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Sample records for geological sulfur isotopes

  1. Sulfur isotopic composition of modern seafloor hydrothermal sediment and its geological significance

    Institute of Scientific and Technical Information of China (English)

    曾志刚; 李军; 蒋富清; 秦蕴珊; 翟世奎

    2002-01-01

    A total of 1 264 sulfur isotopic values for modem seafloor hydrothermel sediments from different hydrothermal fidds have been collected. On this basis, combining our sulfur isotpic data for surface hydrothermal sediments from the Jade hydrohtermal field in the Okinawa Trough and the TAG hydrothermal field in the Mid-Atlantic Ridge, respectively, and comparing the sulfur isotopic compositions and analyzing their sources of sulfur in seafloor hydrothermal sediments from different geologic-tectonic setting, the results show that: ( 1 ) sulfur isotopic values of sulfides and sulfates in modern seafloor hydrothermal sediments are concentrated in a narrow range, δ34S values of sulfides vary from l × 10-3 to 9 × 10- 3, with a mean of 4.5 × 10- 3 ( n = 1 042), δ34S values of sulfates vary from 19 × 10- 3 to 24× 10-3, with a mean of 21.3× 10-3 (n =217); (2) comparing the sulfur isotopic compositions of hydrothermal sediments from the sediment-hosted hydrothermal fields, the range of sulfur isotopic values for hydrothermal sediments from the sediment-free hydrothermal fields is narrow relatively; (3) the differences of sulfur isotopic compositions in sulfides from different hydrothermal fields show the differences in the sources of sulfur. The sulfur of hydrothermal sulfides in the sediment-free mid-ocean ridges is mainly from mid-ocean ridge basalt, and partially from the reduced seawater sulfate, and it is the result of partially reduced seawater sulfate mixed with basaltic sulfur. In the sediment-hosted nid-ocean ridges and the back-arc basins, the volcanics, the sediments and the organic matters also can offer their sulfur for forming hydrothermal sulfides; (4) the variations of sulfur isotopic compositions and the different sources of sulfur for hydrothermal sediments may be attributed to the various physical-chemical characteristics of hydrothermal fluids, the magmatic evolution and the different geologic-tectonic settings of seafloor hydrothermal systems.

  2. Geological Sulfur Isotopes Indicate Elevated OCS in the Archean Atmosphere, Solving the Faint Young Sun Paradox

    DEFF Research Database (Denmark)

    Ueno, Yuichiro; Johnson, Matthew Stanley; Danielache, Sebastian Oscar

    2009-01-01

    Distributions of sulfur isotopes in geological samples would provide a record of atmospheric composition if the mechanism producing the isotope effects could be described quantitatively. We determined the UV absorption spectra of 32SO2, 33SO2, and 34SO2 and use them to interpret the geological re......-rich, reducing Archean atmosphere. The radiative forcing, due to this level of OCS, is able to resolve the faint young sun paradox. Further, the decline of atmospheric OCS may have caused the late Archean glaciation....

  3. Geology and stable isotope geochemistry of Paleoarchean sulfur. Formation, preservation and geobiology of ancient pyrite and barite

    NARCIS (Netherlands)

    Roerdink, D.L.

    2013-01-01

    Sulfur isotopes in ancient sulfate and sulfide minerals provide a comprehensive record of microbial processes involved in the early sulfur cycle on Earth. However, the interpretation of these isotopic signatures requires information on the geological context of such samples, because abiotic reaction

  4. Geological sulfur isotopes indicate elevated OCS in the Archean atmosphere, solving faint young sun paradox

    Science.gov (United States)

    Ueno, Yuichiro; Johnson, Matthew S.; Danielache, Sebastian O.; Eskebjerg, Carsten; Pandey, Antra; Yoshida, Naohiro

    2009-01-01

    Distributions of sulfur isotopes in geological samples would provide a record of atmospheric composition if the mechanism producing the isotope effects could be described quantitatively. We determined the UV absorption spectra of 32SO2, 33SO2, and 34SO2 and use them to interpret the geological record. The calculated isotopic fractionation factors for SO2 photolysis give mass independent distributions that are highly sensitive to the atmospheric concentrations of O2, O3, CO2, H2O, CS2, NH3, N2O, H2S, OCS, and SO2 itself. Various UV-shielding scenarios are considered and we conclude that the negative Δ33S observed in the Archean sulfate deposits can only be explained by OCS shielding. Of relevant Archean gases, OCS has the unique ability to prevent SO2 photolysis by sunlight at λ >202 nm. Scenarios run using a photochemical box model show that ppm levels of OCS will accumulate in a CO-rich, reducing Archean atmosphere. The radiative forcing, due to this level of OCS, is able to resolve the faint young sun paradox. Further, the decline of atmospheric OCS may have caused the late Archean glaciation. PMID:19706450

  5. Geology and stable isotope geochemistry of Paleoarchean sulfur. Formation, preservation and geobiology of ancient pyrite and barite. (Utrecht Studies in Earth Sciences 031)

    NARCIS (Netherlands)

    Roerdink, D.L.

    2013-01-01

    Sulfur isotopes in ancient sulfate and sulfide minerals provide a comprehensive record of microbial processes involved in the early sulfur cycle on Earth. However, the interpretation of these isotopic signatures requires information on the geological context of such samples, because abiotic reaction

  6. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141014Wang Hairan(State Key Laboratory of Continental Dynamics,Department of Geology,Northwest University,Xi’an710069,China);Zhao Hongge Theory and Application of Zircon U-Pb Isotope Dating Technique(Geology and Resources,ISSN1671-1947,CN21-1458/P,22(3),2013,p.229

  7. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    <正>20050934 Chen Zhihong (Chinese Academy of Geological Sciences, Beijing 100037, China); Lu Songnian Age of the Fushui Intermediate-Mafic Intrusive Complex in the Qinling Orogen, New Zircon U - Pb and Whole -Rock Sm and Nd Isotope Chronological Evidence (Geological Bulletin of China, ISSN 1671-2552, CN11-4648/P, 23(4), 2004, p. 322-328, 3 illus. , 3 tables, 10 refs. )

  8. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20132601 Cui Yurong(Tianjin Institute of Geology and Mineral Resources,China Geological Survey,Tianjin 300170,China);Zhou Hongying In Situ LA-MC-ICP-MS U-Pb Isotopic Dating of Monazite(Acta Geoscientica Sinica,ISSN0375-5444,CN11-1856/P,33(6),2012,p.865-876,6illus.,4tables,41refs.)Key words:monazite,U-Pb dating

  9. GEOCHRONOMETRY ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20040631 Chen Jiangfeng (School of Earth and Space Sciences, University of Science and Technology of China, Hefei, Anhui) ; Xie Zhi Relationships Between Rb-Sr, Ar - Ar Geochronometers and Oxygen Isotopic Equilibrium of Intrusions from Eastern Anhui Province, China (Geological Journal of China Universities, ISSN 1006 - 7493, CN 32 -

  10. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20090432 Zhou Shuqing (School of Energy Resources, China University of Geosciences Beijing 100083, China); Huang Haiping Stable Isotopic Records vs. Important Events in Life Evolution and the Concurrent Environment (Geological Review, ISSN0371-5736, CN11-1952, 54(2), 2008, p.225-231, 3 illus., 1 table, 77 refs.)

  11. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072750 Huang Sijing(State Key Laboratory of Oil/Gas Reservoir Geology and Exploitation,Chengdu University of Technology,Chengdu 610059,China);Pei Changrong Age Calibration for the Boundary between Lower and Middle Triassic by Strontium Isotope Stratigraphy in Eastern Sichuan Province

  12. Sulfur isotopic composition of seafloor hydrothermal sediment from the Jade hydrothermal field in the central Okinawa Trough and its geological significance

    Institute of Scientific and Technical Information of China (English)

    曾志刚; 李军; 蒋富清; 翟世奎; 秦蕴珊; 侯增谦

    2002-01-01

    --Eighteen samples of hydrothermal sediments from the Jade hydrotherrnal field in the central Okinawa Trough have been analyzed. Sulfur isotopic values for 10 sulfide samples vary from 5.2 ×10-3to 7.2× 10-3, δ34S valUes for 7 sulfate samples vary from 16.3 × 10-3 to 22.3 × 10-3, and 1 native sulphur sample has a δ34S value of 8.2 × 10-3. The major sources of sulfur for hydrothermal sediment are intermediate to acid volcanic rocks and sea water sulfate, and it is possible that the partial sulfur of hydrothermal sediment is from the pelagic sediment by the interaction between hydrothermal fluid and sediment. The reasons of causing the distinct differences in sulfur isotopic values for sulfide samples from hydrothermal sediment ( compared with other hydrothermal fields), are the differences in the sources of sulfur, the magmatic activity and the tectonic evolution in different hydrothermal fields. The sulfur evolution is a long and complex process in the seafloor hydrothermal system, involving the ascending of heating sea water, the interaction between fluid and volcanic rocks, the mixing of sea water sulfate and sulfur from intermediate to acid volcanic rocks, and the fluid/pelagic-sediment interaction. And the interaction between sea water and intermediate to acid volcanic rocks is an important mechanism for the sulfur evolution in the Jade hydrothermal field.

