncertainty. We have attempted to revise the water, which could have occurred during and/or after the geochemical data by matching the geochemical simulation formation of IOM. results with sampled formation water composition, to make Cody et al. [4] proposed that IOM in chondrites may have more realistic model for long term CO behavior prediction . 2 formed through the polymerization of interstellar A series of trial runs would be needed to gain a good match, formaldehyde after the planetesimal accretion, in the presence and so we used 1-D radial model for simulation-time saving. of liquid water. Our recent study successfully enhanced If a field-scale model is used, we have to consider lots of production of IOM analog materials from formaldehyde in the geological uncertainties simultaneously, which should make presence of ammonia [5]. Using this formaldehyde polymer as the study too complicated and time consuming. an IOM analog we have conducted kinetic hydrogen isotope Formation water was sampled twice after CO injection 2 exchange experiments, starting with (1) deuterated from the observation well OB-2 at the depth of 1118m at the ! formaldehyde polymer and normal water, and (2) normal Nagaoka site. The concentration changes of HCO , Ca, and 3 formaldehyde polymer and deuterated water, both as a Si from the first run to the second run was chosen for function of temperature. The three-dimensional diffusion rate matching data, because only calcite is a carbonate mineral in control model was found to fit well the changes in the D/H the initial mineral composition referring to Mito et al. [1]. 1- ratio with time. The apparent activation energies and the D radial model was constructed with TOUGHREACT, based frequency factors were obtained by the apparent rate constants on the previous study. Since the reservoir pressure is already for each temperature with the Arrhenius equation. Using these stable, CO dissolved water moves mainly by the gravity 2 kinetic expressions, hydrogen isotope exchange profiles were effect, which can’t be expressed in 1-D radial model. Instead, estimated for time and temperature behavior, based on the the diffusion coefficient was adjusted by considering ! assumption that the kinetic rate low is valid over all HCO concentration. We selected reactive surface area (RSA) 3 temperatures. We will discuss the ,D variation observed in for varying geochemical parameter, and the initial data was various chondrites, and the IOM grain size effects, based on based on the experimental results using reservoir rock powder. our hydrogen isotope exchange kinetics. Finally, RSA value was modified to 0.015 times of the initial

model, then a good matching result was obtained. This result [1] Robert & Epstein (1982) GCA 46, 81-95. [2] Herd et al is reasonable because the sandstone of Nagaoka site has some (2011) Science 332, 1304-1307. [3] Alexander et al (2012) conglomerate, and thus should have the narrower contact area Science 337, 721-723. [4] Cody et al (2011) PNAS 108, with formation water than expected. Subsequently, we 19171-19176. [5] Kebukawa et al ApJ under review. performed long term CO2 behavior simulation with this matched model.

[1] Mito, S., et al (2013) Applied Geochemistry 30, p.33-40

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Lithospheric control of plume Biogeochemical Mechanisms impact: Evidence from dyke Underlying the Manganese geochemistry Dependence of Litter Decomposition JAKOB K. KEIDING1*, ROBERT B. TRUMBULL1, MARCO KEILUWEIT12*, PETER S. NICO3, THOMAS M. WILL2, HARTVIG E. FRIMMEL2, MARK HARMON2, SUET LIU4, TIM FILLEY5, MIRIAM WIEGAND3 AND ILYA V. VEKSLER1 JENNIFER PETT-RIDGE1AND MARKUS KLEBER2 1GFZ German Research Centre for Geosciences, Germany 1Chemical Sciences Division, Lawerence Livermore National (*correspondence: [email protected]) Laboratory, Livermore, CA 94550 2University of Würzburg, Germany 2Crop and Soil Science, Oregon State University, Corvallis, 3Karlsruhe Institute of Technology, Germany OR 97331 3Earth Sciences Division, Lawerence Berkeley National Dyke swarms in continental flood basalt (CFB) provinces Laboratory, Berkeley, CA 94720 carry more information about the magmatic systems than 4Advanced Light Source, Lawrence Berkeley National coeval lavas since they often are less differentiated and less Laboratory, Berkeley, CA 94720 prone to removal by erosion. Moreover, dykes directly record 5Department of Earth and Atmospheric Sciences, Purdue the site of magma emplacement whereas eruptive vents for University, West Lafayette, IN 47907 CFB lavas are rarely known and can be distant from the Climate change is predicted to impact the organic and sampling site. Here we report on ~250 samples from the Early inorganic composition of foliar litter, and global warming may Cretaceous Henties Bay Outjo dyke swarm (HOD) in NW increase soil microbial and enzymatic activity, with uncertain Namibia, which is the best exposed major dyke swarm consequences for litter decomposition rates and pathways in associated with South Atlantic rifting and breakup. The goals soils. Recent work has identified the bioavailability of key of this research are to assess the geochemical variability of resources (e.g, assimilable C or inorganic nutrients) as the dyke magmas, to determine the composition of the mantle main control of litter decomposition rates. A particularly source and physical conditions of melting, and to understand strong correlation was established between manganese (Mn) the influence of the continental crust and lithosphere on content in needle litter and litter decomposition rates across a magma composition, ascent and emplacement. And finally, we variety of boreal forest ecosystems, suggesting that Mn is an are interested in the time-space variation of these parameters. essential component of the decomposition pathway. There is Chemical and isotopic compositions distinguish three end- good reason to assume that this is due to the critical role of member magma groups in the HOD. In order of decreasing Mn(III)-ligand complexes acting as potent oxidizers in the abundance these are: (a) crustally-contaminated tholeiites, enzymatic breakdown of lignin. Here we related changes in with “spiky” trace element patterns and enriched isotope ratios 87 86 Mn form and distribution to lignin transformation over the ( Sr/ Sr = 0.710-0.712, !Nd = -2 to -7) very similar to the i i course of a 7-year litter decomposition experiment in an old main series of Etendeka flood basalts, (b) MORB-like growth forest ecosystem. Soft-ionization mass spectrometry, tholeiites with relative flat trace element patterns and depleted 87 86 FTIR and X-ray absorption spectroscopy analyses of fresh isotope ratios ( Sr/ Sri = 0.704-0.705, !Ndi = +2 to +6), and 87 86 needles, litter at different decomposition stages, and mineral (c) alkaline, trace element enriched basalts ( Sr/ Sr = i soil show that the formation of oxidative Mn species is well 0.7055-0.7059, !Nd = 0 to -2). In general, dykes in the i correlated with lignin decomposition. Spatially-resolved southern part of the HOD (lat. 20-23º) are more diverse and synchrotron-FTIR and X-ray microprobe imaging revealed more primitive. Neither picritic nor alkaline dykes have been that microorganisms colonizing individual needles redistribute so far observed to the North (lat. 17-20º). Interestingly, the and transform reduced Mn(II) present in the vascular system most primitive dykes (MgO > 6 wt.%), with the highest of fresh needles into oxidative Mn(II/III) forms at the sites of magmatic temperatures (1350°C) and the greatest apparent lignin decomposition. These mechanistic insights suggest that depth of melting (highest Zr/Y and Dy/Yb ratios) occur in the Mn bioavailability and form are important parameters for southern area although the proposed plume impact is farther improved model predictions of litter decomposition rates in north (Walvis Ridge). The dyke diversity may be controlled forest soils. The response of ecosystem Mn fluxes to rising more by crustal permeability than differences in magma temperatures and CO concentrations and, specifically, its source. 2 implications for litter decomposition rates will be discussed.

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Trace element systematics of pyrite Clumped isotope geochemistry of from submarine hydrothermal vents travertine carbonates in the 22-95 °C M. KEITH1*, F. HÄCKEL1, K.M. HAASE1, temperature range 2 1 U. SCHWARZ-SCHAMPERA , R. KLEMD 1 2 3 3 3 KELE S *, BERNASCONI SM , KLUGE T , JOHN CM , AND S. PETERSEN 2 2 2 MILLÁN MI , MECKLER AN , ZIEGLER, M , 1GeoZentrum Nordbayern, Univ. Erlangen-Nuernberg, BREITENBACH SFM2, CAPEZZUOLI E4, ÖZKUL M5 AND Erlangen, 91054, Germany (*correspondence: GÖKGÖZ A5, DEÁK J6 [email protected]) 1 Institute for Geological and Geochemical Research, RCAES- 2Federal Institute for Geosciences and Natural Resources, HAS, Budapest, Hungary (*[email protected]) Hannover, 30655, Germany 2 3 Dept. of Earth Science, ETH Zurich, Switzerland Geomar, Helmholtz-Zentrum fuer Ozeanforschung, Kiel, 3 Imperial College, London, Earth Sci. and Eng., London, UK 24148, Germany 4 Dept. of Phys., Earth and Env. Sci., Univ. of Siena, Italy 5 Pamukkale University, Denizli, Turkey Submarine hydrothermal sulfide deposits occur at mid- 6 Gwis Ltd, Dunakeszi, Hungary ocean ridges, island arcs, and in back-arc basins. It is believed that the different wall rocks and potential magmatic volatiles The formation temperature of carbonates can be estimated [1] influence the metal budget of the hydrothermal fluid and using both the conventional carbonate-water the composition of the sulfide precipitates to variable degrees. paleothermometry and the newly developed clumped isotope Pyrite is the dominating mineral in these precipitates and method of [1]. However, there is still a large uncertainty in the thus, the trace element composition of pyrite may reflect the published clumped-isotope based temperature calibrations. different metal sources. However, the physicochemical In this work recent travertines forming from natural composition of the fluid phase and processes such as phase springs and wells between 22 and 95 ºC from Hungary, separation [2] largely control the solubility and transport of Turkey and Italy were studied for stable- and ’clumped’ metals and hence, metals enriched in the wall rock or magmas isotopes. Clumped isotope data showed an excellent may not necessarily be concentrated in the sulfides. correlation with temperature indicating equilibrium Here we report on a systematic study of major and trace precipitation close to the spring orifice. $ values decreased element concentrations on pyrites from active and inactive 47 with increasing distance from the springs, which may be hydrothermal fields including the Indian and Mid-Atlantic related to kinetic isotope fractionation due to CO degassing in Ridges, the Tonga-Kermadec arc, Lau back-arc, and the 2 the different depositional sub-environments (e.g. channel, central Okinawa Trough. Preliminary results indicate that the terrace-pool, cascade). pyrites show significant variations in their trace element All vent travertine samples show a strong $ -temperature contents irrespective of the surrounding host rocks. Pyrites 47 relationship (r2>0.9) defining an empirical equation with a from single locations have highly variable concentrations of slightly lower slope (i.e. lower temperature sensitivity) than elements like Cu, Sb, Ag, Au and Co that are most likely that of Ghosh et al. [1]. This empirical calibration significantly related to fluid evolution and changes in fluid compositions. extends the calibration range of the clumped isotope Elements like Sb, Ag and Au have a characteristic affinity to thermometer to temperatures of 95 ºC and can be used to As and Pb in pyrite, Cd correlates closely with Zn. High derive the oxygen isotope composition of travertine-depositing temperature (>240°C) As-Cu-pyrites are often enriched in Co waters from ancient deposits to reconstruct glacial-interglacial and Au, while Ni seems to be unaffected by temperature variations in meteoric water compositions and the variations. The incorporation of Co and Ni into pyrite is wall paleohydrological regimes of the study areas. rock-independent. Bismuth appears to be enriched in pyrites from settings associated with sediments [3] and Mo may be concentrated due to seawater mixing [4]. [1] Ghosh, P. et al. (2006) Geochim. Cosmochim. Acta 70, These results indicate the complexity of trace metal 1439-1456. contents in pyrite as a function of the physicochemical composition of the fluid phase rather than their source.

[1] de Ronde et al. (2011) Miner Deposita, 46, 541-584. [2] Koschinsky et al. (2008) Geology, 36, 615-618. [3] Zierenberg et al. (1993) Econ Geol, 88, 2069-2098. [4] Trefry et al. (1994) J Geophys Res, 99, 4925-4936.

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Some less conventional processes in Reaction-driven cracking subduction zones P.B. KELEMEN P.B. KELEMEN LDEO, Columbia University, ([email protected])

LDEO, Columbia University, ([email protected]) Hydration, carbonation, and oxidation of volatile-poor lithologies are essential to the rheology of oceanic plates, the Emplacement of buoyant, felsic material from subduction structure of subduction zones, global geochemical cycles, and zones into hanging wall crust may be as important as possible capture and storage of CO . There’s plenty of energy. foundering of dense lithologies from the base of the crust. 2 Mantle olivine plus H O or CO contains 5% of the energy Building on the ideas of Hacker et al. (EPSL 2011), we’ve 2 2 density (J/m3) of petroleum fuels (Kelemen and Hirth EPSL proposed an end-member, uniformitarian model in which 2012). Negative feedbacks (fluid consumption fluid, falling continental crust forms and evolves via accumulation of diffusivity, increasing solid mass, decreasing solid density, buoyant, felsic material ascending from the upper crust of the crystallization in pore space, armouring of surfaces) make subducting plate in arc-arc or arc-continent collisions these processes self-limiting under many conditions. Yet, fully (Kelemen & Behn, submitted). hydrated (serpentinite) and carbonated (listvenite) peridotites More generally, fore-arc sediments can be thrust into arc demonstrate that reaction can proceed to completion in some crust during subduction erosion, buoyant material can be cases. Cracking due to stress from volume change can subducted to great depths and then ascend along a “subduction maintain or increase permeability and reactive surface area channel”, or diapirs may rise through the hot mantle wedge (MacDonald & Fyfe Tphys 1985). In systems far from beneath arcs. The latter process can efficiently recycle equilibrium, reactions can produce kilobars of differential components from subducted sediment (greywacke, pelite, stress to fracture rocks, though the effect of confining pressure carbonate; Behn et al. Nature Geoscience 2011), and play a is uncertain. In natural samples that underwent reaction-driven key role in global geochemical cycles. Interaction between cracking, the surface energy density on newly formed metasedimentary diapirs and mantle peridotite may form a fractures corresponds to a strain energy density produced by variety of hybrid rocks, melts and fluids. kilobars of stress, consistent with thermodynamic estimates It is more challenging to understand accumulation and (Kelemen & Hirth EPSL 2012). transport of partial melts of subducting basalt, where these Devolatilization and melting may cause earthquakes and comprise a substantial geochemical component in arc lavas hydro-fracture, if fluid/melt production is rapid and (e.g., W Aleutian primitive andesites). Perhaps, reaction permeability is low. Again, disequilibria in natural systems between SiO -rich melt and peridotite forms an impermeable 2 have energy densities ~5% of petroleum. Reaction of eclogite carapace of pyroxenite, beneath which melt accumulates to melt with peridotite could form an impermeable pyroxenite sufficient thickness to form diapirs (e.g., Ringwood 1975). carapace, beneath which a column of interconnected melt Diapirs may slow or stop near the crust-mantle boundary. grows until buoyancy leads to magma fracture. Volume An intriguing observation in some areas (Mt Shasta, W change due to rapid fluid evolution from cooling melt, or from Aleutians) is the spatial juxtaposition of primitive magmas warming rocks, can cause fracture if relaxation (porous flow, (Mg# ~ 0.7) with very different MgO and H O contents, and 2 viscous deformation) cannot keep pace. Shear-heating could thus different temperatures. Perhaps hydrous, cool, primitive cause rapid fluid production and fracture in localized shear andesites and dacites commonly pond and equilibrate with the zones. If fluid pressure reduces effective stress, heating will mantle just below the base of arc crust, while hotter primitive slow. With different time scales for thermal evolution and basalts rise rapidly through this region in cracks or porous reaction progress, such instabilities could be oscillatory. conduits of focused flow.

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A statistical approach to the volcanic Sulfur isotope systematics of – plutonic connection geothermal fluids, Krafla, Iceland BRENHIN KELLER*, BLAIR SCHOENE, N.S. KELLER1, A. STEFÁNSSON1, S. ONO2 KYLE SAMPERTON, MELANIE BARBONI, AND J. GUNNARSSON ROBIN1 JEFF GRONEWOLD AND JON HUSSON. 1 Institute of Earth Sciences, University of Iceland, Sturlugata Princeton University, Geosciences, Princeton, USA, 7, 101 Reykjavík, Iceland ([email protected]) ([email protected] * presenting author) 2Department of Earth Atmospheric and Planetary Sciences, MIT, Cambridge, MA, USA The geochemical relationship between volcanic and plutonic rocks - whether the two are geochemically identical, Sulfur is among the major components in geothermal or if the choice between eruption and intrusion is correlated systems. It is present in various oxidation states ranging from with magma chemistry - represents a major unanswered sulfide (S-II) to sulfate (S+VI) and present in solid phases and question in igneous petrology. In one endmember scenario, fluids (water and vapor). The source of the various sulfur felsic to intermediate plutons are proposed to represent the compounds and the processes affecting their chemistry and unerupted crystal mush from which crystal-poor eruptible fluxes are complex and in many respects not fully understood. melts are extracted. At the other end of the spectrum, it is In an effort to study the complex geochemistry of sulfur in this argued that a nearly the entire volume of magma is evacuated system, we obtained new chemical and isotopic data for fluids during large silicic eruptions, and that the probability of sampled from the Krafla field, NE Iceland, an active volcanic eruption versus intrusion is instead largely a function of geothermal system. High-temperature well fluids discharging magma flux. water and/or steam were collected having enthalpies ranging In the first scenario, parental magmas originating at depth from 852 to 2774 kJ/kg. The fluids were analyzed for various

experience substantial fractionation during volcanic melt sulfur compounds including, H2S, SO3, S2O3 and S2O3 in the

extraction, leading to complementary volcanic and plutonic water phase and H2S and SO2 in the vapor phase and for sulfur 32 33 34 36 reservoirs. In the second endmember scenario, isotopes including S, S, S and S on H2S and SO4 in the

volcanic/plutonic fractionation is negligible, but geochemical water phase and H2S in the vapor phase. For the sulfur isotope differences on average between volcanic and plutonic rocks analysis the various sulfur oxidation states were sequentially

are still possible if high- and low-flux melts have distinct precipitated as ZnS and BaSO4, converted to Ag2S and geochemical characteristics that are correlated with the analyzed by Fluorination-GC-IRMS.

eruptibility of a magma. The observed concentrations in the waters were SO4 = 5.1-

We have compared the geochemistry of ~300,000 volcanic 280 ppm, H2S = 27.6 to 120 ppm and S2O3 = 0-39.1 ppm. The

and plutonic rocks by Monte Carlo analysis in order to concentrations in the vapor were H2S = 46-2617 mg/kg produce maximally representative average compositions that condensate. No other sulfur phases were detected. The ,34S in

reflect the influence of meaningful physical processes. The SO4 and H2S in the waters were +3.4 to +13.4‰ and -1.8 to -

results indicate that while volcanic and plutonic rocks in 0.2‰, respectively, and H2S in the vapor were +0.1 to +1.3‰. general show remarkably similar major element trends, The 133S and 136S follow the theoretical value for mass- intermediate to felsic plutonic rocks, for a given silica content, dependent fractionation in all cases. 34 display clear enrichments in Sr and Ba and depletions in Zr, The results indicate that the , S for H2S in the total Hf, and HREEs relative to their volcanic equivalents. More discharged fluid are very close to 0.0‰, suggesting magmatic subtly, intermediate volcanic rocks are found to exhibit small origin, either through magma degassing and/or magmatic 34 but distinct enrichments in FeO and depletions in K2O relative sulfide leaching. The , S ratio between H2S in the water and

to equivalent plutonics. These results suggest that, in the first vapor is considered to reflect boiling temperatures. For SO4,

endmember scenario above, volcanic/plutonic fractionation of the positive isotope shift observed may be explained by H2S

plagioclase must be a key factor; while for the second scenario oxidation to SO4 and/or SO4 originated from the surface either to hold, average water content must differ substantially through meteoric water and/or sulfate mineral leaching and/or between extrusive and intrusive equivalents. Further mixing of these two different sources. examination of trace element systematics combined with geochemical modelling allows for the discrimination between the influence of late stage crystal fractionation, versus the influence of water to suppress plagioclase relative to the ferromagnesian minerals and to delay the crystallization of most silicate minerals relative to zircon saturation.

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The relationship between fO2 and Characterisation of active forest soil calc-alkaline affinity of arc magmas Bacteria during mineral weathering K.A. KELLEY1*, E. COTTRELL2 AND M.N. BROUNCE1 KELLY L.C.*, UROZ S1 AND TURPAULT M.-P.2 1GSO, Univ. of Rhode Island, Narragansett, RI 20882 USA 1UMR1136 Interactions Arbres-Microorganismes, Centre (*correspondence: [email protected]) INRA de Nancy, 54280 Champenoux, France. 2NMNH, Smithsonian Inst., Washington, DC 20560, USA 2UR1138 Biogéochimie des Ecosystèmes Forestiers, Centre INRA de Nancy, 54280 Champenoux, France. Calc-alkaline differentiation, a process by which magmas (*correspondence: [email protected]) become rapidly depleted in Fe early in their crystallization history, is observed exclusively in magmas in subduction zone Acidic forest soils, while nutrient-poor, are characterised settings and is thought to drive magmas towards the bulk by a reservoir of inorganic nutrients trapped within the composition of continental crust. Basaltic arc magmas have minerals contained therein. Despite the significance of such been proposed to achieve calc-alkaline affinity through either reservoirs to the long-term functioning of acidic forest

high magmatic H2O, which delays the onset of plagioclase ecosystems, surprisingly little is known regarding the

crystallization, or high magmatic fO2, which enhances the contribution of the resident bacterial communities to the onset of magnetite crystallization, or both. The relative weathering of soil minerals. While the influence of mineralogy

importance of H2O, fO2, and magmatic bulk composition in on the phylogenetic composition of mineralosphere generating calc-alkaline magma series, however, is not yet communities in soil and other terrestrial environments [1, 2, 3] clearly resolved. Here, we present new measurements of the has been demonstrated, determining the activities and oxidation state of Fe (expressed as Fe3+/2Fe ratio) in olivine- contributions of individual microbial taxa to weathering hosted melt inclusions from basaltic arc volcanoes in the processes remains an ongoing challenge. Using DNA Mariana and Aleutian arcs, acquired using X-ray Absorption immunocapture and high-throughput sequencing, in concert Near Edge Structure spectroscopy. These volcanoes span a with geochemistry and traditional culture-based techniques, range of calc-alkaline affinity, with THI ranging from 0.7 to we investigated bacterial communities on a variety of minerals 1.2 (THI = Tholeiitic Index, <1 is more calc-alkaline, >1 is during weathering in laboratory microcosms, seeded with a more tholeiitic [1]). Measured Fe3+/2Fe ratios range on forest soil-derived inoculum. Our primary objectives were i) average from 0.23-0.28 in the Marianas, and from 0.20-0.28 in the comparison of active and inactive bacterial community the Aleutians, which are uniformly more oxidized than more fractions and ii) to determine whether mineralogy influences tholeiitic basaltic glasses from the Mariana trough back-arc the phylogenetic composition of these fractions. Such analyses basin (THI=1.4; Fe3+/2Fe=0.15-0.18) or normal MORB brings us a step closer to understanding the composition and (THI=1.6; Fe3+/2Fe=0.16±0.01). Our results show a activities of mineralosphere bacterial communities in acidic correlation between THI and Fe3+/2Fe ratios at these forest soils, and the likely ecological significance of particular volcanoes, such that more tholeiitic magmas contain a greater taxa. proprtion of reduced Fe, and more calc-alkaline magmas a greater proportion of oxidized Fe. At the same time, the [1] Uroz et al. (2009) Trends Microbiol. 17, 378-387. [2]

maximum dissolved H2O contents of basaltic melt inclusions Kelly et al. (2010) Microbial Ecol. 60, 740-752. [3] Lepleux from these volcanoes also broadly correlate with THI [1], and et al. (2012) Appl. Environ. Microbiol. 78, 7114-7119. with measured Fe3+/2Fe ratios, which is consistent with prior

work [2], although H2O is not the direct cause of oxidation.

These findings suggest that H2O and fO2 may both play key roles in the development of calc-alklaine affinity in arc magmas, but their respective functions in this process may be difficult to separate in natural systems because the subducted slab delivers fluids that generate arc magmas with both

elevated H2O and fO2.

[1] Zimmer, M.M., Plank, T., Hauri, E.H., et al., 2010, J. Pet. 51, 2411-2444, doi:10.1093/petrology/egq062. [2] Kelley, K.A., Cottrell, E., 2009, Science 325, 605-607, doi:10.1126/science.1174156.

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Temporal trends in the seawater Possible PGE nano structures, in osmium inventory and 187Os/188Os magmatic systems B. KENDALL* AND X. LU KENNEDY, B.1*, TREDOUX, M.1, BALLHAUS, C.2, COETSEE, E.3 AND STEYL, G.4 Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada 1Dept. of Geology, University of the Free State, South Africa, (*correspondance: [email protected]) (*correspondence: [email protected]) 2Steinmann Institute, University of Bonn, Germany Recently, several studies have used compilations of redox- 3Dept. of Physics, University of the Free State, South Africa sensitive metal abundances (e.g., Mo, Ni, Zn) from organic- 4Dept. of Chemistry, University of the Free State, South Africa rich sedimentary rocks (ORS) and iron formations to infer first-order temporal trends in oceanic metal inventories. These The retention of platinum-group elements (PGE) in the trends provide critical information about atmosphere and mantle restite is difficult to explain by conventional ocean oxygenation and associated changes in biogeochemical chalcophile models. PGE nano-structures (clusters of 10- cycles and biological evolution. Osmium (Os) is a redox- 100nm), might be the cause that magma can become enriched sensitive metal that can provide information about redox in PGE, during the early stages of magmatic differentiation. conditions and crustal vs hydrothermal fluxes. The study focused on the possible formation of these entitites Most of the Os supplied to the modern oceans is derived in a magmatic system. If these entities do form, to what extend from rivers (via oxidative weathering of the upper crust), with might they contribute to ore forming processes in ultra mafic the remainder coming from cosmic dust dissolution and deposits, like the Bushveld complex. hydrothermal alteration of oceanic crust and peridotites. A synthetic sulphide system was used to replicate the Osmium accumulates in modern oxygenated seawater sulphide portion of a Cu-Ni-S ± PGE system. Sulphides are of (residence time of 104 years) but is sequestered into anoxic, the first ore minerals to crystallize in a magmatic environment organic-rich sediments. Seawater 187Os/188Os (= initial and thus the ideal place to look for clusters. Experiments were 187Os/188Os of ORS at the time of sediment deposition) also run, using the dry powder silica charge technique. A base constrains the relative importance of radiogenic crustal versus mixture of Cu, S and Fe, was doped with variable unradiogenic hydrothermal (and extraterrestrial) inputs to concentration of PGE (Pt, Pd and Ru) and As. As was chosen seawater. Temporal trends in 187Os/188Os have been explored, as stabilising chalcogene ligand. The systems were whereas Os abundances in ORS have received less attention. manipulated to form a mono sulphide or pyrrhotite phase 192 Here, we present a compilation of Os abundances in (FexSx) and a melt (FexCuxSx) phase. ORS (total Os abundances are not used because of 187Os Nano scale PGE-ligand phases, ranging from 10-1000 nm, contributions from 187Re decay). We find that 192Os were measured in the synthetic samples, by high resolution abundances in pre-Ediacaran shales are low, typically <300 SAM and TOF-SIMS. This observation indicated that the PGE ppt, but still elevated above average upper crust (~10-20 ppt). may form phases, on a nano level, without sulphide saturation The 192Os enrichments and chondritic initial 187Os/188Os from having been achieved. The clusters form due to the physio- Archean ORS require a oceanic Os inventory dominated by chemical association of the PGE with chalcogene ligands, hydrothermally sourced Os. However, there is no clear change such as As, Fe and Cu, before formal chemical bonding, to in 192Os abundances across the Great Oxidation Event. This from PGMs. A fraction of the clusters are reabsorbed into the observation contrasts with a shift from chondritic seawater melt, while a fraction may act as nucleation points to form 187Os/188Os in the Archean to moderately radiogenic seawater nano-crystals and minerals in the incompatible sulphide, oxide 187Os/188Os in the Proterozoic, which points to an increase in or silicate phases. The clusters form during the early stages of the riverine flux of radiogenic Os to the oceans. To reconcile magmatic differentiation. these obesrvations, we suggest that continued widespread Chemical behaviour may govern the secondary Proterozoic deep ocean anoxia and declining hydrothermal Os distribution of PGE-phases, but clustering is potentially the fluxes kept the oceanic Os inventory broadly similar to primary (physical) enrichment mechanism. This behaviour Archean levels. Higher 192Os abundances (>300 ppt) and cannot be explained by sub-solidus immiscibility properties as instances of highly radiogenic seawater 187Os/188Os in the has been suggested to account for the frequent presence of Ediacaran Period and Phanerozoic Eon point to an increase in PGE in base metal sulphide minerals. the riverine Os flux and oceanic Os inventory in response to late Neoproterozoic oxygenation.

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Spectroscopically visualising the Submarine meteorite impact craters availability of goethite-sorbed as potential cradles of life: phosphate to soil microorganisms Mineralogical evidence from the JANICE P.L. KENNEY 1*, REINER GIESLER2 Onaping Formation, Sudbury 1 AND PER PERSSON 1 1 G.G. KENNY * AND B.S. KAMBER 1Department of Chemistry, Umeå University, Umeå, Sweden, 1Department of Geology, Trinity College Dublin, Dublin 2, 2Department of Ecology and Environmental Science, Umeå Ireland (*correspondence: [email protected]) University, Umeå, Sweden (*correspondence:

[email protected]) A difference between terrestrial versus lunar and martian

impact basins is the possibility of submarine impacts. The Phosphorus (P) is an essential nutrient, limiting biomass thick meltsheet of a very large terrestrial impact acts as an production in many soils. The biogeochemical cycling of P is effective heat source below water-filled craters and can highly influenced by soil minerals, such as goethite, which has potentially sustain prolonged phreatomagmatic activity. The the ability to strongly sorb soluble phosphates. However, the Sudbury impact basin, Ontario, Canada, is the largest mechanisms by which soil microorganism take up sorbed accessible and well-preserved example of a submarine impact. phosphate is still not completely understood. Although it is mainly known for its magmatic sulphide Ni-Cu In this study we investigate whether soil microorganisms deposits, it also hosts a number of VMS-type base metal can use phosphate pre-adsorbed to goethite. To test this we ran deposits in the crater fill. Using observations from the fill, we experiments under four sets of experimental conditions; with highlight the potential importance of submarine meteorite or without P (+P/-P) and with or without glucose and nitrogen impact craters as a location for the development of the life on (+CN/-CN). The goethite was deposited as a mineral film on the heavily bombarded early Earth. BaF slides, after which the soil (clay-rich oxisol from South 2 We report the discovery of monocrystalline igneous quartz Africa), was deposited onto the goethite films. Prior to in the Onaping Fm. of the Sudbury crater fill – a complex unit addition to the goethite layer, half the soil was amended with composed of both the immediate fall-back of brecciated glucose and ammonium sulphate (2.0 and 0.3 g per g of soil impact material and also later-formed igneous rocks. The organic matter, respectively). crystallisation temperatures of the quartz grains have been The experiments were monitored over 13 days using FT- calculated by applying the titanium-in-quartz thermometer to IR microspectroscopy. During this time it was found that there titanium contents obtained by LA-ICP-MS. was no significant growth of microorganisms from the soil This finding provides support for continued in-crater onto the goethite mineral film in both cases where C and N igneous activity after the initial impact (e.g. [1]), and thus were not amended to the soil (-CN). However, in both cases highlights the potential of submarine impact craters as sites where C and N are amended to the soil (+CN) we see where life might have emerged. Submarine Hadean impacts microbial growth. When there is no P added to the mineral were likely common (e.g. [2]) as there is evidence for a liquid film (+CN/-P), we see only minimal growth of yeast cells hydrosphere at this time (e.g. from abundance of halogens; close to the soil deposition site. When there is P added to the [3]). From an emergence of life point of view, submarine mineral film (+CN/+P) we see significant fungal hyphae craters are contained, confined bodies of water surrounded by growing out onto the goethite within 6 days of incubation. The highly friable rock, supporting a very high nutrient load. In FT-IR microspectroscopy results show distinct differences in addition, the hydrothermal processing of this fluid at volcanic the goethite near the fungal hyphae. These results show that vents was an effective factory for creating complex precursor goethite-sorbed P is bioavailable and can greatly affect the soil molecules. Interestingly, the upper half of the Onaping Fm., microbial growth. like the overlying sedimentary Onwatin Fm., is rich in isotopically light [4] reduced carbon of possibly biologic origin (e.g. [5]).

[1] Grieve et al. (2010) MAPS 45, 759-782. [2] Furukawa et al. (2009) Nat. Geosci. 2, 62-66. [3] Kramers (2003) Precamb. Res. 126, 379-394. [4] Whitehead et al. (1990) Chem. Geol. 86, 49-63. [5] Avermann (1994) GSA Special Paper 293, 265- 274.

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Investigation of fungal decomposition Preliminary evaluation of trace of leaf lignin using synchrotron hydrocarbon speciation and infrared microspectroscopy abundance as an exploration tool for J.L. KERR1, D.S. BALDWIN2, M.J. TOBIN3, L. PUSKAR3, footwall-style sulfide ore, Sudbury G. REES2 AND E. SILVESTER1* Igneous Complex, Ontario, Canada 1 La Trobe University, Australia (*correspondence: 1 2 MITCHELL J. KERR * AND JACOB J. HANLEY [email protected]) 2MDFRC, La Trobe University, Australia 1Saint Mary’s University, Halifax, NS. B3H 3C3 3The Australian Synchrotron, Australia (*correspondence: [email protected]) 2Saint Mary’s University ([email protected]) Fungi are a major decomposer group in the aquatic carbon cycle, and are one of few groups though to be capable of The North Range of the Sudbury Igneous Complex (SIC) breaking down woody (lignified) tissue [1]. Here we have hosts footwall-style Cu-Ni-platinum group element (PGE)-rich used synchrotron Fourier tansform infrared (S-FTIR) sulfide deposits of predominantly magmatic origin but that microspectroscopy to study the interface between fungal tissue have been influenced by multiple syn- and post-magmatic and lignified leaf tissue (xylem) in two eucalypt species (River hydrothermal events. The composition of reduced carbonic Red Gum and Snow Gum) during aquatic decomposition. phases (unsaturated and saturated hydrocarbons, C1 to C6) in Aquatically decomposed River Red Gum leaf samples fluid inclusions within the matrix of Sudbury breccia, a rock show strong depletion of lignin-bound carbohydrate unit that is permeable to circulating volatiles and that immediately adjacent to the fungal tissue, spatially correlated commonly hosts footwall-style Cu-Ni-PGE deposits, has been with oxidation (de-polymerisation) of the lignin framework investigated by in-line rock-crushing gas chromatography. [2]. This observation has now been replicated with Snow Gum This was done on samples from zones of breccia that are leaf samples (Figure 1 (a-c)) and investigated at even greater known to contain economic footwall sulfide deposits and resolution using a synchrotron-coupled Focal Planar Array zones barren of such deposits. Subtle but strategically (FPA)-FTIR spectrometer (Figure 1(d)). S-FPA-FTIR offers significant differences have been found in the composition and sub-micron spatial resolution and can probe more subtle abundance of bulk hydrocarbons that are released from spatial changes in leaf chemistry at the fungal interface. mineralized and barren breccias when fluid inclusions are opened. These findings include: (i) statistically higher average abundances of light, saturated hydrocarbons (C1-C4) in mineralized, embayment-associated footwall packages than in breccia from barren environments (maximum difference of approx. half an order of magnitude for propane abundances; mol/g rock), and (ii) no statistically significant differences in average unsaturated hydrocarbon abundances between the two breccia environments, but differences are present when considering the spatial variations of hydrocarbons within the mineralized breccia package itself relative to massive sulfide mineralization. Additionally, samples of breccia and quartz (from mineralized alteration assemblages) from PGE-rich environments significantly deviate from expected hydrocarbon Figure 1.(a) Bright field image of Snow Gum vein; (b) S- signatures and are considerably more enriched in unsaturated FTIR map of fungi-xylem interface; (c) line scan across hydrocarbons. It is suspected that PGE, particularly Pt, play a interface; (d) S-FPA-FTIR map of fungi-xylem interface. direct role in the catalytic dehydrogenation of saturated, into unsaturated hydrocarbon species in hydrothermal [1] Floudas et al. (2012) Science 336, 1715-1719. [2] Kerr et environments. These findings strongly suggest that fluid al. (2013) PLOS ONE 8(4), doi:10.1371/journal.pone. hydrocarbon signatures should be taken into consideration 0060857 when exploring for Cu-Ni-PGE-rich footwall-style ore bodies as a supplemental criterion to traditional visual and geochemical approaches.

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Coprecipitation: Mechanisms and Arsenate adsorption by akaganéite quantitative models M. KERSTEN1* AND N. VLASOVA2 M. KERSTEN1 1Gutenberg-University, Mainz 55099, Germany 1 (*correspondence: [email protected]) Gutenberg-University, Mainz 55099, Germany 2NAS Institute of Surface Chemistry, Kiev 03164, Ukraine (*correspondence: [email protected])

The %-type is the last among the FeOOH polymorphs for Coprecipitation is referred to as the simultaneous removal which there is yet no multi-site surface complexation of a trace with host constituent in the aquatic environment. (MUSIC) model, which requires information about the proton Solid-solution aqueous-solution (SSAS) equilibrium models affinity of the various types of surface groups. Enigmatic have been developed to close the often huge solubility gap in behavior during acid-base titrations where protons are co- the continuum between surface complexation and single- released from tunnel sites renders interpretation a challenge component precipitation of trace elements [1]. These models for akaganéite. In batch experiments, our akaganéite sample were originally development to explain incongruent show a CIP at pH 7.7. However, the apparent surface charge is dissolution and secondary mineral formation in weathering not equal to zero at this CIP but shows an offset by -0.25 reaction path modeling including carbonates and clay minerals C/m2, obviously due to the excess tunnel site protons. We [2,3]. They became of major interest, however, in long-term propose to monitor the chloride exchange with at least two environmental assessment of radionuclide repositories, in days batch equilibration time (Fig. 1). The chloride is not particular for evaluation of near-field geochemical barrier significantly re-adsorbed on outer surfaces and may be used to performance. Such barrier concepts include radionuclide co- monitor and quantify the excess tunnel HCl release. The thus precipitation with more or less long-term stable minerals like corrected & vs. pH curves become sigmoidal and can be fitted sulfates [4], carbonates [5], and silicate hydrates [6]. More 0 to parameterize a reliable surface complexation model based recently, the SSAS modeling concept became also of interest on recently published site densities for singly and triply to manage enhanced geogenic radium leaching [7], which may coordinated hydroxyl surface groups [1]. This provides a occur during deep geothermal resource exploitation or sound basis to set up CD-MUSIC adsorption models for hydraulic fracking for shale gas recovery. This keynote arsenate and competing oxyanions. Furtheron, breakthrough contribution will give an overview on the most promising curves of akaganéite based GFH fixed-bed adsorber column applications in geochemical engineering, as well as model units can be calculated for different groundwater chemistry concepts spanning from the classical Lippmann equation using a homogeneous surface diffusion model and Langmuir approach for drawing aqueous solubility diagrams of binary adsorption isotherms predicted by the surface complexation solid solutions [8] to the most advanced non-ideal multi-site model. sublattice concept [9,10].

[1] Kersten & Kulik (2005) In: Cornelis et al. (eds.) Handbook

of Elemental Speciation, Vol. 2. Wiley, Chichester, pp. 651-

689. [2] Glynn et al. (1990) Geochim. Cosmochim. Acta 54,

267-282. [3] Zhu et al. (2010) Ceochim. Cosmochim. Acta 74,

3963-3983. [4] Aimoz et al. (2012) Appl. Geochem. 27, 2117-

2129. [5] Kulik et al. (2010) Phys. Chem. Earth 35, 217-232.

[6] Gaona et al. (2012) Appl. Geochem. 27, 81-95. [7]

Fernández-González et al. (2013) Geochim. Cosmochim. Acta

105, 31-43. [8] Kersten (1996) Environ. Sci. Technol. 36,

2919-2925. [9] Rozov et al. (2011) Clays Clay Min. 59, 215- 232. [10] Kulik (2011) Cem. Concr. Res. 41, 477-495.

Figure 1: Tunnel chloride ion release vs. pH at different

NaNO3 electrolyte concentrations

[1] Kozin & Boily (2013) J. Phys. Chem. C117 (Article ASAP, DOI: 10.1021/jp3101046).

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Measuring the isotope fractionation Geochemical fingerprinting of of denitrification in permeable corundum from Fiskenæsset, sediments Greenland A.J. KESSLER1*, L.A. BRISTOW2, M.B. CARDENAS3, NYNKE KEULEN1 AND PER KALVIG1 2 2 1 R.N. GLUD , B. THAMDRUP AND P.L.M. COOK 1 Geological Survey of Denmark and Greenland (GEUS), Øster 1Water Studies Centre and School of Chemistry, Monash Voldgade 10, 1350 Copenhagen, Denmark. [email protected], Univ., Melbourne, Australia (*correspondence: [email protected] [email protected]) 2Nordic Centre for Earth Evolution and Institute of Biology, Since the late 1960s it has been known that pink and red Univ. Southern Denmark, Odense, Denmark corundum occurs in the area near Fiskenæsset 3Department of Geological Sciences, Univ. Texas at Austin, (Qeqetarsuatsiaat) in southern West-Greenland. Corundum is Austin, Texas hosted in the Fiskenæsset complex, which is part of the Archaean basement of the North Atlantic Craton. To date, c. Permeable sediments cover a significant proportion of the 40 corundum localities are known in the area – a few localities continental shelf, yet denitrification and other redox yield stones of gem quality. The most promising locality, biogeochemistry in these sediments remains poorly Aappaluttoq, is likely to be mined in the near future by the understood. This is mostly due to the complex advective Canadian company True North Gems. transport patterns in such sediments [1]. This study is a first attempt to find geochemical Despite benthic denitrification accounting for a significant characteristics that can be used to tie the Greenlandic rubies to oceanic nitrogen sink, no isotope effect (!) associated with their area of origin. Here, we present laser ablation-ICP-MS denitrification in permeable sediment has been published. trace element geochemistry data and oxygen isotope Rather, most models assume an isotope effect of zero for this investigations on samples from the Fiskenæsset area and other process, based on work solely in cohesive sediments [2]. known localities in Greenland (Storø, Maniitsoq, Kapisilit, However, permeable sediments could potentially impose and Nattivit). substantial fractionation if nitrate is only partly comsumed Trace element investigations of corundum grains separated during advective transport through the sediment. from 21 handspecimen from ten localities in the Fiskenæsset We performed flow-through column experiments to complex were performed on 24 different elements with LA- quantify the organism-scale nitrate N isotope effect (!cell) SF-ICP-MS at GEUS, however most of them were not during benthic nitrate reduction, the first step of denitrification detected. Our investigations of the Greenlandic corundum using sand from Kerteminde, Denmark. The value of !cell was were concentrated on the elements Mg, Si, Ti, V, Cr, Fe, and 18 ± 1‰, consistent with !cell values reported in cohesive Ga. Results are compared with data from other localities in sediments [3]. Greenland and from internationally, well-known, ruby In order to estimate the apparent isotope effect (!app) on occurences. Samples from Fiskenæsset show a considerably the overlying water, a computational model was employed to higher amount of Cr (up to 14000 ppm) than found in simulate denitrification and associated N isotope fractionation measurements on samples from other areas in Greenland and in a rippled permeable sediment under varied conditions. literature data on most international samples. The Fiskenæsset Simulations indicate that !app varies between 2‰ and 5‰, rubies are relatively rich in Fe and Si, but relatively poor in Ti driven by advection of partially denitrified nitrate out of the and Ga, while V and Mg do not show very distinctive values sediment. compared to samples from other areas. This work has significant implications for the global Oxygen isotope composition measurements were marine nitrogen isotope budget, and may help to explain performed on 11 samples from Greenland at the University of discrepancies between modelled and measured ocean isotope Lausanne, Switzerland using an isotope ration mass signatures [2]. spectrometer. Samples from the Fiskenæsset region yield ,18O values between 1.62 and 4.20‰, which is low compared to the [1] Boudreau et al. (2001) EOS Trans. Am. Geophys. Union other areas in Greenland and world-wide. 82, 133-136. [2] Altabet et al. (2007) Biogeosciences 4, 75-86. The two methods discussed here are efficient in [3] Lehmann et al. (2007) Geochim. Cosmochim. Acta; 71, characterising the Fiskenæsset rubies. More independent 5384-5404. methods are necessary for a high-confidence fingerprinting.

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The study of polymorphs of Wordian The Role of Swamps in Formation of Amb Formation, Salt Range of Chemical Composition of River Western Pakistan in relation to Waters in Western Siberia Geochemistry J.A. KHARANZHEVSKAYA1, E.S. IVANOVA1*, 1 1 1 2 E.S. VOISTINOVA AND A.A. SINYUTKINA SAJJAD KHAN AND NAGHMA HAIDER 1Siberian Research Institute of Agriculture and Peat, Tomsk, 12 Geoscience advance Research Laboratory, Geological 634050 (*[email protected], [email protected]) Survey of Pakistan, Islamabad ([email protected])

The landscape is characterized by the wide spread The Amb Formation of Wordian age (Martmann, 2003) occurrence of raised oligotrophic swamps with the dominant was investigated for geochemistry. Twenty six samples were role of the ridge-pool and ridge-lacustrine-pool systems in collected from out crop for geochemistry at Zaluch Nala of combination with areas of riams–oligotrophic complex piny- Western Salt Range of Pakistan. suffruticous-sphagnous swamps and narrow bands of The results of the collected samples displayed major transitional swamps along the periphery of watershed areas. oxides of K O, P O3, Na o, MgO, Al O3, TiO , Fe O , FeO, 2 2 2 2 2 2 3 Geographical coordinates of the area are N56"03'07" E82"22'42". P O , SiO & C (with addition of H O). 2 5 2 2 Water samples for the analysis were taken within the basin To find the number of polymorphs of twenty six out crop of the Klyuch River in the most typical swampy sample of thirty grams was processed one by one. geobiocoenoses: piny-suffruticous-sphagnous with a 10-15 The productivity level of each sample was controlled by meter pine (point 2); piny-suffruticous-sphagnous with a the comparative amount of CaO, MgO and C (both inorganic scrubby pine (point 3); sedge-sphagnum (point 5). and organic).

Fifty six polymorphs species of thirty two were reported. Mire

!

