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10Th Applied Isotope Geochemistry Conference

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10Th Applied Isotope Geochemistry Conference 10TH APPLIED ISOTOPE GEOCHEMISTRY CONFERENCE 22–27 SEPTEMBER 2013, BUDAPEST, HUNGARY Hungarian Academy of Sciences Széchenyi István tér 9, H-1051 Budapest, Hungary Central European Geology, Vol. 56/2–3, pp. 1–280 (2013) DOI: 10.1556/CEuGeol.56.2013.2–3.1 002 – DIRECT MEASUREMENT OF PORE WATER d2H AND d18O FROM DRILL CORE SAMPLES VIA H2O(LIQUID) –H2O(VAPOUR) EQUILIBRIUM LASER SPECTROSCOPY Richard Crane1,2 – Adam Hartland3 – Wendy Timms2,4 1School of Civil and Environmental Engineering, University of New South Wales, Sydney, NSW, Australia; e-mail: [email protected] 2National Centre for Groundwater Research and Training 3Chemistry Department and Environmental Research Institute, University of Waikato, New Zealand 4School of Mining Engineering, University of New South Wales, Sydney, NSW, Australia and Australian Centre for Sustainable Mining Practices In the current work a new method to extract and analyse pore water d2H and d18O from drill core samples via H2O(liquid) –H2O(vapour) equilibrium laser spectroscopy is pre- sented. The method combines a H2O(liquid) –H2O(vapour) equilibrium cell with a Los Gatos Research (LGR) cavity ring down mass spectrometer (CRDS) and follows and adaption of the original method presented by Wassenaar et al. (2008). Sediment and rock samples taken from a research site in New South Wales, Australia were first equilibrated in a fixed volume of dehumidified air and then directly sampled by the LGR mass spectrometer. Results provide clear evidence that the technique is repeat- able and can be conducted on geologic media that contain volumetric water content as low as 5%, with H2O(liquid) –H2O(vapour) equilibrium occurring over time periods as short as 120 minutes. The faster sample analysis time and lower associated consum- able and instrumentation costs of the method compared to conventional techniques for pore water extraction (centrifugation, squeezing, installation of monitoring bores, etc.) and analysis therefore presents great potential for field deployment, enabling hydro- geological profiling without the need to remove drill core samples from site. Reference Wassenaar, L.I., Hendry, M.J., Chostner, V.L. and Lis, G.P., High resolution pore water d2H and d18O measurements by H2O(liquid) –H2O(vapour) equilibrium laser spectroscopy. Environ. Sci. Technol., 42, pp. 9262–9267, 2008. 1788-2281/$20.00 © 2013 Akadémiai Kiadó, Budapest 2 AIG10 – 2013 003 – ORIGIN OF NATURAL GAS-FED “ETERNAL FLAMES” IN THE NORTHERN APPALACHIAN BASIN, USA Arndt Schimmelmann1 – Giuseppe Etiope2 – Agnieszka Drobniak3 1Department of Geological Sciences, Indiana University, Bloomington, Indiana, USA; e-mail: [email protected] 2Istituto Nazionale di Geofisica e Vulcanologia, Roma, Italy, and Faculty of Environmental Science and Engineering, Babes-Bolyai University, Cluj-Napoca, Romania 3Indiana Geological Survey, Indiana University, Bloomington, Indiana, USA Natural hydrocarbon gas seeps are surface expressions of petroleum seepage systems, where gas ascends through faults and conduits from pressurized reservoirs that are typ- ically associated with conventional reservoirs in sandstones or limestones. These rare natural gas seeps provide opportunities for direct sampling of gas from subsurface hy- drocarbon accumulations without the need for drilling or other costly means of petro- leum exploration. Figure 1. Eternal flames behind the veil of a waterfall in Chestnut Ridge County Park in New York State (left) and near Clarington in Pennsylvania (right) We have documented a site in the northern Appalachian Basin, at Chestnut Ridge County Park, New York (Fig. 1, left), where gas seepage has supported a spec- tacular “eternal flame” throughout available recorded history, and which may have burnt naturally for many hundreds or even thousands of years. This remarkable flame marks a natural gas macroseep of dominantly thermogenic origin. Gas emanates di- rectly from deep shale source rocks, probably the Rhinestreet Shale of the Upper De- vonian West Falls Group, which makes this a rare case in contrast to most petroleum seepage systems where gas derives from conventional reservoirs. The main flaming seep releases about 1 kg of methane per day and seems to fea- ture the highest ethane and propane (C2 +C3) concentration ever reported for a natural gas seep (~35 vol. %). The same gas is also released to the atmosphere from the ground through nearby invisible and diffuse seepages. The comparison of our chemical and Central European Geology 56, 2013 22–27 September, Budapest, Hungary 3 stable isotope data with available gas-geochemical data of reservoir gases in the re- gion and the stratigraphy of underlying shales suggests that the thermogenic gas origi- nates from Upper Devonian shales without intermediation of a conventional reservoir (Fig. 2). Figure 2. Isotopic composition of methane of seep gases from Chestnut Ridge County Park (New York State, p) and Clarington (Pennsylvania, r) compared with published data on shale gases and conventional reservoir