  13. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20101892 Guo Hongjun (Tianjin Geological Exploration General Survey,Tianjin 300181,China);Lin Xiaohui The Precambrian Geological Characteristics of Kigoma-Mpanda Region,Tanzania and the New Data of U-Pb Age Determination on Zircon

  14. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>20081140 Cheng Peng(State Key Laboratory of Loess and Quaternary Geology,Institute of Earth Environment,CAS,Xi’an 710075,China);Zhou Weijian Advances in Radiocarbon Dating Researches in the Loess-Paleosol Sequences(Marine Geology & Quaternary Geology,ISSN0256-1492,CN37-

  15. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20042213 Chen Qinghua (Department of Geology,Northwest University, Xi’an, Shaanxi); Liu Chiyang The Mathematical Representations and Their Significance of Geological Age with Milankovitch Theory (Journal of Northwest University (Natural Science Edition), ISSN1000 - 274X, CN61 -1072/N, 33(5), 2003, p. 599-602, 27 refs. )

  16. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20091213 Deng Xiaodong(State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074,China);Li Jianwei 40Ar/ 39Ar Geochronology of Weathering Crust: Significance,Problems,and Prospect(Geo-

  17. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141655 Gao Linzhi(Institute of Geology,CAGS,Beijing 100037,China);Ding Xiaozhong The Revision of the Chentangwu Formation in Neoproterozoic Stratigraphic Column:Constraints on Zircon U-Pb Dating of Tuff from the Mengshan Section in Pujiang County,Zhejiang Province(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(7),2013,p.988-995,5 illus.,1 plate,2 tables,24 refs.)

  18. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20041584 Cheng Hai (Department of Geology & Geophysics, University of Minnesota, Minneapolis, United States); Lawrence, R. U/Th and U/Pa Dating of Nanjing Man, Jiangsu Province (Geological Journal of China Universities, ISSN 1006 - 7493, CN 32 -1440/P, 9(4), 2003, p. 667-677, 2 illus. , 2 tables, 28 refs. , with English abstract) Key words: Homo erectus, Nanjing, Jiangsu Province

  19. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072068 Duo Ji(Bureau of Geology and Mineral Resources of Tibet Autonomous Region,Lhasa,Tibet 850000);Wen Chunqi Detrital Zircon of 4 100 Ma in Quartzite in Burang,Tibet(Acta Geologica Sinica(English Edition)--Journal of the Geological Society of China,ISSN1000-9515,CN11-2001/P,80(6),2006,p.954-956,2 illus.,1 table,19 refs.)

  20. GEOCHRONOMETRY&ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20071262 Gong Gelian(Guangzhou Institute of Geochemistry,CAS,Guangzhou 510064, China)Luminescence Dating for Environ- mental Evolution Study in Terrestrial Land, Deep Sea and Coastal Belts:A Review(Ma- rine Geology & Quaternary Geology,ISSN 0256-1492,CN37-1117/P,26(2),2006, p.133-138,2 illus.,34 refs.,with English abstract) Key words:thermoluminescent dating

  1. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111126Ji Honglei(Institute of Hydrogeol-ogy and Environmental Geology,CAGS,Shi-jiazhuang050061,China);Zhao Hua Pre-liminary Study of Re-OSL on Water-De-posited Sediments(Seismology and Geology,ISSN0253-4967,CN11-2192/P,32(2),2010,p.320-326,4illus.,1table,10refs.)Key words:stream sediments,opticalstimulated luminescence dating,HebeiProvinceAccording to measuring the natural TT-OSL signals of the fine-grained quartzfrom both fluvial and lacustrine sediments,the dose recovery experiment and the comparison of the multiple aliquots

  2. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20070454 Bao Zengkuan (Institute of High Energy Physics, CAS, Beijing 100049, China); Yuan Wanming Apatite (U-Th)/He Dating and Its Application (Acta Petrologica et Mineralogica, ISSN1000-6524, CN11-1966/P, 24(2), 2005, p.126-132, 2 illus., 25 refs.) Key words: isotopic geochronology

  3. GEOCHRONOMETRY&ISOTOPE; GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    20151852 Chen Longyao(Institute of Geomechanics,Chinese Academy of Geological Sciences,Beijing100081,China);Luo Yuling LA-ICP-MS U-Pb Geochronology of Detrital Zircons from the Liuling Group in the South Qinling Tectonic Belt and Its Tectonic

  4. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20142333Liao Jin(State Key Laboratory of Biogeology and Environmental Geology,China University of Geosciences,Wuhan 430074,China);Hu Chaoyong Thermoluminescence Based Thermometer from Stalagmites(Quaternary Sciences,ISSN1001-7410,CN11-2708/P,33(6),2013,p.1122-1129,6illus.,1table,48refs.)

  5. GEOCHRONOMETRY &ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131727 Huang Xiaowen(State Key Laboratory of Ore Deposit Geochemistry,Institute of Geochemistry,Chinese Academy of Sciences,Guiyang 550002,China);Qi Liang Preliminary Study on Sample-Preparation for Re-Os Isotopic Dating of Pyrite(Geochimica,ISSN0379-1726,CN44-1398/P,41(4),2012,p.380-386,3illus.,2tables,25refs)Key words:pyrite,Re-Os dating

  6. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111901 Chen Yingtao(State Key Laboratory of Continental Dynamics,Department of Geology,Northwest University,Xi’an 710069,China);Zhang Guowei 40Ar/39Ar Geochronology of the Guozhacuo Fault in the Northwestern Margin of Qinghai-Tibet Plateau--New Evidence for the Western Extension of Altyn Tagh Fault(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,29(8),2010,p.1129-1137,2 illus.,1 table,44 refs.)Key words:Ar-Ar dating,Qinghai-Tibetan Plateau,Altun Fracture ZoneThe samples of mylonite were collected from the Guozhacuo fault,situated in the southwestern e

  7. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>20080453 Gu Zhaoyan(Institute of Geology and Geophysics,Chinese Academy of Sciences,Beijing 100029);Guo Zhengtang 10 Be Concentration Relation to Chemical Compositions of Chinese Loess and Red Clay as a Potential Dating Method(Quaternary Sciences,ISSN1001-7410,CN11-2708/P,26(2),2006,p.244-249,3 illus.,1 table,21 refs.)

  8. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    <正>20122601Cao Kai ( State Key Laboratory ofGeological Processes and Mineral Resources,China University of Geosciences,Wuhan 430074,China );Wang Guocan Restriction on the Application of Thermochronologic Age-Temperature and Age-Elevation Relationships:Some Insights into Sampling Strategies and Age Interpretation ( Earth Science Frontiers,ISSN1005-2321,CN11-3370 / P,18 ( 6 ), 2011,p.347-357,3illus.,85refs. ) Key words:thermochronology

  9. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    20150416Cao Dadi(State Key Laboratory of Marine Geology,Tongji University,Shanghai200092,China);Cheng Hao Recent Advances in Garnet Lu-Hf Geochronology(Geochimica,ISSN0379-1726,CN44-1398/P,43(2),2014,p.180-195,9illus.,92refs.)Key words:Lu-Hf dating,garnet group Garnets with high Lu/Hf ratios can be used to construct high precise isochrones.The garnet Lu-Hf geochronology has been extensively applied in various types of rocks,especially in metamorphic rocks from the orogens.

  10. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20140393Liu Chunru(State Key Laboratory of Earthquake Dynamics,Institute of Geology,China Earthquake Administration,Beijing100029,China);Yin Gongming Research Progress of the Resetting Features of Quartz ESR Signal(Advances in Earth Science,ISSN1001-8166,CN62-1091/P,28(1),2013,p.24-30,3illus.,59refs.)Key words:ESR dating Electron Spin Resonance(ESR)has been becoming one of the key methods of Quaternary Geochronology with wide range of dating,

  11. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20110429 Chang Yuan(State Key Laboratory of Marine Geology,Tongji University,Shanghai 200092,China);Xu Changhai(U-Th)/He Dating Method:α-Ejection Influence and Correction(Advances in Earth Science,ISSN1001-8166,CN62-1091/P,25(4),2010,p.418-427,6 illus.,2 tables,53 refs.)Key words:He-He dating,Th-U datingAccording to the development of this technique,the factors which influence the helium dating results a

  12. Large sulfur isotope fractionations in Martian sediments at Gale crater

    Science.gov (United States)

    Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

    2017-09-01

    Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

  13. Microscale reservoir effects on microbial sulfur isotope fractionation

    Science.gov (United States)

    Louca, Stilianos; Crowe, Sean A.

    2017-04-01

    Microbial sulfate reduction can impart strong sulfur isotope fractionation by preferentially using the lighter 32SO42- over the heavier 34SO42-. The magnitude of fractionation depends on a number of factors, including ambient concentrations of sulfate and electron donors. Sulfur isotope compositions in sedimentary rocks thus facilitate reconstruction of past environmental conditions, such as seawater sulfate concentrations, primary productivity, organic carbon burial, and sulfur fluxes into or out of the ocean. Knowing the processes that regulate the magnitude of sulfur isotope fractionation is necessary for the correct interpretation of the geological record, but so far theoretical work has focused mostly on internal cellular processes. In sulfate-limited environments, like low sulfate lakes and the Archean ocean, microbial sulfate reduction can lead to sulfate depletion in the water column and an enrichment in isotopically heavy sulfate. This reservoir effect in turn mutes the fractionation expressed in the water column and ultimately preserved in sediments relative to the biologically induced fractionation. Here we use mathematical modeling to show that similar reservoir effects can also appear at the microscale in close proximity to sulfate-reducing cells. These microscale reservoir effects have the potential to modulate sulfur isotope fractionation to a considerable degree, especially at low (micromolar) sulfate concentrations. As a result, background sulfate concentrations, sulfate reduction rates, and extracellular ion diffusion rates can influence the fractionation expressed even if the physiologically induced fractionation is constant. This has implications for the interpretation of biogenic sulfur isotope fractionations expressed in the geological record, because the correct estimation of the environmental conditions that would promote these fractionations requires consideration of microscale reservoir effects. We discuss these implications, and

  14. Mixed Population Screening for Sulfur Isotopes

    Institute of Scientific and Technical Information of China (English)

    CUI Bin; ZHAO Lei; ZHAN Zhaoyang; HE Zhijun

    2004-01-01

    Quantitative research of the origin of sulfur isotopes is a difficult problem that has puzzled geochemists all along. In the study of the middle and lower reaches of the Yangtze River and the Dongpo orefield in Hunan Province,the authors successfully applied the mathematical model of mixed population screening to quantitatively resolving the problem on the origin of sulfur isotopes, which is significant in finding out the source of mineralizing matter and metallogenic mechanisms.