!" Among these, eleven genera and nineteen species belong to River t

the Klyuch Index est. Russia est. #$%&!(

trilete, six genera and nineteen species to monosaccates, twele #$%&!' conc. (MAC) Max. allowable P Po in genera and twenty four species to bisaccates. Pollens Colpates P (two species) and acolpate (one species) were also reported #$ 6.5–8.5 6.5 4.4 3.8 4.1 from the samples. mineralization 1000 72.0 30.2 25.1 15.1

+ NH4 1.9 3.8 6.7 6.0 3.5

COD,mg%/dm3 15 122.2 262.4 157.7 162.2

humic acid - 6.7 8.9 9.5 5.5

)*+,$-!.-$/ - 41.1 66.6 53.1 43.3

Fetotal 0.3 2.5 2.9 1.8 1.3 Table: Chemical composition of swamp and river waters for 2006 – 2011 years of research, mg/dm3 The chemical composition of swamp waters of area under study is an averaged sample of the one-meter peat mire layer and represents biochemical and biological processes occurring in them. The content of water-soluble carbon in the water under study at its maximum values varies from 106.6 mgC/dm3 in point 2 to 63.4 mgC/dm3 in point 5. This index for river waters falls by 3-5 times. Due to that fact that the intensity of the peat decomposition processes in a high bog increases from the center to the periphery (from point 5 to point 2), the content of all components of the geochemical + runoff increases in this direction. A high content of NH4 (5.4 mg/dm3) is observed in swamp waters: it almost three times exceeds the maximum allowable concentrations. The + content of NH4 in river water is one and a half time lower –3.8 mg/dm3. It should be also noted that the value of dichromate oxidizability in the swampy area 25 times exceeds MAC, as compared with river waters, where this index is exceeded only by 11 times. Thus, for a number of natural reasons, swamp and river waters contain high concentrations of organic and biogenic substances, the content of which in river waters is several times lower. www.minersoc.org DOI:10.1180/minmag.2013.077.5.11

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Isotopes of oxygen and hydrogen in Low thermal Northern Dvina iodine natural waters from NE of Asia water field: History of prospection N.A.KHARITONOVA, G.A.CHELNOKOV AND I.V.BRAGIN and perspectives of development 690022, Russia, Primorsky region, Vladivostok, Prospect 100- I.L. KHARKHORDIN1*, F.G. ATROSCHENKO1 letya 159, Far East Geological Institute Russian Academy AND V.V. NAZIMA1 of Science ([email protected]) 1 Geostroyproekt Ltd., 22-th Line, 3, St. Petersburg, 199106,

Russia (*correspondence: [email protected]) Isotopes of oxygen and hydrogen are ideal natural tracers 2Geostroyproekt Ltd., 22-th Line, 3, St. Petersburg, 199106, for describing phenomena of the water cycle so they are 18 2 Russia ([email protected]) constituents of the water molecule. The , O and , H in 3 waters violently rely on meteoric processes, and so infiltration Geostroyproekt Ltd., 22-th Line, 3, St. Petersburg, 199106, into specific sediments leads to a characteristic isotopic Russia ([email protected]) signature which tags as the origin of groundwater as surface water–groundwater interactions. 3H is the most attractive Iodine water field is located at Northern Dvina River radioisotope for studying the principles of water circulation in basin, north-west of European part of Russia [1]. Uncommon nature so it is a perfect water tracer. The first particular data features of the field are as follows. about the content of stable and radiogenic isotope of oxygen 1) Depth to iodine water containing aquifer is only 100- and hydrogen in natural water of region were presented in 120 meters. some studies (Chudaeva et al., 1999; Kharitonova et al., 2) Iodine water field was formed at low temperature 2 3 18 2012), however simultaneous measurements , H, H and , O conditions (below 10 oC). were never performed for this area. 3) The source of iodine is organic fosils associated with The aims of this study are to define local meteoric waters marine clays (QIIImk) [2]. This clays was consolidated by ice line of Russian Far East, to identify the forming conditions of shield, iodine water was espressed into upper part of padun various groundwater types of area using isotopic parameters aquifer (V ). and estimate residence time of groundwater basing on tritium pd At present study analysis of hydrodynamic and values. hydrochemical conditions of iodine water field was More than 120 samples of precipitation, seawater, surface water and groundwater were collected across territory of performed, the numerical models of groundwater flow and Russian Far East during last 7 years and then analyzed for iodine transport were created using MODFLOW-96 [3] and isotopic composition. Geochemical characteristics of these MT3DMS [4] computer codes. The main issues are: samples were published earlier (Chelnokov & Kharitonova, • the present day recharge through mikulinski clays is 2008). impotant for iodine water field existence due quarternary Our data let us conclude: time, it partly compensates iodine water discharge into 1. All studied groundwater is meteoric water and shift from Nothern Dvina River; GMWL for some spas is the result of water-rock-gas • resources of iodine water was estimated; interaction. Local meteoric water line for the southern part of • limiting factor of iodine water field exploitation is fresh Russian Far East can be determined by the equilibrium: water upconing from low part of padun aquifer; 18 ,D=7.6385#, O+3.96‰. Continental and lateral zonal • strategy for iodine water field exploitation was elaborated. distribution of stable isotopes on this territory is being observed. [1] Malov (1980) Vodnye Resursy, No. 2, pp. 66-76 (In 3 2.  

the universal increasing in H values in surface Russia). [2] Gurevich (1963) Izv. VUZov, Geologiya i water from ocean to inland
  

 

20 TU in razvedka, No. 7, pp. 123-125 (In Russia). [3] Harbauf & rivers of Amurskiy region, ~13 TU in rivers of Primorsky McDonald (1996) USGS, Open-File Report 96-495. [4] Zheng region and to ~5.5 TU in ones of Kuril Islands. Most of & Wang (1998) Contract Report SERDP-99, 239 p. studied groundwater, excluding brackish waters of Rechitza outlet, have short residence time (less 50 years).

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Provenance tracing of aerosols in the Mineralogy and origin of uranium South Atlantic Ocean using Pb and deposits from central Jordan Nd isotopes and select trace and rare HANI N. KHOURY earth elements Department of Geology The University of Jordan, Amman – 1 1 Jordan 11942 ([email protected]) R. KHONDOKER *, D. WEISS, T. VAN DE FLIERDT , 1 2 2 M. REHKÄMPER , R. CHANCE , A. BAKER , 3 3 3 Secondary uranium surficial mineralization is hosted by S. STREKOPYTOV , E. WILLIAMS AND J. NAJORKA travertine and calcrete in central Jordan [1]. The 1Dept. of Earth Sciences, Imperial College London, SW7 2AZ paleocirculating water in the combusted bituminous marl has , UK ([email protected]) oxidized the dissolved V4+ to V5+ and fixed the uranyl-ion as 2University of East Anglia, Norwich, NR4 7TJ, UK uranyl vanadate in strelkinite and metatyuyamunite. Carnotite 3Natural History Museum, London, SW7 5BD, UK was favored depending on the availability of K in solution. The uranyl vanadate minerals were precipitated from highly The atmosphere is an important pathway of delivering alkaline solutions during the dry periods after the precipitation nutrients to ocean surface waters. These nutrients can play a of the thick travertine deposits. vital role in marine biogeochemical processes and ultimately the global carbon cycle. However, our understanding of the atmospheric inputs and their influences on marine micronutrient cycles is limited, particularly in the South Atlantic, a region where models predict widely variable fluxes of micronutrients to the ocean from the atmosphere. Moreover, in reent years it has become clear that atmospheric emissions from cities and human activities, such as road traffic and industrial plant emissions, can significantly impact atmospheric inputs and thus alter micronutrient fluxes Figure 1: EDS results: UO3 vs V2O5 correlation of the to the ocean. Although air quality studies have been carried uranium minerals out for some cities bordering the South Atlantic Ocean, including São Paulo and Buenos Aires, the impact of Discussion of Results emissions from such cities on marine micronutrient budgets U and V are associated in the same mineral phases as has not been studied in detail. indicated in the figure above. The travertine is an evidence for Here, we present rare earth and selest trace element data as discharges of hyperalkaline groundwater in the past [1]. well as results from Pb and Nd isotope analysis of sediments, Oxidizing alkaline circulating water oxidized dissolved V4+ to volcanic ash, road dusts, aerosol filters and lichens from V5+, and mobilized uranium as uranyl complexes before the Patagonia, recent Cotopaxi, Chaitan and Puyahue volcanic precipitation of uranium vanadate minerals as strelkinite and eruptions, and the cities of São Paulo, Buenos Aires and tyuyamunite and carnotite. Johannesburg. All sites are potential atmospheric aerosol [1] Khoury (2012) Environmental and Earth Science. sources for the South Atlantic Ocean. The rare earth and trace 65:1909-1916. element concentration data and the isotopic results allow characterisation of the different source sites with adequate resolution to distinguish between South American and Southern African as well as anthropogenic and natural aerosol sources. This provenance information will be applied to interpret the first comprehensive geochemical data set (comprising rare earth, other trace element concentrations, and Pb, Nd isotope compositions) for aerosol filters collected in the South Atlantic Ocean at approximately 40° S during the UK GEOTRACES cruises D357 and JC068.

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Investigation of sediment Peat and sapropel as the sources of geochemistry in areas with elevated humus for the restoration of arsenic in groundwater of Matlab, degraded lands of the Amur region Bangladesh and Murshidabad, India (Far East, Russia) M.G. KIBRIA1, M. HOSSAIN2, P. BHATTACHARYA2, VARVARA KICHANOVA AND VALERY KICHANOV K.M. AHMED6, M. VON BRÖMSSEN5 , G. JACKS2, Institute of Geology and Nature Management FEB RAS, M.F. KIRK1, M.S. SANKAR1, K. TELFEYAN3, S. FORD1, Blagoveshchensk, Russia, ([email protected]) A. NEAL4, T.J. HAUG3, K. JOHANNESSON3

AND S. DATTA*1 The natural ability of soil to produce biological products 1Kansas State University, Manhattan, KS, USA decreases each year. The problem of the land resources has ([email protected]) become one of the largest global problems. It is connected 2KTH Royal Institute of Technology, Stockhom, Sweden with the growth of world population and, consequently, 3Tulane University, New Orleans, LA, USA decrease of sown area per capita; increased area of degraded 4Virginia Tech, Blackburg, VA, USA and disturbed soils. In particular, in the Amur region of 5Ramböll Sweden AB, Stockhome, Sweden degraded and disturbed lands is increasing every year. Also 6University of Dhaka, Dhaka, Bangladesh because of the lack of organic fertilizers, that has decreased from 63 kg/ha in 1995 to 5 kg/ha in 2011 [1]. The specific The assessment of the incidence of arsenic (As) and other weight of fertilized area of organic fertilizers in the total sown oxyanions forming trace elements was examined in Bengal area in 1995 was 0.5 %, in 2011 – 0.09%. Only 2% of the soils delta floodplain groundwaters from Matlab Upazila, of the region (660 thousand hectares) are characterized by Bangladesh and Murshidabad District, India. These field areas high soil fertility, where humus horizon reaches 20 - 40 cm 2 cover an area of about ~400km (von Brömssen et al. 2008) sometimes 50 cm. Humus content in the upper part of the soil 2 and ~438km (Datta et al. 2011) respectively. The study is from 4 up to 8%. The annual loss of humus soils of the focuses on the sediment geochemistry and adsorption behavior Amur region is 0.45 tons per ha. At the same time with the of oxidised red brown and reduced grey sediments and their loss of humus, the destruction of soil structure is mentioned, respective capacity to attenuate As. Sediment cores were soil compaction lead to a deterioration of its physical and collected at regular intervals within depth of 125m in Matlab chemical characteristics [2]. Soil restoration is possible with and ~40m in Murshidabad. Detailed sequential extractions of the introduction of organo-mineral fertilizers produced from sediments indicate relatively low amount of As released from peat and sapropel deposits of the Amur region. The region oxidized sediments. The study describes the lithofacies, possesses significant reserves of peat and sapropel. The total mineralogy and results of adsorption experiments on the area of deposits of sapropel, in the border of the industrial sediments from two sites and establishes a relationship depth of the deposits is 1493 ha. The total content of useful between aqueous and solid phase geochemistry along the (1553 g/t) and harmful (436 g/t) elements in sapropels of various depths of the aquifers. DNA recovered from Matlab Amur region in comparison with other sapropels and soils of core samples averaged 450ng/g from course-grained samples Russia has the highest - lowest values [3]. Peat general and 800ng/g from fine-grained samples. Sequencing of the reserves of the Amur region include 600 deposits. The total DNA is utilised to identify microbial communities and their projected resources of peat, including reserves of explored role in the biogeochemical processes controlling the fields, are 158.5 million tonnes, with 40% of the conditional groundwater As levels. Synchrotron aided µXANES and humidity. Total area of the deposits is 5663.5 km2 [4]. These µXRD studies conducted for solid state As and S speciation in reserves are sufficient to restore the fertility of the soils of the the core samples at different depths indicate the occurrences of region. hotspots of As differently distributed in red-brown and grey sediments in both these sites. The projected outcome is to [1] Diachenko et al. Amur statistical Yearbook of 2012: the incorporate detailed sediment characteristics of the different Statistical collection. Blagoveschensk: Zeya. 2012. 602. [2] aquifers including all possible color variations available in Pavliuk (2005) Geography of Amur region: training manual. exploited depths within Matlab and Murshidabad respectively. Blagoveschensk: BGPU. 364. [3] Alekseiko et al. (2003) Porewater from Matlab abstracted from oxidized reddish Sapropel of the Amur region: properties, production and use. sediments, in contrast to reducing greyish sediments contain Blagoveshchensk: Dalnauka. 210. [4] Vasilev et al. Mineral- substantially lower amount of dissolved As and can be a raw material base of the Amur region at the turn of the source of safe water. This study has wider implications century. (2000). Blagoveshchensk: Zeya. 168. towards broad scale regional approach for As mitigation that incorporates the enquiry of efficiency of sediment color as a simple and easy tool for identifying safe aquifers in major As prone areas. [1] Datta S. et al (2011). Geophysical Research Letters. 38.2 [2] von Brömssen M. et al (2008). Journal of Contaminant Hydrology 99.1: 137-149.

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Ethanol Variability in Rainwater and Factors affecting fractionation of Ni its Impact on the Chemistry of the and Cr in ultrabasic soils from Troposphere southwestern Poland R.J. KIEBER1, J.D. WILLEY1, G.B. AVERY1, J. KIERCZAK1, A. P3DZIWIATR1, J. WAROSZEWSKI2, R.N. MEAD1, F.F. GIUBBINA2 AND M.L. CAMPOS2 AND R. TYSZKA2 1University of North Carolina Wilmington, Department of 1University of Wroc&aw, Institute of Geological Sciences, Chemistry and Biochemistry, Wilmington, NC USA Cybulskiego 30, 50-205 Wroc&aw, Poland; 28403 (*correspondence: [email protected]) [email protected], [email protected] 2Departamento de Química, Faculdade de Filosofia, Ciências e 2Wroc&aw University of Environmental and Life Sciences, Letras de Ribeirão Preto, Universidade de São Paulo, Av Department of Soil Sciences and Environmental Bandeirantes, 3900, 14040-901 Ribeirão Preto, SP, Brazil Protection, CK Norwida 25/27, 50-375 Wroc&aw; [email protected], We present the first detailed analysis of the occurrence [email protected] and variability of ethanol in precipitation collected in coastal North Carolina (NC) USA and at the Universidade de São Weathering of ultrabasic rocks, naturally enriched in some Paulo, Brazil. Concentrations ranged from 23 nM to 908 nM trace elements (e.g., Ni and Cr) leads to the formation of soils with a volume weighted average (VWA) concentration of 193 having distinctive properties caused primarily by a specific nM at the NC collection site (n=52). The VWA concentration chemical composition of parent rocks. The parent ultrabasic of ethanol is more than an order of magnitude higher (2.7 µM) rocks commonly cause infertility of serpentine soils, which in Brazilian rain (n=40) relative to the NC site with the highest results from the low ratio of calcium to magnesium, and the concentrations exceeding 10 µM. There was a great deal of high content of Ni and Cr in the parent rock and the soil. variability in the abundance of ethanol between rain events at We have analysed shallow and well drained soils both sites driven primarily by temporal and air mass back (Leptosols) developed on a variety of ultrabasic rocks, from trajectory influences. hornblende peridotite through partially serpentinized peridotite The presence of significant quantities of ethanol in to proper serpentinite. The Ni and Cr concentrations in soils precipitation has important implications for fundamental decrease upwards in analysed pedons and range from 72 to properties of atmospheric waters including the oxidizing and 2350 ppm for Ni and 160 to 3500 ppm for Cr. Studied acid generating capacity of the troposphere, photochemical ultrabasic soils have similar physicochemical charcteristics smog formation, as well as indirect effects on solar radiative (e.g., slightly acidic to neutral pH, clay content approximately transfer and light attenuation. Also, because rainwater is an 10% etc.) however mineralogical composition seems to be important mechanism by which CH3CH2OH is transported strongly influenced by different types of ultrabasic roks. Soils from the atmosphere to surface waters, greater wet deposition developed on peridotites have more complex mineralogy and of ethanol from increasing biofuel usage could dramatically contain important proportions of swelling phases (smectite, influence the biogeochemistry of receiving watersheds which vermicullite, interstratified chlorite/smectite) whereas only typically have concentrations one to two orders of magnitude traces of swelling phases were detected in soil derived from lower than rainwater. serpentinite. Fractionation of Ni and Cr, estimated using the 0.05 M EDTA, aimed to determine the easily mobilizable proportions of these elements. In all studied soils proportions of Ni-EDTA extractable (5-42% of total Ni) are larger than proportions of Cr-EDTA extractable (1-7% of total Cr). The highest proportions of EDTA extractable fractions of both Ni and Cr were noted in topsoil horizons of all studied soils. Soils developed on peridotites have hihger proportions of Ni-EDTA extractable than soils derived from serpentinite. Our study shows that type of parent rock strongly influence fractionaction of Ni and Cr in ultrabasic soils, however other factors (e.g., organic matter content, local climatic conditions etc.) should also be taken into account.

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Residence times of ancient water in Can radioactive cesium be used as a Outokumpu (Finland) revealed by hydrological tracer for crater lake noble gases study? R. KIETÄVÄINEN1*, L. AHONEN1, I.T. KUKKONEN12, YOSHIKAZU KIKAWADA1*, AYA OKAWA1, S. NIEDERMANN3 AND T. WIERSBERG3 KO NAKAMACHI2, TERUYUKI HONDA2, TAKAO OI1 1 1 AND KATSUMI HIROSE Geological Survey of Finland, Espoo, Finland (* correspondence: [email protected]) 1Sophia Univ., Tokyo 102-8554, Japan. 2University of Helsinki, Department of Physics, Helsinki, (*correspondence: [email protected]) Finland 2Tokyo City Univ., Tokyo 158-8557, Japan. 3Deutsches GeoForschungsZentrum, Potsdam, Germany The Fukushima Dai-ichi Nuclear Power Plant (FDNPP) Deep saline groundwaters in the Precambrian crystalline accident in March 2011 resulted in serious radiological bedrock of Outokumpu, eastern Finland, host ecosystems that contamination in areas adjacent to the plant. Meanwhile, may be remarkably old. Based on water stable isotopes, these radioactive cesium originated from the accident was detected waters have been suggested to be recharged during climatic over a wide range of the northeastern half of Honshu, the main conditions up to 100C warmer than at present, which would be island of Japan. In this study, we discuss the possible use of indicative of residence times on the order of tens of millions of radioactive cesium newly deposited on the ground from the years [1]. FDNPP accident as a hydrological tracer for crater lake study In order to better define residence times, concentrations of in Japan, taking crater lakes of the Kusatsu-Shirane volcano, radiogenic (4He, 40Ar), nucleogenic (21Ne) and fissiogenic located about 240 km west-southwest from the FDNPP, for (134Xe, 136Xe) noble gas isotopes were measured in water and example. Water budget of crater lakes, especially on active gas samples covering a depth range from 500 m to 2450 m in volcanoes, is very complicated, because most of them are the Outokumpu Deep Drill Hole. closed ones. The budget and circulation of water in active The observed vertical variation of geochemistry and crater lakes provide very important information connected to microbiology together with hydrogeological and geophysical the hydrothermal activities and subsurface structures of the measurements indicate negligible fluid flow in the bedrock. volcanoes. Furthermore, more than 99 % of the air-corrected He is crustal The Kusatsu-Shirane volcano with three crater lakes on its in origin with an average 3He/4He ratio of 1.5 · 10-8, and no summit area is one of the most famous active volcanoes in concentration gradient indicative of diffusive flux through the Japan. Yugama, the largest and deepest one among the three is crust was observed. Therefore an in situ accumulation model well known as an active crater lake filled with water of high [2] using average values for porosity, density and salinity and strong acidity. We determined the contents of 134 137 concentrations of radioactive elements (U, Th and K) in the radioactive isotope of cesium, Cs and Cs, and the stable 133 Outokumpu deep drill core [3] was applied to calculate isotope, Cs, and their content ratios in waters of three crater residence times. lakes of the Kusatsu-Shirane volcano collected in 2012. The 134 137 Residence times between 12 and 45 Ma are indicated by obtained activity ratio of Cs/ Cs revealed that the the 4He accumulation. Similarly, 21Ne and 40Ar ages fall radioactive cesium released by the accident has reached the between 5 and 70 Ma whereas 134Xe and 136Xe indicate longer summit area of the volcano. However, the concentration of residence times. The results thus confirm the existence of radioactive cesium was not uniform among the three crater ancient groundwaters in Outokumpu. This should be taken lake waters. This ununiformity is most probably ascribable to into account when rates of microbial metabolism, adequacy of the difference in the water supply and circulation system substrates, and biological cycling of elements within the deep among the three. This suggests that the temporal changes in subsurface are considered. the concentration of radioactive cesium and their concentration ratios against the stable isotope can provide us [1] Kietäväinen et al. (2013) Appl. Geochem. 32, 37-51. [2] useful information to clarify the water budget in the summit Torgersen (1980) J. Geochem. Explor. 13, 57-75. [3] area of the Kusatsu-Shirane volcano. In this context, we are Kukkonen (2011) Geol. Surv. Finl. Spec. Pap. 51. now investigating the temporal changes in the concentrations of 134Cs, 137Cs and 133Cs in the crater lakes.

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High-resolution imaging and Investigating the role of noble gases quantification of Au in sulphide as tracers for CO2 storage minerals using NanoSIMS R. KILGALLON1*, S.M.V. GILFILLAN1, 1 1 1 1 C.I. MCDERMOTT AND K. EDLMANN M.R. KILBURN * AND R. LIU 1 1 School of GeoSciences, The University of Edinburgh, King’s Centre for Microscopy, Characterisation and Analysis, The Buildings, Edinburgh, EH9 3JW (*correspondence: University of Western Australia, Crawley, 6009, Australia [email protected]) (*correspondence: [email protected])

The capture and long term storage of carbon dioxide (CO ) With its high lateral resolution and high sensitivity, 2 in the subsurface is one of the most promising ways of NanoSIMS is the ideal tool for mapping the distribution of mitigating the current level of anthropogenic CO being trace elements within sulphide minerals. In Carlin-type 2 released to the atmosphere. A major issue surrounding long deposits, Au is typically present as narrow rims along the term storage is the risk of failure of CO containment. edges or within the matrix of the sulphide grains. The low 2 Developing a monitoring strategy which would allow early concentrations of Au in solid solution with the sulphide are detection of CO leakage would enable measures to be notoriously difficult to detect by most in situ techniques, such 2 implemented to mitigate and remediate the impact of as EPMA, and is thus commonly referred to as ‘invisible containment failure. Experiments and modelling results have gold’. As SIMS is very sensitive to Au, and other commonly shown that noble gases have the potential to act as early associated trace elements such as Te and Sb, NanoSIMS warning tracers for CO arrival [1]. Previous studies highlight provides the ability to image these elements with sub-micron 2 the importance of understanding the transport processes resolution. At such scales it is possible to investigate the involved for calculating tracer arrival times [2]. intricate relationships between the Au and associated elements This study uses specially constructed equipment for to help determine the nature and evolution of the Au-bearing experiments to determine factors affecting the transport of fluids [1]. Furthermore, through the development of ion- noble gases relative to CO . Initial pipeline experiments using implanted standards, it is possible to quantify the 2 argon and CO have determined the parameters required for concentration of Au directly from the NanoSIMS secondary 2 complete mixing of the gases. ion images. Preliminary data also show the potential to obtain We intend to examine conservative transport processes S isotope measurements from the same regions of interest. such as the advection, dispersion and diffusion of noble gases

relative to CO2 in porous media. The existence of any non- conservative transport processes such as sorption and dissolution are also considered. These data are compared to results from core flow experiments in order to determine the

relationship between CO2 and noble gases on rock core samples. The choice of sample used for experiments are low permeability porous sandstones.

Preliminary data will establish how noble gases and CO2 behave in porous media during migration. Upscaling of the initial results will determine how effective different noble gases could be at acting as early warning tracers in a real world storage site.

[1] Cohen et al. (2013) International Journal of Greenhouse Gas Control 14, 18-140. [2] Carrigan et al. (1996) Nature 382, 528 – 531. Figure 1: Secondary ion images showing the distribution of S, As, Te and Au in a pyrite grain from a Carlin-type deposit.

[1] Barker et al. (2009) Econ. Geol. 104, 897-904.

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Antimony in hydrothermal chimneys Statistical Approach and Heavy of Kolumbo shallow-submarine vent Metal Analyses of Konyaalti field (Santorini, Greece) (Antalya, Turkey) Coast Water S.P. KILIAS1*, A. GODELITSAS1, P. GAMALETSOS12, S. KILIC1, F. YALCıN 2 AND M.G. YALCıN3 * ERTZIMEKIS1 OMIKOU1 ÖTTLICHER2 T.J. M , P. N , J. G , 1Akdeniz University, Ar-Ge Lab, 07058, Antalya, Turkey, R. STEININGER2, A. ARGYRAKI1, M. GOUSGOUNI1 1 ([email protected]) AND D. PAPANIKOLAOU 2 Akdeniz University, Department of Mathematics, 07058, 1University of Athens, School of Science, 15784 Zographou, Antalya, Turkey, ([email protected]) Greece (*correspondence: [email protected]) 3Akdeniz University, Department of Geological Engineering, 2KIT, ANKA Synchrotron Radiation Facility, Hermann-von- 07058, Antalya, Turkey, ([email protected]) Helmholtz-Platz 1, 76344 Eggenstein, Germany The aim of the study conducted on Konyaalti (Antalya) Polymetallic sulfide/sulfate chimneys, collected during the coast, which is one of the important coasts of Turkey, is to NA014 expedition of the E/V Nautilus (2011) from the determine the heavy metal (Ni, As, Cr, Pb, Cd, Cu) contents in Kolumbo shallow-submarine hydrothermal field (Santorini, the seawater along the coastline. In this study samples were Greece), are exceptionally enriched in antimony (up to 2.2 taken systematically from 35 different coastal locations. wt%) [1]. SEM-EDS data show that colloform banded trace- According to the EPA method 3005A(EPA 3005A, 1992), element-rich zoned possibly biogenic Fe-sulfides show pre-treatment was applied. The fact that the seawater is rich in oscillatory zoning; zones “bright” in BSE are enriched in Sb the elements such as Na,Ca,Cl posed a problem of (up to 11 wt%), and/or Pb, As and Si. However, preliminary contamination. Coal gas was used to prevent the SR +-XRF elemental maps confirmed that Sb is mostly contamination (e.g.40Ar+35Cl—75As).DRC(Dynamic Reaction concentrated in the core relative to rim (Fig. 1). Cell) method was applied firstly with %0.1 NaCl solution as being a matrix, then by spiking As so that it is to be 20 ppb into %0.1 NaCl solution. According to the recovery data, measurements were analyzed in the ICP-MS device by using EPA method 6020A(EPA 6020A, 1997). Calibration curve (R2) chart was drawn with the standards of 2, 5, 10, 15, 25, 50 and 100 ppb from 100 ppm VHG multi-element standard. These values were between 0.9999-0.9993 through the whole study. In the recovery process the minimum and maximum values of the 6 spikes are as follows: As (14.152 - 16.415), Pb(14.540-16.483), Ni(14.719-16.621), Cr (15.498 - 16.937), Figure 1. Colloform banded masses of amorphous trace-metal Cu(14.999-16.138), Cd(14.349-15.844). According to this, the rich Fe-sulfides surrounded by barite blades mean percentage values of the recovery were calculated as As(%101), Pb(101), Ni(104), Cr(108), Cu (101), Cd(99). The Subsequent +-XAFS spectra, in micro-areas with values were determined as <2 ppb in the locations of accumulated Sb, have indicated a possible dominance of the 7,8,10,13,19,28 and 31 for As; 3,6-8,10,13, 14, 18,19,21,23- relatively more toxic trivalent species (Sb3+) rather than 27,29-34 for Pb; 1-3,5,6,8-27,29-35 for Ni; 3, 5- pentavalent species (Sb5+) forms [2]. It is known that pyrites 8,10,11,13,18-20,22,24-26,30,31 for Cu;2,7,9-16,18, 19, 21- may accommodate Sb-ions and Sb-sulfosalt nanoparticles [3], 27, 29-35 for Cd. Maximum values were observed in the but there are no particular studies on the nature of Sb in stations numbered 35(11.19 ppb) for As;4(75.44 ppb) for Pb; amorphous Fe-sulfides from recent submarine hydrothermal 28(61.3) for Ni;5(114.82 ppb) for Cr;9(65.15 ppb) for Cu; 4 fields, unless stibnite is formed. Future work will include (243.63 ppb) for Cd. It is thought that there is an further evaluation and upgrading of the SR data in anthropogenic effect especially in the locations numbered 4,5 combination with microscopic investigation in nanoscale. and 9.

[1] Kilias et al. Sci Rep (2013-under review), [2] Filella et al. [1] US Method EPA 3005 A, 1992, Acid Digestion of Waters Earth-Sci. Rev. 80 (2007) 195, [3] Deditius et al., Ore Geol. for Total Recoverable or Dissolved Metals for Analysis by Rev. 42 (2011) 32 FLAA or ICP Spectroscopy, Revision 1, [2] US Method EPA, 6020 A, 1997, Coupled plasma mass spectrometry. Revision 1.

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Petrology and geochemistry of mafic Interpretation of hydrochemistry and ultramafic metamagmatic rocks data using Bayesian statistical emplaced within the anatectic series approaches to delineate groundwater of the middle crust of the Variscan contamination vulnerability Pyrenees: example of the Gavarnie- HO-RIM KIM1, KYOUNG-HO KIM1, KYUNG-GOO KANG2, Heas dome, West Pyrenees SOO-HYUNG MOON2 AND SEONG-TAEK YUN1* 1 1 1 1 1 Korea University, KU-KIST Green School and the M. A. KILZI , M. GREGOIRE , M. BENOIT , P. DEBAT , 1 2 Department of Earth and Environmental Sciences, South M. ST. BLANQUAT AND Y. DRIOUCH Korea, [email protected] (* correspondence) 1Laboratoire de Géosciences Environnement Toulouse, 2Jeju Special Self-Governing Province Development Observatoire Midi Pyrénées, Université Paul-Sabatier, Corporation, Jeju, South Korea CNRS, IRD, 14, Avenue Edouard Belin 31400 Toulouse [email protected] Well understanding of the source(s) and landuse control of 2Département de Géologie, Université de Fès, Maroc groundwater contamination is highly needed to better manage groundwater quality. In this context, we perfirmed the Within the anatectic formations of the middle crust of the interpretation of hydrochemical data of groundwater using the Variscan Pyrenees occur in some massifs (Alberes, Aston, Bayesian statistical method in conjunction with a GIS Trois Seigneurs, Lesponne…) ultramafic and mafic rocks technique to produce a spatial map showing groundwater forming polymetric or plutons mileage enclaves. The most vulnerability to contamination. In particular, we used the significant example is the Héas Gavarnie Dome in the Western Weight of Evidence (WofE) method (a Bayesian probabilistic Pyrenees. Within this dome of metasedimentary formations model) and relevance vector machine (RVM) regression (a affected by a common anatexis (peak conditions at around 730 Bayesian machine learning technique) that was recently °C and 4.3 kb) the mafic and ultramafic series form three developed to find out the correlations among factors massifs: the Troumouse massif in the south, mostly made of influencing the occurrence of groundwater contamination. diorites; the Aguila massif consisting of diorites which Hydrochemistry data of 46 groundwater samples from the contains some hornblendite enclaves; the Gloriette massif, Pyosun watershed of Jeju volcanic island, South Korea were consisting of diorites and norites associated with ultramafic used, because the groundwater system has been considered to rocks (orthopyroxenites and hornblendites). All of these rocks be highly susceptible to surface contamination (esp., are affected by variable degrees of metamorphism resulting in agricultural pollution) because of the short residence time in the development of secondary amphibole and biotite and cross permeable basaltic aquifer. cutted by a network of granitic bodies. For the combined use of WofE and RVM, hydrochemistry Petrological and geochemical studies show that theses data were evaluated using multivariate analyses to get the rocks mostly correspond to a basic metamagmatic series with initial information whether a sample is contaminated or not. a calc-alkaline affinity and characterized by enriched REE The results of Principal component analysis (PCA) and (432 ppm) contents, and REE fractionation processes Hierarchical Cluster Analysis (HCA) showed a good spatial (La/Yb)N =7.5; (La/Sm) = 2.5 and (Gd/Yb) = 1). They have control of hydrochemistry data in relation to the topography positive Eu anomalies (Eu/Eu* = 3.5) and the following trace within the watershed. In the next step, we estimated the element characteristics: (1) enrichments in U; (2) Nb and Sr correlation between topography data and the results of a depletion; and (3) large positive Pb anomalies. 87Sr/86Sr binary classification from multivariate analyses. The results isotopic ratios of mafic and ultramafic rocks range from using Bayesian statistical techniques could predict the 0.7045 to 0.7117 and eNd from -5.2 to -10.5. These signatures contamination vulnerability. Thus, the integrated method are typically crustal and show that these rocks have preserved developed in this study can be successfully used for evaluating the isotopic fingerprints of lower crustal magmatic processes the groundwater vulnerability.

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Use of risk-based remediaiton Combined use of ED-EPMA and strategy and concept of attainable ATR-FTIR imaging for clean-up level in management of characterization of individual aged groundwater contaminated sites in Asian Dust particles Korea HYEKYEONG KIM, HAE-JIN JUNG, HYO-JIN EOM, 1 1 1 XUE LI AND CHUL-UN RO HUN-MI KIM *, SEONGSUN LEE , DUGIN KAOWN AND KANG-KUN LEE1 Department of Chemistry, Inha University, 253 Yonghyun- dong, Nam-gu, Incheon, 402-751, KOREA and 1School of Earth Environmental Science, Seoul National [email protected] University, Seoul 151-747, Korea (*correspondence :

[email protected]), [email protected], In our previous works, it was demonstrated that the [email protected], [email protected] combined use of quantitative energy-dispersive electron probe

X-ray microanalysis (ED-EPMA), which is also known as There are recognized needs to establish a reliable and low-Z particle EPMA, and attenuated total reflectance FTIR effective remediation strategy as groundwater and soil (ATR-FTIR) imaging has great potential for a detailed protection from DNAPL(dense non-aqueous phase liquid) characterization of individual aerosol particles. In this study, contamination is one of the critical issues in Korea. extensively chemically modified (aged) individual Asian Dust Remediation performance results at DNAPL contaminated particles collected during an Asian Dust storm event on field sites have shown that achieving groundwater clean-up is November 11, 2002 in Korea were characterized by the very difficult due to the complexity of site characterization combined use of low-Z particle EPMA and ATR-FTIR and contaminants (DNAPL). Therefore, a new approach is imaging. Overall, 109 individual particles were classified into now necessary to determine the reachable clean-up level and four particle types based on their morphology, elemental control the groundwater contaminated sites with DNAPLs. concentrations, and molecular species and/or functional Our research team initiated a 5-year GAIA(Geo-Advanced groups of individual particles available from the two analytical Innovative Action) project to intensively monitor the DNAPL techniques: Ca-containing (38%); NaNO -containing (30%); contaminated site with a focus on developing clean-up options 3 silicate (22%); and miscellaneous particles (10%). Among the under support of Korea Ministry of Environment (KMOE). 41 Ca-containing particles, 10, 8, and 14 particles contained Woosan industrial complex was chosen as our field site and 16 nitrate, sulfate, and both, respectively, whereas only two rounds of groundwater sampling at about 90 monitoring wells particles contained unreacted CaCO . Airborne amorphous were performed from 2009 to 2013. The highest concentration 3 calcium carbonate (ACC) particles were observed in this of trichloroethylene (TCE) which was the main pollutant in Asian Dust sample for the first time, where their IR peaks for the source area of this site was 15 mg/L. According to field the insufficient symmetric environment of CO 2- ions of ACC mornitoring data and hydrogeologic condition, Risk Based 3 were clearly differentiated from those of crystalline CaCO . Corrective Action (RBCA) program and variable remediation 3 This paper also reports the first inland field observation of technologies such as soil vapor extraction, pump-and-treat, CaCl particles probably converted from CaCO through the surfactant enhanced in-situ remediation, in-situ 2 3 reaction with HCl(g). HCl(g) was likely released from the bioaugmentation and Monitoring Natural Attenuation (MNA) reaction of sea salt with NO /HNO , as all 33 particles of were performed. As a result of our field site application, we x 3 marine origin contained NaNO (no genuine sea salt particles propose the following step by step- remediation strategy. The 3 st were encountered). Some silicate particles with minor 1 step is implementation of site-specific characterization and nd amounts of calcium were observed to be mixed with nitrate, risk-based site assessment and 2 step is application of the sulfate, and water. Among 24 silicate particles, 10 particles are chosen remediation technologies to enhance the attenuation, mixed with water, the presence of which could facilitate plume capture and mass reduction in source zone based on the st rd atmospheric heterogeneous reactions of silicate particles 1 step result. The 3 step is establishment of an attainable including swelling minerals and non-swelling ones. Using the clean-up level considering the reulsts of mass reduction when combined use of the two single particle analytical techniques, there is no further contaminant exposures and plume migration this work clearly shows that internal mixing states of the aged and the final step is application of the MNA until the final Asian Dust particles are highly complicated. clean-up level of groundwater remediation is achieved.

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Chemical evolution of perched Ship-plume sulfur chemistry: groundwater flowing through ITCT 2K2 case study weathered bedrock underlying a HYUN S. KIM1, YONG H. KIM1 AND CHUL H. SONG1,* steep forested hillslope, northern 1School of Environmental Science and Engineering, Gwangju California Insititute of Science and Technology, 1 Oryong-dong, Buk-gu, Gwangju 500-712, Republic of Korea 1 12 HYOJIN KIM *,JAMES K.B. BISHOP 1 1 WILLIAM E. DIETRICH AND INEZ FUNG The ship-plume sulfur chemistry was investigated for the 1Univeristy of California, Berkeley Dept. Earth and Planetary ITCT 2K2 (Intercontinental Transport and Chemical Science, 307 McCone Hall, Berkeley CA94709 Transformation 2002) ship-plume experiment, using the ship- [email protected] plume photochemical/dynamic model developed in this study. 2Earth Science Division, Larence Berkeley National In order to evaluate the performance of the model, the model- Laboratory, 1 Cyclotron Road, MS 90-1116, Berkeley CA predicted mixing ratios of SO2 and H2SO4 were compared with 94709, USA those observed. From these comparisons, it was found that the model-predicted levels were in reasonable agreements with At the ~4000 m2 Rivendell study site on a 30O hillslope those observed (0.564R40.71), when the pH of sea-salt underlain by argillite along the South Fork Eel River, we have particles (pHss) was 4~6.5. The ship-plume equivalent monitored the chemistry of rainfall and of groundwater that lifetimes of SO2 ( ) were also estimated/investigated for seasonally perches on dense, fresh bedrock (5 to 20 m below this particular ship-plume case. The magnitudes of the surface) and flows through a weathered bedrock zone to an were found to be controlled by two main factors: (i) the adjacent channel. This is a part of a collaborative study mixing ratios of in-plume hydroxyl radicals (OH) and (ii) pHss. focused on coupling hydrologic, geochemical, ecological, and The former is governed primarily by stability conditions of the atmospheric processes. Water samples were collected every marine boundary layer (MBL), when the ship NOx emission 1 to 3 days for five years from three wells: upslope (Well 10), rate is fixed. The latter determines if the heterogeneous mid-slope (Well 3), and downslope (Well 1). oxidation of dissolved SO2 occurs via reaction with hydrogen At the beginning of the rainy season Well 10 groundwater peroxide (H2O2, when pHss<6.5) or with ozone (O3, when is deep with a constant high concentation of major cations (Ca, pHss>6.5). According to the multiple ship-plume Mg, and Na). New water arriving from seasonal storms photochemical/dynamic model simulations, the estimated causes water-table rise (4 to 6 m), and systematic dilution until over the entire ship plumes ranged from 10.32 to 14.32 rising water levels reach a new, significantly diluted constant hrs under moderately stable (E) to stable (F) MBL conditions. value. Surprisingly, however, Si shows an opposite response These values were clearly shorter than the background SO2 and increases in concentration with rising water level. Well 3 lifetime ( ) of 15.18- 23.20 hrs. In contrast, was response is generally similar. Well 1 behaves differently: its estimated to be 0.33 hrs when the pHss remained at ~8.0 (a water-table is highly responsive to rainfall inputs, but its rather unlikely case). In addition, the SO2 loss budget was chemistry shows no significant change, except briefly during further analyzed to estimate the influences of the two main rainstorms. factors on the ship-plume sulfur chemistry. The changes in the Our data suggests that the deeper groundwater flow which loss budget with pHss clearly showed a shift in the dominant is highly concentrated is in thermodynamic equilbrium with SO2 loss processes from heterogeneous SO2 conversion (when the argillite. Seasonal rainwater passes quickly through the pHss>~6.5) to the gas-phase oxidation of SO2 by OH (when soil and weathered bedrock where it rapidly uptakes major pHss< ~6.5). cations via cation exchange reactions and Si through Acknowledgements. This work was financially supported by amorphous silica dissolution. PCO2 is highly elevated due to biological activity. Intensive biological activities in this layer the Basic Science Research Program through the National increase the rate of mineral dissolution and thus continuously Research Foundation of Korea (NRF) grant from the Ministry replenish exchangeable cations and the amorphous silica pool. of Education, Science and Technology (MEST) (2012R1A1A2041481).

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Mineralogical characterization of Mineralogical and geochemical tremolite asbestos-containing soils characteristics of the Korean coal JUHYUN KIM1*, JAEBONG PARK2, SECKWHAN SONG3, ashes from the perspective of the coal HOJU LIM4 AND YUL ROH5 and combustion types 1 Chonnam National University, Gwangju, South Korea, 1 3 KANGJOO KIM *, GI-YOUNG JEONG AND JAE-CHUL LEE [email protected] 2Chonnam National University, Gwangju, South Korea, 1Department of Environmental Engineering, Kunsan National [email protected] University, Jeonbuk, 573-701, Korea 3Joongbu University, Chungnam, South Korea, (correspondence: [email protected]) [email protected] 2Department of Earth and Environmental Sciences, Andong 4National Institute of Environmental Research, Incheon, South National University, Kyeongpook, 760-749, Korea Korea, [email protected] 3Korea Western Power Co. Ltd., Seoul, 135-984, Korea 5Chonnam National University, Gwangju, South Korea, [email protected] Fly ashes produced from 9 coal burning power plants in Korea were investigated to see the changes in mineralogical Asbestos-containing soils occur mainly at ultramafic rocks and geochemical characteristics according to the coal types and hydrothermally altered carbnate rocks in S. Korea. and combustion methods. Our results indicate that the Remediation of asbestos-containing soils is considered a high mineralogical and geochemical features of the fly ashes are priority by the Korean Government because these soils, if left more dependent on the combustion methods than the coals untreated, represent a hazard to the environment and human used. Five and two out of the nine investigated plants were health. The objective of this study was to show a priori originally constructed to burn bituminous (or subbituminous) physicochemical and mineralogical characterization of coals and anthracite coals, respectively, by applying asbestos-contaminated soil can direct the development of pulverized coal firing system. The remaining two plants burn remediation strategies. anthracite or bituminous coals together with fine sand-sized Two sites (Seosan and Jaecheon, S. Korea) at abandoned limestone grains using the fluidized bed combustion method. asbestos mines were selescted for soil and mineralogical According to the SEM and XRD investigation, it was revealed characterization. Parent rock of the two sites is hydrothermally that spheres, mullite, and glasses were absent and sometimes altered carbnate rocks in S. Korea. At each site, samples were illite, a clay mineral, was present in the fly ashes produced taken at soil surface. Soil preparation consisted of sieving air- from the plants of the fluidized bed combustion method due to dried soil through a 2-mm sieve. The sieved soils (< 2-mm) the low combustion temperature (800 - 850 5). These ashes were used for soil characterization and mineralogical analysis. particularly contains calcite and anhydrite phases due to the Following particle size fractionations, mineralogical co-combustion of limestone grains. The high temperature characterization was investigated by TG-DTA, XRD, PLM, phases such as mullite and glass were observed in all the ashes SEM and EDS analyses. Point counting was used to quantify of the pulverized coal firing plants. However, their contents asbestos in the whole soil and size fractionated samples. were generally higher in the fly ashes of the pulverized The soil color of the both sites was dark red (Seosan site) anthracite coal burning plants. This is due to their higher and dark brown (Jaecheon site). The soil texture of the Seosan combustion temperatures (1200 – 1500 5) than those of the and Jaecheon sites was loam and sand, respectively. XRD bituminous or subbituminous coal burning plants (1200 – analysis showed mineral assemblages of the Seosan and 1300 5). The chemical composition of the ashes also Jaecheon site were tremolite-talc-vermiculite-quartz-diopside reflected the combustion methods. and tremolite-talc-vermiculite-quartz-dolomite, respectively. XRD, PLM, SEM and EDS analyses showed that the needle- shaped tremolite was observed at both soils. Size fraction between 425 ㎛ to 2㎜ of the Seosan and Jaecheon soils contained 1.5 % and 2 % asbestos, respectively. Therefore, the soils of the both sites were designated as asbestos-containing materials (greater than or equal to 1%) according to the criteria of the U.S. EPA. TG-DTA showed that tremolite asbestos at both soils were transformed to diopside with the temperatures about 1,100!. These results indicated that thermal treatment of asbestos-containing soils was effective for phase transformation of the asbestos in soils.

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Estimation of POC and Biogenic Variation of As-leaching from coal silica export fluxes using 234Th/238U ashes according to extractant pH, disequilibrium in the Amundsen sea, reaction time, and shaking methods Antarctic SEOK-HWI KIM, BYUNG-HYO KIM, KANGJOO KIM*, 1 1 2 YUNG ON EONG AND EUNG YUN HOI MI SEON KIM MAN SIK CHOI * AND SANG HEON LEE B -G J S -H C Department of Environmental Engineering, Kunsan National 1Chungnam National University, Daejeon, Korea University, Jeonbuk, 573-701, Korea [email protected] (*correspondence : [email protected]) 2 (*correspondence: [email protected]) Pusan National University, Busan, Korea

[email protected] In this study, the leaching characteristics of arsenic (As)

from the weathered coal ashes (fly ash + bottom ash mixture), In order to understand the carbon cycle in the Amundsen which have been reclaimed in an ash pond of a power plant, Sea, the Antarctic, the export fluxes of organic carbon and and the fresh fly ashes were evaluated using various leaching biogenic silica from the euphotic zone to depth were estimated 234 238 experiments. The As-leaching experiments were performed using Th/ U disequilibrium method. Seawaters in 14 water considering extractant pH (5, 7, and 9), shaking methods, and columns were collected during February and March 2012, and 234 extraction time as variables. Especially, the ashes were analyzed for total and dissolved Th, and particulate organic extracted repeatedly using new extractant to observe the carbon and biogenic silica. leaching characteristics as a function of time. The As The water column activities of total 234Th showed 238 concentration in the fresh fly ash was 16.1 mg/kg. In contrast, deficiency and excess relative to those of U. Deficiency of 234 the weathered coal ashes showed the lower concentrations total Th in the euphotic zone showed mirror images both 5.77-10.0 mg/kg, reflecting that a part of As already has been with chlorophyll-a and fluorescence, and was consistent with leached by the reaction with the pond water. The weathered the loss of nitrate, which indicated the impact of biological 234 ashes showed the more As leaching at lower pH, indicating activity. In addition, deficiency of total Th from deepwater that the contribution from the carbonate-bound fraction was associated with the increase of total Fe/Mn concentration. 234 becomes greater as the pH becomes acidic. The As leaching Excess total Th activity presented below the euphotic zone decreases drastically as the reaction time increases. Our results might be related to the active remineralization process. also show that the As-leaching is dependent not only on the The export flux of 234Th estimated using the steady state 3 2 shaking speeds and stroke distances but also on the bottom model was av. 0.87 (±0.25) 10 dpm/m /day. The export areas of the reaction bottles. For example, the As-leaching was fluxes of organic carbon and biogenic silica, which were greater when the bottles with wider bottom were used even at estimated by the product of total" 234Th flux and ratio of 234 234 the same shaking speed and stroke distance. POC/ Th (7.08 ± 4.27+M/dpm) and BSi/ Th (0.80 ±

0.36+M/dpm) in the sinking particles, were av. 5.85 (±2.42) mmol/m2/day and 0.69 mmol/m2/day, respectively. These fluxes were similar levels to those in the Weddell Sea during February and March 2008. Export ratios (ThE) relative to the primary production in the euphotic zone were in the range of 3~50% (av. 27.8%), which indicated less efficiency in the biological pump than the Ross sea during January and February 1997.