gases in the Northern Appalachian Basin. TO = thermogenic gas with oil; TC = thermogenic gas with condensate; TD = dry thermogenic gas; Ro: vitrinite reflectance index; NY: New York; OH: Ohio; PA: Pennsylvania. Data sources cited in Etiope et al. (in press) A burning seep near Clarington, Pennsylvania (Fig. 1, right), also releases thermogenic gas, but may not represent a natural seep. Instead, the gas likely derives from a conventional reservoir in Venango sandstone (Devonian) and is transmitted to the surface through an abandoned and improperly sealed gas or oil well. Reference 1. Etiope, G., Drobniak, A. and Schimmelmann, A. (in press): Natural seepage of shale gas and the origin of “eternal flames” in the Northern Appalachian Basin, USA. Mar. Pet. Geol. http://dx.doi.org/10.1016/j.marpetgeo.2013.02.009. Central European Geology 56, 2013 4 AIG10 – 2013 004 – APPORTIONING OF A THALLIUM CONTAMINATION TO THE EMITTER BY ITS STABLE ISOTOPE COMPOSITION Michael Kersten1 – Katharina Kreissig2 – Mark Rehkämper2 1Geosciences Institute, Gutenberg-University, Mainz 55099, Germany; e-mail: [email protected] 2Department of Earth Science and Engineering, Imperial College, London SW7 2AZ, UK Thallium compounds are volatile at high temperature and not efficiently retained by emission control facilities of combustion sources. This study represents the first use of stable isotope ratios to apportion near-source Tl deposition to the emitter. In 1979, dust containing Tl was emitted by a cement plant near Lengerich, NW Germany. The emis- sion event was caused by a ferric oxide additive used for the production of special ce- ments, but which contained a Tl-bearing residue of pyrite roasting. Following the emission event, sheep died and rabbits and horses were reported to loose fur and hair in the vicinity of the cement plant [1]. Yet, the cement plant owners denied responsibility for the bulk of the emissions. We determined the Tl isotope composition (e205Tl) by a sophisticated methodology detailed elsewhere [2]. The e205Tl values of the cement dust (black symbol) and soil cores down to 100 cm depth (open symbols) are in accord with a two-source mixing line due to the high-T process emissions (Fig. 1). Our novel isotope analysis approach ultimately helped the plaintiffs to settle the case by showing the causation of the pollution event, even though the emissions happened more than 30 years ago. Figure 1. Tl stable isotope data vs. inverse concentrations for soil samples of increasing depth from left to right Central European Geology 56, 2013 22–27 September, Budapest, Hungary 5 References 1. J. Schoer, Thallium. In: O. Hutzinger (ed.), Handbook of Environmental Chemistry, Vol. 3, Part C. Springer, New York, pp. 143–214, 1984. 2. M. Rehkämper and S.G. Nielsen, The mass balance of dissolved thallium in the oceans. Mar. Chem., 85, pp. 125-139, 2004. 005 – SHRIMP FARM FEED: WHERE DOES THE CARBON GO? Leonel da Silveira Lobo Sternberg1 – Carlos Augusto Ramos e Silva2,3 – Pablo Bezerra Dávalos2 1Department of Biology, University of Miami, Coral Gables, Florida 33124, USA; e-mail: [email protected] 2Departamento de Oceanografia e Limnologia, Universidade Federal do Rio Grande do Norte, Natal/RN, CEP 59075-970, Brazil; e-mails: [email protected], [email protected] 3Programa de Pós-Graduação em Dinâmica dos Oceanos e da Terra, Universidade Federal Fluminense, Niterói/RJ, Caixa Postal: 106051, CEP: 24230-971, Brazil; e-mail: [email protected] Net profits from shrimp farming can run in billions of U.S. dollars with Thailand and China being the leading producers followed by other Asian and Latin American Coun- tries. Feeding shrimp in intensive shrimp farms is one of the most expensive endeavours during the maintenance of the pond. Feed can vary in composition depend- ing on the brand, some providing a mixture of ground fishmeal others providing terres- trial animal and plant proteins. In addition to causing a significant impact on wild fish stocks, use of feed promotes eutrophication and the ensuing anoxic conditions. The latter of which, makes it necessary to artificially aerate pond water by agitation with motor driven paddles. Further, the introduction of feed can promote viral, bacterial and fungal parasites in the shrimp population. We show here, with stable carbon isotope analysis, that adding organic feed to shrimp ponds, with its ensuing environmental problems, provides little if any carbon to shrimp biomass. Most of the carbon from the organic feed is deposited in the sediment and not available for consumption. Results of our findings suggest that intensive shrimp farmers should reconsider the use of organic feed and thereby mitigate some of the environmental problems associated with shrimp farming. References 1. L.S.L. Sternberg and C.A. Ramos e Silva, Traçadores isotópicos. (In: Oceanografia Química. Interciência, Rio de Janeiro, Chapter 5, 2011, pp. 147–188. 2. C.A. Ramos e Silva, P.B. Dávalos, L.S.L. Sternberg, F.E.S. Souza, M.H.C. Spyrides and P.S. Lucio, The influence of shrimp farms organic waste management on chemical water quality. Estuarine, Coastal and Shelf Science, 90, pp. 55–60, 2010.
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