  15. Sulfur Isotopic Characteristics of Coal in China and Sulfur Isotopic Fractionation during Coal—burning Process

    Institute of Scientific and Technical Information of China (English)

    洪业汤; 张鸿斌; 等

    1993-01-01

    The determined results of the sulfur contents and isotopic composition of coal samples from major coal mines in 15 provinces and regions of China show that the coal mined in the north of China is characterized by higher 34S and lower sulfur content, but that in the south of China has lower 34S and higher sulfur content.During the coal-burning process in both indrstrial and daily use of coal as fuel the released sulfur dioxide is always enriched in lighter sulfur isotope relative to the corresponding coal;the particles are always enriched in heavier sulfur isotope.The discussion on the environmental geochemical significance of the above-mentioned results also has been made.

  16. Geology, ore facies and sulfur isotopes geochemistry of the Nudeh Besshi-type volcanogenic massive sulfide deposit, southwest Sabzevar basin, Iran

    Science.gov (United States)

    Maghfouri, Sajjad; Rastad, Ebrahim; Mousivand, Fardin; Lin, Ye; Zaw, Khin

    2016-08-01

    . Chloritization, silicification, sericitization and epidotization are the main wall-rock alterations; alteration intensity increases towards the stringer zone. The δ34S composition of the sulfides ranges from -1.5‰ to +3.69‰ with a general increase of δ34S ratios of massive ore facies to stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones. Sulfur isotopes, along with sedimentological, textural, petrological, mineralogical, and geochemical evidences, suggest that this deposit should be classified as a Besshi-type VMS ore deposit.

  17. Genesis of the Datuanshan stratabound skarn Cu(-Mo) deposit, Middle-Lower Yangtze Valley, Eastern China: constraints from geology, Re-Os geochronology, mineralogy, and sulfur isotopes

    Science.gov (United States)

    Cao, Yi; Gao, Fuping; Du, Yangsong; Du, Yilun; Pang, Zhenshan

    2016-07-01

    Stratabound deposits are the most abundant and economically significant ore type in the Middle-Lower Yangtze River Valley, one of the most important metallogenic belts in China. The Datuanshan deposit is one of the largest and most representative stratabound Cu(-Mo) deposits in the Tongling district of the Middle-Lower Yangtze River metallogenic belt. All the orebodies of the Datuanshan deposit occur around Mesozoic quartz monzodiorite and are tabular or semi-tabular bodies along bedding-parallel faults within upper Permian to Lower Triassic strata. However, discordant and crosscutting relationships (e.g., the host rocks crosscut by skarn- and quartz-sulfide veins, with alteration halos around the veins) have also been found, especially along the skarn-host contact and orebody-host contact, indicating that skarnitization and mineralization postdated the deposition of the host sediments. The skarn consists mainly of prograde garnet and pyroxene and retrograde alteration assemblages of amphibole, epidote, and chlorite, as well as quartz and sulfides. Electron microprobe analyses show that the garnets and pyroxenes are grossular-andradite and hedenbergite-diopside series, respectively, and all samples plot in the field of typical skarn copper deposits worldwide. Molybdenite samples from stratiform copper ores yield Re-Os model ages of 138.2-139.9 Ma with a weighted mean age of 139.2 ± 0.9 Ma. This is reasonably consistent with the ages of the stratiform Mo ores (138.0-140.8 Ma) and genetically related quartz monzodiorite (135.2-139.3 Ma) in the Datuanshan deposit, indicating that the stratiform Cu and Mo mineralization was contemporaneous with emplacement of the quartz monzodiorite magmas in the Early Cretaceous. Fifteen δ34S values for sulfides range from -1.8 to +4.7 ‰, with a mean of 0.5 ‰, indicating that the sulfur was derived mainly from a magmatic source. Moreover, the sulfur isotope values of the ores are consistent with those of Mesozoic intermediate

  18. Triple sulfur isotope composition of Late Archean seawater sulfate

    Science.gov (United States)

    Paris, G.; Fischer, W. W.; Sessions, A. L.; Adkins, J. F.

    2013-12-01

    Multiple sulfur isotope ratios in Archean sedimentary rocks have provided powerful insights into the behavior of the ancient sulfur cycle, the redox state of fluid Earth, and the timing of the rise of atmospheric oxygen [1]. Most processes fractionate sulfur isotopes in proportion to their mass differences, but the Archean sulfur isotope record is marked by pronounced mass-independent fractionation (MIF, Δ33S≠0). The origin of these signatures has been traditionally interpreted as the result of photolysis of SO2 from short wavelength UV light, with positive Δ33S values recorded in pyrite and negative Δ33S values in sulfate-bearing phases [2]. This long-held hypothesis rests on observations of negative Δ33S from enigmatic barite occurrences from mixed volcanic sedimentary strata in Mesoarchean greenstone terrains. Despite forming the framework for understanding Archean sulfur cycle processes [3], it is largely untested [3]. It is largely untested. Consequently, the biggest challenge to our current understanding of the early sulfur cycle is a poor understanding of the isotopic composition of seawater sulfate. Sulfate evaporite minerals are absent from Archean strata and the sulfur isotope record is written entirely by measurements of pyrite. Carbonate associated sulfate (CAS) provides an important archive for assaying the isotopic composition of ancient seawater sulfate It has been exploited in many studies of Phanerozoic and Proterozoic sulfate but have been only marginally used thus far for Archean samples because of the extremely low concentration of CAS in limestones and dolomites from this era. We have developed a novel MC-ICP-MS approach to solve this problem [4]. This new method lowers the detection limit by up to three orders of magnitude for δ34S and Δ33S measurements, enabling to work on a few nmols of sulfate which represent only tens of mg of sample powders micromilled from specific carbonate textures. Two stratigraphic sections from the 2

  19. High sulfur isotope fractionation associated with anaerobic oxidation of methane in a low sulfate, iron rich environment

    Directory of Open Access Journals (Sweden)

    Hannah Sophia Weber

    2016-06-01

    Full Text Available Sulfur isotope signatures provide key information for the study of microbial activity in modern systems and the evolution of the Earth surface redox system. Microbial sulfate reducers shift sulfur isotope distributions by discriminating against heavier isotopes. This discrimination is strain-specific and often suppressed at sulfate concentrations in the lower micromolar range that are typical to freshwater systems and inferred for ancient oceans. Anaerobic oxidation of methane (AOM is a sulfate-reducing microbial process with a strong impact on global sulfur cycling in modern habitats and potentially in the geological past, but its impact on sulfur isotope signatures is poorly understood, especially in low sulfate environments. We investigated sulfur cycling and 34S fractionation in a low-sulfate freshwater sediment with biogeochemical conditions analogous to Early Earth environments. The zone of highest AOM activity was associated in situ with a zone of strong 34S depletions in the pool of reduced sulfur species, indicating a coupling of sulfate reduction and AOM at sulfate concentrations < 50 µmol L-1. In slurry incubations of AOM-active sediment, the addition of methane stimulated sulfate reduction and induced a bulk sulfur isotope effect of ~29 ‰. Our results imply that sulfur isotope signatures may be strongly impacted by AOM even at sulfate concentrations two orders of magnitude lower than at present oceanic levels. Therefore, we suggest that sulfur isotope fractionation during AOM must be considered when interpreting 34S signatures in modern and ancient environment.

  20. Interstellar sulfur isotopes and stellar oxygen burning

    CERN Document Server

    Chin, Y N; Whiteoak, J B; Langer, N; Churchwell, E B; Chin, Y N

    1995-01-01

    A 12C32S, 13C32S, 12C34S, and 12C33S J = 2 - 1 line survey has been made to study interstellar 32S/34S and 34S/33S ratios from the galactic disk. The four CS isotopomers were detected in 20 star forming regions with galactocentric distances between 3 and 9 kpc. From a comparison of line velocities, the C33S J = 2 - 1 rest frequency is about 250 kHz below the value given in the Lovas (1992) catalog. Taking 12C/13C ratios from Wilson & Rood (1994) and assuming equal 12C32S and 13C32S excitation temperatures and beam filling factors, 12C32S opacities are in the range 3 to 15; average 32S/34S and 34S/33S isotope ratios are 24.4 +/- 5.0 and 6.27 +/- 1.01, respectively. While no systematic variation in the 34S/33S isotope ratio is found, the 32S/34S ratio increases with galactocentric distance when accounting for the 12C/13C gradient of the galactic disk. A fit to the unweighted data yields 32S/34S = 3.3 +/- 0.5 (dGC/kpc) + 4.1 +/- 3.1 with a correlation coefficient of 0.84. Since the interstellar sulfur (S) is...

  1. Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

    Science.gov (United States)

    Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

    2014-12-01

    Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

  2. Large Sulfur Isotope Fractionation Does Not Require Disproportionation

    Science.gov (United States)

    Sim, Min Sub; Bosak, Tanja; Ono, Shuhei

    2011-07-01

    The composition of sulfur isotopes in sedimentary sulfides and sulfates traces the sulfur cycle throughout Earth’s history. In particular, depletions of sulfur-34 (34S) in sulfide relative to sulfate exceeding 47 per mil (‰) often serve as a proxy for the disproportionation of intermediate sulfur species in addition to sulfate reduction. Here, we demonstrate that a pure, actively growing culture of a marine sulfate-reducing bacterium can deplete 34S by up to 66‰ during sulfate reduction alone and in the absence of an extracellular oxidative sulfur cycle. Therefore, similar magnitudes of sulfur isotope fractionation in sedimentary rocks do not unambiguously record the presence of other sulfur-based metabolisms or the stepwise oxygenation of Earth’s surface environment during the Proterozoic.