[1] Cochran et al (2000), Deep-Sea Research II 47, 3451- 3490. [2] Rutgers van der Loeff et al (2011), Deep Sea Research Part II 58 (25-26): 2749-2766.

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Characterization of the primary Determination of picomolar Zn in productivity using a year-long high seawater of the North and South Pacific resolution sediment trap experiment with clean sampling methods in the southwestern part of the T. KIM1*, T. GAMO1 AND H. OBATA1 East/Japan Sea 1Atmosphere and Ocean Research Institute, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa-shi, Chiba 277-8564, S.H. KIM*, G.H. HONG, Y.I. KIM, C.S. CHUNG, Japan (*[email protected]) K.Y. CHOI AND Y.H. KIM

1 Korea Institute of Ocean Science & Technology, Ansan, Zinc (Zn) is an essential micronutrient for bacteria and R.Korea 426-744 (*correspondence: [email protected]) phytoplankton in the ocean. However, biogeochemical cycles of Zn have not been fully revealed yet in the ocean since The southwestern East/Japan Sea is one of the world's most determination of Zn in seawater is very difficult because of productive fishing grounds that is readily visible from the contamination problems [1]. We have established a precise space born satellite's day-night band due to bright lights determination method of picomolar level of Zn in seawater emitted from dense assemblage of fishing fleet. Traps were using recent clean technique. Using this method, vertical deployed to collect sinking particles in the depths of 1,020 m distributions of Zn were investigated. and 2,100 m at the inter-plain gap between Ulleung and Dok Seawater samples were collected in the subtropical North, islands (37°25.77'N, 132°30.27'E, 2300 m) in 1999 with South Pacific and subarctic North Pacific during the R.V. shorter than 10 days sampling interval. The water temperature Hakuho-Maru research cruises. We used Teflon-coated X- and current at 350 m depth using RCM 7 at the site adjacent Niskin bottles, which were thoroughly cleaned with to the sediment trap mooring site were also utilized to aid our detergent, acid, and milli-Q water. Zn in seawater was data analysis. determined by cathodic stripping voltammetry after UV- This high resolution temporal observations showed many digestion. ! important characteristics related to the productivity of the We have compared three different seawater sampling southwestern East/Japan Sea: 1) Ulleung Warm Eddy methods. Teflon-coated X-Niskin samplers were 1) enhanced primary productivity as evidenced by a simultaneous deployed on CTD-CMS, 2) attached to Kevlar wire and 3) variation in water temperature at 100 m and particulate attached to titanium wire. Because Zn is used as sacrificial organic carbon fluxes at 1,020 m depth.; 2) Siliceous anode in the research vessel, especially around main propellers phytoplankton species dominated spring and autumn blooms. of the Hakuho-Maru, Zn contamination was observed during The ratio of biogenic silica flux to particulate organic carbon Kevlar wire hydrocasts that were performed from the stern of flux increased during these two seasons; 3) Calcareous the vessel. By minimizing the influence from the propellers, productivity was observed during August when surface water we obtained almost the same Zn concentrations within the temperature was the highest when the ratio of calcium flux to analytical error among those three different sampling methods. aluminum flux peaked its maximum; 4) Small sized primary In the subarctic North Pacific, surface Zn concentrations producers such as nano- or pico- plankton dominated in showed the decrement from west to east, indicating that high summer. Dissolution of sinking particulate organic carbon eolian dust inputs from the Asian deserts may contribute to appeared to be great in the water column between 1,020 m and relatively high Zn concentration in western North Pacific [2] . 2,100 m compare to other seasons; 5) Nitrogen fixer appeared to contribute to comparable high productivity during the [1] Fitzwater et al (1982) Limnology and Oceanography 27, apparent N-poor oligotrophic summer and the ratio of 544-551 [2] Jakuba et al (2012) Global Biogeochemical particulate organic carbon to particulate nitrogen was Cycles 26, GB2015. relatively high compared with that in other seasons.

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Characterization of the white Sorption Behavior of Mercury (Hg) precipitates found in acid mine on Hydroxylapatite drainage YOUNGJAE KIM1 AND YOUNG JAE LEE1* YEONGKYOO KIM*, CHANG-MIN LEE 1Department of Earth and Environmental Sciences, Korea AND HAE-YONG GWAK University, Seoul 136-701, Korea (*Correspondence: [email protected]) Department of Geology, Kyungpook National University,

Daegu 702-701, Korea, [email protected] Hydroxylapatite (HAP) has been known to be ubiqotous in various environments. Mercury (Hg) is notorious in The mobility of heavy metals released from acid mine ecosystems including humans due to its toxicity. drainage can be controlled by sorption on the iron and Neverthelesss, Hg interactions with HAP has been barely aluminum precipitates. There have been plenty of reports on addressed yet. In this study, systematic batch experiments the iron precipitates found in acid mine drainage. However, were conducted to investigate Hg sorption on HAP over a the white precipitates, mainly composed of aluminum, have wide range of physicochemical conditions such as pH, ionic not been throughly investigated. Previous study have reported strenths, and ligands forming complexes. hydrobasaluminite and gibbsite as possbile phases. Recently Hg sorption increases with increasing pH up to pH 6.0 Al -tridecamer was suggested as a possible aluminum phase 13 whereas the sorption decreases with pH at pH 7.0. This in precipitates. We used chemical analysis, XRD, SEM, NMR, result is in good agreement with species modling calculation and sequential extraction method to characterize the white showing that Hg(OH) 0 is dominant at neutral and#! basic pHs. precipitates collected at three different sites. 2 It is found that Hg sorption on HAP increases with increasing XRD and SEM data show that most white precipitates are 27 Hg concentration. At pH 5.0 and 7.0, Hg uptake by HAP amorphous with small amount of gypsum. Al MAS NMR steeply increases up to [Hg] 10 M, and then gently spectra provide more detailed information on the alumiunm ini. increases at higher concentration. At pH 9.0, however, the Hg species in precipitates, showing that there are 4- and 6- sorption on HAP shows linear $slope% with increasing Hg coordinated aluminums in the samples. The aluminum with 4- concentration. coordination can be assigned to Al -tridecamer, which has 13 Upon Hg sorption edges and isotherms, it is shown that been known as one of the most toxic aluminum species. The 27 the sorption is little influenced by variation of ionic strengths. calulations based on chemical and Al MAS NMR data, show This result indicates that Hg would form inner-sphere surface that the relative amounts of Al -tridecamer, 13 complexes at the HAP. In kinetics, Hg sorption on HAP hydrobasaluminite, gibbsite and gypsum are different for each reaches ~70 % of total sorbed Hg within the first 3 hr, sample. The results of sequential extraction experiment also indicating that adsorption plays a major role in cotrolloing the show that each sample has different aluminum and heavy initial uptake of Hg by HAP. During desorption, ~90 % of the metal fractions, indicating that the toxicity caused by sorbed Hg is retained by HAP suggesting that the sorbed Hg is aluminum and heavy metals can be different for each sample. bounded tightly to the surface and irreversible. It is also found Sequential extraction results show that one sample (S-1) has that Hg sorption on HAP is decreased by Cl wheareas Hg higher water soluble fraction and sorebed and exchangeable desorption is enhanced in the presence of Cl. These results fraction of aluminum than other samples. However this sample suggest that Hg interactions with HAP are significantly does not contain Al -tridecamer based on NMR data, 13 influenced by various physicochemical conditions in indicating that careful characterization of white precipiates is ecosystems. needed to estimate the toxicity of aluminum of white precipitates found in acid mine drainage.

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Thermal history energy balance Distribution and migration of compared with convection modeling americium-241 in the East Pacific SCOTT D. KING* NORIKAZU KINOSHITA1*, MIKA NAGAOKA2, TAKAHIRO SUMI3, KIYOTAKA TAKIMOTO3, Department of Geosciences, Virginia Tech, Blacksburg, VA AKIHIKO YOKOYAMA3 AND TAKASHI NAKANISHI3 24061, USA (*correspondence: [email protected]) 1Shimizu Corporation, Tokyo 135-8530, Japan. Thermal history calculations are based on balancing the 2Japan Atomic Energy Agency, Ibaraki 319-1194, Japan. flux of heat into and out of the mantle with the heat generated 3Kanazawa University, Ishikawa 920-1192, Japan. internally due to the decay of radiogenic elements [1]. In order (*[email protected]) to reduce this balance to a tractable equation, a relationship between the surface heat flow and temperature is necessary. Anthropogenic radionuclides of plutonium-239, 240 and Often this is a relationship between the Nusselt number and americium-241, that is, a decay product of 241Pu, are present Rayleigh number and variants of this relationship have been on the earth as a result of atmospheric nuclear tests carried out proposed based on both theory and numerical experimentation during the 1950s and 1960s. It is known that most of the [1, 2, 3]. The power of thermal history calculations is that they nuclides deposited in ocean and deposition in North Pacific is can explore a large parameter space with minimal higher than South Pacific due to location of the test site. Few computational resources; however they provide only an data on 241Am in marine environment have been reported, so average mantle temperature as a function of time. far. Depth profile, residence time, applicability as a tracer of 3D spherical-shell convection calculations are becoming migration of the nuclide have not been well investigated yet. increasingly prevalent. These solve the conservation of mass, We have investigated on its distribution at the East Pacific by momentum and energy in a 3D spherical geometry; however assaying large volume seawater collected in 2003. two important aspects of thermal history modeling are The Am atoms were collected as hydroxides together with infrequently employed in 3D convection calculations: a iron from 250 L of sea water spiked with 243Am yield tracer. cooling core boundary condition and decreasing radiogenic The Am atoms were isolated through a solvent extraction and heating with time. In many recent investigations the time-span anion exchange procedure, followed by an assay in (- of interest is such that these do not vary significantly. spectroemtry. The concentration of 241Am was found low in This raises an interesting question: Just how comparable surface water and the depths below 2000 m as well, and are thermal history calculations and 3D spherical-shell enhanced at the depths around 800 m. The depth profile shows convection calculations? In this presentation I will compare a pattern similar to that of 239+240Pu [1]. Although 3D convection and thermal history calculations with the same concentration and depth of the subsurface maximum were properties. These will include temperature and pressure different depends on the location, the subsurface maximum dependent rheology and a ‘mobile lid’ using the methodology was observed in a isopycnic surface; the distribution is outlined by van Heck and Tackley [4], decaying radiogenic affected by water mass structure. heat sources, and a cooling core boundary condition. Even Comparing the present data on 241Am with previous data with advances in computing power, it is unlikely that solving on 239+240Pu [1], 241Am/239+240Pu activity ratio showed constant the set of conservation equations will replace thermal history value. Substantial differences between different locations and models any time soon. The goal is to assess whether given the depths have not been observed in the profiles of same parameters these two formulations will produce a similar 241Am/239+240Pu ratio. The Am atoms appear to have the same temperature history. While there are a myriad of parameters residence time as those of Pu in the East Pacific. and assumptions, many of which are unknown and perhaps Besides, The 241Am inflow from North Pacific to South even unknowable (e.g., the average mantle temperature at Pacific across the equator is observed in a depth of 500 ) 1500 formation), both 3D and thermal history calculations face m along longitude of 95° W. Similar flows were observed for these challenges. While the observations relevant to Earth’s the Pu isotopes and the nutrients in the same area as well [1]. thermal evolution are being assessed, so to should the Our result supports a model simulation of migration in the computational tools used to model it. East Pacific reported by Nakano et al. [2].

[1] Schubert, Turcotte & Olsen (2001) Mantle Convection in [1] Kinoshita et al. (2011) Sci. Tot. Environ. 409, 1889-1899. the Earth and Planets, Ch 13. [2] Gurnis (1989) GRL 16, 179- [2] Nakano et al. (2010) J. Geophys. Res. 15, C06015. 182. [3] Solomatov (1995) Phys. Fluids 7, 266-274. [4] van Heck & Tackley (2008) GRL 35, L19312.

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Inverse modeling in a CO2 natural Geochemical and petrographical analogue – long term processes in investigation of chromite occurences carbon dioxide storage in Burdur-Salda, Turkey KIRÁLY, CS.1, SENDULA, E.1, SZAMOSFALVI, Á.2, DEMET KIRAN YILDIRIM1, FALUS, GY.2, SZABÓ, CS.1, SZ6CS, T.2 SERENA UZASCI SULTANYAN1, AND FORRAY, V.1 SALIH BURAK KARABEL1, ALEV KAN BOSTANCI1 1 1 AND MUSTAFA KUMRAL , Litosphere Fluid Research Lab, Eötvös University, Hungary 2Geological and Geophysical Institute of Hungary 1Istanbul Technical University, Department of Geological Engineering, 34469, Istanbul, TURKEY To guarantee the long term safety of the geologically

stored CO2, long timescale behavior of the CO2-rock- Lithological units in research area from oldest to youngest porewater system must be well understood. The most suitable are Cretaceous aged ophiolites, intrusive gabbros in ophiolites, way to describe a future CCS system is study of long-term sedimantary units mostly composed of limestones and

natural CO2 accumulations and their footprint on the Quaternary aged alluvials. mineralogical and fluid compositions. One of these natural There are four types of chromite ocurrences in the area.

CO2 occurrences is in the western part of Hungary, in the These are massive, nodular, disseminated and banded ores.

Little Hungarian Plane, where the studied system is composed Chromite ores which include Cr2O3 from 18% to 50% were

by 38 reservoirs (26 CO2, 10 hydrocarbon, and 2 mixed gas). bedded in podiform type. Slope directions of masses are The carbon dioxide is produced since 1948 for industrial different in northern and southern parts. It is estimated that

purposes. The CO2 is contained by the (late Miocene) this diffrences of slope depend on faulting in the region. Pannonian sedimentary sequence of a prograding delta system Chromite deposits are can be seen in the outcrop, have (mainly sandstone, siltstone and clay), in a depth of about continuities in the strike and dip directions and in the form of 1400 m. extensions of each other. Chromite deposits in the middle and Based on the mineralogical composition of the available edge parts of the ophiolitic series are small and individual core samples and water chemistry data from the studied area, appearances.

and using mineralogical composition of a CO2-free brine Samples from the research area were analized for containing sandstone from the same formation, a geochemical determining the petrographical and geochemical modeling was applied with the PHREEQC program to characteristics. Samples were taken from the research region reproduce the observed effects and determine the major fluid- are examined according to major oxide contents to determine rock interactions which could have taken place in the geochemical content ratio of this units.

reservoir. These interactions are believed to have a major The percentage of SiO2 is between 10% an 31% and Al2O3 impact on long term safety of carbon dioxide geological content is approximately %3-3,6. N39, which is one of five

storage as they may strongly affect the petrophysical samples tested to establish Fe2O3 content, have the highest

parameters of storage and sealing lithologies. Fe2O3 content is 15,972%. It is seen that the sample is rich on

The work was carried out in collaboration between Eötvös account of Cr2O3 with the percentage of is 50,181. Moreover, University and Geological and Geophysical Institute of the content of CaO was determined between 0,02% and 0,5% Hungary. for all samples.

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The Olympic Dam giant ore deposit – Calibration of the #47 (clumped a fossil nuclear reactor? isotope) thermometer for biogenic MARIA KIRCHENBAUR1,2, KATHY EHRIG3, and inorganic carbonate using the ROLAND MAAS4, VADIM KAMENETSKY5, MIRA IRMS. CHRIS BALLHAUS2 AND CARSTEN MÜNKER1 R. KIRK1*, P. F. DENNIS1, J. FARKAS2 AND A. MARCA1 1Institut für Geologie und Mineralogie, Universität zu Köln, Germany; 2 Steinmann-Institut, Universität Bonn, 1University of East Anglia, Norwich, NR4 7TJ, UK Germany; [email protected] (*correspondence: [email protected]) 3BHP-Billiton, Adelaide, South Australia, Australia 2Czech Geological Survey, 152 00 Prague 5, Czech Republic 4School of Earth Sciences, University of Melbourne, Australia 5CODES, University of Tasmania, Hobart, Australia Using a suite of brachiopod samples collected from natural marine environments (5-22°C) and inorganic hydrothermal The Olympic Dam (OD) supergiant Cu-U-Au-Ag deposit calcites collected from springs precipitated at up to 56°C we in the Gawler Craton of South Australia occurs within have determined a new calibration for the 147 isotope tectonic-hydrothermal breccia hosted by 1.59 Ga granite of the thermometer. This is the first reported calibration using the Gawler silicic large igneous province. With probable reserves MIRA IRMS. All other previous determinations have been of ~200000 t of U, OD is one of the world’s largest U made using the Thermo-Finnegan 253 IRMS. deposits. The high uranium content and a possible Proterozoic For all samples, 10mg of homogenised powder were age of mineralization raises the possibility of Oklo-style fossil reacted with ca. 2mL of 102% orthophospheric acid for 12 nuclear reactor activity, although a much smaller degree of hours at 25°C. CO2 was collected by cryo-distillation after burn-up, similar to that documented in many other Proterozoic passing through sequential cold traps at -100 and -120°C to and Phanerozoic U deposits, is more likely, given the low ensure complete removal of water vapour. Yields were average U concentration (450 ppm) at OD. We explore this determined barometrically before transferring the CO2, via a possibility using U-Sm-Nd isotope data. short packed column to remove any hydrocarbons, into gas High-precision U isotope data for 43 samples with U tubes for mass spectrometric analysis. The MIRA mass concentrations up to 10.5% were obtained by MC-ICPMS at spectrometer was operated at 8kV energy with an ionising Cologne/Bonn, employing both double spiking and standard- electron current of 750µA and m/z = 44 signal strengths of 238 -8 sample bracketing to correct for instrumental mass bias. , U 4x10 A. Reported measurements are the average of 9 runs of (relative to a 238U/235U of 137.856 for REIMEP 18a) ranges 20 samples-reference cycles, with a 10 second integration per from -0.5‰ to +0.2‰ (average ,238U = -0.2‰). Only four cycle. The measurement precision for ,47 approaches the samples yield the positive ,238U expected from consumption shot-noise limit of ca. 0.01‰. All results are presented on the of 235U in sustained nuclear fission, well below ,238U found at absolute reference frame outlined by Dennis et al. [1]. Oklo (up to 560‰), but consistent with the minute isotopic Between 5 and 56°C the 147 Vs. T relationship for both effects reported for other old U deposits. Depletion of 149Sm biogenic and inorganic calcite can be described by a single by slow neutron capture, observed in many U deposits, equation: reaches 1.5 !-units and only occurs in the few samples with 238 6 -2 positive " U. Isotope ratios of Nd are indistinguishable from 147 = 0.0368 (±0.0037) x 10 .T + 0.2345 (±0.042) normal. We conclude that OD contains U with a near-natural (r2 = 0.92) abundance of 235U, but some U-rich domains appear to have experienced a small degree of induced 235U fission with The gradient of the response, within measurement error, is associated neutron capture effects in other elements. the same as recently reported studies [1, 2] and similar to the The vast majority of our samples (10-8000 ppm U) exhibit theoretical response [3]. There are, however, significant slightly negative ,238U. Consistently negative ,238U (-0.3 to - differences in the intercept that may result from different 0.7‰) was previously found for ‘magmatic’ U deposits, sample reaction conditions and procedures. defined to include hydrothermal (200-400oC) deposits [1]. 238U depletion in such deposits is thought to reflect natural isotope [1] Dennis et al. (2011) Geochim.Cosmochim.Acta, 75, 7117- fractionation during U deposition. 7131. [2] Henkes et al. (2013) Geochim.Cosmochim.Acta, 106, 307-325. [3] Guo et al. (2009) Geochim. Cosmochim. [1]Bopp et al (2009) Geology 37, 611-614 Acta, 73, 7203-7225.

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An experimental study of the Reaction path geochemical modelling geochemical impact of CO2 leakage in of CO2-SO2-water-rock experiments siliclastic aquifers D. KIRSTE1,2, J. PEARCE1,3, S. GOLDING1,3 1,2 1 2 3 A AND A. FRANK KIRSCH, K. , NAVARRE-SITCHLER, A., WUNSCH, A., AND MCCRAY, J.E.3 1Cooperative Research Centre for Greenhouse Gas 1 Technologies, Department of Geology and Geological Engineering, 2Dept. of Earth Sciences, Simon Fraser University, Burnaby, Colorado School of Mines, [email protected] 2 BC V5A 1S6, Canada; [email protected], [email protected] Department of Geology and Geological Engineering, 3School of Earth Sciences, University of Queensland, Colorado School of Mines, [email protected] Brisbane, QLD 4072, Australia; [email protected], 3Department of Civil and Environmental Engineering, [email protected] Colorado School of Mines

The CO CRC has conducted an in depth study of the Leakage of CO from deep storage formations into an 2 2 geochemical impacts of CO storage with co-contaminant SO . overlying potable aquifer may mobilize trace metals leading to 2 2 In this study, laboratory experiments were conducted in static undesireable water quality degradation. Understanding CO - 2 reaction vessels to investigate the chemical evolution of the water-rock interactions under leakage conditions is therefore CO -SO -water-rock system of core samples from 3 different an important step toward the safe implementation of geologic 2 2 geologic formations in the Surat Basin of southern carbon sequestration. In this study we investigated the Queensland, Australia. Numerical modelling of the geochemical response of three sandstone samples from the experiments was undertaken to evaluate modelling capabilities Mesaverde Group in northwestern Colorado. Two batch as well as to determine which factors contribute significantly dissolution experiments were conducted in which samples to the chemical behaviour of the system. were reacted with water and CO at partial pressures of 0.01 2 This work reports on the geochemical modelling component and 1 bar, representing natural background levels and levels of the study. expected in an aquifer impacted by a small leak of CO , 2 The experiments were conducted at 60°C and 120 bar with respectively. The pH dropped sharply after CO was 2 scCO and scCO + SO in a low salinity water and 3 different introduced into the system, and then rebounded slightly as the 2 2 2 rock types (see Pearce et al., Goldschmidt 2013). Changes in minerals in the rocks dissolved. Concentrations of major (e.g., the gas and water chemistry as well as mineralogy were Ca, Mg, Fe) and trace (e.g., As, Ba, Cd, Pb, Sr, U) elements in determined. Static reaction path geochemical modelling using the fluids increased over the 4 week duration of the Geochemist’s Workbench was conducted to simulate the expeirments. These concentrations increased more in the 1 experimental conditions and output of the experiments. The bar CO experiments compared to the 0.01 bar CO 2 2 simulations generated provided a reasonable history match to experiments. Throughout the experiments the concentrations the experiments. It was noted that the experiments and even of potentially toxic constituents remained below regulatory more so the numerical models were very sensitive to redox limits. Sequential extraction results suggest that carbonate state. In the case of the experiments it appeared that the most minerals, although volumetrically insignificant in sandstones, important contribution to redox related to aqueous phase are the dominant source of metals. A simple geochemical species, particular O and Fe. In the geochemical modelling, model was developed that simulates observed changes in fluid 2 the presence of ferric iron (usually initially in the form of composition and supports the interpretation that carbonate hematite) played a significant role in determining model minerals are an important source of metals in silicalstic outcomes. The presence of oxidised iron drove SO oxidation aquifers impacted by CO leakage. 2 2 to H SO to take place as well as the disproportionation 2 4 reaction to H SO and H S leading to increased mineral 2 4 2 dissolution and pyrite precipitation in the simulations.

However, without oxidised iron the disproportionation

reaction dominated leading to elemental sulphur and pyrite

precipitation. The experiments and modelling clearly indicate that understanding the redox state in terms of minerals and aqueous phase of any potential sites will be critical to the geochemical behaviour.

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Impacts of arc collision on small Decreased export productivity at orogens: New insights from the onset of Eocene hyperthermal events Coastal Range detrital record of SANDRA KIRTLAND TURNER1* Taiwan 1Scripps Institution of Oceanography, La Jolla CA, 92093, 1 2 USA *[email protected] LINDA A. KIRSTEIN , ANDREW CARTER 3 AND YUE-GAU CHEN Hyperthermals, or abrupt global warming events, occurred 1School of Geosciences, University of Edinburgh, Edinburgh, frequently throughout the warm early Eocene (~56 to 47 Ma). EH9 3JW, UK ([email protected]) Two lines of evidence widely used in their identification 2Dept. of Earth & Planetary Sciences, Birkbeck College, include a negative "13C excursion recorded in marine and London, WC1E 7HX, UK terrestrial sources of inorganic and organic carbon and a drop 3 Dept. of Geosciences, National Taiwan University, Taipei, in deep sea sedimentary carbonate content (wt% CaCO3), Taiwan, ROC indicative of the release of large quanities of isotopically depleted carbon to the atmosphere and oceans and subsequent Taiwan is seen as the archetypical orogen in the dissolution of deep sea carbonates due to a shoaling carbonate development of critical wedge models of mountain building compensation depth. For a number of the smaller however, despite intense study the issue of how arc collision hyperthermal events, including H2 [1], C22rH2, C22nH2, progressed along the Taiwan margin remains poorly C22nH3, and C21rH1 [2], records from multiple deep sea sites understood. It has been suggested that punctuated collision show a notable offset in the timing of the "13C excursion and took place (e.g. Byrne et al., 2011) and therefore the classic the wt% carbonate minimum, though carbonate content never wedge model may not be applicable. To resolve this, the drops below 10%, indicating deposition above the CCD detrital archive of orogenesis preserved in Coastal Range throughout each event. The minima in wt% carbonate have an rocks of eastern Taiwan was used to reconstruct the erosional apparent lead of ~1 to 20 kyr compared to the minima in response of arc collision. carbonate "13C. For each event, the temporal offsets occur at There is a distinct geographic division to the multiple deep sea sites, though the magnitude of the lead thermochronology data linked to the location of volcanic arc varies between sites. centres of Chimei and Chengkuangao. Detrital zircon fission- Experiments using the intermediate complexity Earth track results record grains that were exhumed from depths of System model cGENIE (Grid-ENabled Integrated Earth 6-8 km ~6 Ma in the region between Chimei and system model) designed to reproduce these hyperthermal Chengkuangao. These grains were transported and deposited events show the same pattern in modeled sediment ‘cores.’ into adjacent retro-foredeep basin(s) bounded by the discrete Hyperthermals are simulated by forcing the addition and volcanic centers starting at 1.9 Myr. removal of isotopically depleted carbon to the atmosphere in South of Chengkuangao rapidly exhumed zircons are order to match the observed "13C excursion, with the results detected in sediments deposited < 1.3 Myr hence both recorded in sediment model tracers of carbonate content and exhumation and deposition must be fast. The pattern of isotopes. In the model, the timing of the minimum in

exhumation and location of exhumation ages is consistent with sedimentary wt% CaCO2 is a function of decreased CaCO3 southwards progression of arc-continent collision in a export from the surface ocean occurring coincident with the punctuated rather than sequential manner and deposition was addition of excess carbon to the atmosphere and oceans. In confined to small foredeep basins. contrast, the carbonate "13C minimum records a whole ocean change in the "13C of dissolved inorganic carbon and is [1] Byrne, T., Chan, Y-C., Rau, R-J., Lu, C-Y., Lee, Y-H., and therefore delayed relative to the carbon addition. Both model Wang, Y-J., 2011, The arc-continent collision in Taiwan, in results and observational data thus indicate an early reduction Brown, D., and Ryan, P.D., eds, Arc-Continent Collision: in export productivity as a consequence of small hyperthermal Springer Verlag, New York, p. 213-245. events.

[1] Stap, L., et al, (2009), Paleoceanography, Vol. 24, PA1211, 13 pp., doi:10.1029/2008PA001655. [2] Sexton, P.N., et al, (2011), Nature, Vol. 471, pp. 349-353, doi:10.1038/nature09826.

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Geochemistry of fluids from the Chalcophile element partitioning Eastern Carpathians and between silicate and sulphide liquids Transylvanian Basin boundary EKATERINA S. KISEEVA1 AND BERNARD J. WOOD1 (Romania)-constraints on the origin 1University of Oxford (*correspondence: of mineral waters and dissolved gases [email protected], [email protected])

1 2 BOGLÁRKA-MERCEDESZ KIS* FRANCESCO ITALIANO We report the partitioning of the elements Cu, In, Tl, Pb, 1 2 C7LIN BACIU ANDREA RIZZO Ag, Zn, Cr, Co, Ni, Sb, Mn and Cd between FeS-rich sulphide 3 AND KRISZTINA KÁRMÁN liquids and anhydrous basaltic melts at high P and T. There 1Babe*-Bolyai University, Fântânele street 30, Cluj-Napoca, are simple relationships between the FeO contents of the Romania (*correspondence: [email protected]) silicate melts and the sulphide-silicate partition coefficients for 2Istituto Nazionale di Geofisica e Vulcanologia, Via Ugo La the individual trace elements. These relationships can be Malfa 153, Palermo, Italy ([email protected]) generally represented as follows: 3 HAS, Institute for Geological and Geochemical Research, sulph / sil n log D ! A + log[FeO] Budaörsi street 45, Budapest, Hungary M 2 The Eastern Carpathians, along the Rodna-Bârg8ului subvolcanic area and C8limani-Gurghiu-Harghita volcanic where A is a constant related to the free energy of Fe-M chain, with the Transylvanian Basin boundary, host important exchange, n is a constant related to the valence of the element and [FeO] is the FeO content of the silicate melt in mole resources of Romanian CO2-rich mineral waters. Results of a comprehensive study on the volatiles dissolved in artesian fraction or weight %. At 1.5 GPa and 1400oC, with [FeO] in thermal waters discharged over a 200 km-long transect show weight %, we report the following values of n and A: At 1.5 GPa and 1400oC we found, with [FeO] in weight large contents of CO2-dominated gases. The circulation of fluids on the study area is enhanced by %, the following values of A and n/2: Cu (3.33; -0.82); In tectonic fragmentations which are considered to be the main (2.24; -1.12); Tl (1.86; -0.76); Pb (2.64; -1.09); Ag (3.47; - 0.82); Zn (1.15; -0.79); Cr (1.23; -0.87); Co (2.76; -1.09); Ni upraising path for CO2 and mineral waters. The geochemical features of the gas phase extracted by water samples reveal (3.65; -0.84); Sb (2.56; -1.23); Cd (2.69; -0.93); Mn (0.46; - 3 0.59). amounts of CO2 up to about 2000 cm STP/LH2O, and helium 3 We calculated the composition of the putative Hadean up to 0.02 cm STP/LH2O. Our investigations show that the wide range of chemical and isotopic composition can be sulphide matte extracted from primitive mantle during the explained in terms of contemporary occurrence of Gas-Water final stages of accretion and possibly responsible for the Interactions (GWI) affecting the circulating waters after their current “spiky” abundance pattern of chalcophile elements in 13 silicate Earth. Starting with the current primitive mantle infiltration. Carbon (" CTDC Total Dissolved Carbon, ranging from -17 to +10‰ vs PDB) and He systematics (He isotopes abundances of these elements and calculating matte in the range of 0.38-0.9Ra, Ra = air-normalized 3He/4He ratio), composition, however, we find that it is not possible to coherently indicate the presence of fluids from sources located generate an initial abundance pattern which approximates at different depths in the crust (e.g. sediments, oil reservoirs) chondritic. The simple “Hadean matte” model is inadequate. besides minor but detectable contributions of We calculated Ce/Pb and Nd/Pb ratios of basalts generated mantle/magmatic-derived fluids. by mantle melting. Calculated Nd/Pb is essentially constant over wide ranges of partial melting and fractional The present work was financially supported by the RNRC, crystallization with a value of ~18.6 if we assume that Project PN-II-ID-PCE-2011-3-0537 and by the European depleted mantle contains 65 ppb Pb. Calculated Ce/Pb varies Social Fund and the Romanian Government through the slightly during batch partial melting from 21-29 with the POSDRU project ”DOCTORAL STUDIES FOR canonical value of 25 being achieved at ~10% partial melting. EUROPEAN PERFORMANCES IN RESEARCH and These trends are in excellent agreement with measurements of INOVATION - CUANTUMDOC” ID79407 oceanic basalt glasses. Our partitioning relationships enable calculation of the concentrations of a number of incompatible chalcophile trace elements in depleted mantle. These are as follows: 30ppm Cu, 65 ppb Pb, 7.6 ppb Ag, 12ppb In, 23 ppb Cd, 1.6 ppb Sb and 1.3 ppb Tl.

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Chemical weathering and regolith A low blank technique for the development over Rajmahal basalt measurement of iron isotopes in and Chotanagpur gneiss: A seawater and results from the comparative study tropical Atlantic Ocean PREMCHAND KISKU1, JITENDRA K. PATTANAIK1*, J. K. KLAR1*, R. H. JAMES1, I. J. PARKINSON2, TARUN K. DALAI1 AND S. BALAKRISHNAN2 E. P. ACHTERBERG1 AND C. SCHLOSSER1 1Department of Earth Sciences, Indian Institute of Science 1National Oceanography Centre, University of Southampton Education and Research-Kolkata, Mohanpur 741252, Waterfront Campus, European Way, Southampton, SO14 INDIA (*correspondence: [email protected]) 3ZH, UK, (*correspondance: [email protected], 2Department of Earth Sciences, Pondicherry University, [email protected], [email protected], Puducherry 605014, INDIA [email protected]) 2Bristol Isotope Group, School of Earth Sciences, University Mineralogical, geochemical and field investigations were of Bristol, Wills Memorial Building, BS8 1RJ, UK, carried out on weathering profiles developed over Rajamahal ([email protected]) basalt and Chotanagpur gneiss in eastern India to study and understand chemical weathering, elemental mobilization and Iron (Fe) is essential for marine photosynthesis, respiration development of regolith. Samples (n=38) were collected from and nitrogen uptake, but low Fe supply and low solubility three different locations, including fresh rock, variably under oxic conditions results in Fe-limitation of microbial weathered saprolite and soil. Variable thickness of soil cover communities in large parts of the world’s ocean. For this and saprolith was observed in the study area. Fresh Rajamahal reason the oceanic Fe cycle is linked to global carbon cycle. basalt consists of plagioclase phenocrysts enclosed by clinopyroxene and plagioclase groundmass, glass and opaque Recent studies [1, 2] have shown that analysis of the Fe minerals. Chotanagpur gneiss is mainly composed of K- isotopic composition can provide unique information about its feldspar, plagioclase, quartz, mica and bands of mafic sources, and Fe cycling within the oceans. Here we present a minerals. Weathered basalt shows red coloration along the protocol for the accurate and precise measurement of Fe fractures indicating precipitation of iron oxy-hydroxides. isotopes in seawater using a low blank, double-spike The Chemical Index of Alteration (CIA) in the weathering technique. To this end, Fe is pre-concentrated from seawater profile developed over the basalt and gneiss varies from 40 to using a NTA resin, and then separated from the sample matrix 95 and 46 to 85, respectively. High CIA values of pedoliths by anion exchange chromatography (AG1-X8 resin). Isotope indicate extensive chemical weathering in the study area. Data ratios are analysed by multi-collector inductively coupled of fresh and slightly weathered rocks plot close to the feldspar plasma mass spectrometry (ThermoFisher Neptune) coupled line in the A-CN-K diagram, indicating that feldspars are the to a sample desolvator (Aridus II or Apex-Q), and corrected most abundant minerals. Weathered samples show loss of for mass bias effects using a double-spike technique. Our CaO+Na2O+K2O, indicating extensive destruction of feldspar model simulations show that the optimal spike composition is and clinopyroxene. XRD analysis shows progressive upward 47% 57Fe, 53% 58Fe, with a small amount (<0.5%) of 54Fe, increase of clay mineral abundance in the soil profile. With which allows precise measurements of a wide range of sample respect to fresh rocks, Fe, Mn, Ti, Ni, Cr, Zr and Al are to spike mixing ratios, the optimum being ~1:1. The precision enriched, and Ca, Mg, Na, Sr and Si are depleted in the of the MC-ICPMS measurements is ,56Fe ~0.05 ‰ (2 SD), weathered basalt, whereas, in the weathered gneiss Si is enriched and Fe and Mn are depleted. For different elements, based on replicate analyses of haematite standards. zones of leaching and accumulation vary within a profile. We also present results of the preliminary analysis of Fe Results of this study bring out the differences in the isotopes in seawater samples (0.2 +m filtered) collected from alteration and weathering of minerals in profiles developed on within the Oxygen Minimum Zone (OMZ) of the tropical basaltic and gneissic rock types. Atlantic Ocean along ~12º N (GEOTRACES cruise GA06, 7 depth profiles sampled at 4 to 9 depths, ranging from surface waters to 5600 m depth). Fe concentrations ranged from 1.04 to 3.77 nM within the OMZ (located between 200 and 1000 m depth). The Fe isotope data will be used to (i) identify the sources of Fe to this region, and (ii) to identify processes of Fe cycling in oxygen minimum zones.

[1] Lacan et al. (2010) Anal. Chem 82(17), 7103-7111. [2] John & Adkins (2010) Mar. Chem 119, 65-79.

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Availability of light and chemical Spational and temporal variation in energy determines the structure of provenance of Eastern natural sulfide oxidizing biofilms Mediterranean sediment: JUDITH KLATT 1*, STEFFI MEYER, DIRK DE BEER1 Implications for Aegean volcanism AND LUBOS POLERECKY1 M. KLAVER*, T.T. DJULY AND P.Z. VROON 1Max-Planck-Institute for Marine Microbiology, Bremen, VU University Amsterdam, De Boelelaan 1085, 1081HV Germany (*correspondence: [email protected]) Amsterdam, The Netherlands (*correspondence:

[email protected]) In the Frasassi cave system, Italy, sulfidic streams and pools are colonized by aerobic chemolithoautotrophic Subducted sediment is one of the principal geochemical biofilms. Upon emergence of this water from the caves, light components of island arc magmas. Along-arc variation in becomes available and gives rise to biofilms that are subducting sediment composition is reflected in geochemical additionally inhabited by highly abundant phototrophic trends in the arc volcanics [e.g. 1]. The predominantly microorganisms. The structure of these biofilms varies Quaternary Aegean volcanic arc is the result of northward between two end-members, one characterized by a subduction of the African plate underneath the Aegean cyanobacterial layer on top of a distinct Beggiatoa layer (C/B microplate. East-west geochemical variation in Aegean arc biofilms) and the other one by an inverted structure (B/C volcanics has often been related to differences in subducted biofilms). We used microsensors to study how this structure sediment composition in the Eastern Mediterranean Sea depends on the availability of light and chemical energy. (EMS) resulting from contrasting source regions. C/B biofilms form where the availability of oxygen, and Recent studies [2,3,4] investigating the provenance of thus of chemical energy, from the water-column is limited (<5 EMS sediment suggest mixing between Sahara dust (old, µM). Aerobic chemolithotrophic activity in the Beggiatoa felsic) and Nile sediment (young, mafic). These studies layer depends entirely on the supply of oxygen from the however, lack a spational and temporal framework as they cyanobacteria, which occurs at high incident light intensities. focus exclusively on Quaternary deposits while the subducted Therefore, light is the energy source that drives the sediment underneath the Aegean arc is Pliocene to Mesozoic community and the main factor that regulates the spatial in age. We present an extensive new geochemical dataset of organization of its dominant functional groups. In B/C EMS sediment samples obtained from DSDP and ODP drill biofilms, which occur at locations where oxygen in the water cores along the Aegean arc from Quaternary to middle column is comparatively abundant (>45 µM) and continuously Miocene age. present, Beggiatoa are independent of the photosynthetic The new dataset, in conjunction with previously published production of oxygen and outcompete the cyanobacteria in the results, allows us to accurately trace the along-arc temporal uppermost layer of the biofilm (i.e., closest to one of the variation of EMS sediment provenance. In line with previous energy sources). The proliferation of cyanobacteria in these results, we conclude that Quaternary EMS is a mix of Nile biofilms seems to be disadvantaged by the extensive interval sediment, Sahara dust and autogenic carbonate or evaporite of darkness during night and by high back scattering of light in components. A clear along-arc trend in principal component the Beggiatoa layer during the day. Therefore, although the can be observed, and the geochemical composition of daily flux of light energy to the biofilm is much greater than subducting sediment is highly variable. However, in the Plio- the daily flux of chemical energy derived from the oxidation to Miocene, the Nile component appears to be dominant in the of sulfide with oxygen, light is only peripherally utilized. entire EMS, leading to much less pronounced geochemical Instead, the continuity of the input of chemical energy appears variation of subducted sediment along the Aegean arc. Hence, to be a more important factor determining the community the assumption that east-west geochemical trends in Aegean structure and its dominant functional traits. Our study thereby arc volcanics are due to differences in subducted EMS introduces a scenario, where apparent uncoupling of sediment composition, may be unjustified. phototrophic and aerobic chemolithotrophic activity leads to

outcompetition of photosynthetic microbes even in the [1] White & Dupré (1986) JGR 91, 5927-5941. [2] Weldeab et presence of light showing that both microbial interactions and al. (2001) Chem. Geol. 186, 139-149. [3] Revel et al. (2010) available thermodynamic energy must be considered to Quat. Sci. Rev. 29, 1342-1362. [4] Padoan et al. (2011) GCA understand the biogeochemical cycling. 75, 3627-3644.

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Chondritic Sm/Nd in the Earth, Investigation of boron, carbon, and Moon and Mars oxygen isotope systematics in the 1 2 1 T. KLEINE , C. BURKHARDT AND P. SPRUNG aragonite-CO2-H2O system 1Institut für Planetologie, University of Münster, 48149 C.D. KLEIN GEBBINCK1, S.-T. KIM1*, M. HENEHAN2 Münster, Germany ([email protected]) AND G.L. FOSTER2 2 Origins Laboratory, Department of Geophysical Sciences, 1 School of Geography and Earth Sciences, McMaster The University of Chicago, IL 60637, USA University, Hamilton, Canada (*correspondence:

[email protected]) One of the most fundamental assumptions in geochemistry 2 Ocean and Earth Sciences, University of Southampton, is that refractory lithophile elements occur in chondritic Southampton, UK relative abundances in the bulk Earth. However, the accessible

silicate Earth exhibits a ~20 ppm higher 142Nd/144Nd than most Calcium carbonate has been ubiquitous on the surface of chondrites [1], and this may reflect a higher-than-chondritic the Earth. Therefore, marine and continental carbonates, such Sm/Nd of the bulk Earth [2-4]. Caro et al. [2] argued that as forams and speleothems, play a critical role in because the 146Sm-142Nd isochrons of the lunar and martian paleoceanography and paleoclimatology as a key climate mantles intersect at a higher-than-chondritic 147Sm/144Nd and archive. Hence, a proper understanding of stable isotope at the 142Nd/144Nd of the modern terrestrial mantle, the Earth, systematics in carbonates with respect to their formational Moon and Mars all are characterized by a common, environment is important for the reconstruction of Earth’s superchondritic bulk composition (termed 'SCHEM' [3]). Such climate history. non-chondritic compositions may result from collisional Stable isotope systematics of boron, carbon, and oxygen in erosion of early-formed crust or may reflect assembly of the the aragonite-carbon dioxide-water system were terrestrial planets from non-chondritic materials [4]. simultaneously investigated using synthetic aragonite as a Here we re-examine the lunar and martian 146Sm-142Nd function of solution chemistry at 25 °C. A refined version of systematics and show that the lunar and shergottite isochrons the constant addition method [1] was used to synthesize a intersect almost exactly at the chondritic 147Sm/144Nd, whereas polymorph of CaCO , aragonite, in aqueous solutions of SCHEM plots off both isochrons. This as well as evidence 3 various, but constant pH values and ionic strengths. The from the Hf-Nd isotope systematics of lunar samples [5] mineralogy of the carbonate was confirmed by XRD analysis indicates chondritic Sm/Nd in the Earth, Moon and Mars. The and their isotopic compositions were determined by either 142Nd/144Nd of the lunar and shergottite isochrons at a IRMS or MC-ICPMS. chondritic Sm/Nd are slightly lower than albeit not clearly Results of our study suggest that the effect of ionic resolved from that of the modern terrestrial mantle, but are strength (~0.7 mol/kg) on the stable isotope fractionation distinctly higher than the mean 142Nd/144Nd of ordinary and between aragonite and water (for oxygen) as well as between carbonaceous chondrites. We interpret these 142Nd/144Nd aragonite and DIC (for carbon) in the aragonite-CO -H O variations to be nucleosynthetic in origin and show them to be 2 2 system is negligible. In addition, boron isotope analysis of consistent with a heterogeneous distribution of s- and p- synthetic aragonite prepared from aqueous solutions of process Nd. Of note, the resulting nucleosynthetic anomalies seawater-like ionic strength indicates that borate ions are in Sm and non-radiogenic Nd isotopes are small and consistent preferentially incorporated into the aragonite crystal. with currently available data for chondrites [e.g., 6].

A nucleosynthetic origin of the 142Nd difference between [1] Kim et al. (2007) Geochim. Cosmochim. Acta. 71, 4704- the Earth and chondrites provides further evidence that the 4715. isotopic composition of the Earth is distinctly non-chondritic

[7]. However, the chemical composition of the Earth, at least

for refractory lithophile elements, appears to be chondritic.

[1] Boyet & Carlson (2005) Science 309, 576-581. [2] Caro et al. (2008) Nature 452, 336-339. [3] Caro & Bourdon (2010) GCA 74, 3333-3349. [4] Campbell & O'Neill (2012) Nature 483, 553-558. [5] Sprung et al. (2013) EPSL, subm. [6] Carlson et al. (2007) Science 316, 1175-1178. [7] Burkhardt et al. (2011) EPSL 312, 390-400.