  3. Large sulfur isotope fractionation does not require disproportionation.

    Science.gov (United States)

    Sim, Min Sub; Bosak, Tanja; Ono, Shuhei

    2011-07-01

    The composition of sulfur isotopes in sedimentary sulfides and sulfates traces the sulfur cycle throughout Earth's history. In particular, depletions of sulfur-34 ((34)S) in sulfide relative to sulfate exceeding 47 per mil (‰) often serve as a proxy for the disproportionation of intermediate sulfur species in addition to sulfate reduction. Here, we demonstrate that a pure, actively growing culture of a marine sulfate-reducing bacterium can deplete (34)S by up to 66‰ during sulfate reduction alone and in the absence of an extracellular oxidative sulfur cycle. Therefore, similar magnitudes of sulfur isotope fractionation in sedimentary rocks do not unambiguously record the presence of other sulfur-based metabolisms or the stepwise oxygenation of Earth's surface environment during the Proterozoic.

  4. Mass-dependent sulfur isotope fractionation during reoxidative sulfur cycling

    DEFF Research Database (Denmark)

    Pellerin, André; Bui, Thi Hao; Rough, Mikaella

    2015-01-01

    of Mangrove Lake appears to include sulfide oxidation to elemental sulfur followed by the disproportionation of the elemental sulfur to sulfate and sulfide. This model also indicates that the reoxidative sulfur cycle of Mangrove Lake turns over from 50 to 80% of the sulfide produced by microbial sulfate...... that the two processes cannot be discriminated from each other....

  5. Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

    Science.gov (United States)

    Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

    1997-01-01

    Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

  6. Paleoarchean sulfur cycling : Multiple sulfur isotope constraints from the Barberton Greenstone Belt, South Africa

    NARCIS (Netherlands)

    Montinaro, Alice; Strauss, Harald; Mason, Paul R D; Roerdink, Desiree; Münker, Carsten; Schwarz-Schampera, Ulrich; Arndt, Nicholas T.; Farquhar, James; Beukes, Nicolas J.; Gutzmer, Jens; Peters, Marc

    2015-01-01

    Mass-dependent and mass-independent sulfur isotope fractionation archived in volcanic and sedimentary rocks from the Barberton Greenstone Belt (3550-3215. Ma), South Africa, provide constraints for sulfur cycling on the early Earth. Four different sample suites were studied: komatiites and tholeiite

  7. Sulfur Isotope Exchange between S-35 Labeled Inorganic Sulfur-Compounds in Anoxic Marine-Sediments

    DEFF Research Database (Denmark)

    FOSSING, H.; THODEANDERSEN, S.; JØRGENSEN, BB

    1992-01-01

    Isotope exchange reactions between S-35-labeled sulfur compounds were studied in anoxic estuarine sediment slurries at 21-degrees-C and pH 7.4-7.7. Two experiments labeled with radioactive elemental sulfur (S-35-degrees) and one labeled with radioactive sulfate ((SO42-)-S-35) were performed as time...

  8. Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana

    Science.gov (United States)

    Yaofa, Jiang; Elswick, E.R.; Mastalerz, Maria

    2008-01-01

    Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur ( 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in ??34S for sulfur species within and between the low-sulfur and high-sulfur coal. The ??34S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the ??34S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the ??34S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of ??34S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in ??34S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition. The ??34S values for fly ash from the high-sulfur Springfield coal (averaging 9.7???) are greatly enriched in 34S relative to those in the parent coal (averaging 2.2???). This indicates a fractionation of sulfur isotopes

  9. A Neogene seawater sulfur isotope age curve from calcareous pelagic microfossils

    Science.gov (United States)

    Burdett, James W.; Arthur, Michael A.; Richardson, Mark

    1989-09-01

    Until now, our knowledge of the sulfur isotopic composition of seawater through geologic time has depended on stable isotopic analysis of sulfate from evaporites. Owing to the sporadic occurrence of evaporites through time, the secular sulfur isotope age curve contains many gaps with little or no data. In order to fill in some of these gaps, particularly the Neogene, we have analyzed the sulfur isotopic composition of carbonate-associated sulfate in carbonate tests of planktonic foraminifera. Other investigators have shown that sulfate may occur in biogenic calcites either lattice-bound, as micro-fluid inclusions, in adsorbed phases, or as protein polysaccharides. Whatever the origin, the sulfur isotopic composition of this sulfate appears to be representative of that of the water in which the organism lived, as shown by results on recent calcareous foraminifera and macrofossils. Using this approach for study of Miocene to Recent pelagic marine sediments supplemented by new data for Miocene marine evaporites from the Gulf of Suez, we have found that the δ 34S of seawater has decreased about 2.5‰ over the past 25 m.y. and that most of the decrease has occurred over the past 5 m.y., parallelling a decrease in the δ 13C of dissolved oceanic bicarbonate from the same interval. Sedimentary redox models based on isotope records suggest that organic carbon and sulfide burial have both decreased over the past 5 m.y. Alternatively, an increase in weathering rates over the past 5 m.y. would not require a decrease in organic carbon or sulfide burial as long as the isotopic effect of the increased river input exceeds the isotopic effect of the burial of the reduced species. In either case, the net result would be a decrease in atmospheric p O 2.

  10. Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle.

    Science.gov (United States)

    Canfield, Donald E

    2013-05-21

    Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth's surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth's history, and our understanding of this history is based mainly on interpretations of the isotope record of seawater sulfates and sedimentary pyrites. The isotope record, however, does not give a complete picture of the ancient sulfur cycle. This is because, in standard isotope mass balance models, there are more variables than constraints. Typically, in interpretations of the isotope record and in the absence of better information, one assumes that the isotopic composition of the input sulfate to the oceans has remained constant through time. It is argued here that this assumption has a constraint over the last 390 Ma from the isotopic composition of sulfur in coal. Indeed, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through the Phanerozoic Eon.

  11. High sulfur isotope fractionation associated with anaerobic oxidation of methane in a low sulfate, iron rich environment

    Science.gov (United States)

    Weber, Hannah; Thamdrup, Bo; Habicht, Kirsten

    2016-06-01

    Sulfur isotope signatures provide key information for the study of microbial activity in modern systems and the evolution of the Earth surface redox system. Microbial sulfate reducers shift sulfur isotope distributions by discriminating against heavier isotopes. This discrimination is strain-specific and often suppressed at sulfate concentrations in the lower micromolar range that are typical to freshwater systems and inferred for ancient oceans. Anaerobic oxidation of methane (AOM) is a sulfate-reducing microbial process with a strong impact on global sulfur cycling in modern habitats and potentially in the geological past, but its impact on sulfur isotope signatures is poorly understood, especially in low sulfate environments. We investigated sulfur cycling and 34S fractionation in a low-sulfate freshwater sediment with biogeochemical conditions analogous to Early Earth environments. The zone of highest AOM activity was associated in situ with a zone of strong 34S depletions in the pool of reduced sulfur species, indicating a coupling of sulfate reduction and AOM at sulfate concentrations oceanic levels. Therefore, we suggest that sulfur isotope fractionation during AOM must be considered when interpreting 34S signatures in modern and ancient environment.

  12. Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs

    Science.gov (United States)

    2014-01-01

    Background The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Results Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6 μmol L-1) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ34S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ34S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur–polysulfide – hydrogen sulfide system. Triple sulfur isotope (32S, 33S, 34S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆33S among

  13. Pyrite sulfur isotopes reveal glacial-interglacial environmental changes

    Science.gov (United States)

    Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina; Revillon, Sidonie; Houghton, Jennifer; Fike, David A.

    2017-06-01

    The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial-interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial-interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial-interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.

  14. The Fate of Sulfur in Late-Stage Magmatic Processes: Insights From Quadruple Sulfur Isotopes

    Science.gov (United States)

    Keller, N. S.; Ono, S.; Shaw, A. M.

    2009-05-01

    Multiple sulfur isotopes (32S, 33S, 34S and 36S) have recently been shown to be useful tracers of fluid-rock interaction in seafloor hydrothermal systems [1]. Here we present the application of multiple sulfur isotopes to subaerial volcanoes with the aim of unraveling the various processes fractionating sulfur in the upper volcanic system. We take advantage of the fact that the ascent of volcanic gases through a hydrothermal system causes complex isotopic fractionation between the quaduple sulfur isotopes. δ34S is thought to trace the source of sulfur as well as magma degassing; at equilibrium, δ33S follows a mass-dependent fractionation relationship such that two phases in equilibrium with each other have equal Δ33S values (Δ33S ≡ ln(δ33S+1) - 0.515×ln(δ34S+1)). Disequilibrium Δ33S values can indicate isotope mixing and other fluid-rock interactions. The ultimate aim of this study is to assess the use of quadruple sulfur isotopes to obtain quantitative information on the sulfur cycle at convergent plate margins. The sulfur mass balance at convergent margins is poorly constrained, partly because late-stage processes are challenging to quantify and lead to large uncertainties in the global output fluxes. Quadruple sulfur isotopes provide a powerful tool to untangle the convoluted history of volcanic systems. Here we report the first quadruple sulfur isotopic values for H2S, SO2 and native sulfur from arc volcanoes. Fumarolic gases (˜100°C) and sulfur sublimates were collected from Poas and Turrialba, two actively degassing volcanoes in Costa Rica. The gases were bubbled in situ through chemical traps to separate H2S from SO2: H2S was reacted to form ZnS, and SO2 to form BaSO4. Sulfur was chemically extracted from the solid phases and precipitated as Ag2S, which was fluorinated to SF6 and analysed by IRMS. Poas and Turrialba have H2S/SO2 ˜1 and 0.01, respectively. δ34SH2S and δ34SSO2 are similar to gases measured at other arcs [2], - 7.9‰ and 0.6

  15. Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

    Science.gov (United States)

    Hackley, Keith C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W.

    1990-01-01

    Hot tetrachloroethene (perchloroethylene, PCE) extracts significant amounts of elemental sulfur (So) from weathered coals but not from pristine coals. The objective of this study was to determine whether So extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted So was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The So was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, So and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. ?? 1990.

  16. Diversity of sulfur isotope fractionations by sulfate-reducing prokaryotes

    DEFF Research Database (Denmark)

    Detmers, Jan; Brüchert, Volker; Habicht, K S

    2001-01-01

    Batch culture experiments were performed with 32 different sulfate-reducing prokaryotes to explore the diversity in sulfur isotope fractionation during dissimilatory sulfate reduction by pure cultures. The selected strains reflect the phylogenetic and physiologic diversity of presently known...... sulfate reducers and cover a broad range of natural marine and freshwater habitats. Experimental conditions were designed to achieve optimum growth conditions with respect to electron donors, salinity, temperature, and pH. Under these optimized conditions, experimental fractionation factors ranged from 2.......0 to 42.0 per thousand. Salinity, incubation temperature, pH, and phylogeny had no systematic effect on the sulfur isotope fractionation. There was no correlation between isotope fractionation and sulfate reduction rate. The type of dissimilatory bisulfite reductase also had no effect on fractionation...

  17. Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    2013-01-01

    Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent...... reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly...... on interpretations of the isotope record of seawater sulfates and sedimentary pyrites. The isotope record, however, does not give a complete picture of the ancient sulfur cycle. This is because, in standard isotope mass balance models, there are more variables than constraints. Typically, in interpretations...

  18. Investigation of a fusion technique for the determination of total sulfur in geological samples by ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Stallings, E.A.; Candelaria, L.M.; Gladney, E.S.

    1988-06-01

    The authors have encountered the need for a rapid, accurate, precise, and sensitive method for measuring total sulfur in large numbers of geological samples. Numerous environmental studies of sulfur deposition due to sulfur dioxide emission from combustion and industry are currently under way. Several techniques for measuring total sulfur in soils and other silicate materials have been published including neutron activation analysis, thermal neutron capture prompt ..gamma..-ray spectrometry, inductively coupled plasma atomic emission spectrometry, isotope dilution mass spectrometry, X-ray fluorescence, turbidimetry, ion chromatography (IC), iodimetric titration, and fluorometry. However, none of these methods is completely satisfactory for routine analysis of large numbers of samples. Many have levels of detection that are inadequate for measuring low levels of total sulfur (<100 ..mu..g/g) often encountered in soils. Several utilize only aqueous extracts of the soils and do not provide a total sulfur determination. Others require extensive sample preparation, are susceptible to loss of sulfur during oxidation, or produce incomplete conversion of sulfur species to sulfate. The objective of this work was to evaluate the accuracy of IC determination of sulfate for Na/sub 2/O/sub 2/ soil fusions by comparing the results obtained for reference materials with literature values reported for other techniques. They were also interested in determining if this fusion method would be rapid enough to handle large numbers of samples.

  19. Sulfur contents and sulfur-isotope compositions of thiotrophic symbioses in bivalve molluscs and vestimentiferan worms

    Science.gov (United States)

    Vetter, R.D.; Fry, B.

    1998-01-01

    Total sulfur (S(TOT)), elemental sulfur (S??) and sulfur-isotope compositions (??34S) of marine animals were analyzed to determine whether these chemical characteristics could help distinguish animals with a sulfur-based, thiotrophic nutrition from animals whose nutrition is based on methanotrophy or on more normal consumption of phytoplankton-derived organic matter. The presence of S??was almost entirely confined to the symbiont-containing tissues of thiotrophs, but was sometimes undetectable in thiotrophic species where sulfide availability was probably low. When S??contents were subtracted, the remaining tissue-sulfur concentrations were similar for all nutritional groups. ??34S values were typically lower for thiotrophs than for other groups, although there was overlap in methanotroph and thiotroph values at some sites. Field evidence supported the existence of small to moderate (1 to 10???)34S fractionations in the uptake of sulfides and metabolism of thiosulfate. In general, a total sulfur content of >3% dry weight, the presence of elemental sulfur, and ??34S values less than + 5??? can be used to infer a thiotrophic mode of nutrition.

  20. Isotopic insights into microbial sulfur cycling in oil reservoirs

    Directory of Open Access Journals (Sweden)

    Christopher G Hubbard

    2014-09-01

    Full Text Available Microbial sulfate reduction in oil reservoirs (biosouring is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of -30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters containing elevated concentrations of volatile fatty acids and injection water containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures.

  1. Sulfur Isotope Analysis of Minerals and Fluids in a Natural CO2 Reservoir, Green River, Utah

    Science.gov (United States)

    Chen, F.; Kampman, N.; Bickle, M. J.; Busch, A.; Turchyn, A. V.

    2013-12-01

    Predicting the security of geological CO2 storage sites requires an understanding of the geochemical behavior of the stored CO2, especially of fluid-rock reactions in reservoirs, caprocks and fault zones. Factors that may influence geochemical behavior include co-injection of sulfur gases along with the CO2, either in acid-gas disposal or as contaminants in CO2 storage sites, and microbial activity, such as bacterial sulfate reduction. The latter may play an important role in buffering the redox chemistry of subsurface fluids, which could affect toxic trace metal mobilization and transport in acidic CO2-rich fluids. These processes involving sulfur are poorly understood. Natural CO2-reservoirs provide natural laboratories, where the flow and reactions of the CO2-charged fluids and the activity of microbial communities are integrated over sufficient time-scales to aid prediction of long-term CO2 storage. This study reports on sulfur isotope analyses of sulfate and sulfide minerals in rock core and in CO2-charged fluids collected from a stacked sequence of natural CO2 reservoirs at Green River, Utah. Scientific drilling adjacent to a CO2-degassing normal fault to a depth of 325m retrieved core and fluid samples from two CO2 reservoirs in the Entrada and Navajo Sandstones and from the intervening Carmel Formation caprock. Fluid samples were collected from CO2-charged springs that discharge through the faults. Sulfur exists as sulfate in the fluids, as sedimentary gypsum beds in the Carmel Formation, as remobilized gypsum veins within a fault damage zone in the Carmel Fm. and in the Entrada Sandstone, and as disseminated pyrite and pyrite-mineralized open fractures throughout the cored interval. We use the stable sulfur (δ34S) and oxygen (δ18OSO4) isotopes of the sulfate, gypsum, and pyrite to understand the source of sulfur in the reservoir as well as the timing of gypsum vein and pyrite formation. The hydration water of the gypsum is also reported to explore the

  2. Multiple sulfur isotope composition of oxidized Samoan melts and the implications of a sulfur isotope 'mantle array' in chemical geodynamics

    Science.gov (United States)

    Labidi, J.; Cartigny, P.; Jackson, M. G.

    2015-05-01

    To better address how subducted protoliths drive the Earth's mantle sulfur isotope heterogeneity, we report new data for sulfur (S) and copper (Cu) abundances, S speciation and multiple S isotopic compositions (32S, 33S, 34S, 36S) in 15 fresh submarine basaltic glasses from the Samoan archipelago, which defines the enriched-mantle-2 (EM2) endmember. Bulk S abundances vary between 835 and 2279 ppm. About 17 ± 11% of sulfur is oxidized (S6+) but displays no consistent trend with bulk S abundance or any other geochemical tracer. The S isotope composition of both dissolved sulfide and sulfate yield homogeneous Δ33S and Δ36S values, within error of Canyon Diablo Troilite (CDT). In contrast, δ34S values are variable, ranging between +0.11 and +2.79‰ (±0.12‰ 1σ) for reduced sulfur, whereas oxidized sulfur values vary between +4.19 and +9.71‰ (±0.80‰, 1σ). Importantly, δ34S of the reduced S pool correlates with the 87Sr/86Sr ratios of the glasses, in a manner similar to that previously reported for South-Atlantic MORB, extending the trend to δ34S values up to + 2.79 ± 0.04 ‰, the highest value reported for undegassed oceanic basalts. As for EM-1 basalts from the South Atlantic ridge, the linear δ34S-87Sr/86Sr trend requires the EM-2 endmember to be relatively S-rich, and only sediments can account for these isotopic characteristics. While many authors argue that both the EM-1 and EM-2 mantle components record subduction of various protoliths (e.g. upper or lower continental crust, lithospheric mantle versus intra-metasomatized mantle, or others), it is proposed here that they primarily reflect sediment recycling. Their distinct Pb isotope variation can be accounted for by varying the proportion of S-poor recycled oceanic crust in the source of mantle plumes.

  3. Coupled Iron and Sulfur Isotope Constraints on the Archean and Paleoproterozoic Ocean Redox State

    Science.gov (United States)

    Rouxel, O. J.; Bekker, A.