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Tracing old SCLM in Pan-African Experimental study of trace element granitoids from Dronning Maud partitioning between spinel and Land (East Antarctica) with Sr-Nd silicate melts: Effects of oxygen isotope signatures fugacity and spinel composition I.C. KLEINHANNS1*, J.JACOBS2, A. K.ENGVIK3, S KLEMME1, CH WIJBRANS1,*, C VOLLMER1, B.BINGEN3, N.W.ROLAND4, A. LÄUFER4 M MENNEKEN1 AND J BERNDT1 1 AND R.SCHOENBERG 1 Institut für Mineralogie, Universität Münster, Germany, 1Universität Tübingen, Wilhelmstrasse 56, D-72074 *[email protected] Tuebingen; *[email protected] 2Universitetet i Bergen, Allégaten 41, NO-5007 Bergen Spinel is a common accessory mineral that occurs in a 3Norges Geologiske Undersøkelse, NO-7491 Trondheim variety of rocks such as evolved basaltic magmas or 4BGR, Stilleweg 2, D-30655 Hannover chromitites in ultramafic rocks. Spinels often contain large amounts of transition metals or other redox sensitive elements, Dronning Maud Land (DML) represents the southern end but the partitioning of these elements in these rocks is not well of the East African Antarctic orogen that was created during constrained, probably because it depends on several the final amalgamation of Gondwana in the Neoproterozoic. parameters which are difficult to disentangle: temperature, The suture between parts of East and West Gondwana spans pressure, oxygen fugacity and composition of the crystals and over more than 8000km from present Egypt-Arabia to present melt. Mozambique-Antarctica. The part north of the Lurio belt (LB) Experiments are performed in 1 atm. gas mixing furnaces is characterised by accretionary tectonics visible in the at temperatures between 1200 and 1430oC and oxygen Arabian-Nubian Shield contrary to the part south that shows fugacities ranging from log -12 to log -0.7. Starting materials

evidence for continent-continent collision. Within southern consist of glasses in the system (Cr2O3-FeO)-CaO-MgO-

Mozambique and DML numerous late-tectonic granitoids are Al2O3-TiO2-SiO2 doped with a large number of trace elements. observed, which are characterised as ferroan A-type granitoids The experimental run products were characterized with that evolved under high-T conditions. The geodynamic regime electron microprobe for major elements and 193nm Laser is explained by extensional tectonics within a collapsing Ablation ICPMS for trace elements. The experiments all orogen accompanied by astenospheric upwelling through contained spinels and glass, some experiments contained delamination of the orogenic root [1]. In this project we additional phases (olivine or plagioclase). studied an E-W-profile along the 72°S-latitude starting from The Fe2+/Mg2+ ratio in spinel has little effect on trace the Mühlig-Hofmann mountains (MH) (4°-7°E) via central element partitioning, but the concentration of trivalent cations Dronning Maud Land (cDML) (8°-14°E) and finally samples such as Al, Fe and Cr appears to have an (large) effect on the from Sør Rondane (SR) (23°-25°E). TDM (Nd) for MH and partitioning of Ti, Sc and the HFSE; D values for these cDML samples are of Meso- to Paleoproterozoic age although elements are lowest in Al rich spinels, are slightly elevated in the oldest (yet detected) crust in that region is of Grenville- spinels that contain chromium, and are about an order of age. We take this as evidence for the existence of an old magnitude higher in spinel high in Fe3+. subcontinental lithospheric mantle underneath this part of East Our results show that partition coefficients for some

Antarctica and its contribution to the granitoids. SR granitoids elements are redox sensitive; DNi, DCo, and DMo decrease

are different as they show grenville-aged TDM (Nd) and could slightly with increasing fO2 and DV decreases over four orders

thus have been developed by simple crustal melting. Initial Sr of magnitude. In contrast, DPt and DRh increase strongly with isotope signatures for both regions are similar and indicate increasing oxygen fugacity. To investigate peculiar high Pt homogenisation during time of emplacement. Finally, samples and Rh concentration in the some of the experimental spinels, from the LB show large similarities with MH and cDML, but a TEM study was performed to investigate the presence of are different to SR granitoids. This allows to place certain platinum group element nuggets as inclusions in the spinel. paleogeographical constraints on Gondwana configuration. However, preliminary TEM results show no inclusions in these spinels suggesting that the measured high D’s are [1] Jacobs et al. (2008) In: Satish-Kumar et al. Geol. Society, correct. London, Spec. Pub. 308, 69-90

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Research of Condensation of Exploring synergies of aerosol and Supersaturated Water Vapor climate mitigation strategies A. KLIMKIN1, A. KOZLOV2, F. KRYMSKIY3, A. KURYAK1, Z. KLIMONT1*, M. AMANN1, S. RAO1 AND F. DENTENER2 2 2 S. MALYSHKIN , A. PETROV 1 IIASA, Schlosspltatz 1, 2361 Laxenburg, Austria AND YU. PONOMAREV1 (*correspondence: [email protected]) 1Institute of Atmospheric Optics SB RAS, Tomsk, Russia, 2JRC/IES, 21027 Ispra, Italy [email protected], [email protected], [email protected]; 2Institute of Chemical Kinetics and Combustion SB RAS, Recent work has highlighted the scope for reductions of Novosibirsk, Russia; short-lived climates pollutants (SLCP) that yield significant 3Institute of Cosmophysical Research and Aeronomy SB RAS, benefits to human health and agricultural crops at the local Yakutsk, Russia scale while limiting temperature increase in the near-term [1, 2]. Identified measures would achieve large cuts in emissions

Clouds in the atmosphere have a significant influence on of CH4 and BC, but minimize further emission reductions of

weather conditions, and play a prominent part in the processes cooling aerosols, such as SO2, beyond what is already implied of energy exchange between the Sun, the surface of the Earth in current legislation. Climate policies, cutting emissions of and the atmosphere. That is why it is important to research the several pollutants, would also bring important health benefits mechanisms of clouds formation and the processes developing [3]. at different stages of formation. It is essential to estimate the While implementation of measures addressing SLCP or influence of cosmic radiation, as well as other natural and specific climate polices would result, beyond climate benefits, anthropogenic factors on these processes. in significant air quality and ecosystem improvements, they Nucleation of droplets in the cooled water vapor requires will not be sufficient to remediate all current air quality the presence of condensation centers [1-3]. In order to observe problems and achieve sustainable air quality around the world. the dynamics of droplets nucleation, the Institute of Additional air quality measures will need to involve further

Atmospheric Optics SB RAS developed a unit on basis of the reductions of cooling aerosols, such as SO2 emissions, which two-chambered cell with capacity exceeding 40 m3 [4] which however will result in a clear climate dis-benefit, at least in the

allows creating supersaturated 92/ vapor. At that, the unit near term (Figure 1). offers the possibility of controlling thermodynamic parameters The presentation will review available emissions scenarios under varied pressure, test gas mixture composition and influence of ionizing radiation. The study was focused on nucleation of nanoparticles and droplets. The nucleation developed under the gradual decrease in pressure of the test gas mixture when the unit conditions were made similar to Wilson chamber, type-II. The gas mixture was also exposed to the charged particle beam under

gradual pressure decrease and supersaturated H2O vapor. To this effect the unit was equipped with the electron gun [5].

Air, binary mixtures of H2O-CO2 and H2O-N2, as well as the

air with high concentration of CO2 and N2 were used as test mixtures.

[1] Marsh N., Svensmark H. // Space Sci. Rev. 2000. V.94, for measures or policies that could compensate climate dis- N 1–2. P. 215–230. [2] Andreas M., et al. // Atmos. Chem. benefits of SO2 mitigation by co-controls of long-lived and Phys. 2008. V. 8, N 16. P. 4911–4923. [3] Krimskiy G.F. greenhouse gases. // Science and Technology in Yakutiya. 2005. N 1(8). P. 3–6. (Russian issue). [4] Ponomarev Yu.N., Tyryshkin I.S. // [1] Shindell et al. (2012) Science, 335, 183—189. [2] Atmospheric and Oceanic Optics Journal. 1993. V.6, N 04. P. Annenberg et al. (2012) Env. Health Persp., 120, 831-839. [3] 360-368. [5] Yu. Ponomarev., et al. // Solar-Terrestrial Rao et al., Global Env. Chnage (in review). Physics. 2012. V.21. P.58-61.

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Geochemistry of organic matter from A microscopic and ToF-SIMS study Triassic U-bearing sandstones of on the Ra uptake by barite Peribaltic Syneclise (N Poland) KLINKENBERG, M1*., BRANDT, F. 1, BREUER, U.2 AND BOSBACH, D.1 KLIMUSZKO E., WOLKOWICZ S.* AND MIECZNIK J.B. 1Institute of Energy and Climate Research (IEK-6) PGI-NRI, 4 Rakowiecka, 00-975 Warsaw, Poland Forschungszentrum Jülich, Germany; m.klinkenberg@fz- ([email protected]) juelich.de(*presenting author), [email protected],

[email protected] In central parts of the Peribaltic Syneclize, Triassic rocks 2ZEA-3 Analytics, Forschungszentrum Jülich, Germany; display sandstone type uranium mineralization. Mineralization [email protected] is related to gray sandstones poor in TOC.

5 samples were covered by geochemical studies, including Long-term safety assessment studies of nuclear waste TOC, bitumen fractions, saturated hydrocarbons and aromatic repositories for spent nuclear fuel commonly consider a hydrocarbons. scenario, in which radium released from the fuel comes into Small TOC values (below 0,1%) indicate poor contact with an aqueous solution saturated with barium [1]. hydrocarbon generation potential. Amounts of bitumens are An open question is whether a Ra containing solution will small, from 70 to 170 ppm. The share of hydrocarbons in these equilibrate with solid BaSO under repository relevant bitumens ranges from 26,7% to 52,3%, being lower than that 4 conditions due to complete recrystallization. Previous studies of the asphaltene and resin fraction. Migration coefficient of have indicated that uptake of Ra is not limited by pure hydrocarbons is raised, ranging from 0,03 to 0,09, which adsorption at close to equilibrium conditions but involves a suggests epigenetic origin of labile components. N-alkanes significant fraction of the bulk solid [2,3]. So far, only with 21 – 24 carbons in chain are most common, suggesting macroscopic data indicate that barite may fully recrystallize to that the organic matter is of the sapropel type. Analyses of radiobarite. For this microscopic (SEM) and ToF-SIMS study, compounds of the terpane group showed predominance of samples of two different barites were prepared in batch pentacyclic compounds over the tricyclic, indicating high sorption experiments to investigate the recrystallization of share of bacteria in original organic matter as well as low level barite in the presence of Ra. Based on gamma spectrometry, it of maturation. The composition changes in lower part of the was observed that one barite incorporates Ra faster than the studied series. In that part, tricyclic compounds predominate other barite. over the pentacyclic which indicates a higher level of A broad grain size distribution was determined via SEM maturation. Moreover, difference between contents of 17: observation for the fine grained barite. During recrystallization (H)-trisnorhopane (Tm) and 18: (H)-trisnorhopane II (Ts) of the crystals, an additional effect on the grain size evolution compounds which further supports higher level of maturation due to the presence of Ra was detected compared to the of the studied organic matter. C27 (cholestane) appears fairly coarsening of a blank sample due to Ostwald ripening. In common in the group of identified steranes but content of contrast, the narrow grain size distribution of the coarse sterane C29 sterane (stigmastane) is higher which suggests grained barite didn’t show significant changes with time and some contribution of terrigenous material in organic matter. no influence of the presence of Ra. Here, morpholgical Significant share of C28 compound (ergostane) was found in changes were observed instead. lower part of the studied series which evidences presence of The results of ToF-SIMS indicate a homogeneous uptake material of the lacustrine origin. of Ra into the crystals. After 443 days the integrated Ra The Triassic rocks are poor in TOC and their hydrocarbon concentration corresponds with the size of the barite particles. generation potential is very low. At the same time they yield The Ba/Ra ratio was calculated from several ToF-SIMS small amounts of labile components which would be measurements. The Ra/Ba intensity distribution has its epigenetic origin. The organic matter was generally of the maximum between 2 and 4 . 10-3, corresponding well with the marine origin. In lower part of the rock series, the parent macroscopic results from bulk solution chemistry. organic matter comprises material of the lacustrine type, and

in the upper – organic matter of the marine type is enriched [1] Grandia, F. et al.: SKB Technical Report TR-08-07 2008 with supposedly allochtoneous terrigenous material. [2] Bosbach, D. et al.: SKB Technical Report TR-10-43, 2010. [3] Curti, E. et al.: Geochim. et Cosmochim. Acta, 2010, 74, 3553-3570.

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Hybrid Multispectral Analysis Abiotic reactions of nitrite during (HMA): Innovative technology for microbial Fe(II) oxidation and their continuously monitoring the influence on cell-encrustation of biogeochemistry of urban waterways nitrate-reducers GARY P. KLINKHAMMER1 AND CHRIS J. RUSSO2 NICOLE KLUEGLEIN, FABIAN ZEITVOGEL, MARTIN OBST 1 AND ANDREAS KAPPLER* CEOAS, Ocean Admin. Bldg. 104, Oregon State University, Corvallis OR, USA 97331 University of Tuebingen, Centre for Applied Geoscience, 2ZAPS Technologies Inc., 4314 Research Way, Corvallis OR, Sigwartstrasse 10, 72076 Tuebingen, Germany USA 97333 ([email protected]) ([email protected]) Hybrid Multispectral Analysis (HMA) uses a fiber optic ([email protected]) spectrometer to analyze source and waste waters for multiple (*correspondence: [email protected]) parameters. Hybrid refers to the HMA capability of measuring fluorescence and absorption as well as scattering to produce a Anoxic, nitrate-reducing bacteria are widespread in soils - rich array of optical data. No chemicals are required in HMA and sediments. They use nitrate (NO3 ) and the following - analysis. The optical information is then used to correct for intermediates (NO2 , NO and N2O) as electron acceptors. In artifacts such as turbidity and signal overlap before calculating addition to heterotrophic denitrifiers, nitrate-reducers have concentrations based on laboratory calibrations performed in a been isolated which were suggested to couple nitrate reduction clean water matrix. HMA data quality is maintained over time to the oxidation of Fe(II). Recently, however, it has been with automated cleaning and correction protocols. The HMA questioned whether the observed Fe(II) oxidation is completly menu for source water includes TOC, nitrate, chlorophylls, enzymatic or whether it is at least partly due to an abiotic turbidity, biochemical oxygen demand (BOD), total suspended reaction between Fe(II) and the reactive N-species formed solids (TSS), color, E. coli bacteria, fluorescent dissolved during mixotrophic growth [1,2,3]. Here we present data that - organic matter (FDOM) and other water quality parameters. demonstrates that NO2 is able to oxidize Fe(II) under pH- Each value is displayed on a graphical web-user interface once neutral and particularly under acidic conditions at high rates. every 2-3 minutes depending on the number of measurements Fe(II) analysis using sulfamic acid instead of HCl prevents the - in the menu. In this paper HMA data will be compared for abiotic reaction of NO2 and Fe(II) during acidic extraction and several urban-impacted waterways including a small creek in yields correct Fe(II)/Fe(III) values. To evaluate the role of Corvallis Oregon (Oak Creek) and a river-estuary in Sydney bacterially produced nitrite in Fe(II) oxidation, we compared Australia (Parramatta River). The biogeochemistry of these two strains that were isolated as nitrate-dependent Fe(II)- urban streams will be compared to the relatively pristine, oxidizers [1,2] with two heterotrophic nitrate-reducers mountain-fed Santiam River in coastal Oregon. The high- (Paracoccus denitrificans ATCC 19367 & 1222) in their resolution data from HMA allows details of important inter- ability to oxidize ferrous iron and the formation of Fe(III) parameter relationships to be examined in detail for the first mineral crusts around the cells. All four tested strains oxidized time. Fe(II) and using SEM/TEM we observed heavy encrustation of all strains. However, the shape, crystallinity and localization of minerals inside and outside the cell varied distinctly between the strains. Applying fluorescent lectins in the CLSM, we also observed a significant production of exopolymeric substances, maybe as a protection mechanism against high Fe(II) concentrations. Our observations suggest that cell encrustation is a side effect caused by abiotic Fe(II) oxidation by nitrite during heterotrophic denitrification.

[1] Klueglein & Kappler (2013) Geobiology 11, 180-190. [2] Weber et al. (2006) Appl. Environ. Microbiol. 72, 686-694. [3] Kopf, Henny & Newman (2013) Environ. Sci. Technol. in press

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Fluid migration along a dense, Constraints for the clumped isotope intersecting array of faults on the application in diagnetic environments outer-shelf of Southern Costa Rica: involving high salt concentrations Insights from 3D seismic attributes TOBIAS KLUGE*, CÉDRIC M. JOHN and multibeam data AND SIMON DAVIS 1 1 1 Department of Earth Science and Engineering and Qatar JARED W KLUESNER , ELI SILVER , STEPHANIE NALE , 2 2 Carbonate and Carbon Storage Research Centre, Imperial NATHAN L BANGS AND KIRK D MCINTOSH College London, SW7 2BP, United Kingdom; 1Earth and Planetary Sci Dept, Univ California Santa Cruz, *correspondence: [email protected] Santa Cruz, CA, USA, ([email protected]) 2Institute for Geophysics, Univ. of Texas, Austin, TX, USA Carbonate clumped isotopes is a promising proxy for the reconstruction of mineral formation temperature and their We use 3D seismic reflection attributes and multibeam parent fluid composition. Clumped isotopes has a wide range data to map and analyze fluid-flow along a dense network of of potential applications, such as the reconstruction of the intersecting normal faults imaged on the outer shelf offshore diagenetic history of sedimentary basins that involve fluids Southern Costa Rica. Faults were imaged on the seafloor using with a high salt concentration and elevated temperatures. As (i) high-resolvability EM122 multibeam data, and (ii) in 3D salt ion effects are known to impact bulk oxygen isotopes, below the seafloor using seismic reflection data, both collected here we assessed the influence of salinity on clumped isotopes during the 2011 CRISP seismic survey. Multibeam in the temperature range from 20-90°C.

bathymetry reveals a series of high-backscatter ridges on the Samples were precipitated from a super-saturated CaCO3

seafloor cut by numerous faults with roughly N-S and E-W solution via N2 bubbling. Prior to starting the carbonate trends. Vertical profiles within the 3D seismic volume reveal precipitation the solution was equilibrated at the respective that faults have normal displacements and extend deep into the experiment temperature. Different salt ions (Na+, Ca2+, Mg2+) sedimentary section, some of which cut through top of the were added to the solution and compared to samples without 13 margin. Numerous indicators of fluid-migration and fluid-rich added NaCl, MgCl or CaCl2 to evaluate ionic effects on C- sediments, such as bright spots, dim spots, and acoustic 18O clumping. No effects were observed for NaCl at turbidity zones, are present along fault traces imaged on temperatures between 23 and 90°C and salt concentrations up vertical inlines and crosslines. Within the seismic volume we to 6 molal. Preliminary results indicate that moderate

use seismic discontinuity attributes (e.g., coherency and concentrations of MgCl2 (0-0.4 molal) and CaCl2 (0-0.5 molal) similarity) of a dip-steered seismic volume to reveal and map have no observable influence on 13C-18O clumping.

fault traces in horizontal time slices. We then use a neural Furthermore, polymorphism of CaCO3 produced no network of multiple seismic attributes to create a ‘fault cube’ observable effect. In summary, our results indicate that and a ‘chimney cube’ to detect high probability zones fluid carbonate clumped isotopes can be applied to carbonates leakage along faults. Indicators of seafloor seepage, such as precipitated from saline parent fluids without the need to high-backscatter pockmarks and mounds, are imaged on the correct for salt ion effects in common NaCl brines or fluids

seafloor along fault traces and above seismic indicators of containing moderate levels of CaCl2 and MgCl2. fluid migration. Use of seismic discontinuity attributes We gratefully acknowledge funding from Qatar massively improves 3D interpretability of a very complex set Petroleum, Shell and the Qatar Science and Technology Park. of intersecting faults, and provides insight into understanding the pathways of fluids and gas within the margin of Costa Rica.

Figure 1. 3D perspective view of subset of 3D seismic data below the outer shelf of southern Costa Rica.

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Petrological constraints on magma Established and advanced solid-state plumbing dynamics of the 2011 El NMR spectroscopy for a better Hierro eruption (Canary Islands) understanding of the structure and A. KLÜGEL*1, M.-A. LONGPRÉ2 AND J. STIX2 function of natural organic matter in 1University of Bremen, Geosciences Department, Bremen, soils, water and sediments Germany [[email protected]] 1 2 2 HEIKE KNICKER , SASCHA LANGE , Earth and Planetary Sciences, McGill University, Montréal, 2 2 BARTH VAN ROSSUM AND HARTMUT OSCHKINAT Québec, Canada [[email protected]] (*correspondence: [email protected]) 1Iinstituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Adva. Reina Mercedes, 10. 4012 Sevilla, Spain A submarine eruption took place off the south coast of El 2Leibniz-Institut für Molekulare Pharmakologie FMP, Robert- Hierro, Canary Islands, from October 2011 to March 2012. Rössle-str. 10, 13125 Berlin, Germany The well-monitored eruption was preceded and accompanied by numerous earthquakes and ground deformation. Eruptive In geobiogeochemistry, 1-dimensional solid-state NMR products sporadically rose to the ocean surface and were spectroscopy has been proven as a powerful tool for the sampled at different stages of the eruption. We carried out a characterization of natural organic matter (NOM) in soils, detailed geochemical and petrological study to constrain sediments and waters. However, compared to solution NMR magma plumbing dynamics associated with the eruption. spectroscopy, this technique suffers from broad resonance All bulk lava samples are basanites with essentially lines and low resolution, which could be overcome by the use identical matrix glass compositions, implying very little of 2-dimenstional solid-state NMR pulse sequences. Until change in magmatic liquid composition through time. The recently, this approach has been unfeasible as a routine tool in MgO content of the bulk lava increased at the late eruptive geochemistry, mainly because of the low NMR sensitivity of phase due to increasing contents of ferromagnesian crystals. the respective samples. Alternative to the use of higher Final phenocryst crystallization took place at 500-710 MPa magnetic fields, considerable signal enhancements can be (17-24 km depth, within the upper mantle), as was determined achieved with the new developments in the field of dynamic by 73 clinopyroxene-melt pairs. This depth range for an nuclear polarization (DNP) solid-state NMR spectroscopy. inferred magma reservoir coincides perfectly with the depths Here, the improvement is achieved by a microwave-driven of syn-eruptive seismicity. In contrast, the analysis of 260 transfer of polarization from a paramagnetic centre to nuclear

CO2-rich fluid inclusions in phenocrysts yields two pressure spins. Application of DNP to magic angle spinning (MAS) ranges, one at 280-440 MPa (10-16 km depth, lower crust to spectra of biological systems (frozen solutions) showed upper mantle) and one at 450-580 MPa (16-19 km). The enhancements by factors of 40 to 50 (Hall et al., 1997). shallower range corresponds well with the depths of pre- Applying this technique for the first time on NOM, lower but eruptive seismicity, and reflects lateral movement of magma still promising enhancement factors were obtained which within the lower crust over a distance of ca. 15 km before allowed the successful acquisition of 2D solid-state NMR ascending to the eruptive site. spectra of such samples. In the present contribution, the Detailed analysis of zoning patterns in olivine and possibilities and limitation of established solid-state NMR clinopyroxene phenocrysts and compositions of melt techniques in NOM research are discussed and first results inclusions reveal that at least two distinct magmas were obtained with solid-state DNP NMR are presented. Those first involved in the eruption. Both magma batches were initially data demonstrate the great potential of the latter and that this stored in the upper mantle, one probably at 19-25 km depth approach opens new doors for a better understanding of and one at 15-18 km. Diffusion modelling indicates that biochemical processes in soils, sediments and water. mixing of these magmas likely began about three months before eruption, resulting in intrusions to the lower crust and associated seismic crisis and surface deformation. Strikingly, mixing must have continued for many weeks after the onset of the eruption. The abundance of complexly zoned phenocrysts in the late eruptive products is interpreted to reflect mobilization of crystal mush and cumulates as a consequence of magma withdrawal and reservoir collapse.

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Coupling of nitrogen inputs and Tellus: Regional-scale baseline losses during the Permian-Triassic geochemical mapping of soil, stream biotic crisis sediment and stream water for the J. KNIES*1, S.E. GRASBY2,3, B. BEAUCHAMP3 island of Ireland 4 AND C.J. SCHUBERT 1 2 KNIGHTS, K.V . AND SCANLON, R. 1Geological Survey of Norway, 7491 Trondheim, Norway 12Geological Survey of Ireland, Beggar’s Bush, Haddington (*correspondence: [email protected]) Road, Dublin 4, Ireland ([email protected], 2Geological Survey of Canada, Calgary, Alberta T2L 2A7, [email protected]) Canada 3University of Calgary, Calgary, Alberta T2N 1N4, Canada Systematic geochemical surveying of the northern region 4Swiss Federal Insitute of Aquatic Science and Technology, of the island of Ireland, comprising Northern Ireland (NI) and EAWAG, 6407 Kastanienbaum, Switzerland the northernmost counties of the Republic of Ireland (RoI), is

now complete. The Geological Survey of Ireland recently We report coupling of dinitrogen (N ) fixation and 2 conducted regional-scale surveying of soils, stream sediments denitrification in oxygen deficient waters in the Sverdrup and stream waters geochemistry across the northern region of Basin, Arctic Canada, during the Permian-Triassic biotic Ireland under the Tellus Border project. A survey of crises. Sediments deposited prior to the latest Permian neighbouring Northern Ireland was completed in 2007 under extinction (LPE) event are characterized by positive "15N the Tellus project by the Geological Survey of Northern values of ~9 ‰ associated with the presence of lycopane Ireland. Multi-element analytical data for the entire region are implying upwelling of denitrified waters from an expanded currently being integrated to provide seamless cross-border oxygen minimum zone (OMZ). The data show anoxic bottom mapped datasets. These surveys also took place alongside water conditions were not developed in northeastern mutiparameter low-level airborne geophysical surveys Panthalassa during the Late Permian. Promoted by dispersing collecting magnetic field, electromangnetic and radiometric coal ash from Siberian Traps volcanic, as marked by abrupt data; resulting in a high-quality and comprehensive geo- rise in C/N ratios (>20) prior to the LPE event, euxinic environmental database. conditions first developed at the LPE. Nutrient-induced anoxia There are challenges in merging these data; with two was likely prevalent during the Early Triassic in the aftermath ground survey designs conducted at differing densities. of the LPE, however, the nutrient N pool was predominantly However the same general field collection, sample preparation fuelled by N -fixing cyanobacteria. 2 and anaytical methodologies have been utilised. Topsoils (c.51 20 cm) have undergone aqua regia ICP analyses, stream sediments (<150 µm wet-sieved fraction) by XRFS and stream waters analysed by IC, ICP-MS and for DOC. Legacy and new data have been combined and are being assessed using multivariate statistical techniques (e.g. factor analyses) to characterise and map factors which help to define geochemical signatures; to understand sources and processes at play. They reveal broad geogenic controls and influence of agricultural practices that overprint the rural geochemical baseline. The region now has a rich geochemical dataset with improved detail across this geologically diverse region. Elements of interest to agricultural applications are compared to results from prior national soil surveys and the European- wide GEMAS study.

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The effect of marine biological Impact of long term wetting on activity on aerosol generation and hydrology and biogeochemistry of a cold cloud formation peat bog in Ontario, Canada D. A. KNOPF1*, P. A. ALPERT1, W. KILTHAU1, KLAUS-HOLGER KNORR1, CHRISTIAN BLODAU1, SVEN J. RADWAY1 AND J. Y. ALLER1 FREI2, KLAUS KASPARBAUER2AND JONAS SCHAPER2 1School of Marine and Atmospheric Sciences, Stony Brook 1Institute for Landscape Ecology, Hydrology Group, WWU Univ., Stony Brook, NY, 11794-5000, USA Münster, Heisenbergstr. 2, 48149 Münster, Germany; (*correspondence to [email protected]) [email protected] 2Department of Hydrology, University of Bayreuth, Sea salt particles are a major contributor to atmospheric Universitätsstr. 30, 95447 Bayreuth, Germany aerosol. Recent observations have indicated that these and other marine derived particles can be enriched in organic Peatlands of the northern hemisphere store vast amounts material (OM), particularly during periods of high primary of carbon but also contribute to global methane emissions. As production. This OM can impact atmospheric particulate large areas in the boreal and temperate zones are predicted to matter loading and the ability of particles to act as cloud undergo significant changes in climate and concomitant condensation and ice nuclei, with subsequent consequences changes in hydrology, it is crucial to understand the response for the global radiative budget. of peatlands to altered climatic and hydrological boundary Here we report the effects of marine biological activity on conditions. In this study we investigated the response of aerosol generation and cloud formation potential. Aerosols peatlands to long term wetting, as especially in winter for were produced by plunging jets and glass frits from 1000L large areas wetter conditions have been predicted. We mesocosms containing three phytoplankton species cultured in hypothesized that long term wetting will result in changes in artificial seawater, exudates derived from phytoplankton, a vegetation, concomittant changes in peat decomposability and bacterial culture, and a natural seawater microbial community. also nutrient input from the adjacent water body. The 14-day experiments simulated bloom development as To this end, we chose the Luther Marsh site in Ontario, evidenced by changes in cell numbers. At each sampling time, Canada, that has been partly flooded since the 1950s due to aerosolized particles were size discriminated under dry and the construction of a reservoir. Water management in the 80% humidified conditions, collected, and characterized. reservoir flooded a large part of the peatland, but also causes Bubble-size spectra were determined. To interpret seasonal flooding and draining, shifting hydrological flow relationships between biological activity and aerosol size patterns and vegetation gradients. Hydrology was monitored distributions, we characterized concentrations of dissolved by means of piezometers and pressure transducers over one and particulate organic matter, transparent exopolymer growing season over a transect of 7 sites from the reservoir to particles, and microgels; numbers of phytoplankton and virus- the inner, pristine part of the bog. At the same sites, we like particles; and the proportion of live:dead bacteria. obtained pore water chemistry data and dissolved gases. Aerosols were collected on substrates for single particle Partial flooding resulted in obvious changes in vegetation, chemical analyses using electron and X-ray micro- increased nutrient availability, and thus increased spectroscopy. Water uptake and ice nucleation capabilities for decomposition activiy in the wet part. This was reflected more

temperatures as low as 200 K were determined. narrow CH4 to CO2 ratios in the pore water and higher As phytoplankton growth reached stationary phase, the concentrations and calculated turnover rates. Advective number of particles smaller than 100 nm increased threefold. transport removed decomposition end products and introduced Ice active particles in a population characterized by a sea salt nutrient enriched reservoir water, as indicated by elevated pH core with OM coating are 1.0-5.0 µm in diameter. Water amd increased concentrations in Ca and Mg. DOC quality as uptake is observed until 220 K and 60% RH. Immersion assessed by fluorescence spectroscopy also gradually freezing occurs between 80% and 100% RH. Deposition ice approached quality indices observed in the reservoir. nucleation occurs below 215 K and around 70% RH. Our This study demonstrated that partial flooding of a peatland experiments show that biological activity can affect marine significantly changes vegetation and the nutritional status, derived aerosol, with implications for cloud formation and the resulting in a shift towards more CH4 production and higher radiative budget. turnover rates.

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Molecular Dynamics Study of Subducted halogens and noble gases Cement-Aqueous Solution Interfacial in the mantle wedge peridotites System: Cesium Ion Fixation M. KOBAYASHI1*, H. SUMINO1, K. NAGAO1, 2 3 4 1 1 2 S. ISHIMARU , S. ARAI , M. YOSHIKAWA , K. KOBAYASHI , Y. LIANG , I.C. BOURG 5 5 6 1 T. KAWAMOTO , Y. KUMAGAI , T. KOBAYASHI , AND T. MATSUOKA R. BURGESS7 AND C.J. BALLENTINE7 1Environment and Resource System Engineering Lab., Kyoto 1GCRC, Univ. Tokyo, Tokyo 113-0033, Japan Univ., Kyoto 615-8540, Japan (*correspondence: [email protected]) ([email protected], 2Kumamoto Univ., Kumamoto 860-8555, Japan [email protected], 3Kanazawa Univ., Kanazawa 920-1192, Japan [email protected]) 4 2 Kyoto Univ., Beppu 874-0903, Japan Earth Science Division, Lawrence Berkeley National Lab., 5Kyoto Univ., Kyoto 606-8502, Japan Berkeley, CA 94720, USA ([email protected]) 6Kagoshima Univ., Kagoshima 890-0065, Japan 7 + SEAES, Univ. Manchester, Manchester M13 9PL, UK Cs ion is one of radioactive species generated by nuclear

electric power. It is one of the most problematic ions because Halogen and noble gas compositions are complementary of its long half-life and high mobility. Cement material is + tracers of H O (or aqueous fluids) in the mantle. Via considered as a candidate for the solid fixation of Cs ions, 2 subduction of sedimentary pore-fluids, halogens and noble and the engineered barrier for the geological disposal of such gases are carried into the mantle [1, 2]. Here, we present the radioactive species. The structures of the cement is halogen and noble gas compositions of mantle peridotites complicated, and considered as nano-crystalline aggregation from subduction zones (the Avacha volcano in Kamchatka, the phase with two distinct local structures, tobermorite and Pinatubo volcano in Philippines, and the Horoman massif in jennite, by the difference of Ca/Si ratio and the silica-chain Japan) to investigate how far the influence of subducted pore length. The goal of this research is to detect which structural fluids extends in the mantle wedge. H O-rich fluid inclusions or compositional feature is essential to ionic adsorption into 2 are present in the studied peridotites as previously described cement matrix. [3–5]. To determine noble gas and halogen compositions of By using molecular dynamics simulations, we have the fluid inclusions and bulk peridotites, we converted studied the aqueous solution-mineral (cement) interfacial halogens (Cl, Br and I) to Ar, Kr and Xe isotopes by neutron systems for two different cement local structures (tobermorite irradiation, and extracted the noble gases by in vacuo crushing and jennite) and two different solutions (NaCl and CsCl). It + or heating. was found that Na ion could form both inner-sphere complex The Br/Cl and I/Cl values of the fluid inclusions obtained and outer-sphere complex, without full hydration shell and by crushing show a sedimentary pore-fluid signature with with full hydration shell at the time of adsorption, + some variation between localities. The halogen ratios obtained respectively. In contrast, Cs ion could only form inner-sphere by heating are slightly lower than crushing suggesting the complex for both mineral cases. This finding is in good presence of additional Cl in minerals such as amphibole and/or correspondence with previous NMR studies[1]. Furhtermore, + silicate glass [3] in the peridotites. Slab-derived, seawater-like we found that the inner-sphere complex Na is tightly binded noble gases are also dominant in fluid inclusions as previously with the depronated oxygen. More importantly, it was found reported [6, 7]. that tobermorite presents better binding property than that of The composition of subducted halogens and noble gases in jennite. The fact that differences in cement structure and ion the mantle peridotites demonstrates that sedimentary pore- spiecies may cause these differences in adsorption state and fluid signatures are carried beneath the island arcs through binding property will enhance our understanding on cement subduction and survive in the mantle wedge. Deeper materials in the case of the solid fixation and the geological subduction of pore-fluid like noble gases into the deep mantle disposal. accounts for the same signature of the convecting mantle [2].

[1] Sumino et al. (2010) EPSL 294, 163-172. [2] Holland & [1] Viallis et al. (1999) J. Phys. Chem. B 103, 5212-5219 Ballentine (2006) Nature 441, 186-191. [3] Ishimaru et al. (2007) J. Petrol. 48, 395-433. [4] Kumagai et al. (2011) JpGU Meeting 2011, SCG060-P07. [5] Hirai & Arai (1987) EPSL 85, 311-318. [6] Hopp & Ionov (2011) EPSL 302, 121-131. [7] Matsumoto et al. (2001) EPSL 185, 35-47.

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Zinc isotopes as a tool to study zinc Noble gas signature of Tertiary uptake by marine phytoplankton alkaline basalts and xenoliths from M. KÖBBERICH1*, A. D. COX2, AND D. VANCE1 central Europe 1Institute of Geochemistry and Petrology, ETH Zurich, YU. KOCHERGINA1,2, S. NIEDERMANN3, V. RAPPRICH1 Switzerland AND T. MAGNA1 2 School of Earth and Space Exploration, Arizona State 1 Czech Geological Survey, Klarov 3, CZ-11821 Prague, Czech University, USA Republic; [email protected] 2 Faculty of Science, Charles University, Albertov 6, CZ-12843 The availability of metals to marine phytoplankton has Prague, Czech Republic been suggested to control oceanic carbon uptake from the 3GFZ Potsdam, Telegrafenberg, D-14473 Potsdam, Germany atmosphere and its sequestration to the deep sea. Metal variability across glacial/interglacial periods could have driven We present preliminary He and Ar isotope data for two changes in the composition of atmospheric greenhouse gases suites of pristine alkaline basaltic rocks associated with the [1]. Many transition metals, including zinc, are often Eger Rift, Bohemian Massif, in order to deconvolve the noble extremely scarce in the euphotic zone and are coupled with gas signature of the sub-continental lithospheric mantle be- deep enrichments, consistent with biological uptake at the neath central Europe. In addition, He and Ar data were col- surface and regeneration at depth. However, abiotic processes, lected from xenoliths enclosed in these alkaline basalts in such as scavenging, can also contribute to this depth cycling order to compare the noble gas isotope signature of the mant- [2]. If the surface to depth cycling is associated with zinc le source of the xenoliths, thought to be located at shallower isotopic fractionation, then isotopic studies should be able to depths than that inferred for alkaline volcanic rocks. elucidate the key contolling processes, both now and in the 3 4 Most xenolithic and phenocrystic olivines have He/ He past. ratios between 4.7 and 6.6RA, clearly more radiogenic than Here we seek to evaluate zinc isotopes as a potential tool 4 MORB, and rather constant despite He concentrations to track metal cycling in the oceans. Recently obtained depth –8 3 varying by nearly two orders of magnitude (0.1–8.9*10 cm profiles of dissolved zinc isotopes from the NE Pacific reveal STP/g), although the highest 4He concentration is associated anomalously light compositions in the shallow sub-surface 3 4 with an elevated He/ He of 7.2R . The latter may suggest immediately below the isotopically heavier euphotic zone. A sampling of a convective mantle similar to MORB. This dataset suggests shallow zinc recycling in the upper Homogeneous 3He/4He ratios (5.5–5.7R ; n=3) are found for ocean, possibly caused by the release of biologically bound A olivines from the Doupovske hory volcanic complex, whereas light zinc [3,4]. To our knowledge, the diatom Thalassiosira clinopyroxene shows a slightly more radiogenic signature oceanica is thus far the only planktonic organism that has (4.1R ). Collectively, He isotope data shows a remarkable been shown to fractionate zinc isotopes during uptake [5]. We A homogeneity across two chemically distinct volcanic centres have cultured this organism, and a variety of other marine associated with the major Eger rift lineament, attesting to their phytoplankton strains, in order to explore systematic and temporally and spatially invariant lithospheric mantle source, species-dependent changes in their isotopic fractionation. and confirms further the observations of a homogeneous He Thermodynamic reaction modelling of our experiments and isotope signature of the sub-continental mantle beneath central natural systems elucidates zinc isotopes as a potentially Europe [1]. 40Ar/36Ar ratios for the same samples are between powerful tool to reconstruct biological metal cycling in both 306 and 3690. Atmospheric Ar could be admixed by modern and past oceans. infiltration of air from basaltic melts; such a process of

metasomatism of mantle xenoliths by basaltic melts has been [1] Martin (1990), Paleoceanogr. 5(1), 1-13. [2]. Little et al. reported from other localities of the Eger rift [2]. Further He (in review), Global Biogeochem. Cy. [3] Lohan et al. (2002) and Ar isotope analyses of alkaline basaltic and basanitic Deep-Sea Res. II 49(24-25), 5793-5808. [4] Vance et al. rocks and xenoliths of distinct mantle layers from between 32 (2012), Mineral. Mag. 76(6), 2486. [5] John et al. (2007), and 70 km in depth are in progress. Limnol. Oceanogr. 52(6), 2710-2714.

[1] Gautheron et al. (2005) Chem Geol 217, 97-112; [2] Ackerman et al. (2013) J Petrol, under review

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Trace metals in plants of Chadak Platelet degradation in diamonds. gold ore field, Uzbekistan Insights from infrared microscopy O.KODIROV1* , F. MARTIN 2 AND N. SHUKUROV 1 and implications for the thermal 1Institute of Geology and Geophysics, Academy of Sciences evolution of cratonic mantle. of Uzbeksitan, 49-Olimlar, 100041, Tashkent, Uzbekistan S.C. KOHN*, E. WIBBERLEY, C.B. SMITH, (*correspondance: [email protected]) G.P. BULANOVA AND M.J. WALTER 2University of Granada, University Campus Fuentenueva s/n 18071- Granada, Spain ([email protected]) School of Earth Sciences, University of Bristol, Queens Rd., Bristol, BS8 1RJ, UK (*[email protected]) Among the set of conditions that determine the status of the biota and the environment in general, geochemical factors Crystallographic defects in diamonds provide a wealth of related to the geologic history of the area and its constituent information that can, in principle, be used to constrain the chemical composition of rocks and soils play a major role. It is thermal evolution of diamond source regions. The simplest known that the chemical composition of plant communities method consists of using the average N concentration and are closely related to the concentration of some elements in aggregation of whole diamonds of known age to obtain an soil. From this perspective, the study of the relationship estimate of residence temperature in the mantle. Detailed between the components of geochemical environment is the studies of the spatial dependence of N abundance and main objective of our investigation. aggregation provide an improvement in temperature The study area is characterized by a relatively developed estimation and can provide constraints on multistage diamond mining industry, here since 1970 operates the Chadak mine growth events (Kohn et al., in prep). However, temperature and the gold-extracting factory. estimates can only be obtained if the diamond has been dated Plant samples (Artemísia absínthium and Phrágmites by an independent method and the temperature obtained is austrális) were collected in the vicinity of Chadak mining area neither the maximum nor mean temperature experienced and in tailing dumps which were formed as a results of mining during residence in the mantle, because of the exponential activity. Dry ashing was conducted in a muffle furnace at temperature dependence in the kinetic equation. temperatures of 450 to 5000C for 3-4 hours. After the ashing In the present study we are exploring the potential of

the ashe dissolved in dilute HNO3+3HCl. The final solution platelet degradation rate as an additional constraint on thermal was analized for Cu, Zn, Pb, Mn and As with ICP-MS. histories of diamonds and their cratonic mantle hosts. The Results show that trace elements were to exceed normal approach is to measure nitrogen abundance and aggregation in concentration in plant leaves [1] and reaching (mg/kg): Cu – core-to-rim profiles across diamonds from Argyle (Australia) 37-639, Zn – 174-1798, Pb – 5-282, Mn – 361-2969, and As – to determine apparent temperature profiles. These profiles are 2-341, respectively. then compared with the degree of platelet degradation at each As can be seen from the results trace elements are found in point. If platelet degradation occurs at a fixed rate for a given excessive or toxic concentration despite the fact, that some of temperature, then for diamonds with a single mantle residence these elements are essential for plants. Not always observed time there should be a clear correlation between the degree of relationship with the soil composition as the concentration of platelet degradation and temperature. Our data show that for a trace metals are much higher than in soil samples. Perhaps this single diamond such a correlation usually exists, but that for is due to selective ability of some plant species or such high the whole data set there are wide variations in the apparent content of trace metals related to ore deposit. degradation rate. The diamonds with the slowest apparent Many studies have shown that there is a correlation of rates were found to have eclogitic (E) inclusions while those trace metals in plants on the content of their mobile forms in with the fastest rates are peridotitic (P). For Argyle the mantle soil solution. With this respect, future investigations on the residence times are around 0.4 and 1.4 Ga for E and P mobile forms of trace metals are required in our studied area. respectively [1], suggesting that the degradation rate could be constant at a given T, and that the different degrees of [1] Kabata-Pendias, Alina (2011) 4-th ed. CRC Press, 505. degradation reflect the different residence times of the two parageneses. The potential role of plastic deformation and other complicating factors in modifying the calculated temperatures and degree of platelet degradation will also be discussed.

[1] Luguet et al. (2009) Lithos 112S, 1096-1108.

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OH incorporation in quartz as Ion microprobe U-Pb dating of a tracer of formation conditions individual phosphate grains in MARZENA A. KOHUT1 ROLAND STALDER1 Martian meteorite 1 AND JÜRGEN KONZETT 1 1 1 1 M. KOIKE *, Y. OTA , N. TAKAHATA , Y. SANO 1Institute of Mineralogy and Petrography, University of AND N. SUGIURA2 Innsbruck, Austria, [email protected], 1 AORI, Univ. of Tokyo, Chiba, Japan, [email protected] [email protected], [email protected] tokyo.ac.jp (*presenting auther) 2 School of Science, Univ. of Tokyo, Tokyo, Japan Quartz as a common nominally anhydrous mineral of the Earth’s crust contains traces of hydrogen as a molecular water A Martian meteorite ALH 84001 shows extremely old age in fluid inclusions, or as structurally incorporated hydroxyl of over 4 Ga and is expected as a key to the ancient history of ions. The structurally bound hydrogen commonly acts as Mars. Its crystallization age is still controversial due to the a charge compensator, associated with point defects, such as complicated impact history. While volumetrically minor, substitution of Si4+ by Al3+ and/or B3+ with charge balance phosphates are important carriers of trace elements. Previous maintained by monovalent cations substitutions (H+, Li+ and SIMS U-Pb dating of several merrillite and apatite grains in Na+). The occurence of hydrogen affects thermodynamic ALH 84001 showed ~4 Ga [1]. However, intra-grain properties of minerals and influences their kinetic behavior systematics was not observed because of limited spatial during diffusion and phase transformations. Even small resolution. In-situ analysis of a single grain will provide amounts of OH defects can dramatically change physical further information regarding cooling and reheating process. properties of minerals that are a key to understand rock- Here we measured single grain U-Pb ages using a laterally formation mechanisms within the crustal conditions. high-resolution secondary ion mass spectrometer (NanoSIMS) The geochemical behavior of OH incorporation in quartz at Atmosphere and Ocean Research Institute, University of in the systems granite-tourmaline-water and granite- Tokyo. spodumene-water was studied in order to explain the effect of Two polished thick sections of ALH 84001 were firstly pressure and temperature on structural defect generation. observed by SEM-EDS. Two merrilite grains with ~100 µm in Piston-cylinder experiments were carried at pressures between diameter were found. The sections were polished again, gold- 5 and 25 kbar and temperatures between 800 and 1050 C. coated and baked overnight, and then analyzed by a Oriented and polished quartz crystals from each run were NanoSIMS. A 2-10 nA O- primary beam was used with spot characterized with FT-IR spectroscopy and water contents& size of ~10-20 µm. An apatite from Prairie Lake circular were calculated using mineral-specific and general complex, PRAP, with a known age of 1155 ± 20 Ma [2] was wavelength-specific calibrations. 3+ used as a standard of UO/UO2-Pb/UO calibration. The OH absorption features were assigned to Al - 238 206 For both analyzed grains, the obtained U- Pb and substitution (Al-H defect, band-triplet at 3320, 3383 and 3434 206 207 Pb- Pb ages show good agreement with ~4 Ga, suggesting cm-1), B3+ -substitution (sharp absorption band at 3597 cm-1), the intra-grain U-Pb system is concordant. There is also Li+ -substitution (weak absorption band at 3475 cm-1) and chemical zoning of U abundance. Since diffusion rate of U in hydrogarnet (4H) defect (absorption at 3585 cm-1). Si apatite is slower than Pb by ~4 orders of magnitude [3], the In this study point defects cause various OH contents in observed zoning was possibly made during crystal growth and quartz, depending on different pressures, temperatures and preserved since then. Meanwhile, Pb may have been chemical environments. Synthesized crystals showed homogenized within a grain at crystallization (and/or later a negative correlation of calculated water content vs. pressure. impacts), which makes single grain U-Pb dating possible. The Under lower pressures quartz incorporates more hydrogen (5 interpretation of the ages (igneous or impact-reset) is related to kbar: 450-750 ppm H O) than at higher pressures (25 kbar: 72- 2 the processes of crystallization and impacts. Further studies 106 ppm H O). Therefore, our results imply that IR spectra of 2 including micro scale analyses of other elements are required. quartzes have a potential to be used as a geobaromether to This is the first report of single grain U-Pb dating of indicate petrological formation conditions. Moreover, the B- phosphates using a NanoSIMS. and Li-specific OH absorption bands may be used to quantify

the charge balancing B3+- and Li+- content that could be used [1] Terada et al. (2003) Meteorit. Planet. Sci. 38, 1697-1703. as a novel and indirect analytical tool to detect traces of B and [2] Sano et al. (2006) Geochem. J. 40, 597-608. [3] Cherniak Li in quartz crystals. (2005) Chem. Geol. 219, 297-308

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The effect of carbon dioxide on metal Using model mineral-organic matter- transport by geological fluids water interfaces as a step towards MARIA A. KOKH1*, GLEB S. POKROVSKI1, determining the fate of pollutants in DAMIEN GUILLAUME1 AND STEFANO SALVI1 the environment 1 GET, CNRS, University of Toulouse, France 1 1 1 P.E. KOLIC , B. SUBRAMANIAN , D.A. SPIVAK (*[email protected]) 1 AND R.L. COOK *

Carbon dioxide is the second major component (after 1Department of Chemistry, Louisiana State University, Baton water) of most crustal fluids responsible for metal ore deposit Rouge, LA 70803, USA (*correspondence: formation. Its contents amount up to 10-20 wt% in porphyry [email protected]) Cu-Au-Mo fluids [1] and more than 50 wt% in metamorphic, skarn, orogenic gold, and PGE deposits [2]. In contrast to Mineral-organic matter-water interfaces play a valuable

H2O-dominated fluids, models of metal transport and role in our ecosystem and are a major role player in

deposition by high-temperature and pressure (T-P) CO2-rich determining the bioavailability as well as the fate and transport fluids are subjects to debate. of anthropogenic contaminants (ACs) in the environment. In this contribution, we combined thermodynamic Anthropogenic contaminants include a vast amount of modeling, based on few data available from the literature, with compounds that are harmful to the environment and its

new solubility experiments in H2O-CO2-salt-sulfur systems to inhabitants. The mineral-organic matter component of the

assess, in a systematic way, the role of CO2 on the behavior of mineral-organic matter-water interface has been found to play metals at hydrothermal conditions. Our analysis shows that the a major role in the sorption of ACs in soils and sediments, thus

presence of CO2 may have the following impacts on metals decreasing their presence in other environmental

transport: a) the presence of CO2 expands the field of vapor- compartments, such as groundwater. This mineral-organic liquid immiscibility, which causes both changes in metal matter component is highly complex, especially in terms of solubility in the liquid phase (mostly owing to changes in pH), the organic matter constituent, leading to a lack of detailed and a redistribution of metals between vapor and liquid; b) chemical insight into AC sorption. In order to address this

CO2 decreases both water activity and the dialectric constant void and gain valuable information that a real soil and of the solvent, which in turn affects ion pairing and the sediment samples cannot provide, a simpler more activity coefficients of charged species; c) the formation of homogeneous mineral-organic matter model system is needed 2- – complexes with C-bearing ligands (CO3 , HCO3 , CO, COS) to serve as a model system. To better understand the chemical may be important for some metals (e.g., Rare Earth Elements, mechanism of pollutant sorption to the mineral-organic matter

U, Sn, Fe, Ni); and d) at high concentrations (>~50 wt%), CO2 component, this project uses a combination of highly may also specifically solvate some non-polar complexes (e.g., adjustable model synthetic mineral-organic matter sorbent

AuHS(H2S) [3]) and thus enhance their solubility. systems. The model system consists of silica, a model mineral To evaluate the contribution of these factors, we are surface, functionalized with alkyl, aromatic, and O-alkyl currently investigating experimentally the solubility of major groups to echo the natural structure of organic matter. Solid

ore minerals (FeS2, CuFeS2, MoS2, SnO2, PtS, and Au) in state Nuclear Magnetic Resonance (NMR) as well as a range

H2O-KCl-CO2-H2S supercritical fluids in the presence of of other techniques are used for characterization of the model

acidity and redox mineral buffers, and as function of CO2 synthetic mineral. Sorption and desorption batch experiment

content. Data obtained in H2O-dominated experiments allow a studies are performed using commonly used pesticides as revision of the available speciation models for metals in high model organic pollutants as an initial step towards T-P aqueous fluids. These results will provide the necessary understanding the geochemical mechanisms that occur at

basis for interpreting experimental runs in CO2-rich fluids, mineral-water interfaces. which are in progress.

[1] Kouzmanov & Pokrovski (2012) Society of Economic Geologists, Inc. Special Publication 16, 573-618. [2] Phillips & Evans (2004) Nature 429, 860-863. [3] Pokrovski et al. (2008) Earth & Planet. Sci. Letters 266, 345-362.

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Geochemistry of uranium in lakes of Evaluating the efficiency of a West Mongolia synthetic amorphous manganese KOLPAKOVA M. N.12* oxide for chemical stabilization of Cu 1Tomsk Department of the Trofimuk Institute of Petroleum- in a contaminated soil Gas Geology and Geophysics, Siberian Branch of the M. KOMÁREK*, L. TRAKAL, Z. MICHÁLKOVÁ Russian Academy of Sciences, Academichesky ave. 4, AND L. DELLA PUPPA Tomsk, 634055, Russia, [email protected] 2National Research Tomsk Polytechnic University, Lenin ave. Czech University of Life Sciences Prague, Department of 30, Tomsk 634050, Russia Environmental Geosciences, Kam;cká 129, 165 21, Prague 6, Czech Republic Natural lakes with high concentrations of uranium are (*correspondence: [email protected]) widespread, for example, Van in Turkey (110 +gL-1) [1],), Mono in the USA, California (300 +gL-1), Shar Burdiin in Chemical stabilization techniques aim at rendering less Eastern Mongolia (15000 +gL-1) [2]. In Western Mongolia, we available the metal(loid) fractions that can pose significant have also discovered lakes with concentrations of uranium as environmental and toxicological risks and protecting the high as 3000 +gL-1. In the arid climate of western Mongolia, functionality of the soil environment [1]. Recently, a synthetic where evaporation is by 2-3 times higher than the amount of amorphous manganese oxide (AMO) has been proposed as an precipitation, evaporation concentration processes contribute efficient metal sorbent and stabilizing agent for contaminated to the growth of salinity and content of the U. However, our soils [2]. This work aims to evaluate AMO (up to 2 wt.%) investigation indicated a significant role in uranium stabilization efficiency in a soil contaminated predominantly accumulation in the waters of the upper hydrodynamic zone is with Cu (400 mg/kg; pH 3.6) using (i) batch experiments with provided by aquiferous rock catchment lakes. Geologically, soil solution samplers (rhizons), (ii) small-scale columns and granite massifs are widespread on the studied territory, which (iii) a novel set-up of a large-scale column experiment are known to be possessed of natural radioactivity. But the together with direct sampling of the soil solution and chemical type of rock is not the main factor. The time of water–rocks extraction methods (0.01 M CaCl2, 0.05 M EDTA, BCR interaction which determines the degree of accumulation of U sequential extraction procedure). in the lakes is more important. Precisely, the equilibrium- The results suggest that the application of the AMO nonequilibrium state of the system water-rock determines the increased the soil pH and its high reactivity resulted in possibility of U concentration in the water during the whole increased DOC concentrations originating from dissolved soil time of its interaction with rocks: the longer interaction time, organic matter (SOM). The AMO was efficient in stabilizing the more uranium will be concentrated in the water, of course, Cu proved by significant decreases in Cu in soil solution, in the other things being equal. Analysis of the lake waters the exchangeable fraction and CaCl2/EDTA extracts. When equilibrium with uranium minerals shows that only a few can further metals (Cd, Cu, Pb, Zn) were added to the soil precipitate out of solution and only three lakes with total columns, the AMO was able to stabilize them in the salinity more than 300 gL-1 equilibrium with the investigated subsurface layers. However, due to SOM dissolution, metals minerals. Water store U by getting into the rocks of any (especially Cu) bound to the organic soil phase can be released composition and dissolving them. Uranium, in turn, forms to the soil solution. This preliminary study assess the complexes with carbonate-ions and migrate to the lakes, and efficiency of the AMO for metal stabilization in a Cu- precipitates in lake sediments by influence of evaporation and contaminated soil and proposes a combination of experimental water-rock interaction time. In this case, the more uranium set-ups evaluating the efficiency of stabilizing amendments in will be accumulated in the water for the entire migration path general. to the lake, the greater amount will be precipitated. Consequently, the lakes are a unique geochemical barrier for [1] Komárek et al. (2013) Environ. Pollut. 172, 9-22. [2] Della the migration of uranium which forms oxides, hydroxides, Puppa et al. (2013) J. Colloid Interf. Sci., in press. carbonates, phosphates, fluorides and other minerals in lakes sediment.

[1] Mehmet et al. (2011) Clean-Soil, Air, Water 39(6), 530- 536. [2] Linhoff et al. (2011) Environ. Earth Sc. 62, 171-183.

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Simultaneous determination of LIME Olivine and Pyroxene: Multi- carbon and hydrogen isotope Stage Thermal Histories of AOAs enrichment factors of methane M. KOMATSU1*, T. FAGAN2 AND T. MIKOUCHI3 during microbial oxidation in a 1Waseda Institute for Advanced Study, Waseda University. natural water environment Tokyo 169-8050, Japan (*[email protected]) 2Dep. of Earth Sciences, Waseda University. 1 1 2 D. D. KOMATSU , U. TSUNOGAI , S. SATO , 3Dep. of Earth and Planetary Science, University of Tokyo. 2 3 F. NAKAGAWA AND A. TANAKA 1Graduate school of Environmental Studies, Nagoya Low-iron, Mn-enriched (LIME) silicates are interpreted as University, Nagoya, 464-8601, Japan (*correspondence: indicators of nebular condensation conditions [1-4]. They [email protected]) have been identified in IDPs [1], in rare chondrules and 2Graduate school of Science, Hokkaido University, Sapporo matrices of primitive chondrites [2, 3], and in Wild 2 cometary 060-0810, Japan grains [4]. LIME olivine has also been observed in amoeboid 3NIES, Tsukuba, 305-8506 Japan olivine aggregates (AOAs) in primitive chondrites [6, 7]. In this study, we compare the roles of nebular and asteroidal The stable carbon and hydrogen isotope compositions thermal processing on formation and alteration of LIME 13 2 silicates in AOAs. (" C and " H) of methane (CH4) were analyzed using a newly developed CF–IRMS method in a hydrothermal plume in the Most AOAs in Y-81020 (CO3.0) are compact, with closely intergrown minerals. The compact AOAs have concentric water column of Lake Towada, Japan. The CH4 concentration, 13 2 textures of anorthite
spinel cores, Al-diopside-rich mantles " C-CH4, and " H-CH4 in the lake water column varied widely, ranging from 0.6 to 246.5 nM, –54.9 to +54.2‰ (vs and closely-packed forsterite rims. Some AOAs appear to be VPDB), and –258 to +762‰ (vs VSMOW), respectively, more loosely-bound (fluffy). The fluffy AOAs have more irregular shapes, contain less Al-diopside and lack the well- reflecting rapid CH4 oxidation in the water column. Rapid CH4 oxidation was further confirmed through bottle incubation defined concentric textures of the compact AOAs. experiments of the lake water sampled below 150 m, which LIME olivines are commonly observed in AOAs in Y- 13 81020. They typically occur (i) in the rims of compact AOAs, found an extreme increase in the values of both " C-CH4 and 2 and (ii) as uniformly distributed grains in fluffy AOAs (see " H-CH4 corresponding to a decreasing CH4 concentration, after the incubations of more than 48 hours. The isotope [7]). Most olivines in both types of AOAs are nearly pure enrichment factors for carbon and hydrogen were determined forsterite (Fo99-100). LIME low-Ca pyroxenes are also observed through incubation experiments to be –26.2 ± 0.9‰ and –233 in rims of some AOAs. Their MnO concentrations are similar ± 12‰, respectively, and the rapid rate constants ranged from to those of coexisting LIME olivines. 0.05 to 0.67 day-1. These enrichment factors were the highest LIME olivine and pyroxene both occur in the rims of values ever reported in natural environments. In addition, we compact AOAs in Y-81020, consistent with a model found that a greater isotope fractionation occurred at larger calculation that predicts Mn-enrichment with decreasing condensation temperature in the nebula [5]. AOAs in rate constants, i.e., higher populations of CH4 oxidizing microbes. However, we also found that the ratios between the metamorphosed type 3 carbonaceous chondrites apparently isotope enrichment factors of hydrogen and carbon (+ values) lack LIME silicates [8]. We suggest that LIME silicates were were always constant around 11.3 ± 0.9, which coincides well originally present as primary phases in many AOAs, and then with previous laboratory and field observations under elevated were lost during asteroidal thermal processing.

CH4 concentration. The coincidence in the + value of approximately 10 between this study and previous studies [1] Kl!ck W. et al. 1989. Nature 339: 126-128. [2] Ichikawa indicates that the + value can be a robust tracer for O. and Ikeda Y. 1995. Proc. of NIPR Symp. 8:63-78. [3] Rubin

distinguishing microbial CH4 oxidation from the other A. 1984. American Mineralogist 69:880-888. [4] Zolensky M. processes such as mixing, even in environmental samples of E. et al. 2006. Science 314: 1735-1753. [5] Ebel D. S. et al. nanomolar per liter quantities of CH4. 2012. MaPS 47:585-593. [6] Weisberg M. K. et al. 2004. MaPS 39:1741-1753. [7] Sugiura N. et al. 2009. MaPS 44:559-572. [8] Komatsu M. et al, 2014. LPSC #1847.

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Ocean sections and stoichiometry of Heavy metal attenuation and mobility dissolved bioactive trace metals in the in the Wood Creek Sand Channel North Pacific Ocean aquifer: Correlation of experimental WATARU KONAGAYA1, LINJIE ZHENG, and field study TOMOHARU MINAMI AND YOSHIKI SOHRIN 1,3 2 MACOURA KONÉ *, K. ULRICH MAYER Institute for chemical research, Kyoto University, Uji, Japan, AND ANIA C. ULRICH3 ([email protected]) 1 Suncor Energy Inc., [email protected] (*presenting

author), Bioactive trace metals have strong influence on production 2 University of British Columbia, Earth and Ocean Sciences, and community structure of phytoplankton. In turn, such [email protected] biological processes affect the distribution of bioactive trace 3 University of Alberta, Department of Civil & Environmental metals. So it is clear that bioactive trace metals have Engineering, [email protected] interactive influence with biological processes in the ocean. The Subarctic North Pacific Ocean is an important area The storage of process affected (PA) water in tailings sensitive to the effects from the Asian continent, where the ponds over glacial till formations in the oil sands region in Subpolar Gyre, consisting of the Kamchatka Current and Alberta (Canada) has the potential to cause contamination of North Pacific Current, makes the southern boundary. groundwater and surface water with trace metals and dissolved We report the distribution of dissolved bioactive trace major ions. To predict the fate of contaminants in the aquifers metals from the subtropic to subarctic region in the North underlying and adjacent to tailings impoundments, a detailed Pacific Ocean. In this study, we used of a new automated understanding of the processes controlling metal release and preconcentration system and determined the concentration of attenuation is required. In this study, column experiments nine elements. were performed under anaerobic conditions to simulate Sea water samples were collected using clean technique in interactions between aquifer soils and PA water. Experimental accordance with the GEOTRACES protocol. The bioactive results were compared with and correlated to field trace metals were preconcentrated by solid extraction using observations obtained from monitoring of groundwater wells NOBIAS CHELATE-PA1 chelating resin (Sohrin et al., 2008) located in an oil sands facility over a time period of 6 years. in an automated preconcentration system and determined by Results from the column experiments indicated that Fe, HR-ICP-MS. Mn, Ba, and Si were released from the sediments while other The blank value of a procedure with the automated trace metals present in PA water (Zn, Cr, Ni, U, Mo, As, B, preconcentration system was low enough. In recovery tests, etc.) were either weakly attenuated or completely retained by target metals were quantitatively recovered at 90-110% from the soils. A DNA extraction performed on the columns seawater. The measured values of them in seawater reference sediments identified iron and sulphate reducers suggesting that material NASS-5 agreed with the certified values. We are microbial reductive dissolution of Mn(IV) and Fe(III) is likely going to report the results on ocean sections along 47°N and the geochemical process by which the metals were released 165°E. and mobilized into the effluent solution. The groundwater monitoring results are in agreement with those from the columns. However, observed metal concentrations are much higher in the field than in the columns. Variation in the released amounts may be attributed to different materials characteristics, but are most likely due to longer residence times, and longer flow paths. Results also demonstrate that microbial reduction of Mn(IV) and Fe(III) may have important environmental implications on water quality. Potential metals of concerns include Fe, Mn, Zn, Cr and B. Concentrations of these elements measured in both the column effluent and the groundwater were above environmental standards. These results have important applications in the prediction, protection and potential evaluation of remedial technologies for the immobilization of metals.

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Evidence for mantle heterogeneity Depressurization-induced gas from Selenium-Tellurium systematics production from methane hydrate in peridotites sediment formed in a giant cell 1 1 STEPHAN KÖNIG* , AMBRE LUGUET , JEAN-PIERRE- YOSHIHIRO KONNO*, YUSUKE JIN, AND JIRO NAGAO LORAND2, D. GRAHAM PEARSON3 1 ProTech, MHRC, National Institute of Advanced Industrial AND ALESSANDRO BRAGAGNI Science and Technology (AIST), Sapporo 062-8517, 1Universität Bonn, Steinmann Institut für Mineralogie, Japan (*correspondence: [email protected]) Germany, [email protected] (* presenting author), We have conducted a gas production test from methane- 2 Laboratoire de Planétologie et Géodynamique de Nantes, hydrate-bearing sediment artificially formed in a giant University of Nantes, France, pressure-cell to evaluate feasibility of depressurization 3 University of Alberta, Department of Earth and Atmospheric method. Unique apparatus named High-pressure Giant Unit Sciences, Edmonton, Canada for Methane-hydrate Analyses (HiGUMA), which is consist of a pressure-cell with an internal volume of 1710 liter, a vertical Selenium and Tellurium belong to the group of highly well system, and a separator for gas and water, was used for siderophile elements (HSE), which may constitute key tracers the test. for planetary processes such as formation of the Earth’s core Methane hydrate with saturation of over 60% was formed and the Late Veneer composition. Constraints on HSE in artificial sediment made of Toyoura standard sand within systematics on the planetary scale require a solid the pressure-cell. Production test was performed by decreasing understanding regarding the behaviour of these elements the pressure of vertical well from 10 MPa to 5.0 MPa. Gas during petrogenetic processes and their abundances in the production rate showed the increasing tendency during Earth’s mantle. However, the upper mantle has been shown to pressure reduction of the well. The gas water ratio of bear significant long-term geochemical and lithological production fluid increased to about 150 with time. Gas from heterogeneities as a result of repeated melt depletion and re- methane hydrate was successfully produced by this method. enrichment processes. In addition to petrographic and mineralogical investigations and geochemical and isotopic studies on platinum group element systematics, these mantle heterogeneities can now be further constrained with new results obtained from Se and Te geochemistry. Recent studies have shown systematic differences in Se/Te between fertile lherzolites and depleted harzburgites from both oceanic and continental settings. In contrast to fertile lherzolites which scatter around broadly chondritic values of ca. 9 [1,2], depleted peridotites are generally highly fractionated with up to suprachondritic Se/Te (up to 35). The increase of Se/Te correlates with decreasing Te concentrations [3]. Similar fractionations are also observed at the scale of single samples and likely result from the heterogeneous distribution of micrometer sized Te-bearing host phases in Figure 1: Time-dependent variations of gas production rate highly depleted harzburgites. The marked differences in Se-Te and well pressure. systematics observed between fertile lherzolites and depleted Acknowledgment harzburgites as well as the µm-scale heterogeneity can be This study was financially supported by the Research explained by the combined effect of i) different abundances Consortium for Methane Hydrate Resources in Japan (MH21 and proportions of residual and metasomatic base metal Research Consortium) that carries out Japan’s Methane sulfides and ii) discrete micrometric to nanometric platinum- Hydrate R&D Program conducted by the Ministry of group minerals. Together with platinum group elements, the Economy, Trade and Industry (METI). Se-Te systematics in ophiolitic peridotites, mantle-derived peridotite xenoliths (both alkali-basalt and kimberlite-hosted) and orogenic massifs therefore provide further evidence for the mineralogical control on the heterogeneity of highly siderophile elements as well as osmium isotope signatures in the Earth’s mantle.

[1] Lorand and Alard (2010) Chem Geol 278, 120-130. [2] Wang et al. (2013) GCA 108, 21-44. [3] König et al. (2012) GCA 98, 354-366.

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Timing and sources of pre-collisional Geochemical zoning of the Neoproterozoic sedimentation along spodumene vein series of the mineral the SW margin of the Congo Craton deposit Tastig Tuva, Central Asia (Kaoko Belt, NW Namibia) S. I. KONOVALENKO J. KONOPÁSEK12*, J. KO

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The composition of the spodumene of Combined accessory mineral Asian pegmatite fields micro-analysis: The strength of a S.I. KONOVALENKO multi-phase approach Tomsk State University, Tomsk, Russia ([email protected]) ELLEN KOOIJMAN12, BRADLEY HACKER2, ANDREW KYLANDER-CLARK2, LOTHAR RATSCHBACHER3 4 The composition of the rock forming spodumene from rare AND VLAD MINAEV metal pegmatite of the Enisei ridge, the Sangilen Plateau, the 1Swedish Museum of Natural History, Stockholm, Sweden, Southern Tian-Shan, the Pamir, and the Gindukush was [email protected]. studied using a X-ray microprobe analysis. The age of them 2Department of Earth Sciences, UC Santa Barbara, USA. ranges from Pre-Cambrian to Palaeogene inclusively. The 3Institut für Geologie, TU Freiberg. Germany. spodumene demonstrates two types of bodies: classic albite- 4Tajik Academy of Sciences, Dushanbe, Tajikistan. spodumene veins with profile lithium specific, and spodumene-microcline-albite complex ones (Li, Rb, Cs, Ta, Accessory mineral micro-analysis provides a diverse and Nb, Be) from zoning pegmatite fields. It is found that the main versatile toolbox for deciphering the timing and conditions of components defining a mineral composition, except of kind- petrological processes. We explore the use of multi-mineral U- forming (Li, Al, and Si), are Fe, Mn, Na, K, Ti, and partly Ca (Th-)Pb geochronology and trace-element analysis using LA- and Mg. In addition, the spodumenes of linear separate lithium ‘split-stream’-ICP-MS in a study of rare near-UHP crustal vein series of albite-spodumene type are always significantly xenoliths in the Pamir (peak conditions 2.5-2.8 GPa, 1000- more enriched in Fe, Mn, Ti, Ca, Mg despite their age, 1100 °C, eruption ~11 Ma [1]). These direct samples of the whereas the complex-type spodumenes of spodumene- deep crust recovered from under an active collisional orogen microcline-albite veins from zoning fields are constantly provide a unique opportunity to assess how orogenic roots enriched in Na and K. The same tendency was found while form and evolve. sampling the spodumenes with different generations of all We analyzed zircon, monazite, and rutile from a variety of vein types. An early spodumene is always more contaminant rocks (eclogites to grt-ky-qtz granulites) in thin section using than a later one, especially with Fe, Mn, and Ti. Generally, an excimer laser couped to a Nu Plasma HR and a Nu AttoM. late spodumenes are less contaminant, but have more Na and This set-up provides REE-HFSE concentrations and U-Th-Pb K. The discovered tendency correlates with changing the color isotope ratios—hence, petrogenetic, thermometric and age of a mineral from greenish-grey to white and pinkish-white, data—for small amounts of ablated analyte. Our analysis and with growth of excretion size (from sm to dm). Ca and Mg yielded 1) U-Pb ages, Ti concentrations and REE in zircon, 2) as contaminants are not very typical for a spodumene and U-Pb and Th-Pb ages and REE in monazite, and 3) U-Pb ages always seen in minerals of lithium pegmatites from the and HFSE concentrations (incl. Zr) in rutile. Sangilen (Central Asia). That is probably related to Zircon and monazite defined 6 age populations between localization of province veins in the carbonate suite, which is 55-11 Ma, each typically having uncertainties of 1 Ma or responsible for modification of initial melts that enriches these better. The Ti-in-zircon and zircon U-Pb ages imply a three- veins in Ca and Mg. Sampling demonstrates direct correlation stage P-T-t history, involving Barrovian metamorphism (55-20 between Al and Si. At the same time, significant Al- Ma), deep burial leading to near-UHP conditions at ~12 Ma, abundance is often seen while calculating the crystal chemical and rapid magmatic heating shortly before the 11-Ma eruption. formulas. This all indicates that the isomorphic replacement of Monazite data complement this history. Rutile yielded ~11- silicon by the element takes place in tetrahedrons of mineral Ma U-Pb dates exclusively, demonstrating the reliability of structure. this thermochronometer. This study was funded by the Russian Ministry of Education The data show that different accessory mineral techniques and Science (projects 5.3143.2011, 14.B37.21.0686, are largely complementary and that their combined use is very 14.=37.21.1257). powerful in refining and redefining geodynamic models. In addition, we demonstrate that, through ongoing development in LASS-ICP-MS technology, we are able to identify and resolve a wide range of petrological processes on a Myr time scale for Cenozoic rocks.

[1] Hacker et al. (2005) J. Petrol. 46, 1661-1687.

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Using DMT and AF4-HR-ICP-MS to Use of 1012 and 1013 Ohm resistors in characterize trace metal speciation in TIMS analysis of Sr and Nd isotopes soil water extracts in sub-nanogram geological and GERWIN F. KOOPMANS, INGE C. REGELINK environmental samples AND ROB N.J. COMANS 1 2 2 J.M. KOORNNEEF , C. BOUMAN , J.B. SCHWIETERS 1Dep. of Soil Quality, Wageningen University, Wageningen, AND G.R. DAVIES1 The Netherlands 1 Faculty of Earth and Life Sciences, Vrije Universiteit (*correspondence: [email protected]) Amsterdam, the Netherlands, [email protected]

2Thermo Fisher Scientific, Bremen, Germany Diffuse contamination of soils with trace metals like Cu and Zn is an ubiquitous problem all over the world. Trace Analysis of isotope ratios in small geological and metals in 0.45 µm-filtered soil solution samples can be present environmental samples such as inclusions in diamonds or in the free form or they can be associated with inorganic individual human hairs is ultimately limited by the detection ligands, DOM, and inorganic colloids. Inorganic colloids like system of the mass spectrometer. We report a technique using clay and Fe-(hydr)oxide nanoparticles can pass the 0.45 µm- a TRITON Thermal Ionisation Mass-Spectrometer (TIMS) to filter, but their concentration, composition, and effect on trace measure sample sizes up to 10 times smaller than currently metal speciation is largely unknown. For ecological risk 12 13 feasible. Use of current amplifiers with 10 Ohm and 10 assessment of contaminated soils, total trace metal Ohm resistors instead of the standard 1011 Ohm resistors concentrations in soil solution are often measured. However, promises a 2-3 fold and 4-5 fold improvement in signal to uptake of trace metals by plants and soil organisms is not noise ratios, respectively. This improvement results in higher necessarily related to their total dissolved concentrations, but precision on analyses of small ion beams. generally correlates best with their free concentrations. Hence, Internal precision and external reproducibility are both the speciation of trace metals in soil solution needs to be better for Sr and Nd isotope ratios collected on small samples known to understand their bioavailability in soils. During the using 1012 Ohm and 1013 compared to the standard 1011 Ohm presentation, we will focus on the Donnan Membrane 87 resistors. At a Sr intensity of 3 mV the internal precision Technique (DMT) and Asymmetric Flow Field-Flow 87 86 12 (2SE) of Sr/ Sr is twice better for 10 Ohm and 5 times Fractionation (AF4), which can be used to measure the trace better for 1013 Ohm resistors compared to 1011 Ohm resistors. metal speciation in soil solution. The DMT allows for the The external reproducibilities (2SD) at this beam intensity are measurement of free trace metal concentrations in solution [1]. 4 and 9 times better, respectively. Using a chemical equilibrium model in combination with the We additionaly tested the precision of 143Nd/144Nd NICA-Donnan model, the complexation of trace metals with 13 measured by 10 Ohm resistors in the beam intensity range inorganic ligands and DOM can be predicted [2]. However, 5 usually covered by ion counting (< 3 mV or 2#10 cps). For a the role of inorganic colloids in soil solution in the binding of 143Nd intensity of 6.25#104 cps (1 mV) the precision is 480 trace metals remains poorly understood when using this 3 ppm (2SE) and at 2#10 cps (32 µV) it is 1%. At intensities approach. An emerging analytical technique with a high 4 13 higher than 2#10 cps the precision using the 10 Ohm potential to analyse the colloidal trace metal fraction in 0.45 resistors is better than 0.2%, which is the lower limit for ion soil µm-filtered solution samples is AF4. AF4 is a counting owing to the instability and non-linearity of ion chromatographic-like technique for size fractionation of counters. This observation indicates that the high gain colloids, and allows for online multi-element detection in amplifiers can be used instead of multi ion counting or combination with HR-ICP-MS. We will briefly describe the 11 Faraday cups equipped with the standard 10 Ohm resistors in analytical developments in the DMT and present examples of 4 the range between 2#10 cps and 20 mV. the application of both DMT and AF4-HR-ICP-MS to The reproducibility of 143Nd/144Nd and 87Sr/86Sr ratios for measure specific trace metal forms in soil solution extracts to 12 100 pg standards using 10 Ohm resistors is 176 ppm for Nd demonstrate (i) the complementary character of both analytical 13 (2RSD, n=28) and 92 ppm for Sr (2RSD, n=20). Using 10 techniques and (ii) their potential to obtain a full speciation of Ohm resistors the reproducibility is twice better. Thus, total dissolved trace metals. variability in Nd and Sr isotope ratios in the 4th decimal place, 143 144 87 86 e.g. Nd/ Nd 0.5110 – 0.5119 or Sr/ Sr 0.7100-0.7109, [1] Temminghoff et al. (2000) Anal. Chim. Acta 417, 149-157. can be resolved in such small samples provided that the [2] Weng et al. (2002) Environ. Sci. Technol. 36, 4804-4810. procedural blanks and chemical separation are optimal.

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Using stable isotope tracers to Highly dynamic cellular-level elucidate the in situ metabolic activity response of symbiotic coral to sudden of microbial populations in the cystic increase in environmental nitrogen fibrosis lung C. KOPP1, M. PERNICE2, I. DOMART-COULON3, 4 5 6 1,4 2 2,3 2 C. DJEDIAT , J.E. SPANGENBERG , D.T.L. ALEXANDER , S. KOPF *, R. HUNTER , A. LARIVIERE , Y. HU , 7 8 9 2 1 1 M. HIGNETTE , T. MEZIANE AND A. MEIBOM * M. DIETERLE , A. SESSIONS , V. ORPHAN AND D. NEWMAN1,2,4 [email protected] [email protected] 1Divison of Geological and Planetary Sciences and 2Division of [email protected] Biology, Caltech, Pasadena, CA 91125, USA [email protected] 3Children’s Hospital, Los Angeles, CA 90027, USA [email protected] 4Howard Hughes Medical Institute, Pasadena, CA 91125, USA [email protected] (*correspondence: [email protected]) [email protected] 8 [email protected] Background 9 [email protected] Cystic fibrosis is a genetic disorder that causes the

accumulation of mucus in a variety of organs. The genetic Metabolic interactions with endosymbiotic photosynthetic defect allows for the colonization and chronic infection of the dinoflagellates Symbiodinium sp. are fundamental to reef- pulmonary system by opportunistic pathogens and ranks as the building corals (Scleractinia) thriving in nutrient-poor tropical most common lethal genetic disorder in Caucasian seas. Yet detailed understanding at the single cell-level of populations. The formation of complex microbial communities nutrient assimilation, translocation, and utilization within this and their physiological heterogeneity within the cystic fibrosis fundamental symbiosis is lacking. Using pulse-chase 15N- lung are suspected to contribute to rapid disease progression labeling and quantitative ion-microprobe isotopic imaging and antibiotic resistance. However, because of the inherent (NanoSIMS) we visualized these dynamic processes in tissues challenges of working in situ with human patients, very few of the symbiotic coral Pocillopora damicornis at the sub- studies of the in situ metabolic programs of infectious agents cellular level. Assimilation of ammonium, nitrate, and aspartic exist and the development of effective antimicrobial therapies acid resulted in rapid incorporation of nitrogen into uric acid is often hindered by our limited knowledge of the crystals (after ,45 minutes), forming temporary N-storage physiological state of microbial populations within the human sites within the dinoflagellate endosymbionts. Subsequent host. It is currently unknown how even basic metabolic intracellular remobilization of this metabolite was indicators, such as microbial growth rates, may correlate with accompanied by translocation of nitrogenous compounds to disease progression. the coral host, starting at ,6 hours. Within the coral tissue,

Discussion nitrogen is utilized in specific cellular compartments in all four epithelia, including mucus chambers, Golgi bodies, and Here, we present a novel approach based on techniques vesicles in calicoblastic cells. Our study shows how nitrogen- developed in the (bio)geochemical sciences to tackle this limited symbiotic corals take advantage of sudden changes in knowledge gap. Using 2H and 15N isotope tracers, combined nitrogen availability and opens new perspectives for functional with GC-IRMS and nanoSIMS analytical techniques, we studies of nutrient storage and remobilization in microbial characterize the growth rate, community structure and symbioses in the changing reef environment. metabolic state of microbes within the lungs of cystic fibrosis

patients. Contrary to the traditional model of a rapidly

multiplying infectious population, our results from compound specific lipid analysis of biosynthetic 2H incorporation suggest microbial activity consistent with slow growth (a physiological adaptation known to confer antibiotic resistance in the laboratory). At the same time, analyses of spatial variation in microbial activity using fluorescent in situ hybridization and nanoSIMS highlight metabolic heterogeneity within the microbial community. This approach provides a first glimpse at the in situ biosynthetic activity of pathogens involved in chronic infection of the cystic fibrosis airways and contributes to building a basis for physiologically informed laboratory experiments.

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Primary alkali kimberlite melt: Composition of hydrocarbon source The myth dispelled rocks of the Hayrettin Formation M.G. KOPYLOVA1, S.I. KOSTROVITSKY2 (Denizli/Western Turkey): 3 AND K.N. EGOROV Provenance, source weathering and 1University of British Columbia, Vancouver, BC V6T 1Z4, tectonic setting Canada (*correspondence: [email protected]) 1 2 Institute of Geochemistry SB RAS, 1. Favorskogo St., DEMET BANU KORALAY Irkutsk, Russian Federation, 664033 1 3 Pamukkale University Engineering Faculty, Department of Institute of the Earth’s Crust SB RAS, 128 Lermontova St. Geological Engineering, 20070 Denizli/TURKEY Irkutsk, Russian Federation, 664033 [email protected]

After decades of studies, the composition of the primary The geochemical composition of the Oligocene kimberlite melt is still poorly constrained. One of the models hydrocarbon source rocks of the Hayrettin Formation of for the kimberlite origin suggests the melt is low in H2O and Denizli (Western Turkey) province were analyzed for major high in alkalies, as observed in the “uniquely fresh” and selected trace elements to infer their provenance, intensity Udachnaya East kimberlite. Papers that proposed the alkali- of palaeoweathering of the source rocks and tectonic setting. rich affinity for the melt focused on geochemical evidence and Total organic carbon (Corg, %) contents of organic matter rich did not report petrography or geology of the rocks, which are rocks are between 0.21 % and 39.61 %. Plots of organic critically important for the geochemical interpretation. We matter rich rocks on Al2O3 wt.% versus TiO2 wt.% diagram present geological, petrographic and geochemical evidence and discriminant functions diagram indicate that the samples that the alkali-rich affinity of the Udachnaya kimberlite and plot between the granodiorite and gabbro field, and quartzose other kimberlites in Southern Yakutia relates to crustal sedimentary and mafic igneous rocks constitute the source contamination. Alkali carbonates, sodalite, gypsum, anhydrite, rocks in the provenance. To constrain the climatic condition halite and sylvite are present in the groundmass and matrix of during sedimentation of organic matter rich rocks on SiO2 the Udachnaya, Mir and International’naya pipes (southern wt.% versus (Al2O3+K2O+Na2O) wt.% diagram the samples Yakutia). The kimberlites were emplaced through 2 km-thick plot in the field of semiarid climate. Plots of samples on evaporite-bearing carbonate sediments saturated with brines. bivariate discriminant function diagram reveal an active In the global context, southern Yakutian kimberlites are continental margin setting for the provenance. The chemical unprecedented in the amount of the crustal carbonate and index of alteration (CIA) monitors the progressive alteration evaporite material included in the pipes. The secondary, of plagioclase and potassium feldspars to clay minerals. CIA crustal origin of Na, K, Cl and S-rich minerals is supported by values for the Oligocene Hayrettin Formation organic matter the following: 1. A regional correlation between the geology rich samples vary from 26 to 81 with an average 70 indicating and hydrogeology of the local country rocks and the significant weathering at the source areas. kimberlite mineralogy, in particular the difference between southern and northern Yakutian kimberlites; 2. A restriction of halite or gypsum mineralization in the Mir and International’naya pipes to depths where pipes intersect country rock strata with the similar mineralogy; 3. The localization of the highest abundances of Na-K-Cl-S-bearing minerals in the Udachnaya East kimberlite at a depth interval that correlates across three magmatic phases of kimberlites and coincides with the roof of the halite-bearing country rock and an aquifer carrying anomalously Na-rich brines; 4. The presence of evaporite xenoliths and veins of halite, gypsum and carbonate cutting through the kimberlite and xenoliths; 5. The geochemical and Sr, C, O, Cl and S isotopic evidence for crustal contamination. Addition of crustal salts to kimberlite melt began prior to the volcanic fragmentation as a result of preferential melting and assimilation of evaporite xenoliths and may have continued in-situ after the pipe emplacement via reactions with external saline fluids. The hybrid, alkali-, S- and Cl-rich compositions of residual melts and fluids were trapped in secondary inclusions in olivine. Alkali-rich compositions of fluids trapped in fibrous diamonds shortly febore the kimberlite emplacement cannot support the model of the alkali-rich primary kimberlite melt, as the latter is significantly more Ca-, Na-, B-, and S-rich than the K- and Ba-rich fluid inclusions.

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Origin of High-K Ignimbrite in the Metal mobilization by iron- and Miocene Volcanism Surrounding sulfur-oxidizing bacteria in a multiple U$ak Region (Western Turkey): extreme mine tailings in the Atacama Rb-Sr, Sm-Nd Isotopic Evidence Desert, Chile [2] T. KORALAY1, Y. K. KADIOGLU2-3, S.Y. JIANG4, H. KOREHI1, M.BLÖTHE1, M.A. SITNIKOVA1, B. DOLD2, K. DENIZ3 AND B. GÜLLÜ5 AND A. SCHIPPERS1* 1Pamukkale Univ., Geol.Eng. Dept., 20017 Denizli TURKEY 1Federal Institute for Geosciences and Natural Resources [email protected]; [email protected] (BGR), Stilleweg 2, D-30655 Hannover, Germany 2Ankara Univ. Earth Sci. Application&Res. Center-TURKEY ([email protected]; [email protected]; 3Ankara Univ., Geol. Eng. Dept., 06100, Ankara-TURKEY [email protected]; 4Nanjing Univ., Dept. of Earth Sci., 210093, P.R.China [email protected]) 5Aksaray Univ. Dept. of Geological Eng., Aksaray 2FCFM- Universidad de Chile, Departamento de Geología, Departamento de Geología, Plaza Ercilla 803, Santiago de The Western Turkey is an active region formed in a Chile, Chile ([email protected]) complex crustal extensional regime, generating large volume of subduction and post-collisional-related magmas took place The marine shore sulfidic mine tailings dump at the during the Middle Miocene-Quaternary time. The ignimbrite Chañaral Bay in the Atacama Desert, northern Chile, is is mainly composed of plagioclase (oligoclase, andesine) + characterized by extreme acidity, high salinity and high heavy biotite + Fe-Ti oxides (magnetite, hematite) ± amphibole metals concentrations. Due to pyrite oxidation, metals (brown hornblende) and has eutaxitic texture. Whole rock (especially copper) are mobilized under acidic conditions and geochemical data reveal that ignimbrite, characterized by their transported towards the tailings surface and precipitate as trachy-andesite composition, high-K in character, show secondary minerals [1]. Depth profiles of total cell counts in fractional crystallization primarily controlled by plagioclase, this almost organic-carbon free multiple extreme environment biotite, Fe-Ti oxide. The ignimbrite samples have Th/Nb showed variable numbers with up to 108 cells g-1 dry weight (1.00-1.20), Nb/Ta (3.57-14.67), Ba/Nb (37.32-64.43), Hf/Th for 50 samples at four sites. Real-time PCR quantification and (0.18-0.44), K/P (16.99-34.76), Ce/P (0.06-0.10) and Th/U bacterial 16S rRNA gene diversity analysis via clone libraries (1.60-4.03) incompatible element ratios and show Volcanic revealed a dominance of Bacteria over Archaea and the Arc Basalts (VAB) in character. According to spider frequent occurrence of the acidophilic iron(II)- and sulfur- diagrams; ignimbrite exhibits a clear enrichment in LILE and oxidizing and iron(III)-reducing genera Acidithiobacillus, HFSE. Although it is close to Continental Crust value, there Alicyclobacillus and Sulfobacillus. Acidophilic are generally slight decreases in the content of Sr, Ba, Nb, P chemolithoautotrophic iron(II)-oxidizing bacteria were also and Ti ratios reflecting subduction related magma (Wilson, frequently found via most-probable-number (MPN) 1989). In REE diagram, it displays marked enrichment in light cultivation. Halotolerant iron(II)-oxidizers in enrichment rare earth elements (LREE) ((La/Sm)N = 5.03-5.97) relative to cultures were active at NaCl concentrations up to 1 M. heavy rare earth elements (HREE) ((Sm/Yb)N = 4.36-5.15). Maximal microcalorimetrically determined pyrite oxidation Furthermore, all samples have negative Eu anomalies rates coincided with maxima of the pyrite content, total cell ((Eu/Eu*)N = 0.77-0.90), indicating the significant role of counts and MPN of iron(II)-oxidizers. These findings indicate plagioclase in the fractional crystallization. The ignimbrite that microbial pyrite oxidation and metal mobilization display limited range in 87Sr/ 86Sr (0.708048 to 0.708782) and 143 144 preferentially occur in distinct tailings layers at high salinity. Nd/ Nd (0.512420 to 0.512436) isotopic ratios and similar Microorganisms for biomining with seawater salt to Continental Margin Volcanics. Petrographic, geochemical concentrations obviously exist in nature [2]. and Sr-Nd isotope datas indicate that the ignimbrite evolved through fractional crystallization and crustal contamination of [1] B. Dold (2006). Environ. Sci. Technol. 40, 752-758. [2] H. the parent magma were formed during the partial melting of Korehi, M. Blöthe, M. A. Sitnikova, B. Dold, A. Schippers the lower crust and mixing with the upper crust material. (2013). Environ. Sci. Technol. 47, 2189-2196.

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The biogeochemical system of Accumulation mechanisms and chemical elements distribution in the bonding of high-tech metals in hydrosphere marine ferromanganese crusts V.D. KORZH A. KOSCHINSKY1*, J. HEIN2, D. MOHWINKEL1, A. FOSTER3 AND J. BARGAR4 Shirshov Institute of Oceanology, Nakhimovsky pr. 36, Moscow 117997, Russia (E-mail: [email protected]) 1Jacobs University Bremen, D-28759 Bremen, Germany (*correspondence: [email protected]) The chemical elements composition of the oceanic water 2U.S. Geological Survey, Santa Cruz, CA 95060 is a result of substance migration and transformation on river- 3U.S. Geological Survey, Menlo Park, CA 94025 sea and ocean-atmosphere boundaries. Stability of these 4SLAC National Accelerator, Menlo Park, CA 94025 processes is the main condition of the hydrosphere ecosystems stability. Detailed studies revealed three types of chemical Marine ferromanganese crusts (Fe-Mn crusts) are element distribution in the ocean: 1) Conservative: abundant throughout the global ocean and provide a potential concentration normalized to salinity is constant in space and economic resource for a wide range of rare metals for high time; 2) Nutrient-type: element concentration in the surface technology applications. Understanding the geochemical waters decreases due to the bio-consumption; and 3) Litho- processes that govern the interactions of these rare metals with generative: complex character of distribution of elements, natural Fe-Mn oxides has far reaching implications that span which enter the ocean with the river runoff and interred almost the range from global-ocean geochemical balances to the entirely in sediments. The correlation between the chemical development of new techniques for extractive metallurgy. In elemental compositions of the lithosphere and ocean is our project we used synchrotron-based XANES spectroscopy relatively weak (r = 0.68) while for river and oceanic water it to assess oxidation states in natural samples and samples in is high (r = 0.94). which metals were sorbed onto synthetic and natural Fe and In our presentation, we shall show intensities of global Mn oxides. EXAFS spectroscopy was used to resolve the local migration and average concentrations in the ocean in the structure around the metals in these same samples. We coordinates lg Cocean – lg -ocean , where Cocean is an average focussed on the metals Te, Pt, Mo, Zr, and Pb. element concentration and -ocean is its residence time in the Our results confirm that Te is largely Te(VI) in Fe-Mn ocean. In this plot elements form groups reflecting the crusts and predominantly bound to FeOOH by inner-sphere similarity of their properties. The System indicates an complexation. For most model compounds, most Te(IV) existence of the relationship between three main geochemical transformed into Te(VI) during sorption. These data confirm parameters of the dissolved forms of chemical elements in the that oxidative surface adsorption is the process responsible for hydrosphere: 1) average concentration in the ocean, 2) average the extremely high enrichment of Te in crusts (up to about 200 concentration in the river runoff and 3) the type of distribution ppm) as compared to seawater. Since Pt concentrations are too in oceanic water. This allows using knowledge of two of these low in natural Fe-Mn crusts, we investigated Pt only on parameters to gain theoretical knowledge of the third. Finally, sorption samples. As for Te, the results suggest that during the mean concentrations of elements and patterns of their uptake of Pt(II) from seawater a surface oxidation to Pt(IV) on distribution in the ocean can be used to determine pre-techno- the crusts takes place, explaining the high enrichment of Pt in generative concentrations of elements in the river runoff [1, 2, crusts (up to 1-3 ppm). Of the model compounds, especially 3]. Mn oxide was very effective in oxidizing Pt(II). Molybdenum (as Mo(VI)) shows a strong association with the [1] Korzh (1974), Journal de Recherches Atmospheriques. Mn oxide phase of crusts, while in sorption and sequential 8(3-4), 653-660. [2] Korzh (2008), J. Ecologica 15, 13-21. [3] leaching experiments it also strongly binds on FeOOH. Lead Korzh (2012), Journal of water science and its practical displays a complex distribution, especially in phosphatized application 1, 56-62. crusts, where it seems to form unsoluble phosphate compounds. Zirconium was found to be bound as Zr(IV) to

both FeOOH and MnO2 phases, in contrast to the expected predominant binding to FeOOH. A more detailed evalution of the spectra is presently carried out to resolve open questions.