    2009-05-01

    The rise of atmospheric oxygen level by ca. 2.3 Ga have led to dramatic shifts in the iron and sulfur oceanic cycles. Past studies of non-mass dependent and mass dependent sulfur isotope record in sedimentary sulfides over geological time have placed important constraints on biogeochemical cycle of sulfur and evolution of Precambrian ocean chemistry. Recently, we applied a similar time-record approach to explore potential changes in Fe isotope composition of pyrite in black shales. Although the underlying mechanisms for Fe isotope fractionation in organic-rich sediments are debated, we identified direct link between the rise of atmospheric oxygen and changes in the Fe ocean cycle suggesting that Fe isotopes are useful proxies to the past ocean redox state. Since biogeochemical cycles of Fe and S are closely coupled in marine systems, Fe-limitation and S-limitation for pyrite formation in black shales should leave imprint on the isotopic record of both elements. Coupled Fe and S isotope systematics of Devonian pyrite display a range of 50‰ in δ34S values whereas δ56Fe values vary between - 1.0 and +0.1‰ consistent with Fe isotope variations in modern marine sediments. Similarly, pyrite in the 1.88 Ga Gunflint Formation has δ34S values ranging from - 32‰ to +10‰ and displays a range of δ56Fe values between 0 to - 0.4‰. In contrast, Archean black shales (e.g. Manjeri Fm., Belingwe Belt and Jeerinah Fm., Hamersley Basin) display a smaller range of δ34S values between together with ubiquitous non-mass dependent S-isotope fractionation but a larger range of δ56Fe values from - 3.5 to +0.2‰. A transitional period between ca. 2.3 and ca. 1.8 Ga is marked by a larger spread of δ34S values from - 34 to +28‰, disappearance of MIF and a larger range of δ56Fe values from - 1.7 to +1.1‰. These results confirm that after the rise of atmospheric oxygen by ca. 2.3 Ga, Paleoproterozoic ocean became stratified and gradually affected by an increase of seawater

  4. Sulfur Isotopic Fractionation During Dissimilatory Sulfate Reduction from the Perspective of an Entire Microbial Metabolism

    Science.gov (United States)

    Webber, B.; Lau, L.; Wing, B.

    2009-05-01

    Whether in the investigation of the most ancient life on Earth, examination of surface oxidation properties across geological timescales, or the estimation of microbial metabolism in inaccessible environments, dissimilatory sulfate reduction (DSR) constrains biogeochemical processes in a variety of spatial and temporal scales. Pioneering work in the 1970s established the importance of DSR to biogeochemical processes and its potential as a geochemical tracer, and models for biological controls of DSR were published from empirical results of in vitro microbial cultures. Recent efforts have expanded upon this body of work and further extended toward multiple sulfur isotopes and through the more precise definition of the biological processes themselves. Resulting from these recent efforts is an rigorous description of DSR of the sulfur metabolism of sulfate-reducing bacteria. However, despite these efforts, the exact mechanisms of DSR within the scope of a complex system such as microbial metabolism remain incomplete and obscure. We will be presenting ongoing work coupling together recent mathematical models of isotopic fractionation with a flux-oriented, genomically-derived software model of the metabolism of Desulfovibrio vulgaris, a patent sulfate-reducing bacterium. Our presentation will explore the effects on isotopic fractionation throughout the sulfate reduction pathway of D. vulgaris by a multitude of separate and distinct biological pathways within the bacterial metabolism. Further, we will be discussing both the pitfalls and promise of such an approach and its implications for future research.

  5. Sulfur isotopic zoning in apatite crystals: A new record of dynamic sulfur behavior in magmas

    Science.gov (United States)

    Economos, Rita; Boehnke, Patrick; Burgisser, Alain

    2017-10-01

    The mobility and geochemical behavior of sulfur in magmas is complex due to its multi-phase (solid, immiscible liquid, gaseous, dissolved ions) and multi-valent (from S2- to S6+) nature. Sulfur behavior is closely linked with the evolution of oxygen fugacity (fO2) in magmas; the record of fO2 evolution is often enigmatic to extract from rock records, particularly for intrusive systems. We apply a novel method of measuring S isotopic ratios in zoned apatite crystals that we interpret as a record of open-system magmatic processes. We interrogate the S concentration and isotopic variations preserved in multiple apatite crystals from single hand specimens from the Cadiz Valley Batholith, CA via electron microprobe and ion microprobe. Isotopic variations in single apatite crystals ranged from 0 to 3.8‰ δ34S and total variation within a single hand sample was 6.1‰ δ34S. High S concentration cores yielded high isotopic ratios while low S concentration rims yielded low isotopic ratios. We discuss a range of possible natural scenarios and favor an explanation of a combination of magma mixing and open-system, ascent-driven degassing under moderately reduced conditions: fO2 at or below NNO+1, although the synchronous crystallization of apatite and anhydrite is also a viable scenario. Our conclusions have implications for the coupled S and fO2 evolution of granitic plutons and suggest that in-situ apatite S isotopic measurements could be a powerful new tool for evaluating redox and S systematics in magmatic systems.

  6. Mass independent sulfur isotope signatures in CMs: Implications for sulfur chemistry in the early solar system

    Science.gov (United States)

    Labidi, J.; Farquhar, J.; Alexander, C. M. O.'D.; Eldridge, D. L.; Oduro, H.

    2017-01-01

    We have investigated the quadruple sulfur isotopic composition of inorganic sulfur-bearing phases from 13 carbonaceous chondrites of CM type. Our samples include 4 falls and 9 Antarctic finds. We extracted sulfur from sulfides, sulfates, and elemental sulfur (S0) from all samples. On average, we recover a bulk sulfur (S) content of 2.11 ± 0.39 wt.% S (1σ). The recovered sulfate, S0 and sulfide contents represent 25 ± 12%, 10 ± 7% and 65 ± 15% of the bulk S, respectively (all 1σ). There is no evidence for differences in the bulk S content between falls and finds, and there is no correlation between the S speciation and the extent of aqueous alteration. We report ranges of Δ33S and Δ36S values in CMs that are significantly larger than previously observed. The largest variations are exhibited by S0, with Δ33S values ranging between -0.104 ± 0.012‰ and +0.256 ± 0.018‰ (2σ). The Δ36S/33S ratios of S0 are on average -3.1 ± 1.0 (2σ). Two CMs show distinct Δ36S/33S ratios, of +1.3 ± 0.1 and +0.9 ± 0.1. We suggest that these mass independent S isotopic compositions record H2S photodissociation in the nebula. The varying Δ36S/Δ33S ratios are interpreted to reflect photodissociation that occurred at different UV wavelengths. The preservation of these isotopic features requires that the S-bearing phases were heterogeneously accreted to the CM parent body. Non-zero Δ33S values are also preserved in sulfide and sulfate, and are positively correlated with S0 values. This indicates a genetic relationship between the S-bearing phases: We argue that sulfates were produced by the direct oxidation of S0 (not sulfide) in the parent body. We describe two types of models that, although imperfect, can explain the major features of the CM S isotope compositions, and can be tested in future studies. Sulfide and S0 could both be condensates from the nebula, as the residue and product, respectively, of incomplete H2S photodissociation by UV light (wavelength H2S

  7. Photochemical mass-independent sulfur isotopes in achondritic meteorites.

    Science.gov (United States)

    Rai, Vinai K; Jackson, Teresa L; Thiemens, Mark H

    2005-08-12

    Sulfides from four achondrite meteorite groups are enriched in 33S (up to 0.040 per mil) as compared with primitive chondrites and terrestrial standards. Stellar nucleosynthesis and cosmic ray spallation are ruled out as causes of the anomaly, but photochemical reactions in the early solar nebula could produce the isotopic composition. The large 33S excess present in oldhamite from the Norton County aubrite (0.161 per mil) suggests that refractory sulfide minerals condensed from a nebular gas with an enhanced carbon-oxygen ratio, but otherwise solar composition is the carrier. The presence of a mass-independent sulfur effect in meteorites argues for a similar process that could account for oxygen isotopic anomalies observed in refractory inclusions in primitive chondrites.

  8. Biosynthesis and Isotopic Composition of Bacteriochlorophyll a and Okenone in Purple Sulfur Bacteria

    Science.gov (United States)

    Smith, D.; Scott, J. H.; Steele, A.; Cody, G. D.; Ohara, S.; Bowden, R.; Fogel, M. L.

    2011-12-01

    Phototrophic sulfur bacteria play an integral part in the anaerobic cycling of sulfur. Bacteriochloroyphll a (Bchl a) is a well-studied photosynthetic compound required for photosynthesis in the organisms that possess it. The only known fossil of purple sulfur bacteria (PSB) in the geologic record is okenane, believed to be of biologic origin originating from the carotenoid pigment okenone, which has only been documented in eleven species of Chromatiaceae. Organic geochemical studies have identified okenane in preserved organic matter in rocks and ancient sediments and further, okenone production has been observed in modern water columns and sediment surfaces. We have undertaken a comprehensive study on the biosynthesis of bacterial pigments including okenone and C, N, and S isotopic fractionation during various growth modes in controlled laboratory experiments of purple sulfur bacteria. Cultures of Marichromatium purpuratum 1591, M. purpuratum 1711, Thiocapsa marina 5653, and FGL21 (isolated from the chemocline of Fayetteville Green Lake, NY) were grown under autotrophic and photoheterotrophic (e.g. acetate or pyruvate) conditions in batch cultures. Concentrations of okenone and Bchl a were quantified as a function of time and growth by Ultra Performance-Liquid Chromatography-Mass Spectrometry (UP-LC-MS) and spectrophotometry. Overall okenone and Bchl a concentrations reached μM levels in the cultures. At stationary phase, all four strains achieved concentrations of okenone and Bchl a that were approximately 2.5 fM and 0.2 fM per cell, respectively, with okenone to Bchl a ratios of approximately 12 to 1. Isotope Ratio Mass Spectrometry (IRMS) was performed on bulk cells and compound specific analysis of Bchl a and okenone to better understand the fractionation associated with the production of the compounds.

  9. High-resolution (SIMS) versus bulk sulfur isotope patterns of pyrite in Proterozoic microbialites with diverse mat textures

    Science.gov (United States)

    Gomes, M. L.; Fike, D. A.; Bergmann, K.; Knoll, A. H.