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Petrology and geochemistry of mafic The heavy metals in Halocynthia rocks in the Acasta Gneiss Complex aurantium tissues of the Japan Sea KEIKO KOSHIDA1*, AKIRA ISHIKAWA1, HIKARU KOSJANENKO >.>.* AND KOSJANENKO D.V. IWAMORI2 AND TSUYOSHI KOMIYA1 V. I. Il’ichev Pacific Oceanological Institute, 43, Baltiyskaya 1Earth Science and Astronomy, The University of Tokyo, Street, Vladivostok, 690041, Russia. Tokyo 153-8902, Japan, [email protected] (E-mail: [email protected])* 2Earth & Planetary Sciences, Tokyo Institute of Technology, Tokyo 152-8550, Japan The problem of concentration of elements of living organisms of the marine environment is of great importance. Eoarchean crustal records are rare, so that the details of This problem was first posed VI Vernadsky [1]. Intermediate early Earth are not revealed yet. Acasta Gneiss Complex stage in the cycle of TM in the estuaries of the seas is a (AGC), located in the western part of the Slave Province, planktonic organisms that accumulate TM and send them to Canada, is one of the Early Archean terranes, and contains the the bottom [2]. Ascidians (A), as bottom marine animals, are oldest rocks in the world [1]. It is dominated by ca. 3.6-4.0 Ga the final link in the cycle TM of the oceans and seas. felsic and layered gneiss suites, but minor mafic to The aim was to determine the selectivity of HM intermediate gneiss occur as rounded to elliptical enclaves and accumulation various tissues ascidian H. aurantium. In inclusions [2]. The Acasta mafic rocks are composed of addition, ascidians tissue use in medical applications: in recent variable amounts of hornblende ± plagioclase ± quartz ± years, mining H. aurantium is to produce raw materials for the chlorite ± epidote ± biotite ± apatite ± sphene ± garnet ± production of biologically active food supplement "Haurantin" clinopyroxene ± opaque ± cummingtonite, and are classified (POI FEB RAS) Overseas pharmacists from the body squirts into hornblendite, garnet-bearing and garnet-free amphibolites. identified cancer drugs ezteinastsidin-743 and ascidin [3]. The garnet-free amphibolites can be further subdivided into Individuals of H. aurantium were collected in the Kievka Bay fine- and coarse-grained amphibolites. Petrological (Sea of Japan) in 2011. For the analysis of seized samples of examination and mineral composition demonstrate that all the following tissues: stomach, digestive gland, gonads, rocks underwent up to upper amphibolite facies muscle and tunic. Analyses of the composition of animal metamorphism. tissues were determined by atomic absorption spectroscopy. The composition of our studied samples ranges from

basalt to basaltic andesite (SiO2 = 43-57 wt%, MgO=4.1-19.1 Tissue Fe Zn Cu Mn Ni Cd Pb Co wt%). Some systematic differences can be seen among each t 140,6 13,9 2,7 30,8 1 0,1 1 0,3 group in terms of major elements and chondrite-normalized m 48,6 65,3 1,4 4,9 0,1 0 22,2 0,1 REE patterns. The hornblendites have high MgO contents and dg 898,3 29,5 7,1 24 1,3 0,2 1,4 0,8 show strong negative Eu anomaly, reflecting the effect of g 41,4 202 4,3 12 0,7 0 34,1 0,4 anatexis. The garnet amphibolites have high FeO contents and s 344 188,4 4,2 21,1 0,9 0 344 0

slightly fractionated REE patterns (LaN/SmN=1.2-1.8, Table: The concentration of heavy metalls in H. aurantium

GdN/YbN=2.0-2.2). The coarse-grained amphibolites are tissues (t – tunic, m – muscle, dg – digestive glands, g –

enriched in Al2O3 and LREE contents (LaN/SmN=1.3-5.4) with gonads, s – stomach, mcg/g.) moderately fractionated MREE to HREE patterns

(GdN/YbN=1.2-2.0), whereas the fine-grained amphibolites Thus, we can judge the selective accumulation of certain

display flat REE patterns (LaN/SmN=0.8-1.4, GdN/YbN=1.0- tissues purple ascidian TM in large enough quantities that can 1.2). MORB-normalized trace element patterns show be explained by their peculiarities of life, the structure of depletion in Nb and Zr relative to Th and LREE for all studied tissues themselves and also, to a large extent, the state of their samples. Although variable incompatible trace element environment. patterns were possibly due to alteration during regional metamophism, depletion in Nb and Zr contents suggest [1] Vernadsky V.I. (1965) Moscow: Nauka, 374. [2]Kasatkina subduction zone magmatism for the mafic rock inclusions in A.P. et al. (1994) Biologiya morya 20, ?4, 247-251. [3] Dobryakov Y.I. et al. (2003) Intern. J. on the AGC. Immunorehabilitation 5, ? 2, 181.

[1]Bowring & Williams (1999) Contrib. Mineral. Petrol., 134, 3-16. [2]Iizuka et al. (2007) Precamb. Res. 153, 179–208.

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Factors controlling elemental Metagenomic insights into the fractionation in laser ablation response of indigenous microbial ICP-MS zircon geochronology communities in beach sands to the JAN KOSLER1,2*, SIMON E. JACKSON2 Deepwater Horizon oil spill 2 AND ZHAOPING YANG 1 1 1 J.E. KOSTKA , L.M. RODRIGUEZ-R. , W.A. OVERHOLT , 1Centre for Geobiology and Department of Earth Science, X. LIN1, K. MARKS1, K. KONSTANTINIDIS University of Bergen, Allegaten 41, Bergen, N-5007, AND M. HUETTEL2 Norway (*correspondence: [email protected]) 1 Georgia Institute of Technology, Atlanta, GA, USA 2Geological Survey of Canada, Natural Resources Canada, 2Florida State University, Tallahassee, FL, USA 601 Booth St., Ottawa, Ontario, K1A 0E8, Canada ([email protected], [email protected]) Biodegradation mediated by indigenous microbial

communities is the ultimate fate of the majority of Fractionation of elements during laser ablation (LA) is a hydrocarbons that enter the marine environment. A large significant source of error in quantitative and isotope ratio amount of oil from the Deepwater Horizon oil spill was analysis by ICP-MS. It has been demonstrated that phase transported to and subsequently buried in Gulf of Mexico separation and formation of particles of variable size and beaches. The objective of this research is to characterize the in composition are the primary cause of laser-induced elemental situ response of microbial communities in parallel with the fractionation [1], and that the element decoupling can be fate and chemical changes in oil hydrocarbons. Our time series further enhanced by variable aerosol transport and processes database encompasses >500 sediment and water samples in the ICP [2]. Interaction of laser radiation with zircon collected from Pensacola Beach, FL, USA, from 2010 to 2012. (ZrSiO ) typically results in its thermal breakdown to ZrO 4 2 Illumina MiSeq and HiSeq platforms were used to obtain an and SiO and formation of aerosol particles with different 2 average of 10000 SSU rRNA gene amplicon sequences and 35 composition, size and transport properties [3]. As a result of million (100bp) paired-end reads on a subset of these samples. the preferential partitioning of U+Th and Pb into ZrO and 2 A bloom of bacteria was observed in parallel with oxygen SiO phases, respectively, the decomposition of zircon by 2 consumption rates and the depletion of the majority of highly transfer of laser heat can efficiently fractionate these degradable oil hydrocarbons during the first 4 months after oil geochronologically important trace elements, resulting in came ashore. SSU rRNA gene amplicon and metagenome erroneous U-Th-Pb ages obtained by LA-ICP-MS dating. analysis revealed an initial sharp drop in community diversity Previous studies have related the laser-induced decoupling after oiling. Moreover, evidence of succession was detected of U+Th from Pb in zircon to different element volatilisation across the time-series, featuring a marked increase in relative temperatures [2], chemical composition of the zircon matrix abundance of Alcanivorax spp. during the first two months (up [4] and radiation damage accumulated since the last closure to 40% of the community) followed by enrichment in other for annealing in zircon [5]. Recently obtained laser ablation members of the Gammaproteobacteria (Parvularcula, ICP-MS data for a suite of well characterized zircon samples Hyphomonas, Xanthomonadales) in subsequent months. By with range of composition and accumulated radiation damage July 2011, community diversity had sharply rebounded, and suggest that these factors alone cannot explain the observed sequences of taxa associated with oligotrophic conditions, variations in the rate of laser-induced elemental fractionation; such as the Thaumarchaeota (Nitrosopumilus) were detectable, they may, however, affect the kinetics of the phase separation whereas phylotypes associated with the oiling event were during the thermal breakdown of zircon. Additional undetectable. Finally, we observed that genes for central- parameters that will be evaluated for effects on laser-induced metabolism functions were enriched in clean samples, while fractionation include the composition of ambient gas during genes related to peripheral metabolism (e.g. aromatics the ablation and transport properties of aerosol particles degradation, nitrogen fixation, phosphorus uptake) were formed by laser ablation of zircon. enriched in oiled samples, reflecting the community response

to a oil-derived carbon source and nutrient depletion. Overall, [1] Kuhn & Günther (2003) Anal Chem 75, 747-753. [2] multiple lines of independent evidence from a time series Guillong & Günther (2002) JAAS 17, 831-837. [3] Kosler et describe the microbial response to hydrocarbon discharge as a al. (2005) JAAS 20, 402-409. [4] Black et al. (2004) Chem succession dynamics model driven by nutrient availability and Geol 205, 115-140. [5] Allen & Campbell (2012) Chem Geol hydrocarbon chemistry. 332-333, 157-165. (* Funding received from Czech Science

Foundation - project number P210/12/2114).

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Provenance and metamorphic Is there an extreme pressure conditions of very low-grade dependence of sulphur solubility in metasedimentary rocks of the hydrous silicate melts? Variscan accretionary prism of the A.V. KOSTYUK* AND N.S. GORBACHEV Kaczawa Mts (SW Poland): Institute of Experimental Mineralogy RAS, Academica Geochemical and mineralogical Osipyana 4, Chernogolovka, Russia (correspondence*: [email protected], [email protected]) evidence 1 1 The question of the dependence of the solubility of JOANNA KOSTYLEW , RYSZARD KRYZA AND JAN ZALASIEWICZ 2 sulphur in hydrous silicate melts on the pressure still remains one of the most discussed and relevant. There are a lot of 1 Institute of Geological Sciences, University of Wroc&aw, ul. experimental works studying the SCSS in silicate melts, but Cybulskiego 30, 50-205 Wroc&aw, Poland, there is no clear answer on the effect of pressure on it. We e-mail: [email protected] have proposed an alternative hypothesis about existence of 2 Department of Geology, University of Leicester, University extreme pressure dependence of sulphur solubility with a Road, Leicester LE1 7RH, UK maximum at 1.5-2.0 GPa [1]. Since, the available literature data are quite extensive at P from 0.5 to 3 GPa [2-4], we The Kaczawa Complex in the West Sudetes (SW Poland) decided to study experimentally peridotite-basalt-sulphide-

is interpreted as a fragment of a Variscan accretionary prism. H2O system at P=0.1-0.5 GPa and T=1200-1300°C. Together with neighbouring basement units, it forms a Experiments were carried out in an internal-heated structural mosaic of the Sudetes at the NE edge of the pressure vessels by a quenching technique. We used Pt- Bohemian Massif. peridotite ampoules filled with powder of tholeiitic basalt and Some previous studies of the Kaczawa Complex aimed at FeS as starting compositions in the ratio of 3:1. The total determination of the provenance and metamorphic conditions volatile (H2O) in system were 5 wt.%. Fugacity of sulphur and of metasedimentary rocks of the complex. These questions oxygen buffered by Pt-PtS and WM buffers respectively. have become particularly important since the 1970’s when Duration of experiments was 24 hours. Products of some of the rocks were classified as mélange, rather than experiments were studied by microprobe. fragments of coherent stratigraphic successions as previously There was a positive dependence of the solubility of thought. Their depositional age remains controversial, though sulphur on the pressure after experiment. The concentration of scarce conodonts suggest a Devonian - Early Carboniferous sulphur in the water-containing silicate melt at T=1200°C was age. 0.2±0.12wt.% at P=0.1GPa; 0.35±0.03wt.% at P=0.3GPa; We present new results of mineralogical (microprobe, 0.42±0.19wt.% at P=0.5 GPa. The sulphur concentration at XRD) and bulk-rock chemical investigations of various T=1300°C was 0.2± 0.12wt.% at P=0.1GPa; 0.27±0.06wt.% at metasedimentary rocks from different structural units of the P=0.3GPa; 0.46±0.12wt.% at P=0.5GPa. These data confirm Kaczawa Complex. our previous assumption about extreme pressure dependence The provenance of metasedimetnary rocks of the Kaczawa of sulphur solubility in hydrous sulphide-bearing silicate Complex is assessed based on the Chemical Index of melts. Confirmation of this theory can be very useful for a Alteration (CIA) and discrimination function analysis, using better understanding of transport of sulphide sulphur and ore major-element and selected trace-element data (i.e. Eu/Eu*, elements from the deep magmatic centres to the upper levels Zr/Sc, Th/Sc Th/U and GdN/YbN). The results point to an old of the Earth crust where most of known sulphide ore deposits continental crust as the likely main source for the sediments, were discovered. with minor recycled sedimentary and trench-derived Supported by grant RFBR ? 12-05-31113 components. Based on the white mica and chlorite chemistry, as well as [1] Gorbachev N.S. et al. (2005) Doklady Earth Science, on illite ‘crystallinity’ index, we provide further evidence that V.401, N.3, P.421-423 [2] Mavrogenes, O’Neill (1999) the mélange and some other metamudstones in the Kaczawa Geochim. Cosmochim. Acta. 63, 1173-1180. [3] Mysen, Popp Complex were metamorposed under very low-grade (1980) Amer.J.Sci. 280, 78-92. [4] Wendlandt (1982) Amer. conditions (T < 250°C) which is in line with the accretionary Mineral. 67, 877-885. prism model.

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U-Pb, Ar-Ar isotopic dating of Geochemistry of sediments from the Kalba-Narym polychronic batholith Khai River – Nha Trang Bay (East Kazakhstan) estuarine system, South China Sea P.D. KOTLER12*, A.G. VLADIMIROV123, S.E KOUKINA*, N.V. LOBUS, V.I. PERESYPKIN, S.V. KHROMYKH12, A.V. TRAVIN1 AND O.V.NAVOZOV4 G.N. BATURIN AND N.A. SHULGA 1Institute of geology and mineralogy SB RAS, Novosibirsk, PP Shirshov Institute of Oceanology of RAS, 117997 630090, Russia (*: [email protected]) Nakhimovsky pr. 36, Moscow, Russia 2Novosibirsk State University, 630090, Novosibirsk, Russia (*correspondence: [email protected]) 3Tomsk State University,Tomsk 634050, Russia 4“Topaz” geological exploration company LTD, Oskemen, The Khai River and the Nha Trang Bay form one of the 070001, Republic of Kazakhstan major estuarine systems in the South China Sea that is inhabited by unique biota. This area now experiences a Kalba-Narym granitoid batholith located on the territory significant anthropogenic load from the local people activities of East Kazakhstan. Batholith has a polychronic structure and and, especially, from the quickly growing tourist industry. is composed of rocks of five intrusive complexes, which differ Trace (Cr, Ni, Cd, V, Zn, Cu, Pb, Sb, Bi, Sn, Ag, Li, Co, in composition and formation time [1]. As, Zr, Mo, Hg), minor (Mn) and major (Al, Fe, Ti, Mg, Ca, Results of U-Pb and Ar-Ar granitoids complexes isotopic Na, K) along with nutrients (TOC, TS, TP) and TIC were first dating are:1) kunush plagiogranite complex (U-Pb, Zrc - determined in surface sediment samples from the Khai River 306±9, 299±2 Ma); 2) kalguta association of Bt-Grt- and Nha Trang Bay along the salinity gradient. granodiorites and Hbl-granite (Ar-Ar, Hbl (2 dates) - 286±3 According to the sediment quality guidelines and Ma, Bt - 272±1 Ma); 3) Kalba granodiorite-granite complex reference background values data on the shale, pelagic clays, (Ar-Ar, Bt - 5 dates from 291 to 273 Ma); 4) monastyr average river bed sediments and rural and industrial leucogranite complex (U-Pb, Zrc - 284±4 Ma, Ar-Ar, Bt - 6 Vietnamese soils most of the element contents that were dates from 285 to 269 @.); 5) kainda granite complex (Ar-Ar, studied were below the threshold levels, while the content of Bt - 5 dates from 290 to 267 @.). Cu, Pb, Ni and, especially Ag exceeded significantly the Obtained results allow us to determine the maximum hazardous levels in the most of the samples from the Nha duration of formation of Kalba-Narym batholith at ~ 30 Trang Bay. million years. The formation of the main volume of granitoids Aluminum normalization and Spearman correlation occurred during a short interval - no more than 10 million analysis revealed some specific features in distribution of years (290-280 Ma), which corresponds to most of the Ar-Ar elements along the salinity gradient. Thus, Ca, Ba and Sr are dates. Younger Ar-Ar dates from 280 to 270 Ma can be largely dependent on the carbonates content in sediments. interpreted as the result of later disbalance in K-Ar isotopic Sedimentary P, Al, Fe, Mn, Ti, Na, K, Li, Co, Cs, Zn and V system because the north-eastern part of the batholith is are most likely controlled by the accumulation of their fine adjacent to a major fault - Irtysh shear zone, within which the grained aluminosilicate host minerals and therefore tend to fixed stages of tectonic activity are 280-275 Ma and 270-265 increase seaward. The contents of S, As, Sn, Bi, U, Cd and Mo Ma[2]. are slightly elevated in sediments of estuarine part of the river The work was supported by the Presidium of SB RAS – sea transect. These elements may be scavenged by and/or (project ? 17, 77,123), RFBR (project ? 10-0500913-A), co-precipitated with the dissolved and particulate materials of FGP “Research and scientific-pedagogical personnel of the river discharge and further deposited on the geochemical innovative Russia” (? 2012-1.2.1-12-000-2008-8340). barrier within the river – sea water mixing zone. The distribution of Ni, Cr, Zr, Cu, Pb, Sb, Hg and, [1] Navozov O.V. et al. (2011) Geologiya i ohrana nedr, 4, especially, Ag was characterized by anomalous high 66-72. [2] Travin et al. (2001) Geochemistry Int. 12, 1347– concentrations in the urban area of river-sea transect. This 1351 might be due to the point anthropogenic pollution from local human activities, i.e., fishing, shipping, fueling, and waste and sewage sludge outflow. The anthropogenic and/or environmental sources of Ag in the region need special study.

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Integrated geological and geophysical Influence of long-term diagenesis on probing of lithospheric dynamics in a the REE content in marine reptile young extensional basin (Carpathian- remains from the Middle Triassic Pannonian Region) bonebed (S Poland) 1 2 ISTVÁN KOVÁCS1, GYÖRGY FALUS1, CSABA SZABÓ 2, MONIKA KOWAL-LINKA *, KLAUS PETER JOCHUM 3 JÁNOS KISS1, TAMÁS FANCSIK1, ENDRE HEGEDAS1, AND DAWID SURMIK 2 2 2 ZSANETT PINTÉR , NÓRA LIPTAI AND LEVENTE PATKÓ 1A. Mickiewicz University in Pozna&, Institute of Geology, 1Geological and Geophysical Institute of Hungary, H-1143, Poland, (*correspondence: [email protected]) 2 Srefánia út 14, Budapest, Hungary Max-Planck-Institut für Chemie, Mainz, Germany, 2Lithosphere Fluid Research Lab, Institute of Geography and ([email protected]) 3 Earth Sciences, Eötvös University, Budapest, Hungary, H- University of Silesia, Faculty of Earth Science, Sosnowiec, 1117, Pázmány Péter sétány 1/c Poland ([email protected])

Detailed analysis of numerous of mantle xenoliths from The geochemical signals recorded in fossil bones are the Carpathian-Pannonian region revealed that the present commonly used to reconstruct conditions of sedimentary and lithosphere may be divided into two major sub-horizontal diagenetic environments, but recent data suggest insufficient domains. recognition of particularly the long-term impact of diagenesis The shallower “layer” is characterized mostly by fine on vertebrate remians. We have examined with LA-ICPMS 29 grained, equigranular to porphyroclastic xenoliths, generally bones of marine reptiles collected from the ~247-245 Ma old displays an ’axial [010]’ deformation pattern. Mineral (Middle Triassic) bonebed, outcropped in Byglin (S Poland). This bonebed (a crinoidal limestone) comprises reworked constituents show high Mg#, low H2O content in nominally anhydrous minerals (NAMs) and depleted in basaltic major vertebrate remains deposited originally in various coastal and elements implying that this layer may have undergone marine settings and at different times. The two main considerable depletion. objectives of the present study are: (1) to check whether The xenoliths from the deeper “layer” show mainly coarse concentrations and ratios of REE and other trace elements are grained, protogranular texture with ’A-type’ deformation useful to distinguish between relatively younger and relatively pattern. Minerals usually have lower Mg# and richer in older bones in the marine bonebed, and (2) whether the early basaltic major elements. The NAMs from this “layer” show diagenetic element contents and ratios characteristic for the various depositional settings can still be deciphered. higher H2O content than those in the shallow layer. This layering may also be seen as seismic reflections in the present The REE concentrations in the profiles (average 2REE in lithospheric mantle 10-15 km below the MOHO, accompanied individual profile is ~2900-3500 ppm) tend to be more or less by a considerable increase in seismic velocities. Anomalous constant. All samples are enriched in REE with regard to the seismic anisotropy pattern showing E-W direction in contrast PAAS. The samples/PAAS diagrams reveal “bell shaped” to the general NNW-SSE trend may be due to the fossil patterns with two peaks for Sm and Gd, a small low for Eu, directions frozen in the juvenile deeper lithosphere which may and with HREE values far below the LREE values. The bones be the result of an asthenospheric flow related to the Alpine form a small cluster in the (La/Sm)N vs. (La/Yb)N diagram, collision. although some samples are located distinctly outside the cluster margin. In the Ce/Ce* vs. Pr/Pr* diagram the bones

reveal a slightly negative CeN anomaly or lack of it, and

smoothly positive and negative LaN anomaly. Most of the samples display similar REE concentrations and distribution patterns, probably due to long-term diagenesis which obliterated the early diagenetic geochemical signals. Only several samples show different features. M. Kowal-Linka is supported by the NCN grant 2011/01/B/ST10/04889, and Dawid Surmik by the NCN grant 2011/01/N/ST10/06989.

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Fractionation of Si isotopes during Characteristics of metal bearing core formation from first principles phases in MSWI residues from calculations Poland PIOTR M. KOWALSKI*1 AND SANDRO JAHN2 P. KOWALSKI1*AND M. MICHALIK1 1Forschungszentrum Jülich GmbH, Institute of Energy and 1Institute of Geological Sciences, Jagiellonian University Climate Research - IEK-6: Nuclear Waste Management, ul.Oleandry 2a, 30-063 Krakow D-52425 Jülich, Germany (*correspondence: (*correspondence: [email protected]) [email protected]); 2GFZ German Research Centre for Geosciences, Mineralogical characteristic of MSWI (municipal solid Telegrafenberg, D-14473 Potsdam, Germany. waste incineration) residues is important, especially in time of ongoing changes in municipal waste management system in Recently, we have developed an efficient ab initio based Poland. These changes leads to significant reduction of the computational approach to predict equilibrium isotope amount of landfilled raw wastes. A way to achieve this goal is fractionation factors between chemically and structurally construction of nine incineration power plants with assumed complex crystalline solids, fluids and melts at high T and P slags production around two hundred thousand tons per year. [1,2]. Our method has been successfully applied to “non- The increasing slag production makes that it is essential to traditional” stable isotopes of light elements such as B and Li, take a closer look into this material in terms of possible which are important geochemical tracers widely used in environmental pollution. petrology. We have shown that we are able to correctly The aim of this study is mineralogical and chemical reproduce the experimentally observed fractionation characteristics of the metal-bearing phases of the MSWI sequences: fluid-tourmaline-mica for B and staurolite-fluid- residues. Slags were collected from two the biggest mica-spodumene for Li isotopes with a computational incineration power plants in Poland. One of them is oriented to uncertainty comparable to the experimental error. Moreover, incineration of non-hazardous municipal waste and the other with the calculations we explained the discrepancy between on industrial and hazardous municipal wastes. the results of in-situ experiments and measurements on natural Slags from incineration of wastes are non-consolidated, samples [2]. grainy materials, containing large amount of amorphous With this well tested methodology we investigate here the phase, mostly composed of Si-rich glass. Si isotope fractionation between silicate melt and liquid metal Metals in slags are present in several forms: under the extreme P-T conditions of Earth’s core formation 1. As large fragments which are mixed with slags grains and (P~25 GPa, T~3000 K) that are not yet accessible to part of uncombusted materials (rock fragments, glass and experiment [3]. The equilibrium Si isotope fractionation ceramics), factors between these materials are of great interest as they are 2. In form of metallic inclusions in glass or minerals, needed to understand the origin of the difference in the 3. As a component of mineral and amorphous phases. isotopic signatures observed between the Bulk Silicate Earth Metals in form of metallic inclusions are monometallic (BSE) and Chondrite meteorites [3]. It has been proposed that (mainly Fe, Al, Pb, Zn, Cu) or in form of alloys (Fe-Ti, Fe-Ni, the observed difference reflects the fractionation of Si isotopes Fe-Cu, Cu-Sn+Pb and Cr-Fe). Metals in minerals are between silicate melt and iron-rich metal during the formation concentrated mostly in form of oxides (mainly Fe and Al of Earth's core [4]. We will present a comparison of our oxides) and in silicates, aluminosilicates and sulfates (e.g. Cu). predictions with the available experimental data and discuss The content of metals in glass varies in wide range. High the effect of the pressure-induced changes in the melt structure concentration of them is connected with presence of metallic on the fractionation of Si isotopes. Our results shed new light inclusions inside the glass. Content of metals in slags varies on the origin of the excess of the heavy Si isotopes in BSE and within broad range – e.g. Cu from 330 to 4900 ppm, Zn from may also help to further constrain the silicon content of the 1500 to 4700 ppm, Pb from 50 to 6300 ppm and Cr from 300 Earth's core. to 600 ppm in municipal slags and from 2000 to 2500 ppm in industrial slags. These concentrations could be potentially [1] Kowalski, P. M. and Jahn, S. (2011) Geochim. hazardous and further studies about leaching potential and Cosmochim. Acta 75, 6112-6123. [2] Kowalski, P. M. mobility of these metals are needed. Wunder, B. and Jahn, S. (2013) Geochim. Cosmochim. Acta 101, 285-301. [3] Shahar, A. et al. (2011) Geochim. Cosmochim. Acta 75, 7688-7697. [4] Georg, R. B. et al. (2007) Nature 447, 1102-1106.

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Electrolyte ion binding at iron Petrogenesis of mafic-ultramafic oxyhydroxide surfaces rocks from the Berit metaophiolite PHILIPP A. KOZIN*, ANDREI SHCHUKAREV massif: implications for REE, PGE, AND JEAN-FRANÇOIS BOILY base metal and Al-rich chromitite *correspondence [email protected] composition

1 2A Electrolyte ion loadings at the surfaces of synthetic H. KOZLU AND V. RUDASHEVSKY ((-FeOOH) and lepidocrocite (.-FeOOH) nano-sized goethite 1General Directorate of Mineral Research & Exploration, particles that were pre-equilibrated in aqueous solutions of 10 Mineralogy-Petrography, 06800 TR Çankaya/Ankara mM NaCl and NaClO were investigated by means of 4 Turkey, E-mail:[email protected] cryogenic X-ray photoelectron spectroscopy (XPS) [1]. 2 - - CNT Labs, 1 Roentgena Str.197101, St.Petersburg, Russia Atomic concentrations of Cl and ClO4 in acidic pH regions and of Na+ cations [2] in alkaline pH regions were correlated Mantle heterogeneity in terms of corundum bearing to potential determining ion (p.d.i; H+, OH-) adsorption mafic rocks, as including eclogite and/or pyroxenite within obtained by potentiometric titrations. (Fig. 1) peridotite is observed in Berit massif. The bulk chemical analytical results of the patterns from mafic and ultramafic rocks indicate that they relatively enriched in the REE-PGE and base metals. The refertilized and inhomogeneous mantle is capable of yielding more voluminous and compositionally diverse magma than normal. The REE and PGE distribution of high-Al chromitite patterns and mafic layers in Berit peridotite are, therefore, very important geochemical tool for determining the upper mantle heterogeneity. REE values of mafic rocks are between (La/Ce: 0.40-0.69, Ce/Yb: 1.05- 16.29, La/Yb: 0.44-7.62, La/Sm: 0.88-6, La/Lu: 2.8-55) 12- 165 ppm. The LREE-enrichment in peridotites are explained by interaction of the peridotites with LREE-enriched melts. The REE and PGE are generally considered to be relatively immobile during low-temperature alteration. However some elements, such as Eu, can be modified some what by Figure1. Ionic surface loadings as a function of surface charge hydrothermal processes. It has been determined the positive developed on rod- (RL) and lath-shaped (LL) lepidocrocite, as Eu anomalies in the normalised diagram for some chromitites well as in two different goethite with specific surface area of and ultramafic mafic rock samples (dunite-pyroxenite-gabbro- 69 (GT69) and 122 (GT122) m2/g. diabase) from Berit metaophiolite. A relative enrichment in

siderophile elements (as ppm) in the both of mafic and The data revealed a strong dependency of p.d.i. and ultramafic rocks and in the high-Al chromitites for base metals electrolyte ion adsorption on mineral particle morphology, as (Ag: 0.3-0.9, Bi: 0.03-0.11, Cu: 13-2626, Ni: 134-7172, and seen by comparison of rod- (RL) and lath-shaped (LL) Te: 0.1-3 ppm) is also determined. It is noteworthy that lepidocrocite particles, as well as on surface roughness, as in especially Pt (2.5 ppm) and Pd (4 ppm) enrichments are case of samples with different surface porosity (Fig. 1). LL encountered in the high-Al chromitites. particles with a predominantly proton-inactive (010) surface Two chromite generations are determined in Berit:1) acquired greater sodium but lower anion loadings. GT122 primary spinel component-rich (Al2O3-and MgO-rich particles contained greater surface roughness and thereby compositions); 2) developed on the boundary of grains of acquired greater p.d.i. and anion loadings than GT69. chromite I – chromite and II enriched by chromite and

magnetite minerals (in Fe, Cr and Ti). The association of base [1] Shchukarev (2010), Journal of Electron Spectroscopy and metals (Cu, Ni, Bi, Se, Te, Au, Ag) and Ti as well as Pd and Pt Related Phenomena 176, 13–17. [2] Shimizu, Shchukrev, itself in composition of accessory minerals has been suggested Kozin and Boily (2012), Surface Science 606, 1005-1009. that they may be brought into chromitites by fluids in basic composition.

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Migration of hydrocarbons recorded Gramaccioliite-(Y) – rare yttrium in calcite-hosted inclusions, Dead Sea carrier in metamorphic rocks area: trace elements and isotopic (Subpolar Urals, Russia) evidence KOZYREVA I.V1., AND SHVETSOVA I.V. O.A. KOZMENKO*, E.V. SOKOL AND V.N. REUTSKY Institute of Geology Komi SC UB RAS, Syktyvkar 167982, Russia ([email protected]) V.S.Sobolev Institute of Geology and Mineralogy, prosp. Koptyuga 3, Novosibirsk, 630090, Russia Gramaccioliite-(Y) is related to crichtonite group which (*[email protected]) includes the series of complex titanium and iron oxides with

general formula A=- C O , where A = Sr, Pb, Ca, Na, R, The mechanisms of hydrocarbon (HC) migration with 18 2 38 REE, Ba, U; B = Mn, Y, REE, U, Zr; C = Ti, Fe3+, Cr D T = water fluids, as well as the ability of container minerals such Fe3+, Mg. For the first time it was found in biotite gneisses of as vein calcite to preserve HC geochemical tracers, have Piedmont province (Italy) and named in honor of Professor of received much recent interest [1]. Calcitic veins enclosing HC Milan University Carlo Maria Gramaccioli [1]. We found and soot carbon have been discovered in the western side of gramaccioliite-(Y) on Maldynyrd Ridge (Subpolar Urals) in the Dead Sea rift, where basin opening induced venting of hematite-sericite shales. This is the first find in Russia. The water-methane fluids [2]. All veins share similar REE spectra mineral was found as well composed tabular crystals with defined by the calcite rare earths patterns. Calcite crystallized trigonal habit with rhombohedral side planes, with black from solutions with seawater chemistry signatures [3]. The coloring and metal shine. In association with it we found reconstructed water generation temperatures of 55-90°C fit the leucoxene, rutile, anatase, apatite, cyanite, epidote, garnet, regional “oil window” located at the depths 2.5-4 km. tourmaline, monazite and fuchsite, gold in important Significant negative Ce/Ce* anomaly indicates calcite growth quantities. Gramaccioliite-(Y) was studied with scanning at high oxygen fugacity. The organic matter hosted by calcite electron microscope JSM-6400 with energy spectrometer has C:N:S ratios from 30:2:15 to 15:0.1:2 (in mole fraction) Link. The calculated empirical formulas of gramaccioliite-(Y) and contains abundant asphaltenes with trace amounts of are as follows: alkanes and carbonyl groups. Measured values "13C (–26.9 org (Pb Sr Ba U ) (Y Mn Ce Ca Nd La ) to –27.2 ‰ PDB) and "34S (+5.5 ‰ CDT) are similar to those 0.61 0.27 0.02 0.02 0.93 0.49 0.37 0.08 0.04 0.02 0.02 * (Ti Fe Zn V Nb ) O [1]. of the Dead Sea asphaltenes [4]. As the obtained data imply, 1.01 13.53 5.49 0.22 0.04 0.04 19.33 38 (Pb Sr ) (Y Mn ) (Ti Fe Zn V ) O the calcite veins with inclusions of both oxidized and 0.60 0.39 0.99 0.55 0.42 0.97 13.32 6.01 0.53 0.18 20.04 38 – our data. biodegraded HC and soot carbon precipitated from Ca-Na- It is noticeable that the mineral, discovered by us, differs HCO -Cl sediment waters that entrained crude oil drops. 3 from the one, discovered in Italy, by considerably lower quantity of impurities, and its formula is practically identical [1] Rongxi et al. (2011) Rus. Geol.Geoph. 52, 1491-1503. [2] to approved one (IMA 2001–034): (Pb,Sr)(Y,Mn) Gvirtzman & Stanislavsky (2000) Basin Research 12, 79-93. (Ti,Fe)18Fe2O38 [1]. The formation of gramaccioliite-(Y) is [3] Bau & Dulski (1996) Precamb. Res. 79, 37-55. [4] conditioned by geochemical and mineralogical features of Nissenbaum & Goldberg (1980) Org. Geochem. 2, 167-180. metamorphized rocks, formed on Precambrian substrate of contrasting content and modified by hypergenic processes. On the one hand the high titanium content of basites, presence of lead and zinc as galenite and sphalerite inclusions, on the other hand – rare earth and manganese anomaly, which is characteristic for rhyolites of this region – all these were favorable formation factors for complex titanium and iron oxide - gramaccioliite-(Y). The work is completed with financial support from the Program of Basic Researches of UB RAS #12-C-5-1020 “General and local criteria of difference between high-disperse exogenous and low-temperature hydrothermal ore-forming systems”.

[1] Orlandi P.et al/ (2004) European Journal of Mineralogy 16, 171–175.

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Benthic nutrient fluxes and iron- Mapping lead contamination of soil phosphorus cycling in sulfidic due to mining in Peru estuarine muds S.X. KRAGIE1 AND A. VAN GEEN1 PETER KRAAL12, EDWARD D. BURTON1, 1Lamont-Doherty Earth Observatory of Columbia University, RICHARD T. BUSH1, ANDREW L. ROSE1, Palisades, NY10964, USA MICHAEL D. CHEETHAM1 AND LEIGH A. SULLIVAN1 An estimated 1.6 million people live within 5 km of an active 1Southern Cross GeoScience, Southern Cross University, PO mine, ore processing plant, smelter, or former mining site in Box 157, Lismore, New South Wales, Australia 2 Peru [1]. In a country with such a long mining history, towns As per June 1, 2013: Department of Geochemistry, Utrecht have often been built on top of former mine tailings University, Budapestlaan 4, 3584 CD Utrecht, The contaminated with Pb. The health consequences of allowing Netherlands children to play in soil contamined with Pb have been well documented. What is less widely know is that the distribution Estuaries are crucial geochemical filters at the land-ocean of Pb in soil contaminated by mining activities can be spatially interface that have been widely impacted by human activities. highly heterogeneous. One such example along the railroad We investigated sediment biogeochemistry and benthic track that links the capital Lima to the main mining centers in nutrient fluxes in the shallow, eutrophic Peel-Harvey Estuary the Andes is illustrated below. in Western Australia. Our results reveal localized deposition

of organic-rich, fine-grained surface sediments characterized

by high sulfate reduction rates and abundant accumulation of

metastable iron (Fe) monosulfides. Core incubations showed

high rates of nitrogen and phosphate release from these

sulfidic surface sediments, even though they are reworked and ([email protected]) overlain by a well-mixed, oxygenated water column. This

suggests decoupling between bottom water oxygenation and sedimentary phosphorus (P) retention. Phosphate sorption experiments emphasized the stark contrast in phosphate binding capacity between the ‘normal’ estuarine sediments Figure 1: Concentrations of Pb in surface soil measured with and the strongly reducing muds. a handheld X-ray fluorescence analyser. In addition, we observed rapid and extensive sulfidization of reactive Fe within centimeters of the sediment surface The data show concentrations exceeding 10,000 mg/kg Pb below the oxygenated water column, indicating that Fe along a 200 m section of the railroad while other sites along speciation may not necessarily reflect bottom water the rail road generally are well within the current US EPA oxygenation, at least under the investigated environmental standard of 1,200 mg/kg for residential soil where children do conditions. These findings may be of importance to the use of not play. The particularly contaminated area is a turning point Fe-based paleoredox-proxies. for railroad cars containing ore concentrate and this has been Despite strongly reducing conditions, our results associated with contamination of an area commonly used as a suggested that Fe-associated P may be an important P sink in walkway. Additional examples of Pb hot-spots will be the investigated muds. Using a combination of sequential included in the poster, typically from older mining sites. chemical Fe and P extractions, Fe Extended X-ray Absorption Results of soil surveys around modern mining operations Fine Structure (Fe EXAFS) and micron-scale multi-energy X- showing little Pb contamination will also be shown. ray element mapping, we examine the nature of this Fe-P association. Handheld XRF analysers are relatively expensive and their Overall, our detailed geochemical results and benthic flux deployment requires training. We have therefore also been measurements challenge some of the existing paradigms testing the soils collected in Peru with a simple Pb extraction regarding the links between bottom water oxygenation and the and detection protocol relying on citric acid and rhodizonate. The poster will include results from this alternative approach. cycling of essential elements such as Fe and P.

[1] van Geen et al. (2012) Bull. WHO 90, 878–886.

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U phase evolution in the bedrock Drainage water chemistry reflects around Forsmark, eastern Sweden monolithologic Critical Zones L. KRALL1*, B. SANDSTRÖM2 AND E-L. TULLBORG3 P. KRÁM*, J. EUFÍK, F. VESELOVSKG, O. MY

Elevated gamma emisisons from some pegmatites, Three small (27-55 ha) catchments covered by spruce, cataclasites, and vein fillings were found in drillcores from each underlain by geochemically contrasting rocks (LYS: Forsmark, Sweden. A proposed host for nuclear waste granite, NAZ: amphibolite, PLB: serpentinite) were studied in repositories, these findings prompted interest in the the Slavkov Forest, Czech Rep [1]. Hydrochemical patterns geochemistry of U in the local bedrock. Coupled with existing were ascertained by concurrent stream water sampling (2001- knowledge of the site, characterization of solid-phase U has 2013) and soil water sampling by lysimeters placed at five implications for the deposition, evolution, and behavior of U depths in 2012-2013 (Fig. 1). Three boreholes drilled to 26-30 in this environment. A model of the low- to moderate- m probed deep critical zones. Strongly acidified LYS temperature evolution of the area was established during exhibited incomplete neutralization of acidic deposition and preceding fracture mineral studies. Four generations of had chronically low drainage water pH and elevated levels of fracture minerals record the relative timings and types of fluid toxic Al [2]. PLB exhibited the most efficient neutralization migration and have been traced to regional events, such as by chemical weathering. LYS was Mg deficient with respect orogeny and glaciation, by means of stable isotope, fluid of spruce and ectomycorrhizal fungi, PLB was P and K inclusion, radiometric dating, and fracture orientation analysis deficient and NAZ was not deficient in any nutrients [1,3]. [1]. This model has contributed to a working hypothesis on the stages of U alteration: 1) Palaeoproterozoic, U was introduced, likely as uraninite, by pegmatitic intrusion, 2) formation of cataclasite, U was mobilized and uraninite was altered to pitchblende then partially coffinitized, 3) Palaeozoic, U was remobilized and U-phospate precipitated on fracture surfaces and 4) Palaeozoic or later, amorphous U-silicate formed in fractures. Thin sections from zones of elevated gamma radiation have been analyzed using SEM-EDS. A primary (U,Pb)-oxide mineral (250 +m) confined by a rim of (Fe, Mn)-chlorite has been found in a small pegmatite. Most U phases found in pegmatites are low-Pb, probably secondary U-silicates (10-30 +m) of mutually different habit and composition (e.g. Ca, Fe, Ti, Mn, Al, and/or Ba) and are associated with minerals like chlorite, hematite, quartz, K-feldspar, and calcite. In the cataclasite, both primary (Th, U, REE)-silicates (150 +m) within pegmatite clasts and secondary U(Ca, A1)-silicates were along calcite and quartz grain boundaries. In vein

fillings, disseminated grains of secondary U-silicate were Figure 1: Temporal patterns of stream water (str) and organic found associated with laumontite, a marker within the fracture horizon soil water (org) at Lysina (LYS), Na Zeleném (NAZ) mineral generation of 1.10 – 1.03 Ga. Additionally, and PluhIv Bor (PLB) in March 2012 - March 2013. U-phosphates were found with pyrite, mixed layer clays, and

Palaeozoic asphaltite. These findings complement the This study was supported by the EC (FP7 SoilTrEC 244118). hypothesisized stages of evolution and offer new U phases for

integration. [1] Krám et al. (2012) Appl. Geoch. 27, 1854-1863. [2]

Banwart et al. (2012) Compt. Rend. Geosci. 344, 758-772. [3] Sandström et al. (2009) Tectonophysics 478, 158-174. [1] Berner (2013) Doct. Thes., Lund Univ., Sweden.

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Indirect evidence for the presence of Enhanced calcite dissolution in the secondary phosphorus in continental presence of aerobic methanotrophic fine aerosol bacteria K. KRASSOVÁN1*, Z. KERTÉSZ2, K. IMRE3 KRAUSE S.1, ALOISI G.1, 3, ENGEL, A.2, LIEBETRAU V.1, AND A. GELENCSÉR1,3 AND TREUDE T. 1 1Institute of Environmental Sciences, University of Pannonia, 1GEOMAR Helmholtz Centre of Ocean Research, Department Veszprém 8200, Hungary (*correspondence: of Marine Biogeochemistry, Wischhofstrasse 1-3, 24148 [email protected]) Kiel, Germany, [email protected], 2Institute of Nuclear Research of the Hungarian Academy of [email protected], [email protected] Sciences, Laboratory of Ion Beam Applications, Debrecen 2GEOMAR Helmholtz Centre of Ocean Research Department 4032, Hungary ([email protected]) of Biological Oceanography, Düsternbrooker Weg 20, 3Air Chemistry Group of the Hungarian Academy of Sciences, 24105 Kiel, Germany, [email protected] Veszprém 8200, Hungary 3Laboratoire d’Océanographie et du Climat : Expérimentations ([email protected] ) et Approches Numériques, UMR 7159, Université Pierre et Marie Curie, 4, Place Jussieu, 75252, Paris, France, The role of the atmosphere in the biogeochemical cycle of [email protected] phosphorus is generally associated with the emission of soil dust, sea-salt particles, bioaerosols and industrial aerosols. Aquatic microbial aerobic methane oxidation (MOx) Quite independently, a reduced gaseous phosphorus causes the production of carbon dioxide, leading to decrease compound (phosphine, PH3) was measured over various of liquid phase pH. Therefore, MOx activity impacts the sources such as marshes and sewage plants [1] and also in the carbonate system, potentially favouring dissolution of calcium global troposphere. Given that phosphine is a reactive gas that carbonates. In addition, carbonate dissolution has recently also rapidly yields low-volatility phosphoric acid in the atmosphere been attributed to microbially produced organic polymers. To [2], secondary aerosol formation can be an important sink that date, the impact of metabolic products from MOx on has never been considered in the global phosphorus cycle. In carbonates has been poorly constrained. To discriminate our study we present mass size-distribution measurements of between different mechanisms acting on carbonate stability, phosphorus in aerosol samples collected at two locations in calcite dissolution experiments were conducted with (1) Hungary. The bimodal size distribution of phosphorus prospering cells (2) starving cells, and (3) dead cells of the indicated two distinct formation mechanisms in the fine and methanotrophic bacterium Methylosinus trichosporium, as coarse modes. As expected, the mass concentration of well as abiotic controls, under brackish conditions (salinity 10) phosphorus was dominated by the coarse particles near calcite saturation (saturation state (J) 2.22 to 1.76). (aerodynamic diameter >1 µm), the contribution of fine mode Abiotic controls showed no calcite dissolution during the phosphorus was in the range of 10–27 % (median 19 %) of the experiment. In contrast, dissolved calcium and total alkalinity total. The contribution of biomass burning to the fine mode markedly increased in experiments containing M. phosphorus was inferred from measured K concentrations and trichosporium cells, indicative for calcite dissolution. After P/K ratios reported for biomass smoke [3]. It was found that initial system equilibration, calcite dissolution, ranging from biomass burning accounted for only a small fraction of fine 29.6 to 14.9 µmol l-1 d-1 between treatments, was observed. mode phosphorus, the rest of which likely formed as While concentrations of transparent exopolymer particles secondary aerosol component from gaseous phosphine. concentrations declined considerably over time in the presence Secondary aerosol phosphorus can be even more important in of prospering and starving cells, concentrations increased in providing this essential nutrient for remote ecosystems since it experiments with dead cells. Scanning electron microscopy of is associated with fine aerosol particles which have longer calcite crystals revealed surface corrosion after exposure to residence time and thus are more prone to long-range prospering, starving, and dead M. trichosporium cells. The atmospheric transport than coarse primary particles. results of this study demonstrate a strong potential impact of MOx bacteria on calcite stability, clearly facilitating calcite [1] Dévai et al. (1988) Nature 333, 343–345. [2] Frank & dissolution. In addition to CO2 production by Rippen (1987) Lebensmitteltechnik 7-8, 409-411.[3] Echalar et methanotrophically active cells and starving cells, we suggest al. (1995) Geophysical Research Letters 22, 3039–3042. that the release of acidic and/or calcium-chelating organic carbon compounds also facilitated enhanced calcite dissolution.

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Glass ceramics and mineral materials Stable isotope composition of for the immobilization of lead and anthropogenic thallium deposition cadmium from Municipal Solid Waste K. KREISSIG1, M. REHKÄMPER1* AND M. KERSTEN2 Incinerator ashes 1ESE, Imperial College, London SW7 2AZ, UK 1 1 (*correspondence: [email protected]) KATERINA KRAUSOVA *, LAURENT GAUTRON , 2 1 2 Gutenberg-University, Mainz 55099, Germany GILLES CATILLON AND STEPHAN BORENSZTAJN

1Laboratory of Earth Materials and Environment, University Thallium compounds are volatile at high temperature and Paris East – Marne la Vallée, 77454, France, not efficiently retained by emission control facilities of (*[email protected], [email protected], combustion sources. This study represents the first use of [email protected]) stable isotope ratios to apportion near-source Tl deposition to 2Laboratory of Interfaces and Electrochemical the emitter. In 1979, dust containing Tl was emitted by a Systems,University Pierre and Marie Curie, France cement plant near Lengerich, NW Germany. The emission ([email protected]) event was caused by a ferric oxide additive to the powdered lime (used for the production of special cements), which Waste management is one of the major global issues. contained a Tl-bearing residue of pyrite roasting. Following Incineration is an efficient treatment since it offers both a the emission event, sheep died and rabbits and horses were reduction of mass and volume and a possibility of energy reported to loose fur and hair in the vicinity of the cement recovery. One of the problems of incineration is the plant [1]. The cement plant owners denied responsibility for production of bottom and fly ashes which are considered as the bulk of the emissions. We determined the Tl isotope hazardous waste with obligation of final disposal into a compositions (!205Tl) of the cement dust (open symbol) and specific landfill. soil cores down to 100 cm depth (black symbols), and the data The objective of the present study is to investigate glass are in accord with a two-source mixing line (Fig. 1). Our novel ceramics and sintered ceramics as new mineral materials for a isotope analysis ultimately helped the plaintiffs to settle the sustainable immobilization and possible recycling of these case by showing the causation of the pollution event, even incineration wastes. Toxic elements can be incorporated into though the emissions happened more than 30 years ago. embedded crystals in a glass matrix which has a function of the second barrier, or in highly resistant crystalline structure. Based upon cations size considerations, this study is focused on Ca-rich or Ba-bearing minerals as possible hosts of lead and cadmium.

Promising results have been obtained for CaMgSi2O6

diopside-bearing glass ceramics and sintered Ba1.5Mg1.5Ti6.5016 hollandite, both in terms of toxic elements incorporation and of chemical and mechanical resistance.

Figure 1: Tl stable isotope data vs. inverse Tl concentrations for soil samples of increasing depth from left to right.

[1] Schoer (1984) In: Hutzinger (ed.), Handbook of Environmental Chemistry, Vol. 3c. Springer, New York, 143– 214.

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Fractionation of Cd isotopes during A method to constrain the size of the evaporation and re-condensation Protosolar Nebula V. KREMSER1, F. WOMBACHER1, W. ERTEL-INGRISCH2, KRETKE, K. A.1*, LEVISON, H. F.1, BUIE, M. W. 1 D. B. DINGWELL2 AND C. MÜNKER1 AND MORBIDELLI, A.2 1Universität zu Köln, Institut für Geologie und Mineralogie, 1Southwest Research Institute, Department of Space Studies, Köln, Germany ([email protected]) 1050 Walnut Street, Suite 400, Boulder, CO 80302, USA 2Ludwig-Maximilians-Universität, Department für Geo- und *correspondence: [email protected] Umweltwissenschaften, München, Germany 2Observatoire de la Côte d'Azur, BP 4229, 06304 Nice Cedex 4, France Stable isotope studies of volatile elements can provide constraints on possible scenarios of volatile element loss and Observations indicate that the gaseous circumstellar disks redistribution [e.g, 1, 2]. Here, Cd stable isotope and volatile around young stars vary significantly in size, ranging from element fractionation during evaporation from silicate melt at tens to thousands of AU. Models of planet formation depend

about 1300 °C and during re-condensation onto Al2O3 critically upon the properties of these primordial disks, yet in condensation plates is studied experimentally, at atmospheric general it is impossible to connect an existing planetary

pressure in air and in CO-CO2. The experiments can serve to system with an observed disk. We present a method by which address questions that are important for the interpretation of we can constrain the size of our own protosolar nebula using volatile element stable isotope data in cosmochemistry, e.g.: the properties of the small body reservoirs in the solar system.

How much do atmospheres with variable fO2 suppress (Cd) In standard planet formation theory, after Jupiter and Saturn isotope fractionation? Are there conditions where volatile formed they scattered a significant number of remnant metal loss by evaporation can occur without measurable stable planetesimals into highly eccentric orbits. In this paper, we isotope fractionation? Will (kinetic) condensation result in show that if there had been a massive, extended protoplanetary significant stable isotope fractionation? disk at that time, then the disk would have excited Kozai Our experiments show that evaporation at atmospheric oscillations in some of the scattered objects, driving them into pressure only yields strongly suppressed Cd isotope high-inclination (i >~ 50°), low-eccentricity orbits (q >~ 30 fractionation, with a vapor-melt fractionation factor : for AU). The dissipation of the gaseous disk would strand a subset 114Cd/110Cd that corresponds to -1.6 ‰ (air) and -0.3 ‰ of objects in these high-inclination orbits; orbits that are stable

(CO-CO2). This compares to about -10 ‰ observed for on Gyr timescales. To date, surveys have not detected any evaporation into vacuum [3] and the theoretical prediction of Kuiper-belt objects with orbits consistent with this dynamical -17.7 ‰ as calculated from Graham’s law. mechanism. Using these non-detections by the Deep Ecliptic In addition, Cd also displays isotope fractionation along Survey and the Palomar Distant Solar System Survey we are

the temperature gradient of the Al2O3 condensation plates with able to rule out an extended gaseous protoplanetary disk (RD light Cd isotopes being enriched in the condensates closest to >~ 80 AU) in our solar system at the time of Jupiter's the melt. formation. Future deep all sky surveys such as the Large The observed suppressed isotope fractionation during Synoptic Survey Telescope will allow us to further constrain evaporation may result from back reaction into the melt phase the size of the protoplanetary disk. and more efficient Cd0 vapor formation at reduced conditions.

[1] Humayun & Clayton (1995) GCA 59, 2131-2148. [2] Wombacher et al. (2008) GCA 72, 646-667. [3] Wombacher et al. (2004) GCA 68, 2349-2357.

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Speciation and mobility of trace Juvenile crustal growth during the elements in wetland soils Palaeoproterozoic: U-Pb-O-Hf RUBEN KRETZSCHMAR isotopes of detrital zircon from Institute of Biogeochemistry and Pollutant Dynamics, ETH Ghana Zurich, Switzerland ([email protected]) 1 1 BÁRA D. KRISTINSDÓTTIR , ANDERS SCHERSTÉN , 23 1 ANTHONY I.S. KEMP AND ANDREAS PETERSSON Wetlands including peatlands, riparian floodplains, and paddy soils play key roles in the biogeochemical cycling of 1Department of Geology, Lund University, Sölvegatan 12, SE- carbon, sulfur, phosphorus, and many essential or potentially 223 62 Lund, Sweden. [email protected]; toxic trace elements (e.g., As, Se, Hg, Zn, Cu, Cd). [email protected] Understanding the solid-phase speciation, micro-scale 2School of Earth and Environmental Sciences, James Cook distribution, and mobility of trace elements in such soils is an University, Townsville, Queensland 4811, Australia. important challenge in soil biogeochemistry. Prof. Willem van [email protected] Riemsdijk and his coworkers were among the leaders in 3School of Earth and Environment, the University of Western developing our current understanding of competitive sorption Australia, Crawley, Western Australia 6009, Australia. of cations, anions, and NOM to soil mineral surfaces. Competitive sorption of arsenate or arsenite with other anions The Palaeoproterozoic domains of the West African such as phosphate or carbonate, for example, are now rather Craton (WAC) (~2.15 Ga) have been described as a fast well understood and can be modelled quantitatively using the growing segment of juvenile crust based on geochronological CD-MUSIC approach [1]. However, sorption and speciation data and Nd-model ages. Detrital zircon from four rivers in changes of trace elements during reduction/oxidation cycles in Ghana, southeastern WAC, were analysed for U-Pb, O and soils, often coupled to iron mineral transformations and sulfur Lu-Hf isotopes and a zircon population from a fifth river was redox reactions in the presence of NOM, are still poorly analysed for U-Pb and Lu-Hf isotopes. U-Pb crystallisation understood. We therefore explored the influence of soil ages mainly cluster between 2.24 and 2.09 Ga with a peak at flooding on trace element speciation and mobility and found ~2.14 Ga, reflecting peak magmatic activity. The zircon formation of metallic Cu(0) and metal sulfide nano-particles population from the Birim river, representing the Kibi- by suspended bacteria to be an important mechanism Winneba belt, in southeast Ghana have zircon with U-Pb ages controlling pore water concentrations of Cu, Hg, Zn, and Pb >2.2 Ga, which is nearly absent in other rivers. [2]. More recently, we explored the speciation of As in The entire zircon population has 'Hf values ranging from different wetlands and found As(III) bound to reduced sulfur 0.9 to 7.1, except four grains from the Birim river population groups of NOM to be the dominant species in anoxic peat that have negative 'Hf. Although there are contrasts between layers [3]. Subsequent model studies confirmed this newly the zircon populations from the different rivers, the data imply discovered binding mechanism of As to NOM [4], which may relatively juvenile crust without any significant reworking of of great importance in other NOM-rich, reducing ancient crustal components. ~2.2 Ga zircon from the Birim environments. In contrast, in a mining-affected river river have depleted 'Hf, while a younger (2.15 Ga) subset of floodplain, As was mainly present as As(V) coprecipitated zircon requires a reworked Archaean component. Zircon from with Fe(III) in poorly-crystalline mineral phases, exhibiting Sihili and Black Volta rivers form a losely defined trend that similarity to amorphous ferric arsenates, partly forming rims suggest the reworking of mafic crust, while the others do not. around weathering pyrite and arsenopyrite grains. The solid- Contribution of reworked supracrustal rocks were minor phase speciation greatly influences the kinetics of microbial during the initial growth stages as indicated by the absence of Fe and As reduction and release, and is therefore important for zircon with ,18O>6.5‰ prior to 2.174 Ga. The proportion of understanding As release under reducing conditions in soils grains with elevated ,18O gradually increases after 2.174 Ga, [5]. suggesting increasing amounts of reworked supracurstal sedimentary components. However, these zircon grains with 18 [1] Stachowicz et al., J. Colloid Interf. Sci. 320: 400, 2008. [2] high , O have depleted KHf, which suggests fast reworking of Hofacker et al., Geochim. Cosmochim. Acta 103: 316, 2013. young supracrustal rocks, perhaps in a maturing arc system. [3] Langner et al., Nature Geoscience 5: 66, 2011. [4] Hoffmann et al., Environ. Sci. Technol. 46: 11788, 2012. [5] Weber et al., Environ. Sci. Technol. 44: 116, 2010.

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Are mafic microgranular enclaves in Near-field measurements durbachites plutonic equivalents of of volcanogenic sulfur: Emissions, common minettes? oxidation, and neutralization LUKÁ< KRMÍEEK1* AND ROLF L. ROMER2 EBEN CROSS1, SIDHANT PAI1, ZARA L’HEUREUX1, 1 2 2 1 JAMES HUNTER , PHILIP CROTEAU , JOHN JAYNE , Brno University of Technology, Faculty of Civil Engineering, LISA WALLACE3, JENNIFER MURPHY4, COLETTE HEALD1, VeveLí 95, CZ-602 00 Brno, Czech Rep. AND JESSE KROLL1 (*correspondence: [email protected]) 2Deutsches GeoForschungsZentrum (GFZ), Telegrafenberg, 1Department of Civil and Environmental Engineering, D-14473 Potsdam, Germany Massachusetts Institute of Technology, Cambridge MA, USA Durbachites are K-feldspar-phyric biotite-bearing MgO- 2Center for Aerosol and Cloud Chemistry, Aerodyne rich rocks of syenitic composition whose formation involves Research, Inc., Billerica MA, USA the mixing of mafic high-potassium partial melts from an 3Clean Air Branch, Hawai’i State Department of Health, enriched mantle with granitic melts. Due to this process, Honolulu HI, USA durbachites encompass a broad compositional range and 4Department of Chemistry, University of Toronto, Toronto contain variable amounts of mafic microgranular enclaves ON, Canada (MME). The mafic members are considered to be the plutonic * correspondence: [email protected] equivalent of common mica lamprophyres, i.e., minettes [1]. Large volumes of durbachites (e.g., the TLebíM Massif) have Volcanic activity represents a major natural source of

been emplaced in the Moldanubian Zone of the Bohemian sulfur dioxide (SO2) to the Earth’s atmosphere, and thus is an Massif. Regionally contrasting geochemical fingerprints of important component of the global sulfur cycle. In addition,

mantle metasomatism and the role of mantle contribution in the very high concentrations of SO2 and particulate matter in durbachtite magmatism may be the key control on the the areas immediately surrounding volcanoes can have serious distribution of durbachites in the Bohemian Massif. MME effects on human and ecological health. In order to better from the TLebíM Massif have been investigated petrologically understand the atmospheric fate of volcanogenic emissions in and geochemically (including Sr-Nd-Pb isotopes) and the near field (in the first few hours after emission), we have compared with Variscan mafic dikes of the Bohemian Massif. carried out in situ studies of key sulfur species on the Big The geochemical composition of the MME does not Island of Hawai’i. Measurements were made as part of MIT’s correspond to the composition of typical minettes from which Traveling Research Environmental eXperiences (TREX) they are noticeably shifted toward higher 87Sr/86Sr(i) values program, aimed at introducing undergraduate students to and more negative KNd(i) values. Moreover, the composition environmental fieldwork. A suite of instruments for of MME also differs from newly recognised peralkaline characterizing oxidized sulfur in both the gas and particle

lamproitic rocks cropping out around the TLebíM Massif [2]. phase, including an SO2 monitor and an Aerosol Chemical Instead, the MME compositionally overlap with micaceous Speciation Monitor (ACSM), were deployed on a mobile mafic dykes that could be best described as cocites [2]. Both ground-based platform, with sampling carried out at a range of cocites and MME show high Mg-values and are characterized locations on the island. To our knowledge these – in comparison with minettes and lamproites – by a measurements represent the first real-time measurement of the remarkable negative Eu anomaly, an extremely high positive chemical composition of volcanic aerosol. The high time Pb anomaly, and an unusually high Sm/La ratio. It is the resolution of the instruments, combined with the high spatial particular geochemical and isotopic signature of mantle coverage of the mobile measurements, enables the metasomatic component that is common for the durbachites characterization of the volcanic plume at different and the cocite dykes and that distinguishes them from times/distances downwind of the point of emission. From Variscan minettes of other parts of the Bohemian Massif. these measurements we are able to track the initial lifecycle of volcagenic sulfur, including emission, oxidation to particulate Acknowledgements. This work was supported by the sulfuric acid, and neutralization by ammonia. Results are project FAST-S-12-1774 from BUT. compared with continuous measurements taken by air quality monitoring sites on the island. [1] Parat et al. (2010) Contrib. Mineral. Petrol. 159, 331–347. [2] KrmíMek (2011) PhD thesis, Brno, 1–160.

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Origin of water on the chondrite Nucleosynthetic W isotope anomalies asteroids: Evidence from in CAI: Implications for Hf-W oxygen-isotope compositions of chronology aqueously-formed minerals T.S. KRUIJER1,2,*, T. KLEINE1, C. BURKHARDT3 2 1,2 1,2 1 AND R. WIELER A. N. KROT *, P. M. DOYLE , K. NAGASHIMA , K. JOGO3, S. WAKITA3, F. J. CIESLA4 AND I. HUTCHEON5 1Institute for Planetology, University of Münster, Germany 2 1 Institute of Geochemistry and Petrology, ETH Zürich HIGP, University of Hawai‘i, Honolu, HI 96822, USA. 2 (*correspondence: [email protected]) Hawai‘i NASA Astrobilogy Institute, University of Hawai‘i 3Origins Laboratory, Department of the Geophysical Sciences, 3Tohoku University, Sendai 980-8578, JAPAN 4 The University of Chicago University of Chicago, Chicago, IL 60637, USA 5 Glenn Seaborg Institute, LLNL, Livermore, CA 94551, USA 182 182 The application of the short-lived Hf- W decay system to investigate the timing of early solar system processes Fayalite and magnetite in CV3.1 and CO3.1 carbonaceous requires knowledge of the initial Hf and W isotope chondrites (CCs) resulted from water-rock interaction on their compositions at the beginning of the solar system [1,2]. These parent asteroids at water/rock volume ratio of ~0.2 and 53 55 can most directly be determined from Ca-Al-rich inclusions temperatures of ~100)200°C [1,2]. The inferred Mn/ Mn (CAI), which are the oldest yet dated objects that formed ratios in fayalite in Asuka 881317 (CV) and MacAlpine Hills within the solar system [e.g., 3,4]. However, the interpretation 88107 (CO-like) are (2.77±0.48)#10)6 and (2.45±0.33)#10)6 53 53 of W isotope data in CAI is complicated by the presence of [3] The Mn- Cr ages of the CV and CO fayalite formation nucleosynthetic W isotope anomalies [1], which may anchored to D'Orbigny angrite [4,5] are 3.7 (+1.1/)0.9) and significantly bias the inferred initial 182W/184W of CAI [2]. The 4.4 (+0.9/)0.7) Ma after CV CAIs [3] having an absolute age aim of this study is to explore the range of nucleosynthetic W of 4567.3±0.16 Ma [6]. These ages are indistinguishable from 53 53 isotope variations in CAI to better quantify the initial Hf and the Mn- Cr ages of calcite in CMs [7] and dolomite in CMs W isotope compositions of the solar system. and CIs [7,8]. The high peak metamorphic temperatures Here we report W isotope compositions for six bulk CAI experienced by CVs and COs of petrologic type > 3.6 (one type B, five type A) from the Allende CV3 chondrite. (>600°C) and the old formation ages of fayalite imply a rapid Tungsten isotope compositions of the CAI were measured on a accretion of their parent asteroids after chondrule formation Neptune Plus MC-ICPMS at the University of Münster and (~2)2.5 Ma after CV CAIs) followed by a short onset of are reported as KiW (i.e., 0.01 % deviations from terrestrial aqueous alteration. The accretion of CVs and COs predated by values). The investigated CAI display large variations in ~ 1Ma accretion of the more extensively aqueously-altered, K183W, extending to much larger anomalies than previously but less metamorphosed CMs and CIs [7,8]. Near terrestrial observed [1,2] and indicating variable abundances of s- and r- oxygen-isotope compositions of the CV and CO fayalite and 17 process W isotopes in CAI. The CAI define a precise magnetite ($ O ~ )1‰), and CM and CI carbonates and 183 182 17 empirical correlation between K W and initial K W, which magnetite ($ O ~ +2‰ to )3‰) may indicate water in the CC allows correction of measured K182W for nucleosynthetic parent asteroids had preferentially a local, inner Solar System heterogeneity. The corrected K182W vs. 180Hf/184W define a bulk origin, consistent with the inferred hydrogen-isotope CAI isochron (MWSD=1.5) with a precise initial 182Hf/180Hf of composition of the CC asteroidal water [9]. The low influx of -4 17 18 N1.0#10 , which when anchored to the angrite D'Orbigny [5] isotopically heavy (i.e., enriched in O, O, and D/H) water corresponds to an absolute age of CAI that is in good ices from the outer Solar System at the time of accretion of agreement with their Pb-Pb ages [3,4]. The bulk CAI isochron CC asteroids may be due to an early growth of Jupiter that confirms the recently revised CAI initial of K182W N )3.5 [2]. could have prevented significant radial transport of dust and Relative to this value, magmatic iron meteorites have more gas from outside its orbit. radiogenic neutron capture-corrected K182W [6], corresponding

to core formation timescales of N1-3 Ma after CAI formation [1] Krot A. N. et al. (1998) MAPS 33, 1065. [2] Zolotov M. and indicating a time gap of N 0.5-1 Ma between the formation Yu. et al. (2006) MAPS 41, 1775. [3] Doyle P. M. et al. (2013) of the first solids and accretion of the oldest planetesimals. LPSC 44, #1793. [4] Amelin Y. (2008) GCA 72, 221. [5]

Glavin D. M. et al. (2004) MAPS 39, 693. [6] Connelly J. N. [1] Burkhardt et al. (2008) GCA 72, 6177-6197. [2] Burkhardt et al. (2012) Science 338, 651. [7] Fujiya W. et al. (2012) et al. (2012) APJ Lett. 753, L6. [3] Amelin et al. (2010) EPSL Nature Commun. 3, 1. [8] Fujiya W. et al. (2013) EPSL 362, 300, 343-350. [4] Bouvier & Wadhwa (2010) Nat. Geosci. 3, 130. [9] Alexander C. M.O’D. et al. (2012) Science 337, 721. 637-641. [5] Kleine et al. (2012) GCA 84, 186-203. [6] Kruijer et al. (2013) EPSL 361, 162-172.

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Re–Os Age and Gold Source for Experimental and computational Mayskoe Quartz-Vein Deposit spectra and thermodynamics of (Northern Karelia, Baltic Shield) biogeochemical interfaces R.KRYMSKY1, B.BELYATSKY2, N.GOLTSIN1, S.SERGEEV1 JAMES D. KUBICKI1 AND NADINE KABENGI2 2 AND S.BUSHMIN 1 Dept. of Geosciences, The Pennsylvania State University, 1CIR VSEGEI, St.Petersburg, Russia, University Park, PA 16802 USA (*correspondence: [email protected] [email protected]) 2IPGG RAS, St.petersburg, Russia, [email protected] 2Dept. of Geosciences and Chemistry, Georgia State University, Atlanta GA 30303 Mayskoe deposit located in Northern Karelia within the Svecofennian orogen near the boundary with the Belomorian– The molecular-level chemistry of biogeochemical Lapland orogen is the only known gold deposit of the quartz– interfaces influences dissolution of minerals, transport of vein type in the Karelian–Kola region. The host bacteria and degradation of contaminants. Detailing these Paleoproterozoic volcanogenic–sedimentary rocks interactions is problematic, however, because surfaces are metamorphosed from greenschist to amphibolite facies within difficult to characterize and biological compounds can be the Svecofennian time. Metamorphic rocks are strongly complex. Significant advances have been made by collecting scheared and metasomatized, where early quartz and late gold- spectra (e.g., ATR-FTIR, NMR, etc.) of samples representing bearing quartz veins are located. Ore association in quartz key biogeochemical reactions and interpreting the spectra with veins is represented by native gold, chalcopyrite, pyrrhotite, quantum mechanical calculations. Generally, these galena, pyrite, and sphalerite, as well as Se and Te minerals. experimental studies are performed on simplified binary We investigated the Re–Os isotope system of native gold systems with one substrate and one adsorbent. Predictions of and syngenetic chalcopyrite from the eastern lode-gold quartz biogeochemistry in the field may be erroneous because vein. Gold grains and chalcopyrite were manually collected competing reactions are not considered in the laboratory-based from two gold-bearing milky–white quartz samples. Re and studies. Os contents in the analyzed gold range from 1.8 to 13.8 and A missing component of these types of studies is the from 0.2 to 2.3 ppb, which is comparable with the thermodynamics of the adsorption reactions. One can model concentrations measured in syngenetic chalcopyrite: 0.5–2.1 surface complexes and the spectroscopic properties observed, ppb Re and 0.1–1.0 ppb Os. According to the Os but without knowledge of the thermodynamic favorability of concentration, the studied samples differ significantly from the surface complexes, one cannot estimate their prevalence or hydrothermal sulfide gold deposits and are comparable with dominance in natural systems. those associated with conglomerates [1]. The correlation This talk will focus on progress in developing methods to between Re/Os and Os isotope composition for the studied calculate spectroscopic properties and thermodynamics of samples corresponds to the age of 397 ± 15 Ma and adsorption in biogeochemical systems. The incorporation of (187Os/188Os)i = 0.1469 ± 0.0051 (.Os = +18). thermodynamic data from flow-adsorption calorimetry into The measured Os composition of gold and chalcopyrite modeling of these adsorption reactions will also be discussed. (187Os/188Os = 0.2160–0.4376) differs significantly from Examples of test systems such as goethite-phosphate will be typical crustal (> 1.0) and mantle values (0.1296), and may be used as the basis for more complex reactions with biological obtained either by mixing of Os from these sources or as a compounds. result of in situ Re decay. The age character of obtained trend is provided by the model Re–Os age of the samples: from 430 to 515 Ma, similar to the isochron one. Thus, the ore-forming fluid may have been formed in the Early Paleozoic by mixing of 75% upper mantle material and 25% Proterozoic crust and have come to quartz veins 400 m.y. ago. The primitive upper mantle (Os = 2.5 ppb and 187Os/188Os = 0.1239), in this case, was the main source of gold. Alternatively, formation of gold- bearing mineralization was plausible realised under the influence of the Caledonian mantle plume due to remobilization of basic–ultrabasic matter (or mantle restites) of Paleoproterozoic rocks (2.0–2.2 Ga) of the Karelian–Kola region characterized by high concentrations of gold and PGEs.

[1] Kirk et al. (2002) Science 297, 1856 – 1860.

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Modeling of TiO2 nanoparticles Hybrid Pressure Coring System of interactions with water and ions D/V Chikyu JAMES D. KUBICKI1, SUNG-YUP KIM2, YUSUKE KUBO1, YASUHIKO MIZUGUCHI2 ADRI C. VAN DUIN2, MOIRA RIDLEY3, AND FUMIO INAGAKI3 4 5 MIKE MACHESKY ,DANIEL HUMMER 1 CDEX, JAMSTEC, 3173-25 Showa-machi, Kanazawa-ku, AND PAUL R. KENT6 Yokohama, Japan 236-0001. [email protected] 1Dept. of Geosciences, The Pennsylvania State University, 2CDEX, JAMSTEC, 3173-25 Showa-machi, Kanazawa-ku, University Park, PA 16802 USA (*correspondence: Yokohama, Japan 236-0001 [email protected]) Submarine Resources Research Project and Kochi Institute for 2Dept. of Nuclear & Mechanical Engineering, The Core Sample Research, JAMSTEC, Monobe B200, Pennsylvania State University, University Park, PA 16802 Nankoku, Kochi 783-8502, Japan USA 3Dept. of Geosciences, Texas Tech University, Lubbock, TX Pressure coring is a technique to keep in-situ conditions in USA recovering subseafloor sediment samples, which are 4Illinois State Water Survey, University of Illinois, potentially rich in soluble or hydrated gas. Gas fractions are Champaign, IL 61820 USA easily lost in regular core sampling through the pressure and 5Department of Earth and Space Sciences, University of temperature change during core recovery, and subsequently California, Los Angeles CA USA change the chemical components of the sample: e.g., 6Center for NanoMaterials Science,Oak Ridge National degassing may cause critical changes and/or damages of Laboratory, Oak Ridge, TN USA original structures. To study original characteristics of gaseous subseafloor sediment, a New Hybrid Pressure Coring

Although TiO2 is not a major rock-forming mineral, it is System (Hybrid PCS) was developed for the D/V Chikyu an important technological material, and it has been used operation by adapting some of the existing pressure sampling extensively as a model for oxide-water studies. Because the technologies. Hybrid PCS is composed of three main parts:

surfaces of the common TiO2 phases, rutile and anatase, have top section for the wireline tool, middle section for the been characterized experimentally and modeled with density accumulator and pressure controlling system, and the bottom functional theory (DFT), they serve as good model systems for section for the autoclave chamber. The design concept is understanding the size and shape effects of nanoparticles on based on that of Pressure Core Sampler used in Ocean Drilling the oxide-water interface. Program, and of Pressure Temperature Core Sampler (PTCS) In this talk, we will present results of DFT calculations on and Non-cooled PTCS of Japan Oil, Gas and Metals National rutile and anatase surfaces and nanoparticles interactions with Coporation (JOGMEC). Modifications were made on the ball

H2O. The relationship of surface site defects (i.e., corner and valve, which operates to close the autoclave after coring. The

edge sites) to H2O adsorption energy is investigated. DFT core samples are 51 mm in diameter and up to 3.5 m in length. calculations on anatase surfaces with adsorbed ions are also The system is combined with the Extented Shoe Coring presented. System on the Chikyu and best suited for coring of semi- These DFT calculations were then used in developing a consolidated formation up to about 3400 m from the sea level. reactive classical force field, ReaxFF, for the Ti-O-H system. Sample autoclave is compatible with Pressure Core Analysis The ReaxFF was used to perform molecular dynamics and Transfer System of Geotek Ltd for sub-sampling and simulations of rutile and anatase particles in water and analysis under in-situ pressure. The analysis includes X-ray aqueous salt solutions. Differences in the electrical double CT scan and core logging with P-wave velocity and gamma layer around finite nanoparticles as compared with flat, density. Depressurization provides accurate volume of gas and infinite surfaces will be discussed. its sub-sampling. Hybrid PCS was first tested during the Chikyu Exp. 906 at a submarine mud-volcano in the Nankai Trough. A 0.9 m of hydrate rich material was recovered from the summit (water depth: 2000 m) and the intact hydrate structure was observed by X-ray CT scan. Hybrid PCS was also used in the following JOGMEC methane hydrate cruise, resulting in the good recovery of methane hydrate-bearing cores (approx. 69%).

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Trace elements in ectomycorrhizae Depth-dependent links between determined by neutron activation surface and subsurface as reflected analysis by microbial community structures in JAROSLAVA KUBROVÁ12 AND JAN BOROVIEKA2* limestone aquifers 1Institute of Geochemistry, Mineralogy and Mineral KIRSTEN KUESEL*, MARTINA HERRMANN, ANNA Resources, Faculty of Science, Charles University, RUSZNYAK, DENISE AKOB, UTE RISSE-BUHL, Albertov 6, CZ-128 43 Prague 2 SEBASTIAN OPITZ AND KAI-UWE TOTSCHE 2Nuclear Physic Institute, v.v.i., Academy of Sciences of the Friedrich Schiller University Jena, Jena, Germany Czech Republic, FeO 130, CZ-250 68 FeO near Prague *correspondence: [email protected] (*correspondence: [email protected])

One quarter of the drinking water supply for the world´s In recent years, interest in the biochemical roles of population is derived from limestone aquifers, yet they are to macrofungi in the environment has increased rapidly. date poorly represented in studies focussing on surface- Macrofungi play important roles in biogeochemical cycling of subsurface interactions. Lithoautotrophy might be an chemical elements in the critical zone and many species are important metabolic strategy in these oligotrophic habitats for known as effective accumulators of toxic metals. coupling carbon cycling to the cycling of other elements, e.g. Ectomycorrhizal fungi live in symbiosis with vascular nitrogen, metals or sulphur accumulated from rock plants. In this reciprocally profitable relationship, the weathering. Within the framework of the AquaDiva project we exchange of nutrients occurs in a mutual organ called started to explore the influence of surface conditions on the ectomycorrhiza (pl. ectomycorrhizae). Ectomycorrhizae are subsurface biosphere. We compared the diversity of microbial formed on fine roots of host plants, distributed throughout the communities, some of their key functions, and potential links soil profile in both organic and mineral horizons, and are within food webs in the groundwater of a shallow, suboxic, composed of plant biomass and fungal hyphae. and a deep, oxygen-rich limestone aquifer located in the As has been repeatedly demonstrated, metal-adapted Hainich region (Thuringia, Germany) below sites subjected to mycorrhizal fungi play as an effective biological barrier different land management. against metal toxicity in trees. Only few data have been Pyrosequencing of 16S ribosomal RNA revealed a clear published on concentrations of heavy metals in separation of the shallow and the deep aquifer based on the ectomycorrhizae: a relatively high degree of accumulation of structure of the active microbial communities. Results of Cd, Cu, Pb and Zn was observed from polluted sites in quantitative PCR targeting cbbL and cbbM genes encoding Norway and Poland. RubisCO type I and II suggested that approximately 0.3 to 14 In this study, we have focused on natural concentrations of % of the groundwater bacterial population had the genetic trace elements in ectomycorrhizae and fine roots of Picea potential to fix CO via the Calvin Cycle. Analysis of cbbM abies from pristine sites above gneissic and granitic bedrocks. 2 and cbbL transcripts showed that the active CO -fixing Trace elements were analyzed using short-term thermal and 2 bacterial communities were dominated by organisms related to long-term epithermal neutron activation analysis. The Sulfuricella denitrificans, Sideroxydans lithotrophicus, individual fungal species in analyzed ectomycorrhizal tips Acidithiobacillus sp., and Nitrosomonas ureae with the latter were determined by DNA sequencing (rDNA ITS molecular being more abundant in the deep, oxygen-rich aquifer. marker, semi-nested PCR). Our data provide strong evidence that chemolitho- According to our preliminary results, the most striking autotrophy linked to metabolisms involving sulphur, iron, and accumulation was noted in Cd. Its concentrations, however, nitrogen contributes to the carbon flow in a limestone aquifer. varied in a wide range (with the highest content of 50 mgPkg-1 Moreover, analyses of the eukaryotic microbial communities dry weight). On the other hand, very low concentrations in the groundwater revealed a diverse protist community (mostly below 20 mgPkg-1 dry weight) were found for Cu. consisting mainly of bacterial feeders such as ciliates, This research was supported by the projects 535112 flagellates and amoeba but also representatives of higher (Grant Agency of Charles University in Prague) and trophic levels such as heliozoa and nematodes, suggesting P504/11/0484 (Czech Science Foundation). complex food web interactions. In the light of surface- subsurface interactions, the observed geochemical and microbial patterns point to a depth-dependent impact of surface activities on the aquifer system with the shallow aquifer being more strongly affected by agricultural practices.

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Origin of refractory organics in Don't forget the salty soup: chondrites: An experimental study Calculations for bulk marine M. KUGA1*, B. MARTY1 AND Y. MARROCCHI1 geochemistry and radionuclide 1CRPG-CNRS, Université de Lorraine, Nancy, France geochronology (*[email protected]) 1 GERHARD KUHN

Most organic matter found in chondrites occurs as 1Alfred-Wegener-Institut Helmholtz-Zentrum für Polar- und insoluble organic matter (IOM). This refractory organic Meeresforschung, Am Alten Hafen 26, 27568 material has been studied through a wide range of techniques, Bremerhaven, Germany ([email protected]) which has provided insights in its molecular structure [1-2]. Despite these efforts, the origin, nature of precursors and In reference to marine sediments I would like to add to the synthesis of this IOM is still debated [1-3]. theme of this session: "Your data are only as good as your This study describes a Miller-Urey inspired experiment standards and methods!" if you remember to correct your [4], designed to produce organics by condensation and analytical data for pore water salt. polymerisation from gas molecules representative of the Performing sophisticated analytics in marine geochemistry protosolar nebula. The experiment consists of a gas mixture constantly aims at improving the detection limits as well as

(CO:N2:noble gases = 5:0.5:0.5 + traces of H2O) flowing at ~ minimizing the margin of error regarding the precision and 1 mbar in a quartz reactor through an electric discharge. accuracy of the method. However, this holds true only if you Electrons from the plasma (average energy ~ 2 eV) initiated are genuinely aware of what are you actually analyzing. The gas-phase chemistry by dissociating and ionizing gas normal procedure of sample preparation for marine sediments molecules. At the end of the experiment, dark solids deposited consists of drying and grinding. Thereafter, these samples are on the reactor wall were recovered for ex-situ analysis by analyzed with regards to their elementary or mineral SEM, TEM, py-GC-MS, Raman and FTIR techniques. Noble concentrations. In the best case scenario, sampled water gases and C, H, N content and isotopes were also measured. content data are available for calculations of physical TEM imaging indicates that these solids are mainly properties, such as porosity and dry bulk density, which are composed of amorphous carbon with small domains showing both absolutely necessary for the calculation of elementary stacks of a few graphene layers. The poorly organized carbon flux or geochemical budgets. In addition, based on the water structure was confirmed by Raman spectroscopy. Py-GC-MS, content (w, in % of the wet weight) and a normal salinity of FTIR and elemental analyses indicate an aromatic material 3.5% (or 35 PSU), the amount of salt (s in mass%) in the dry composed of small units (1-3 rings). O (carbonyl, phenol) and sample can be determined by: N (nitrile, heterocycles) functional groups were also identified. 1. Calculating the mass percentage of the salty pore Elemental and isotopic fractionation of noble gases, similar to water (w') as: w'=w•100/96.5 that observed for Q relative to Solar [4] were measured. This 2. Calculate the salt as: s=100•(w'-w)/(100-w). preliminary characterization of these synthetic organic This is especially important for samples with water material shares similarities with features of IOM. contents above 50% (s=3.6%; w=80% s=14.5%), which are Both characterization of experimental organics and the very common in the biogenic opal-rich, diatomaceous trapped noble gases suggest that ionization and dissociation of sediments of the Southern Ocean around Antarctica. These

CO and N2 in the disk, either by electrons or far-UV photons, calculations could be improved by using known salinities, could be a possible mechanism for formation of precursors of obtained through chlorine determinations, of samples or pore organics recovered in chondrites. Subsequent reaction and water directly. processing of these organic precursors during evolution of the Although these calculations are simple, they are often protoplanetary disk could form the complex organic ignored, giving rise to two potential errors, sometimes greater macromolecule we call IOM. than 14% (relative concentration). The first, greatest and often neglected mistake is a "wrong" net weight - the input is not the [1] L. Remusat et al. (2007) CGR 339, 895-906, [2] S. pure sediment but sediment + salt. For most ratios of elements, Derenne and F. Robert (2010) MPS 45, 1461-1475, [3] G. the salt content is irrelevant, but every calculation of Cody et al. (2011) PNAS 108, 19171-19176, [4] S. Miller and concentrations must be corrected accordingly, also radiogenic H. Urey (1959) Science 130, 245-251. [4] R. Busemann et al. activity calculations (e.g. 210Pb, 230Th). Geochemists try to (2000) MPS 35, 949-973 avoid the second error by using a salt correction when subtracting the salt related element concentrations directly from the composition analyzed.

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18 Visualization of dynamic changes and Water H2 O isotope studies in the the effects of coatings on silver AIDA cloud simulation chamber nanoparticles by Surface Enhanced B. KUEHNREICH1, J. LANDSBERG2, J. HABIG4, Raman Spectroscopy S. WAGNER1, E. MOYER3, H. SAATHOFF4, V. EBERT1 AND E. KERSTEL2 M. KÜHN*, N.P. IVLEVA, R. NIESSNER 1PTB/TU Darmstadt, Germany ([email protected]) AND T. BAUMANN 2University of Grenoble, France ([email protected]) Institute of Hydrochemistry, Technische Universität München, 3University of Chicago, USA ([email protected]) 81377 Munich, Germany (*correspondence: 4Karlsruhe Institue of Technology, Germany [email protected]) ([email protected])

A wide variety of applications for engineered Isotopic studies can provide additional information on nanoparticles leads to increasing emissions into the cloud physics, which have a significant impact on global environment. After entering the aquatic or terrestrial climate. The conventional isotope-selective measurement compartment, nanoparticles likely undergo changes caused by technique, Isotope Ratio Mass Spectrometry (IRMS) is weathering or interactions with dissolved substances forming however not adapted to study dynamic processes such as cloud coatings on the particles. Hence, the surface properties will no formation. Laser based measurement techniques offer both longer be characterized by the nanoparticle itself, but rather by high precision and a fast response to follow the cloud the properties of the coating material. Stability and transport formation process in real time. In the recent ISOCLOUD properties particles will be altered significantly by different campaign at the AIDA cloud and aerosol chamber, different coating materials. laser-based instruments were used to jointly obtain Knowledge of the development and stability of coatings is information about isotope ratio changes in both the water therefore crucial to predict the fate of nanoparticles in the vapor and ice phases during simulated cloud formation environment. Surface enhanced Raman Spectroscopy (SERS) processes. Here we report on two instruments used to quantify 18 16 is a spectroscopic technique, which makes use of the signal the H2 O/H2 O ratio. One of the instruments, ISO-APicT enhancement caused by surface plasmon resonance and (PTB/KIT), an open path spectrometer based on tunable diode chemical enhancement typically found at silver nanoparticles laser absorption spectroscopy (TDLAS) measures the isotopic and other nanostructured metals (e.g. Au, Cu). Thus the signal ratio of the vapor phase. Open-path TDLAS has been 16 of the molecules adsorbed to the nanoparticles will be successfully applied to in-cloud studies on H2 O [2]. The enhanced significantly and dynamic changes of the materials second instrument based on Optical Feedback Cavity adsorbed to the particles can be studied. SERS is rather Enhanced Absorption Spectroscopy (OF-CEAS, insensitive to dissolved molecules since the electromagnetic Grenoble/KIT) extractively samples either total water or, if SERS enhancement strongly decreases with growing distance connected behind a pumped counterflow virtual impactor, the (, d-12). The technique works with little sample preparation ice phase only. The OF-CEAS technique has already been and sample volumes suitable for microfluidic experiments and used in different water isotope studies, including airborne environmental samples. studies [3]. We show a characterization of both instruments, Citrate reduced and stabilized as well as hydroxyl- including their time response to sudden isotope ratio changes, ammoniumchloride reduced silver nanoparticles were coated as well as preliminary results obtained during ice cloud with humic acid, seeweed extract, and polygalacturonic acid. formation. After adding the coating materials, the suspensions were centrifuged to remove excess coating materials. Changes of [1] Krämer M. et al., Atmos. Chem. Phys. 9, 3505-22 (2009). the pH-value of the solution and an exchange of the coating [2] Gurlit, W. et al., Applied Optics 44, 91–102 (2005) [3] material were done to study the stability of the coating. Here, Iannone R.Q. et al., J. Geophys. Res. 115, D10111 (2010) ; Raman spectroscopy gives direct access to the protonation of Isot. Env. Health Stud. 45, 303-20 (2009) humic acid on the surface which immediately effects the spectrum. The characterized nanoparticles were then brought into contact with physically and chemically heterogeneous surfaces to investigate the attachment coefficients and potential blocking. Chemical mapping using Raman microspectroscopy and SERS not only gives access to the spatial distribution of the nanoparticles but also to the chemical environment around the nanoparticles.

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Dissolved organic matter composition New experimental data on TiO2 across a coastal-open ocean gradient solubility in hydrous rhyolite melts: in the eastern Pacific Ocean Implications for titanium-in-quartz ELIZABETH B. KUJAWINSKI*1, WINIFRED JOHNSON2 thermobarometry 1 AND KRISTA LONGNECKER 1 1 K. KULARATNE AND A. AUDÉTAT * 1Department of Marine Chemistry and Geochemistry, Woods 1Bayerisches Geoinstitut, Universität Bayreuth, 95440 Hole Oceanographic Institution (WHOI), Woods Hole Bayreuth, Germany (*correspondence: MA 02543 [*correspondence: [email protected], [email protected]) [email protected]] 2MIT/WHOI Joint Program in Oceanography and Applied Application of the titanium-in-quartz (TitaniQ) Ocean Sciences, Woods Hole, MA 02543 thermobarometer to natural magmas requires estimation of the [[email protected]] activity of TiO because most natural magmas are not TiO - 2 2 saturated. However, currently available methods to calculate Dissolved organic matter (DOM) in marine systems is an TiO activities in silicate melts return highly inconsistent important component of the global carbon cycle whose 2 results that commonly differ by a factor of up to two, which molecular-level composition is determined by a combination introduces large uncertainties in the calculated TitaniQ of abiotic and biotic factors related to sources, sinks and temperatures or pressures. In order to further constrain TiO transformations. Molecular-level characterization of this 2 solubility in silicic melts we conducted experiments at 800- heterogeneous mixture has become practical only recently 900 °C and 2 kbar in H O-saturated haplogranite melts with with the advent of ultrahigh resolution mass spectrometry (ESI 2 molar Al/(Na+K)-ratios ranging from 0.81 to 1.2. FT-ICR MS). To date, systematic surveys of DOM Due to the slow diffusivity of Ti in silicate melts at these composition in the surface and deep oceans are rare, but those conditions we developed a new method to determine TiO conducted to date have highlighted the potential of this tool to 2 solubility. In a first step, anhydrous glasses with smooth TiO identify new marker compounds for different biological 2 concentration gradients over several millimeters were processes. Here we examine the DOM composition along Line produced in an 1 atm high-temperature furnace. Pieces of P in the eastern Pacific Ocean, collected during the these glasses were then hydrated for 3 days at 750 °C and 2 interdisciplinary GEOMICS cruise in May 2012. We explore kbar at H O-saturated conditions in cold-seal pressure vessels, the shifts in DOM composition from the coast to the open 2 which caused crystallization of rutile in the TiO -rich parts of ocean as well as down the depth profile at selected locations. 2 the samples. Finally, the recovered pieces were welded We further explore the source of surface DOM through together with untreated ones (plus H O) into new Au capsules comparison with culture-based investigations of metabolites 2 and were equilibrated at 800-900 °C and 2 kbar for 7 days, exuded by phytoplankton and heterotrophic bacteria. Using after which time the samples were rapidly quenched. In this multivariate statistical tools, we observe significant changes in way, forward and reverse runs could be conducted within compound distributions along the primary spatial gradients of single experiments. TiO concentrations measured at the Line P, notably an increase in N:C and S:C ratios with depth. 2 contact between rutile-bearing and rutile-free glass agree well We hypothesize that microbial activity is responsible for these between forward and reverse runs, suggesting that equilibrium changes and leads to the sequestration of N and S in was obtained. increasingly recalcitrant molecules. These data will provide An empirical best-fit model to our data predicts TiO important chemical contexts for other omics-based analyses 2 solubilities that are similar to those measured by [1], thus undertaken by GEOMICS colleagues and are an integral validating the TitaniQ model and corresponding tests on component of an emerging systems-biology view of the ocean. natural samples published in [2].

[1] Hayden&Watson (2007) Earth Planet. Sci. Lett. 258, 561- 568. [2] Huang&Audétat (2012) Geochim. Cosmochim. Acta 84, 75-89.

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GEMS: Gibbs energy minimization Southward transport of the software for geochemical modeling Fukushima-derived radiocesium due D. A. KULIK1*, S.V. DMYTRIEVA2, T. WAGNER3, to the subtropical mode water 1 1 T. THOENEN AND U. BERNER 1 1 1 Y. KUMAMOTO *, A. MURATA , T. KAWANO 1Laboratory for Waste Management, Paul Scherrer Institut, AND M. AOYAMA2, 5232 Villigen, Switzerland (*[email protected]) 1 2Institute of Environmental Geochemistry, Kyiv, Ukraine Japan Agency for Marine-Earth Science and Technology, 2- 15 Natsushima-cho, Yokosuka 237-0061, Japan 3Department of Geosciences and Geography, University of (*correspondence: [email protected], Helsinki, Finland [email protected], [email protected])

2Meteorological Research Institute, 1-1 Nagamine, Tsukuba Geochemical modeling is relevant in ore geochemistry, 305-0052, Japan ([email protected]) CO /radioactive/toxic waste disposal, cosmochemistry, 2 petrology, and hydrogeochemistry. GEMS is an advanced Fukushima-derived Radiocesium software tool for modeling complex systems that involve non- The massive Tohoku earthquake and consequent giant ideal solid solutions, fluids and aqueous solutions, mineral tsunami of March 11, 2011 resulted in releases of radiocesium phases metastability, adsorption, and ion exchange. GEMS from the Fukushima Dai-ichi nuclear power plants. The total (http://gems.web.psi.ch) comprises the GEM-Selektor code; amount of the radiocesium derived from the direct discharge default thermodynamic databases; the GEMS3K kernel code into the North Pacific Ocean was estimated to be about 4 PBq [1,2] included into the GEMSFIT code [3] and available open- for Cs-137 [1, 2]. However, that from the atmospheric source for coupling into reactive transport codes. deposition contains large uncertainty mostly due to the The GEM-Selektor v.3 is the main tool for interactive restriction of available data in the open ocean. geochemical thermodynamic modeling. It integrates a multi-

document graphical user interface with a built-in script Sample Collection and Radiocesium Analysis interpreter, a database management system, and a context- We measured the radiocesium in seawaters from surface to driven help browser. These features support forward- or 800-m depth at stations along approx.149°E line more than inverse modeling tasks, plotting or exporting results, and hundreds km away from the plants in the western North creating GEMS3K input files. The usage is focused around a Pacific Ocean in January and February 2012. Radiocesium in modeling project database that accumulates all input data and the seawater was concentrated onto ammonium results for a given application. Any project can be shared with molybdophosphate and then measured using a gamma- others, which greatly facilitates the data exchange in teams. spectrometry with Ge detectors. GEMS databases equally support thermochemical and

reaction-based formats of standard-state thermodynamic data. Results and Discussion Creation of new projects is facilitated by the supplied Cs-134 was found in surface waters at all the stations from thermodynamic databases, derived from the PSI/Nagra 12/07 20°N to 42°N. Activity of Cs-134 in the surface mixed layer [4] and the SUPCRT92 [5] datasets. Third-party databases for was highest (~ 20 Bq m-3) in the transition area between the specific application fields are also available in GEMS format. subarctic and subtropical regions, which was due to the direct Current development is focused on adding the kinetics of discharge into the transition area. Below the surface mixed mineral-aqueous reactions and trace element uptake; layer Cs-134 activity decreased sharply and was not detected implementing sorption models using a concept of linked phase in deeper layers than 400-m depth in the subarctic region and metastability; improving GEM numerical algorithms; moving transition area. However, in the subtropical region we to industrial NoSQL database format in connection with the observed Cs-134 maxima just below the mixing layer that general parameter-fitting code GEMSFIT. Our goal is to make corresponds to about 25.3 sigma-theta, implying that the Cs- GEMS the software of choice for all kinds of geochemical 134-rich waters in the transition area have been transported modelling applications. southwardly to the subtropical region due to formation of the

subtropical mode water. [1] Kulik et al. (2013) Comput. Geosci. 17, 1-24. [2] Wagner

et al. (2012) Can. Mineral. 50, 701-723. [3] Hingerl et al. [1] Kawamura et al. (2011) J. Nucl. Sci. Technol. 48, 1349– (2013) Comput. Chem. Eng. (submitted). [4] Thoenen et al. 1356. [2] Tsumune et al. (2012) J. Environ. Radioactiv. 111, (this conference). [5] Shock et al. (1997) Geoch. Cosmoch. 100–108, doi:10.1016/j.jenvrad.2011.10.007. Acta 61, 907-950.