    2015-12-01

    Sulfur (S) isotope signatures of sedimentary pyrite preserved in marine rocks provide a rich suite of information about changes in biogeochemical cycling associated with the evolution of microbial metabolisms and oxygenation of Earth surface environments. Conventionally, these S isotope records are based on bulk rock measurements. Yet, in modern microbial mat environments, S isotope compositions of sulfide can vary by up to 40‰ over a spatial range of ~ 1 mm. Similar ranges of S isotope variability have been found in Archean pyrite grains using both Secondary Ion Mass Spectrometry and other micro-analytical techniques. These micron-scale patterns have been linked to changes in rates of microbial sulfate reduction and/or sulfide oxidation, isotopic distillation of the sulfate reservoir due to microbial sulfate reduction, and post-depositional alteration. Fine-scale mapping of S isotope compositions of pyrite can thus be used to differentiate primary environmental signals from post-depositional overprinting - improving our understanding of both. Here, we examine micron-scale S isotope patterns of pyrite in microbialites from the Mesoproterozoic-Neoproterozoic Sukhaya Tunguska Formation and Neoproterozoic Draken Formation in order to explore S isotope variability associated with different mat textures and pyrite grain morphologies. A primary goal is to link modern observations of how sulfide spatial isotope distributions reflect active microbial communities present at given depths in the mats to ancient processes driving fine-sale pyrite variability in microbialites. We find large (up to 60‰) S isotope variability within a spatial range of less than 2.5cm. The micron-scale S isotope measurements converge around the S isotope composition of pyrite extracted from bulk samples of the same microbialites. These micron-scale pyrite S isotope patterns have the potential to reveal important information about ancient biogeochemical cycling in Proterozoic mat environments

  10. Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

    Science.gov (United States)

    Pribil, Michael; Ridley, William I.; Emsbo, Poul

    2015-01-01

    Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

  11. Influence of sulfur-bearing polyatomic species on high precision measurements of Cu isotopic composition

    Science.gov (United States)

    Pribil, M.J.; Wanty, R.B.; Ridley, W.I.; Borrok, D.M.

    2010-01-01

    An increased interest in high precision Cu isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has developed recently for various natural geologic systems and environmental applications, these typically contain high concentrations of sulfur, particularly in the form of sulfate (SO42-) and sulfide (S). For example, Cu, Fe, and Zn concentrations in acid mine drainage (AMD) can range from 100??g/L to greater than 50mg/L with sulfur species concentrations reaching greater than 1000mg/L. Routine separation of Cu, Fe and Zn from AMD, Cu-sulfide minerals and other geological matrices usually incorporates single anion exchange resin column chromatography for metal separation. During chromatographic separation, variable breakthrough of SO42- during anion exchange resin column chromatography into the Cu fractions was observed as a function of the initial sulfur to Cu ratio, column properties, and the sample matrix. SO42- present in the Cu fraction can form a polyatomic 32S-14N-16O-1H species causing a direct mass interference with 63Cu and producing artificially light ??65Cu values. Here we report the extent of the mass interference caused by SO42- breakthrough when measuring ??65Cu on natural samples and NIST SRM 976 Cu isotope spiked with SO42- after both single anion column chromatography and double anion column chromatography. A set of five 100??g/L Cu SRM 976 samples spiked with 500mg/L SO42- resulted in an average ??65Cu of -3.50?????5.42??? following single anion column separation with variable SO42- breakthrough but an average concentration of 770??g/L. Following double anion column separation, the average SO42-concentration of 13??g/L resulted in better precision and accuracy for the measured ??65Cu value of 0.01?????0.02??? relative to the expected 0??? for SRM 976. We conclude that attention to SO42- breakthrough on sulfur-rich samples is necessary for accurate and precise measurements of ??65Cu and may require

  12. Sulfur isotopic characteristics of volcanic products from the September 2014 Mount Ontake eruption, Japan

    Science.gov (United States)

    Ikehata, Kei; Maruoka, Teruyuki

    2016-07-01

    Components and sulfur isotopic compositions of pyroclastic materials from the 2014 Mt. Ontake eruption were investigated. The volcanic ash samples were found to be composed of altered volcanic fragments, alunite, anhydrite, biotite, cristobalite, gypsum, ilmenite, kaolin minerals, native sulfur, orthopyroxene, plagioclase, potassium feldspar, pyrite, pyrophyllite, quartz, rutile, and smectite, and most of these minerals were likely derived from the acidic alteration zones of Mt. Ontake. The absence of juvenile material in the eruptive products indicates that the eruption was phreatic. The sulfur isotopic compositions of the water-leached sulfate, hydrochloric acid-leached sulfate, acetone-leached native sulfur, and pyrite of the samples indicate that these sulfur species were produced by disproportionation of magmatic SO2 in the hydrothermal system at temperatures of 270-281 °C. This temperature range is consistent with that inferred from the hydrothermal mineral assemblage (e.g., pyrophyllite and rutile) in the 2014 pyroclastic materials (200-300 °C). Except for the sulfur isotopic compositions of anhydrite, which may have been altered by incorporation of sulfate minerals in a fumarolic area with lower sulfur isotopic values into the underground materials during the 1979 eruption, no significant differences in the mineral assemblages and sulfur isotopic compositions of the pyroclastic materials were identified between the products of the 2014 and 1979 Ontake phreatic eruptions, which suggests geochemical similarities in the underlying hydrothermal systems before the 2014 and 1979 eruptions.

  13. Sulfur dioxide from Nevado del Ruiz volcano, Colombia: total flux and isotopic constraints on its origin

    Science.gov (United States)

    Williams, Stanley N.; Sturchio, Neil C.; Calvache V., Marta Lucia; Mendez F., Ricardo; Londoño C., Adela; García P., Nestor

    1990-07-01

    Nevado del Ruiz volcano has been releasing extraordinarily large volumes of sulfur dioxide gas from its Arenas crater since September, 1985 and probably since the renewal of volcanic activity began in late 1984. The combined release from eruptive and passive flux has been approximately (3.4 ± 1.0) × 10 6 metric tons in the four years after November, 1984. This value combined with data of others on pre-eruption sulfur content of the magma, allows the calculation of a minimum required volume of magma of 0.92 km 3. Consideration of the continued high flux and typical ratios of erupted to degassed magma indicate that the true minimum volume of magma involved is probably at least 4.6-9.2 km 3. A systematic study of the various species of sulfur in the volcanic plume and the hydrothermal system has provided a characterization of the geochemistry and sulfur-isotopic variation. Consideration has been given to five potential sources of the sulfur dioxide: dissolution of subvolcanic evaporites; remobilization and oxidation of native sulfur within summit crater fumaroles; large-scale release from the hydrothermal system by reduction of sulfate or water-rock interaction; assimilation and oxidation of a pre-existing sulfide deposit; and magmatic volatiles. The data are most realistically explained by the passage of magmatic gas through the hydrothermal system, with some disproportionation of sulfur dioxide to produce the high sulfate content and low pH of the waters. This model is also most consistent with the distribution of acid-sulfate-chloride hot springs, high chloride and fluoride content of the hydrothermal waters, sulfide deposition within the volcanic pile, and the transient increase in sulfate content of the acid-sulfate-chloride hot springs that reached a maximum approximately one year after the November, 1985 eruption. The magmatic model is in apparent conflict with the absence of general deformation from the time that data began to be collected, about one week

  14. Sulfur Isotope of Epilithic Mosses to Trace Variation of Atmospheric Sulfur Sources

    Directory of Open Access Journals (Sweden)

    HU Fei-fei1,2;PAN Jia-yong1,3;ZHANG Liang1,2;XIE Shu-rong3;CHEN Yi-ping3;XIA Fei1,3

    2016-08-01

    Full Text Available 全文: PDF (5099 KB HTML (1 KB 输出: BibTeX | EndNote (RIS 摘要 为探讨石生苔藓硫同位素组成特征对区域性大气硫源的指示作用,连续两年采集鄱阳湖生态经济区内的石生苔藓样品,测定δ34S值;并结合已有的雨水、煤的硫同位素值等相关研究数据进行对比分析。样品δ34S值均偏正,平均为+4.9‰,取值范围为+1.9‰~+9.6‰;石生苔藓δ34S值与空气中SO2浓度呈负相关关系;南昌、抚州两市苔藓δ34S值的取值范围与其对应城市大气降水δ34S值的变化区间相接近;研究区内土壤相对富集重硫,且土壤中可溶性硫主要受大气硫沉降影响。结果表明,石生苔藓的硫同位素组成对区域性大气硫源具有指示意义,鄱阳湖生态经济区大气硫沉降的硫源主要来自人为成因硫和生物成因硫,可能还有远距离传输硫等其他硫源的影响。 服务 把本文推荐给朋友 加入我的书架 加入引用管理器 E-mail Alert RSS 作者相关文章 胡菲菲 潘家永 张良 谢淑容 陈益平 夏菲 关键词 : 石生苔藓, 硫同位素, 大气硫源 Abstract: The variation of atmospheric sulfur sources in Poyang Lake Eco-economic Region was explored by sulfur isotopes in epilithic mosses which collected from the research area during 2012 to 2013, and then compared it with the existing research δ34S values of rain and coal. The results showed that all of the δ34S values of epilithic mosses performed as positive value at a range of 1.9‰ to 9.6‰, the average was 4.9‰. It was found a significant negative correlation existed between the δ34S values of epilithic mosses (x and atmospheric SO2 concentration (y (y=-82.61x+7.63, R2=0.85. The δ34S values of epilithic mosses in Nanchang and Fuzhou were close to the δ34S values of its corresponding city’s atmospheric precipitation. The δ34S values of soil total sulfur were higher than that of epilithic mosses

  15. Searching for Life in the Sulfur Isotopic Analysis of Surface Sulfates on Mars

    Science.gov (United States)

    Parnell, J.; Boyce, A. J.; Osinski, G. R.; Izawa, M.; Lee, P.