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Isotopic characterization of winter The ocean’s biological pump in deep time aeolian dust over Cape Verde time A. KUMAR1*, W. ABOUCHAMI1,2, S.J.G. GALER1, LEE R. KUMP K.W. FOMBA3 AND M.O. ANDREAE1 Dept. of Geosciences, Penn State, University Park, PA 16802 1Biogeochemistry Department, Max Planck Institute for USA [email protected] Chemistry, Mainz, Germany (*[email protected]) 2Westfälische Wilhelms Universität, Institut für Mineralogie, The importance of biotic processes in the functioning of 48149 Münster, Germany the Earth system is perhaps nowhere better demonstrated than 3Department of Chemistry, Leibniz Institute for Tropospheric by the vertical chemical stratification of the ocean. In the face Research, Leipzig, Germany. of physical forces of homogenization, life transforms the ocean into a chemically heterogeneous environment, depleted Radiogenic isotope tracers are robust tools for tracking of nutrients, and through fractionation, 12C in surface waters dust provenance and atmospheric transport pathways. Recent and enriched at depth. This biological pumping of nutrients to studies of African sources have shown spatial isotopic depth occurs with the sinking of organic matter and its heterogeneity locally and on short time scales. High-temporal- remineralization in the deep ocean. The “health” of the resolution isotopic time series are thus essential for resolving ocean’s biota has been inferred from reconstructed gradients seasonal changes in dust provenance. Here, we report Sr, Nd in "13C, with strong gradients implying a strong biological and Pb isotopic compositions of aeolian dust collected during pump and loss of the gradient, e.g., during the Cretaceous- a campaign in late winter (1-20 February 2012) on the island Paleogene extinction event implying collapse. However, of São Vicente at the Cape Verde Atmospheric Observatory today, the magnitude of the surface-to-deep gradient is (16.9°N, 24.9°W). inversely related to the rate of export of organic matter to the Total suspended particulate (TSP) and PM10 (particulate deep on a regional basis. Rather, it is the efficiency of the matter less than 10 µm aerodynamic diameter) were collected biological pump, the ability of organisms to extract nutrients on acid-cleaned cellulose filters on a daily basis (~24 hrs). from upwelling waters before those waters mix physically During the dust storm event, from 6-8 February 2012, samples with waters at depth, that is reflected in the gradients, and the were collected at shorter time intervals (every 5-8 hrs). About most efficient removal occurs in the oligotrophic gyres. The 1-20 cm2 of filter was leached with ultrapure MilliQ water to biological pump appears as a robust feature of ocean remove sea-salt Sr and subsequently leached with 0.5 N HBr ecosystems over geologic time, as evidenced through detailed to extract the anthropogenic Pb and soluble particulate investigations of the carbon isotope gradients inferred from fraction. The remaining silicate fraction was fully dissolved carbonate rocks deposited during the Paleoproterozoic, end

using HF-HNO3 acids. Isotopic measurements were obtained Permian, and throughout the Cenozoic. on all fractions by TIMS; Pb isotope ratios were corrected for instrumental mass bias using a triple spike. The silicate fractions show consistently more radiogenic Pb and Sr compared to those of the leachates, while Nd isotopic compositions are nearly uniform in both fractions. A shift towards higher Pb isotope ratios is observed during the dust event, followed by a continual decrease. By comparison, Sr and Nd isotopes record small changes, with a noticeable excursion to low values after the dust event. Lead and Nd isotopic compositions of TSP and PM10 are similar during dusty days, in contrast to less-dusty days, suggesting that grain-size fractionation depends on dust loading. The radiogenic isotope time-series of winter dust at Cape Verde pinpoints Northwest Africa as a persistent source of dust, while an additional emission source, with more radiogenic Pb, was active during the dust storm event. These inferences are entirely consistent with analysis of air-mass back-trajectories.

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Heinrich Holland’s big event: Organic genesis of the sulphur The Great Oxidation occurences and their relationship LEE R. KUMP1 with black shales in the Isparta 1Dept. of Geosciences, Penn State, University Park, PA 16802 Region, SW, Turkey USA [email protected] 1 1 MUSTAFA KUMRAL AND MURAT BUDAKOGLU

Although his research delved into many problems in the 1Istanbul Technical University, Department of Geological geochemistry of Earth, for much of his career H.D. Holland Engineering, 34469, Istanbul, TURKEY was most passionate about what he termed “the Great Oxidation Event,” i.e., the establishment of an oxygen-rich The study area is located in the triple conjunction area of atmosphere in the early Paleoproterozoic. From the early the "Isparta Angle" in the Western Taurus region of SW 1960’s until his passing in 2012, Holland developed and Turkey. Due to Neotectonic evolution of Eastern refined a deep understanding of the geological and theoretical Mediterranean Region, the study area is a geologically very constraints on the chemical composition and evolution of the complicated region. The rock units are divided into two atmosphere and ocean. This understanding, and the way that groups as either allocthonous or autochtonous. Tectono- only Holland could provide simple yet deep quantification to stratigraphically, the allocthonous units are Paleozoic the problem, is perhaps most elegantly displayed in his 1984 quartzite, black shale, limestone, arkozic sandstone, book The Chemical Evolution of the Atmosphere and Oceans, interlaminated radiolarite and autochtonuous units are Triassic the manuscript of which served as my introduction to and Jurassic limestones, and Upper Cretaceous ophiolite. Holland’s work when I was a graduate student studying under Trachyte, trachyandesite, feldspathoidal trachyandesite lifelong friend and scientific foil to Holland, Robert Garrels. porphyry, tuff and pumice were formed by volcanism during Holland sought to answer the questions of “when did the GOE the Plio-Quaternary. Recent alluvium and slope detritus cover occur?”, “why did it occur?”, and “how high oxygen levels all the rock units. rose during the event and subsequently?”. For Holland, the Sulphur outcrops are exposed in the Keciborlu native answer to “when” has been fairly well constrained by the sulphur, Uyuzpınar volcanic gases, Darıdere altered volcanic mass-independent sulfur isotope record of the rocks , Darıdere pyrite in volcanic rocks, Yakaören altered Paleoproterozoic. The answer to “how high” is rather poorly volcanic rocks, Kasımlar blackshales , Kesme road native constrained by geological proxies but approximately 10% of sulphur in blackshales , Qbi*ler village in native sulphur, today’s level just following the GOE. But the answer of “why” Afyon volcanics, Kınık Kızıltepe altered volcanic rocks, continued to perplex him to the end. A diverse group of Gölba*ı realgar, Gölba*ı gypsum and $arkikaraagac barite researchers has been entrained by Holland’s passion for the occurrences. The most important sulphur deposits are found in GOE and will carry the torch forward as the timing, pathway, volcanic tuff and siltstone - marl - shale interbedded unit and mechanisms of the GOE become fully illuminated. which contains an organic matter. Sulphur may accumulate around recent fumeroles existing and also as massive mineralization. Field studies and sulphur isotope data show that the sulphur originated from the uppercrust and probably comes from organic matter- rich Paleozoic and Triassic sedimentary rocks. The sulphur did not migrate between the Triassic and Pliocene periods. However, Plio-Quaternary volcanism was the cause of mobility of the sulphur and was followed by formation of the secondary sulphur mineralization due to post tectonic geothermal activities. ,34S values of the samples coincide with other samples from different shallow marine environments. Since the isotope values of the sulphur samples are quite similar to those of organic materials, it can be concluded that the sulphur might have occurred in the same anoxic environment together with petroleum source rocks.

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Seismic evidence for the !-" quartz Isotopic and Geochemical transition beneath Taiwan from Constraints on the Origin of Post- Vp/Vs tomography Collisional Mafic Tholeiites from H. KUO-CHEN123, F. T. WU13, D. M. JENKINS1, Erkilet, Central Anatolia 4 5 2 J. MECHIE , S. W. ROECKER , C.-Y. WANG 1 2 6 BQLTAN KÜRKCÜOGLU *, TANYA FURMAN , AND B.-S. HUANG 2 1 3 MEGAN PQCKARD , ERDAL $EN , BARRY HANAN , 1Department of Geological and Environmental Sciences, State PıNAR $EN4, KAAN SAYıT3 AND TEKQN YÜRÜR1 University of New York at Binghamton, NY, USA. 1 Hacettepe University , Dept. of Geological Engineering, 2Institute of Geophysics, National Central University, Jhongli, 06800 Beytepe-Ankara, Turkey, [email protected] Taiwan. 2 Pennsylvania State University, Dept.of Geosciences, 3Department of Earth Sciences, University of Southern University Park, PA,16802,USA [email protected] California, Los Angeles, California, USA. 3San Diego State University, Dept. of Geological Sciences, 4Deutsches GeoForschungsZentrum – GFZ, Section San Diego, CA, USA, [email protected] “Geophysical Deep Sounding“, Telegrafenberg, 14473 4 General Directorate of Mineral Research and Exploration Potsdam, Germany. (MTA) Balgat-Ankara, Turkey, [email protected] 5Department of Earth and Environmental Sciences, Rensselaer

Polytechnic Institute, New York, USA. Central Anatolia is one of the most interesting region 6Institute of Earth Sciences, Academia Sinica, Taipei, Taiwan. displaying extensive volcanic activity related to post-

collisional extension. Besides stratovolcanoes, most Knowledge of the rock types and pressure-temperature monogenetic vents and smaller volcanoes (e.g., Karapınar, conditions at crustal depths in an active orogeny is key to Develida", Sivas, Erkilet) are characterized by basaltic lavas understanding the mechanism of mountain building and its that may be alkaline or tholeiitic or both. The field and associated modern deformation, erosion and earthquakes. geographical occurrance of Erkilet mafic lavas are generally Seismic-wave velocities by themselves generally do not have similar to those observed in the Sivas area some 100 km to the the sensitivity to discriminate one rock type from another or to northeast (1). These two volcanic provinces are located along decipher the P-T conditions at which they exist. But an ancient suture separating the Anatolide-Tauride blocks. laboratory-measured ratios of velocities of P to S waves Erkilet basalts have incompatible trace element abundances (Vp/Vs) have been shown to be effective. Results of 3-D Vp that are enriched overall relative to primitive mantle values, and Vp/Vs tomographic imaging based on dense seismic but they lack the unusually high contents of large ion arrays in the highly seismic environment of Taiwan provides lithophile and light rare earth elements that typify Sivas the first detailed Vp/Vs structures of the orogen. The sharp basalts, Erciyes tholeiites, and products of the regional mantle reduction in the observed Vp/Vs ratio in the felsic core of the lithosphere (2). The Erkilet basalts have low Nb-Ta contents mountain belts implies that the :-R quartz transition (but not Ti, Zr, Hf) that are typical of arc lavas and suggest a temperature is reached at a mean depth of 24 ± 3 km. The contribution from a source area with rutile that remains stable transition temperature is estimated to be 750 ± 25 °C at this during shallow melting. Their high Ba/Nb (25-36) and La/Nb depth, yielding an average thermal gradient of 30 ± 3°C/km. (~2) values reflect these low Nb contents, and require a source In a young orogen such as Taiwan where an extensive root region distinct from that for MORB or Sivas basalts. Low system is extant and rapid deformation and uplifting are well- Rb/Sr (~0.01) and moderate Ba/Rb (33-36) values suggest a documented, the knowledge of the present P/T conditions and source with modal amphibole but not phlogopite, consistent materials in the core of the orogen could help in the with low Tb/Ybn values that indicate melting within the understanding of the dynamics of mountain building. The shallow mantle, i.e., above the garnet stability field. The Sr- presence of abundant quartz in the continental crust is Nd isotopic signatures of Erkilet mafic lavas are depleted important in localizing deformation; while hydration relative to those of Sivas and Erciyes basalts (~0.7037, weakening as one of the conditions in the feedback processes 0.5128), consistent with their smooth and OIB-like the :-R quartz transition in Taiwan may play the role. In any incompatible trace element abundance patterns. Their Pb case, Taiwan is an excellent site where patterns of strain isotopic values, however, plot within the range of Sivas and focusing and crustal weakening during the early stages of Erciyes basalts that are interpreted as including contributions tectonic deformation can be explored in detail. from a mantle lithosphere affected by enrichment in fluid- mobile trace elements during an ancient subduction event (3). These isotopic signatures are consistent with trace element evidence supporting existence of an arc environment during the evolution of the source region for Erkilet basalts. Further work will explore the nature and degree of interaction between identifiable lithospheric and asthenospheric sources during extension-related melting along this ancient suture zone. [1] Kurkcuoglu 2013, submitted, [2] IGR, 43, 508, [3] Picard, 2012, Goldschmidt, 2012, 2231.

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Single-crystal elastic properties of Sedimentary osmium isotopic records Fe0.04Mg0.96SiO3 – perovskite at high of Mediterranean basins pressure JUNICHIRO KURODA1*, FRANCISCO J. JIMENEZ-ESPEJO12, 1 1 1 1 1 TATSUO NOZAKI AND KATSUHIKO SUZUKI A. KURNOSOV * , D. M. TROTS , T. BOFFA BALLARAN , AND D.J. FROST 1 1Japan Agency for Marine-Earth Science and Technology 1 (JAMSETC), Yokosuka 237-0061, Japan Bayerisches Geoinstitut, Universität Bayreuth, 95447 (*correspondance: [email protected]) Bayreuth, Germany. 2 Nagoya University, Nagoya 464-8602, Japan

Perovskite structured MgSiO is widely accepted to be the 3 Mediterranean Sea has experienced an extreme event dominant phase in the Earth’s lower mantle where it coexists called Messinian Salinity Crisis (MSC) that represents a with ferropericlase. An understanding of the plausible formation of gigantic evaporite deposits in deep basins (e.g., chemical variation of MgSiO -perovskite (enrichment with 3 Ryan et al., 2009). In this study we report sedimentary Os Fe/Al) in addition to the consequent effects on density and isotopic record of marine sediment cores from four Deep-Sea elastic properties is important in order to understand the origin Drilling Project (DSDP) sites in the Mediterranean Sea (Hsü of seismic velocity anomalies in the lower mantle reported in a & Montadert, 1978); DSDP Site 372 in the western number of studies [1-3]. Mediterranean (Balearic Basin), DSDP Site 374 in the central In this study two differently oriented single-crystals of Mediterranean (Ionian Basin), and DSDP Sites 375 and 376 in magnesium silicate perovskite containing 4 mol% of the the eastern Mediterranean (Florence Rise). Osmium isotopic Fe2+SiO component [(Mg,Fe)SiO ] have been studied by 3 3 ratios of the pre-MSC sediments of Miocene (Burdigalian to means of Brillouin spectroscopy and X-ray diffraction in-situ Serravallian) in the western Mediterranean are identical to that in diamond anvil cells. Helium was used as the pressure of the coeval ocean water. In contrast, the pre-MSC sediments transmitting medium and experiments were performed in the (Langhian to early Messinian) in the eastern Mediterranean pressure range from 2 to 31 GPa. Ruby pressure markers were have significantly low 187Os/188Os values than those of the used to obtain similar pressure conditions in both diamond Middle to Late Miocene ocean water. This suggests that Os in anvil cells. The Brillouin spectra were measured in symmetric the eastern Mediterranean was not fully mixed with that of platelet geometry for each crystal at different orientations in other seas such as western Mediterranean and North Atlantic, the plane of the platelet. The data at each pressure were fitted and that the basin isolation has already started before the for both crystals simultaneously in order to reduce correlations MSC, probably as early as Middle Miocene. The of Cij constants. Using the data from two crystals with unradiogenic Os would have been supplied to the eastern different non-specific orientations we were able to obtain all 9 Mediterranean by selective weathering of ultramafic rocks in independent Cij elastic constants for orthorhombic symmetry the surrounding ophiolite bodies, which contains high amount at 8 different pressure points. The orientation matrix and cell of non-radiogenic Os. The isotopic compositions of Os in parameters for each crystal at every pressure point were gypsum samples from all sites are significantly lower than the refined using in-situ x-ray diffraction measurements. From end-Miocene ocean water values, suggesting isolation of all sample densities obtained from x-ray diffraction data and Messinian basins. Sediments from Pliocene show Os isotopic simultaneous measurements of the adiabatic bulk modulus ratios more radiogenic, and close to the seawater values of obtained from Brillouin measurements, it was possible to Pliocene but slightly less radiogenic, indicating that Os started calculate the absolute pressure for all our experimental points. mixing with global seawater again. We will further discuss This approach allowed the elastic properties of (Mg,Fe)SiO - 3 possible scenarios about Mediterranean hydrology during the perovskite to be determined as a function of primary pressure, MSC, based on the sedimentary Os isotopic records. i.e. without resort to a secondary pressure standard. This

consequently provides a more reliable data set to be compared [1] Hsü, K.J. & Montadert, L. (1978) Initial Reports of the with seismic data for the lower mantle. Deep Sea Drilling Projects 42A, Ryan, W.B.F. (2009)

Sedimentology 56, 95-136. [1] Ni et al. (2005), Geophys. J. Int. 161, 283–294. [2]

Masters et al. (2000), AGU Monograph Series, 117, 63–87. [3] Garnero et al. (2005), The Geological Society of America Special Paper, 430, 79–101.

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Helium isotopic and concentration The Mo-isotopic composition of late variations in a clinopyroxenite vein: Archean Iron Formations Implications for mantle evolution F. KURZWEIL1*, M. WILLE1, R. SCHOENBERG1 2 1 1 2 1 AND M. VAN KRANENDONK M.D. KURZ , V. LEROUX , J.M. WARREN , J. CURTICE , AND S. NIELSEN1 1Department of Geoscience, University of Tuebingen, 1 Wilhelmstr. 56, 72074 Tuebingen, Germany, Quissett Campus, Woods Hole Oceanographic Institution, (*correspondence: [email protected]) Woods Hole, MA 02543, USA 2 2 School of Biological, Earth and Environmental Sciences, Geological and Environmental Sciences, Stanford University, University of New South Wales, Kensington, NSW 2052, 450 Serra Mall, Stanford CA 94305-2115,USA Australia

In an effort to constrain the behavior of noble gases during The timing of the first appearance of free oxygen in melting and melt migration in the mantle, we have measured Earth’s atmosphere remains highly debated in the literature. helium concentrations and isotopic compositions in a 10 The general view places the Great Oxidation Event (GOE) centimeter transect through a clinopyroxenite vein in the between 2.4 and 2.32 billion years ago (Ga), when oxygen Josephine Ophiolite (Oregon, USA). The 4 cm thick concentrations rose for the first time from 10-5 to 10-2 of the clinopyroxenite is hosted by harzburgite and was sampled 4 present atmospheric level. However, some redox-sensitve with 1-2 millimeter resolution. The vein has He elements seem to indicate a pre-GOE increase in atmospheric concentrations up to 10 times higher than the host harzburgite oxygen concentrations at extremely low levels. Mo isotopes (5.0 to 9.0 x 10-7, as compared to 3.4 x 10-8 to 1.7 x 10-7 cc and concentrations in late Archean sediments (carbonates and STP/gram). Because the veins are thought to form through black shales), for example, show 298Mo values higher than the mantle melt percolation, the enrichment confirms that helium continental crust average some 100 million years before the behaves as an extremely incompatible element. There is a GOE. These positive 298Mo values are attributed to oxidation- sharp helium concentration contrast at the vein/host interface, reduction processes that per se require oxygenated oceans, in suggesting that the concentration variations were produced which light Mo is preferentially adsorbed onto Mn- and Fe- during vein emplacement, and that clinopyroxene has higher 98 3 4 (oxyhydr)oxides. The subsequent increase in seawater 2 Mo helium storage capacity. Total He/ He in the host harzburgite is thought to be preserved in black shales and carbonates. The ranges from 6.5 to 7.1 times atmosphere (Ra), in agreement occurrence of heavy Mo-isotope signatures in late Archean with previous measurements of the area, suggesting that shales and carbonates infers the presence of a light Mo- mantle helium isotopic compositions are dominant (Recanati 3 4 reservoir in the sedimentary record. Fe-(oxyhydr)oxides are a et al., 2012). The bulk He/ He in the vein varies between 4.5 possible candidate for such a light Mo reservoir. During early and 5.3Ra, significantly lower than the harzburgite, reflecting diagenesis they would form Fe-carbonates, -oxides, or radiogenic production since vein emplacement or slab related -silicates and eventually iron formations (IF’s). Consequently, fluxes. These data demonstrate that isotopic and concentration IF’s may represent the missing late Archean reservoir for variations have been preserved since emplacment at ~ 157 Ma, isotopically light Mo. and that mantle helium isotopic compositions are retained. Here, we tested this hypothesis by measuring Mo isotopes The isotopic variations suggest that it may be possible to in 2.63 to 2.45 Ga old black shales and IF’s of the Pilbara determine Th-U-He vein emplacement ages. The short length Craton, Australia. Both, black shales and IF’s show a similar scale variations place time limits for diffusion and post- increase in 298Mo as time-equivalent shales and carbonates emplacement cooling below the closure temperature. This from the Kapvaal craton, South Africa. The youngest IF shows study may not be representative of the mantle, as the a highly positive 298Mo!,.+*3!#)!1.5‰. Thus, the proposal that Josephine veins are thought to derive from a sub-arc or back- IF’s represent the reservoir for light Mo is not confirmed by arc basin setting, and are preserved only by rapid cooling. our measurements. The similarity in magnitude and trend of However, these preliminary data do suggest that preferential 98 3 4 2 Mo through time suggests a similar removal mechanism of melting of this vein type will yield lower He/ He than the host molybdenum from seawater by carbonates, shales and IF’s. mantle, and that vein melting models therefore may not Furthermore, this observation requires the build-up of a explain elevated values (unradiogenic helium) found in some sizeable seawater Mo-reservoir that was linked to more oceanic basalts. oxidizing conditions before the GOE.

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Cathodoluminescence An apatite-halogen based probe for characterization of Norsethite fluid-rock interaction events 1 1 BaMg(CO3)2 CHRISTOF KUSEBAUCH , TIMM JOHN , 2 3 1 1 2 MARTIN WHITEHOUSE AND ANE ENGVIK N. KUSANO , H. NISHIDO , M.MAKIO AND K. NINAGAWA3 1Institute for Mineralogy, Uni Muenster, Germany; 1 [email protected] Department of Biosphere-Geosphere Science, Okayama 2Swedish Museum of Natural History, Stockholm, Sweden University of Science, 1-1 Ridai-cho, Okayama 700-0005, 3Norwegian Geological Survey, Trondheim, Norway Japan (correspondence: [email protected]) 2 Graduate School of Social and Cultural studies, Kyushu Apatite is a typical accessory mineral in many geological University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395 settings and is stable over a wide range of pressure and Japan 3 temperature. Natural apatite usually occurs as a solid solution Department of Applied Physics, Okayama University of of three end members, i.e. fluor-, hydroxy- and chlorapatite Science and therefore reflects the F-Cl-OH activity conditions of its formation. Apatite crystallized during fluid-rock interaction Anhydrous double salts of MgCO and BaCO such as 3 3 can be used as a fluid probe for halogens as it reflects not only norsethite BaMg(CO ) have not been investigated up to date 3 2 F and Cl, but Br and I concentration in the fluid. Also apatite with respect to CL properties, whereas CL of dolomite is rather sensitive to changes in fluid composition, undergoing structurally similar to norsethite has been extensively used to dissolution-precipitation reactions leading to formation of an geoscience application. In this study, we have measured CL apatite with a changed composition. This facilitates constraints spectra of norsethite and characterize its CL emission centers. on the number of fluid events and the characteristics of their Norsethite sample from Kremikovtsy, Bulgaria was potential sources. selected for CL spectral measurements. SEM-CL analysis was Here, we present a halogen concentration and ,37Cl study conducted using an SEM combined with a grating of apatite from an alteration sequence from a regional-scale monochromator to measure CL spectra ranging from 300 to metasomatic event (Bamble Sector, SE Norway). The 800 nm in 1 nm steps with a temperature controlled stage from alteration sequence comprises a complete profile from -190 to 250 ºC. All CL spectra were corrected for the total unreacted to fully altered gabbro, close to a shear zone from instrumental response. which a high salinity fluid pervasively altered the gabbro. Norsethit exhibits a red broad band emission in red region Halogens in apatite, measured in-situ by ion microprobe, between 570 and 770 nm at room temperature. This emission 2+ show marked diversity. Whereas Br concentrations constantly can be assigned to Mn as an activator by comparing with the decrease from the least altered (100-500 ppm) to most altered emissions of other carbonates, but with too low concentration 2+ samples (10-20 ppm), F shows the opposite trend, with a of Fe as a quencher. A Gaussian curve fitting of the spectra constantly increasing concentration from 40-100 ppm to 2000- was carried out to clarify emission components in energy 12000 ppm. Apatite from the most pristine samples shows low units. One emission component at around 1.93 eV (641 nm) F/Cl ratios and high Br/Cl, while apatite from strongly altered was found without the others related to defect centers. samples is characterized by high F/Cl and low Br/Cl ratios. Dolomite has two emission components at 1.84 eV (673 nm) I/Cl ratios show no correlation with alteration. for Mn2+ activator in Mg site and another component at 2.15 Apatite from the pristine gabbro has ,37Cl values <+0.4‰. eV (576 nm) for same activator in Ca site. This fact implies With increasing alteration ,37Cl values increase to as high as that Ba ions with large ionic size might alternate crystal field +3.5‰. Furthermore, there is a strong correlation between strength around Mg site in norsethite structure. ,37Cl values and F concentrations within individual apatite crystals. The observed halogen concentrations and ,37Cl values of apatite formed during the metasomatic event can be explained by a single fluid event. Characteristics of the fluid are best represented by apatite from highly altered samples (high ,37Cl, high F concentrations). Due to interaction with the gabbro this fluid constantly evolves to lower F concentrations and lower ,37Cl values.

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Ancient mobilisation of radiogenic Quantitative 18S rDNA analysis Pb and Ti during high-grade using 3rd generation sequencing metamorphism methods to determine the effects of M.A.KUSIAK123* , M.J.WHITEHOUSE1, S.A.WILDE2, Modified Circumpolar Deep Water, D.J.DUNKLEY2, A.A.NEMCHIN2, R.WIRTH4 iron and siderophores on AND K.MARQUARDT4 phytoplankton assemblage 1Swedish Museum of Natural History, Stockholm, Sweden, 2Dept. of Applied Geology, Curtin University, Perth, composition in the Ross Sea Australia, 3 ADAM B. KUSTKA, ASHLEY M. NEW Polish Academy of Science, Inst. of Geol. Sci., Warsaw, AND BETHAN M. JONES 1 Poland 1 4Deutsches GeoForschungsZentrum, GFZ, Potsdam, Germany Rutgers University, Newark, NJ [email protected] Many zircons from early Archaean gneisses in the Napier Complex of East Antarctica, are reversely discordant. High We participated in the SEAFARERS cruise (along with spatial resolution ion microprobe imaging reveals Y and U other investigators Hatta, Kohut, Lam, Measures, Milligan and zonation, characteristic of magmatic zircons, together with a White) in the Ross Sea to test hypotheses regarding the micro-scale patchy distribution of 206Pb and 207Pb that does not influence of Fe supplied from Modified Circumpolar Deep correspond to either growth zonation or crystal imperfections. Water (MCDW) and from putatively accessible and somewhat 207 206 Some of these patches yield Pb/ Pb ages >4 Ga, whereas refractory forms (FeCl3 and Fe-enterobactin) on primary others yield ages younger than the magmatic crystallization production. Incubation experiments revealed widespread and age. Zircons from Dallwitz Nunatak record detrital ages chronic Fe limitation that was more pronounced in surface between 3.5 Ga and 2.5, whereas those from Gage Ridge waters above Joides Trough than on Pennell Bank. Addition define multiple age groups, with concordant data between 3.6 of MCDW did not stimulate growth at any station. Iron Ga and 3.3 Ga and reversely discordant data that form a supplied as the Fe- catecholate complex enterobactin distinctive ca. 3.8 Ga population. These oldest zircons are stimulated bulk chlorophyll production in a station dependent interpreted as xenocrysts, with the age of the protolith being manner, which might be explained by clade-specific ca. 3.3 Ga or younger. The patchy distribution of Pb is the differences in Fe-catecholate bioavailability. We developed a result of mobilisation of ancient radiogenic Pb, which can lead quantitative approach to characterize community composition to reverse discordance [1]; this is independent of the degree of - based on amplification of the v7-v9 regions of 18S rDNA metamictisation, oxygen isotope and REE content of the (>500 bp) and single-molecule real-time (SMRT) sequencing - zircons. Zircons from Mount Sones which show this effect which increased phylogenetic resolution compared to some underwent high-grade metamorphism at both ~2.8 Ga and 2.5 previous methods. The inclusion of various xenobiotic Ga, the latter reaching temperatures of >1000°C. It is likely standards immediately prior to DNA extraction and to PCR that one or both of these events caused re-mobilisation of Pb. amplification allow us to evaluate absolute changes in However, the precise mechanism is unclear and further work community composition, facilitating the calculation of clade- is in progress in an attempt to constrain this. Importantly, Ti specific growth rates under various treatments. To our also exhibits a random, patchy distribution in some zircon knowledge, this is the first quantitative application of third grains. This has the potential to affect Ti-in-zircon generation sequencing methods in marine environments. thermometry, with implications for the accurate determination of zircon crystallization temperatures.

[1] Kusiak et al. (2013), Geology 41, 291-294.

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Impact of increasing MoO3 loading Correlative imaging of microbial on incorporation properties of transformations in Nature multi-component borosilicate glass M. M. M. KUYPERS A. KUTZER1*, T. VITOVA1, K. KVASHNINA2, MPI for Marine Microbiology, Bremen, Germany T. PRÜßMANN1, J. ROTHE1, E. SOBALLA1, C. ADAM1, ([email protected]) P. KADEN1, M. A. DENECKE1, S. WEISENBURGER1, G. ROTH1 AND H. GECKEIS1 Correlative imaging is widely applied to obtain 1 comprehensive information on the identity, activity and Institute for Nuclear Waste Disposal (INE), KIT, 76021, physiology of cells in eukaryotic cell biology. However, in the Karlsruhe, Germany field of environmental microbiology this method is still little (*correspondence: [email protected]) 2 used despite its obvious potential. During the past years European Synchrotron Radiation Facility (ESRF), 38043, substantial progress was made at the MPI for Marine Grenoble, France ([email protected]) Microbiology (MPI-MM) to establish this method for our field. A particularly powerful approach used in our institute is Mo(VI)-rich residual material remaining after vitrification the use of nano-scale Secondary Ion Mass Spectrometry of high level liquid waste (HLLW) at the ‘Karlsruhe Repro- (nanoSIMS) coupled to stable and radio-isotope labelling cessing Plant’ (WAK) site can potentially be immobilized in experiments to determine single-cell activity in the borosilicate glass for ultimate disposal. Due to its low environment. By combining this approach with Fluorescence solubility in borosilicate glass melts, Mo(VI) tends to form in situ Hybridization (FISH) we are able to link the identity of molybdate-rich phases during the vitrification process. [1] microbial cells in a complex microbial community to their in These phases may crystallize during melt cooling and are able situ nutrient incorporation, which allows us to calculate to incorporate radionuclides within their crystal structure. If cellular uptake rates and directly determine nutrient fluxes. water soluble alkali molybdates are formed, the release of The recent acquisitions of an Environmental Scanning radioactivity into the environment will be facilitated in case of Electron Microscope combined with an EDX system water intrusion into a deep geological repository. The che- (ESEM/EDX) and a confocal laser Raman microscope mical composition of the formed phases is strongly dependent coupled with an atomic force microscope provides further on the borosilicate glass composition used. Understanding elemental, chemical-bond and structural information at a factors favoring the formation of stable crystalline Mo(VI) single cell level. I will present results of our correlative phases in borosilicate glasses allows development of glass imaging studies of complex microbial communities in various compositions capable of incorporating high Mo loadings, yet marine environments. avoiding formation of soluble phases.

In this work nuclear waste simulate with varying MoO3 concentrations vitrified in a multi-component borosilicate glass ([2]) was characterized. Powder X-ray diffraction and Raman spectroscopy studies confirm formation of crystalline

CaMoO4 and BaMoO4 phases for MoO3 concentrations above 4.5 wt%. Observed Mo K-edge high resolution X-ray absor- ption near edge structure (HR-XANES) spectral changes are correlated to different molybdate environments in the glass

depending on the MoO3 concentration. Fit analyses show that Na+ cations preferably compensate molybdate charge over Ba2+ and Ca2+ at low concentrations. 29Si nuclear magnetic resonance (MAS NMR) spectroscopic investigations show a

strong impact of the different MoO3 loadings on the degree of silicon network polymerization of the glass. No evidence for the formation of water soluble crystalline molybdates is found, indicating that the chemical composition of the glass used is favorable for immobilization of Mo-rich nuclear waste with this specific chemical composition.

[1] Lutze and Ewing (1988), Radioactive Wasteforms for the Future, North Holland, Amsterdam. [2] Grünewald et al. (2009), Proceedings of Global 2009, Paris.

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Gold-sulfide jasperoids of East Rare elements of diamond-forming Kazakhstan melt chambers formed in the mantle KUZMINA O.N.12, DYACHKOV B.A.13, peridotite (estimation with use of VLADIMIROV A.G.245, KIRILLOV M.V.2, experimental KD at 7.0-8.5 GPa) KOLPAKOV V.V.2, MIZERNAYA M.A.1 AND MAYOROVA N.P.1 KUZYURA A.V.* AND LITVIN YU.A. 1D. Serikbaev EKSTU, Ust-Kamenogorsk, Kazakhstan Institute of Experimental Mineralogy Russian Academy of ([email protected]) Sciences, ul. Ak. Osip’yana, 4 , Chernogolovka, Moscow 2Sobolev Institute of geology and mineralogy SB RAS, region, (*correspondence: [email protected]) Novosibirsk, Russia ([email protected]) 3TOO “Altaiski GEI”, Ust-Kamenogorsk, Kazakhstan Based on the experimental data at 7.0-8.5 GPa [1] rare 4Novosibirsk State University, Novosibirsk, Russia elements (RE) in the diamond-forming mantle peridotite- 5Tomsk State University, Tomsk, Russia carbonatite and eclogite-carbonatite systems are characterized RE by similar partitioning coefficients (KD ) mineral-melt. These Zaisan structural zone refers to traditional auriferous values are also closely comparable with those for the silicate region of East Kazakhstan [1]. This zone includes paleozoic and carbonatite melts in equilibrium with mantle silicate ofiolites and volcanic-sedimentary sequences, those were minerals [2]. formed as the result of oblique collision of Kazakhstan and It can be assumed that a chamber of diamond-forming Siberian paleocontinents [2]. Terrigen-carbonate sedimentary melts was formed witin the host garnet lherzolite mantle when sequences are characterized by high contents of gold, but the it was affected by a reactive "metasomatic agent» [2, 3]. It is ore deposits are associated with the introduction of of interest to identify those RE that came to diamond-forming granodiorite-plagiogranite collision magma (Kunush complex, melts with the mantle components, as well as those RE that 310-300 Ma). In result of acid magmas and carbonates were infused by the "metasomatic agent". interaction were formed Carlin-type gold-sulfide jasperoids The contents of RE in diamond-forming carbonatite melt [3]. This type includes the Suzdal deposit, and a number of chambers were calculated based on the real content of RE in promising gold objects (Baibura, Jhaima, etc.)[2]. In the minerals of peridotite and eclogite parageneses in diamonds article it is given the characteristic of Baibura ore field. Native and diamond xenoliths of several kimberlite pipes [4-6] and RE gold from this ore field jasperoids is uniform in morphology experimental KD . The main contribution of RE in them is and geochemical features. The most part of gold granes is of made by the mantle component. Parental melt of diamonds medium and fine dimension, preferably <0.25 mm. Gold and inclusions in them are depleted by medium (Sm, Eu, Gd) granes are not rounded, of yellow color and interstiton, rarely and heavy RE (Tb, Dy, Ho, Er, Yb, Lu, Hf), in contrast to crystal, morphology. Grade of gold indicates the unity of its primitive peridotite [7]. They are enriched in light (Sc, Rb, Sr, source and the one-step process of its formation, lying in a Ba, La, Ce, Pr, Nd) RE and Nb, but their content by 1-2 orders narrow range of values 923-959‰. It was indicated the of magnitude lower than in the primitive mantle peridotite. impurity of mercury in amounts up to 0.7%. Presence of High Sr can be associated with "the metasomatic agent". mercury confirms ore field belonging to the Carlin-type gold Support: Grants of the President # @S-1386.2013.5, the mineralization. Ministry of education and science of Russia (agreements 8317, 8378) D RFBR grant 11-05-00401, 12-05-33044, 13-05- [1] Narseev V.A. (2002) Ores and Metals, 1, 67-70. [2] 00835. Dyachkov B.A., et al. (2009) Ores and Metals, 3, 1-21. [3] Emsbo P., et al. (1999) Geology, 27, 59-62. [4] Kovalev K.R., [1] Kuzyura et al. (2013) DES. in print. [2] Litvin (2011) et al. (2012) Geology of ore deposits, 54, 4, 305-328. H.DES RAS 3, NZ6066. [3] Litvin et al. (2012) GeoChem. Int. 9, 818-847. [4] Harte & Kirkley (1997) ChemG 136, 1–24. [5] Ionov (2004). J.Pet. 45, 343–36. [6] Stachel & Harris (1997) CMP 127, 336-352. [7] Lyubetskaya & Korenaga (2007) JGR 112, B3.

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Mechanisms of replacement reactions Vertical lithofacies changes of the of single cerussite PbCO3 crystals by Jeonchong tuff cone in the Miocene pyromorphite, mimetite and Eoil Basin, SE Korea: Implication of vanadinite a series of eruptive and depositional MONIKA KWA(NIAK-KOMINEK1 AND MACIEJ MANECKI1 processes 1AGH – University of Science and Technology, Krakow, C.W. KWON Poland ([email protected]) Geological Research Division, Korea Institute of Geosciences

and Mineral Resource, SE Korea ([email protected]) Formation of thermodynamically stable phases like pyromorphite Pb (PO ) Cl, mimetite Pb (AsO ) Cl and 5 4 3 5 4 3 The Miocene Eoil Basin, SE Korea, contains abundant vanadinite Pb (VO ) Cl are common in the environment. It is 5 4 3 volcanic and volcaniclastic deposits because of active hypothesised here that lead carbonate PbCO , cerussite, can be 3 volcanism during basin formation. The Jeonchon tuff cone readily replaced by polycrystalline lead apatites. This process refers to an about 25 m-thick sequence of basaltic lapilli tuff in is analogous to the calcium carbonate – calcium the central part of the basin. The tuff cone is underlain by hydroxylapatite system, where such transformation is pahoehoe lavas (the Lower Eoil Basalt), lacustrine mudstone, observed. However, the mechanisms of formation of and mouth-bar sandstone in ascending order, indicating pyromorphite, mimetite and vanadinite in the presence of hydrovolcanic eruption in a shallow lake. It is composed of cerussite are unknown. seven sedimentary facies: massive tuff breccia (TBm), crudely The aim of this study was to experimentally determine the stratified lapilli tuff (LTb), inverse-to-normally graded lapilli mechanism of the transformation of cerussite to pyromorphite, tuff (LTin), normally graded lapilli tuff (LTn), massive coarse mimetite and vanadinite and the conditions under with these tuff ( Tm) and massive medium to fine tuff ( Tm & Tm). It phases can form. The parameters of the experiments include C M F can be divided into five depositional units (unit I to V in pH (alkalic or acidic), the presence or absence of chloride ion, ascending order) based on facies characteristics and and temperature (140 or 5 °C). Experiments were carried out componentry. Unit I, about 4 m thick, consists of quartz- in order to produce partially reacted crystals to provide bearing massive tuffs ( Tm & Tm), suggesting contact- information about structural and textural relationships between M F surface steam explosivity within mouth-bar sand. Unit II, parent and product phases. Cerussite crystals were put into 2M about 1.5 m thick, consists of graded lapilli tuffs (LTin & (NH )H PO , 2M (NH )H VO or 2M (NH )H AsO to form 4 2 4 4 2 4 4 2 4 LTn) with abundant accidental basalt clasts, suggesting bulk- pyromorphite, vanadinite and mimetite, respectively. interaction steam explosivity within the Lower Eoil Basalt and X-Ray powder diffraction was used to identify and deposition from pyroclastic surges and ballistic fallouts of characterize the reaction products. Microstructural relationship basalt clasts. Unit III consists of tuff breccia (TBm; about 3.5 between parent and product phases were determined by m thick) and overlying stratified lapilli tuff (LTb; about 0.5 m scanning electron microscopy (SEM-EDS) and electron thick), which are interpreted to have resulted from debris microprobe analysis. flows and Surtseyan fallouts associated with vent-widening In every case single cerussite crystal were replaced by explosions. Unit IV, 0.8 m-thick and composed of massive pollycrystaline pyromorphite, mimetite and vanadinite through coarse tuff ( Tm), suggests remobilization of pyroclasts by dissolution of PbCO followed by precipitation of lead apatite. C 3 debris flows during volcanic quiescence. Crudely stratified In acidic conditions formation of shultenite PbHAsO or 4 lapilli tuff (LTb) of Unit V, about 15 m thick, is interpreted to phospho-shultenite PbHPO were also observed. Products of 4 have formed by sustained Surtseyan finger jets without further the reaction in every case are porous, allowing fluid transport excavation of the substrate. The vertical lithofacies changes to the reaction interface. At all temperatures the product phase suggest that the Jeonchon tuff cone experienced a series of and its morphology are the same. Interface coupled eruptive and depositional processes during growth because of dissolution-precipitation mechanisms are confirmed by the the changes in depositional environments, types of the textural relationships. substrate (sand vs. lava), and vent geometry. This project is supported by Polish NCN grant No 2011/01/M/ST10/06999.

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Geochemical characteristics and Titanite Geochronology by microbial community composition of LA-ICPMS: Advantages and Future toxic metal-rich sediments Objectives contaminated from mine tailings ANDREW R.C. KYLANDER-CLARK, BRADLEY R. 123 1 1 1 HACKER, PAUL R. RENNE AND MICHAEL A. STEARNS MAN JAE KWON , BAKNOON HAM , YUNHO HWANG , JAEYOUNG CHOI1, MAXIM BOYANOV2, KEN KEMNER2, 1University of California, Santa Barbara, 93106-9630 EDWARD O’LOUGHLIN2 AND JUNG-SEOK YANG1 2Berkeley Geochron Center, Berkeley, CA 94709 1 *correspondence: [email protected] Korea Institute of Science and Technology (KIST) –

Gangneung Institute, Gangneung 210-340 S. Korea, Titanite has been dated by U/Pb TIMS for many years, but [email protected] 2 the application of this technique has been tempered by the Biosciences Division, Argonne National Laboratory, Lemont, recognition that titanite in single samples can yield a range of IL 60439 USA dates, and moreover, titanite dating by TIMS relies on either

time/cost-intensive analysis of multiple titanite fractions, or on The effects of extreme geochemical conditions on Pb measurement of an assumed-coeval low-U/Pb phase, such microbial community composition were investigated using as feldspar, to establish an isochron. One of the great strengths two distinct sets of sediment samples collected near weathered of LA-ICPMS dating is rapid throughput; by analyzing many mine tailings from the Songcheon Au-Ag mine, Korea. One spots with differing concentrations of common Pb, isochrons set (SCH) was gray-colored and showed extraordinary can be established from titanite analyses alone, in a fraction of geochemical characteristics: As (6.7-11.5%), Pb (1.5-2.1%), the time it takes for a single TIMS analysis. Furthermore, Zn (0.1-0.2%), and pH (3.1-3.5). The other set (SCL) was measuring composition at the same time—in this case laser brown-colored and had As (0.3-1.2%), Pb (0.02-0.22%), and ablation split-stream ICP petrochronology (LASS)—allows Zn (0.01-0.02%) at pH of 2.5-3.1. Terminal Restriction one to discriminate among titanite populations. Fragment Length Polymorphism revealed that the bacteiral Here, we present two examples of the strength of the communities in SCL were more diverse than those in SCH. LASS technique on titanite: 1) grains from the Western The clones identified in SCL were closely related to Gneiss Region in Norway that (re)crystallized during acidophilic bacteria within the genus of Acidobacterium exhumation, and 2) those from volcanic tuffs at/near the (18%), Acidomicrobineae (14%), and Leptospirillum (10%). Cretaceous–Tertiary boundary. Both cases yield dates Most clones in SCH were closely related to Methylobacterium equivalent to those produced by conventional techniques. For (79%) and Ralstonia (19%), both of which are well-known the Norwegian samples, younger grains contain elevated Al, metal-resistant bacteria. The archaeal community in SCL was Ce/Ce*, and Eu/Eu* and depleted Fe,Ta,Zr,Hf, and LREE relatively simple: Thermogymnomonas (32%) and unclassified compared to the inherited portions of the grain, exemplifying Euryachaeota (48%). No archaeal community was detected in the opportunities this techinique offers with respect to SCH sediments. Although total As was extremely high, over understanding petrologic/geochemical systematics of 95% of it was in the form of scorodite (FeAsO ·2H O), as 4 2 metamorphic/igneous processes. confirmed by XAFS analysis. Water-soluble As was only Although natural standards exist with little variability in ~208 and ~0.06 ppm in SCH and SCL, respectively, which is age, the incorporation of variable amounts of common Pb not known to be toxic to bacteria; As(V) as much as 1000- results in variable 23XU/20XPb ratios, thus negating the use of 1300 ppm did not influence bacterial growth. Because As was that material as a primary reference material. New standards present in an oxidized and stable form it is likely that other (natural or synthetic) and/or data processing methods are metals released from the sediment were responsible for the required to enhance the effectiveness of this technique in the differences in microbial community structure (e.g., water future. soluble Zn was ~234 and ~6.8 ppm in SCH ad SCL, repectively).

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Novel applications of geochemistry to mineral exploration and remediation KURT KYSER Department of Geological Science and Geological Engineering, Queen’s University, Canada ([email protected])

Mineral deposits are in fact geochemical anomalies, and as such their detection and assessment of their impact on the environment should be facilitated using geochemical techniques. Although geochemistry has been used directly in the discovery of mineral deposits and more indirectly in shaping deposit models, much of the novel application of geochemistry is in formulating effective exploration and remediation strategies. Areas where recent research, application and policy intersect in the extraction of metals from the geosphere include: (1) the use of element mobility in the near surface environment to detect deposits at depth, (2) revealing element distributions in and around deposits to adequately assess the total chemical environment associated with the deposit and to refine effective and relatively beneign extraction and waste disposal techniques, (3) understand the effects of both macro- and micro-environments on element mobility across the geosphere-biosphere interface to define appropriate remediation techniques associated with the extraction of diverse commodities. Research, both pure and applied, play a fundamental role in providing the techniques for these areas, but this is driven largely by what industry requires, which is driven largely by policies formulated in government agencies. Research in applied geochemistry can add value to exploration and remediation stratigies provided the results are adequately conveyed to the appropriate individuals in both industry and government and there is a perceived need to develop new and novel techniques by all concerned. For example, the application of isotope tracing to elucidate the processes by which various elements move through the geosphere and into the biosphere is a novel area of research with boundless potential for exploration and remediation. This area, which is largely driven by those in research, is an evolving one wherein the historically high costs, slow turnover and general mystic are being overcome by a concerted need by all involved to better understand the processes mining has on the total environment.

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