    2011-03-01

    Sulfur isotopic measurements on Mars are likely to be limited to sulfates due to oxidation of sulfides. We show that evidence for life can be determined from sulfate data alone, using an analogue for a robotic traverse.

  16. Advances in the measurement of sulfur isotopes using laser ablation MC-ICP- MS

    Science.gov (United States)

    Ridley, W. I.; Pribil, M. J.; Koenig, A. E.; Fayek, M.; Slack, J. F.

    2008-05-01

    Although sulfur is poorly ionized in an argon plasma, there are many applications for sulfur isotope analysis using an ICP source. Studies using a desolvation system (DSN) and an aqueous source of sulfur, where the sulfur is complexed with a cation to form a sulfur salt, e.g., calcium or sodium to provide a stable delivery of sulfur through the sample introduction system indicate that precision (~ 0.3 per mil) and accuracy are maintained at sulfur concentrations as low as 1 mg/L. Based on this data, solid sampling of sulfides and sulfates can provide an adequate amount supply of sulfur to an ICP source, even allowing for the relatively poor transport efficiency of laser ablation systems. The main limitations on accuracy and precision are the initial sampling volume, principally a function of spot size and laser fluence and the decreased instrument sensitivity resulting from the pseudo- medium or high resolution mode of analysis required to eliminate polyatomic isobaric interferences. These factors, in turn, determine the minimal grain size necessary for analysis. There are also fit-for-purpose considerations. For instance, many base metal sulfide systems have large variations in sulfur isotope composition, so that precision as poor as one per mil can still provide useful information. Here, we describe the methodology used at the USGS for laser ablation analysis of sulfides and sulfates using a second generation MC-ICP-MS and demonstrate the accuracy of the method based upon a grain-by-grain comparison of laser ablation and ion microprobe sulfur isotope data. A laser ablation MC-ICP-MS study of base metal mineralization at Dry Creek deposit, east-central Alaska demonstrates that the range in sulfur isotope composition of pyrite, sphalerite and galena, based on analysis of individual grains, is almost twice that reported for any other individual VMS deposit. Analysis on the microscopic scale thus provides additional insights into the potential sources of sulfur for

  17. Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

    Science.gov (United States)

    Wang, P.; Sun, C.; Ono, S.; Lin, L.

    2012-12-01

    Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates

  18. Synthesis of l-cysteine derivatives containing stable sulfur isotopes and application of this synthesis to reactive sulfur metabolome.

    Science.gov (United States)

    Ono, Katsuhiko; Jung, Minkyung; Zhang, Tianli; Tsutsuki, Hiroyasu; Sezaki, Hiroshi; Ihara, Hideshi; Wei, Fan-Yan; Tomizawa, Kazuhito; Akaike, Takaaki; Sawa, Tomohiro

    2017-05-01

    Cysteine persulfide is an L-cysteine derivative having one additional sulfur atom bound to a cysteinyl thiol group, and it serves as a reactive sulfur species that regulates redox homeostasis in cells. Here, we describe a rapid and efficient method of synthesis of L-cysteine derivatives containing isotopic sulfur atoms and application of this method to a reactive sulfur metabolome. We used bacterial cysteine syntheses to incorporate isotopic sulfur atoms into the sulfhydryl moiety of L-cysteine. We cloned three cysteine synthases-CysE, CysK, and CysM-from the Gram-negative bacterium Salmonella enterica serovar Typhimurium LT2, and we generated their recombinant enzymes. We synthesized (34)S-labeled L-cysteine from O-acetyl-L-serine and (34)S-labeled sodium sulfide as substrates for the CysK or CysM reactions. Isotopic labeling of L-cysteine at both sulfur ((34)S) and nitrogen ((15)N) atoms was also achieved by performing enzyme reactions with (15)N-labeled L-serine, acetyl-CoA, and (34)S-labeled sodium sulfide in the presence of CysE and CysK. The present enzyme systems can be applied to syntheses of a series of L-cysteine derivatives including L-cystine, L-cystine persulfide, S-sulfo-L-cysteine, L-cysteine sulfonate, and L-selenocystine. We also prepared (34)S-labeled N-acetyl-L-cysteine (NAC) by incubating (34)S-labeled L-cysteine with acetyl coenzyme A in test tubes. Tandem mass spectrometric identification of low-molecular-weight thiols after monobromobimane derivatization revealed the endogenous occurrence of NAC in the cultured mammalian cells such as HeLa cells and J774.1 cells. Furthermore, we successfully demonstrated, by using (34)S-labeled NAC, metabolic conversion of NAC to glutathione and its persulfide, via intermediate formation of L-cysteine, in the cells. The approach using isotopic sulfur labeling combined with mass spectrometry may thus contribute to greater understanding of reactive sulfur metabolome and redox biology. Copyright © 2017 Elsevier

  19. Strategies for Mars remote Laser-Induced Breakdown Spectroscopy analysis of sulfur in geological samples

    Energy Technology Data Exchange (ETDEWEB)

    Dyar, M. Darby, E-mail: mdyar@mtholyoke.edu [Department of Astronomy, Mount Holyoke College, 50 College St., South Hadley, MA 01075 (United States); Tucker, Jonathan M., E-mail: jtucker@mtholyoke.edu [Department of Astronomy, Mount Holyoke College, 50 College St., South Hadley, MA 01075 (United States); Humphries, Seth, E-mail: sethdh@lanl.gov [Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Clegg, Samuel M., E-mail: sclegg@lanl.gov [Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Wiens, Roger C., E-mail: rwiens@lanl.gov [Los Alamos National Laboratory, P.O. Box 1663, Los Alamos, NM 87545 (United States); Lane, Melissa D., E-mail: lane@psi.edu [Planetary Science Institute, 1700 E. Ft. Lowell, Suite 106, Tucson, AZ 85719 (United States)

    2011-01-15

    The key to understanding the sulfur history on Mars is to identify and determine sulfate and sulfide compositions and then to draw from them geologic clues about their environments of formation. To lay a foundation for use of remote LIBS to sulfur analysis in planetary exploration, we have undertaken a focused study of sulfur LIBS in geological samples in a simulated Mars atmosphere, with experimental parameters replicating the ChemCam LIBS instrument. A suite of twelve samples was selected, including rocks rich in minerals representative of sulfates and sulfides that might be encountered on Mars. Univariate analysis of sulfur emission lines did not provide quantitative information. Partial least squares (PLS) analysis was successful at modeling sulfur concentrations for a subset of samples with similar matrices. Sulfide minerals were identified on the basis of other siderophile or chalcophile peaks, such as those arising from Zn and Cu. Because the S lines are very weak compared to those of other elements, optimal PLS results were obtained by restricting the wavelength range to channels close to the most intense sulfur lines {approx} 540-570 nm. Principal components analysis was attempted on the dataset, but did not differentiate the samples into meaningful groups because the sulfur lines are not strong enough. However, areas of the relatively weak S, H, and O peaks may be used to correctly classify all samples. Based on these outcomes, a flowchart that outlines a possible decision tree for identification and quantification of sulfur in remote LIBS analysis was constructed. Results suggest that LIBS data acquired under Mars conditions can meet the science requirements for the ChemCam instrument.

  20. Isotopic evidence in tree rings for historical changes in atmospheric sulfur sources.

    Science.gov (United States)

    Kawamura, Hidehisa; Matsuoka, Nobuaki; Momoshima, Noriyuki; Koike, Masami; Takashima, Yoshimasa

    2006-09-15

    Little is understood about the usefulness of sulfur isotopic ratios (sigma 34S) in tree rings because the sulfur content in rings is generally insufficient for analysis using conventional methods. We present sigma 34S values of the water-soluble and the organically bound sulfur fractions in rings of coniferous trees grown in Japan, analyzed using a large-volume oxygen bomb. Comparing the sigma 34S values of the organically bound fraction in tree rings with past atmospheric sulfur concentrations and with those of their sources, we find clear evidence that the sigma 34S values of the organically bound fraction in the rings are dependent upon the values of the atmospheric sulfur sources. The evidence suggests that the sigma 34S values in tree rings are a useful chronological proxy for evaluating possible causes of past atmospheric sulfur pollution.

  1. Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients

    Science.gov (United States)

    Balter, Vincent; Nogueira da Costa, Andre; Paky Bondanese, Victor; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

    2015-01-01

    The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper (65Cu/63Cu) and sulfur (34S/32S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is 63Cu-enriched by ∼0.4‰ and sulfur is 32S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The 32S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

  2. Natural variations of copper and sulfur stable isotopes in blood of hepatocellular carcinoma patients.

    Science.gov (United States)

    Balter, Vincent; Nogueira da Costa, Andre; Bondanese, Victor Paky; Jaouen, Klervia; Lamboux, Aline; Sangrajrang, Suleeporn; Vincent, Nicolas; Fourel, François; Télouk, Philippe; Gigou, Michelle; Lécuyer, Christophe; Srivatanakul, Petcharin; Bréchot, Christian; Albarède, Francis; Hainaut, Pierre

    2015-01-27

    The widespread hypoxic conditions of the tumor microenvironment can impair the metabolism of bioessential elements such as copper and sulfur, notably by changing their redox state and, as a consequence, their ability to bind specific molecules. Because competing redox state is known to drive isotopic fractionation, we have used here the stable isotope compositions of copper ((65)Cu/(63)Cu) and sulfur ((34)S/(32)S) in the blood of patients with hepatocellular carcinoma (HCC) as a tool to explore the cancer-driven copper and sulfur imbalances. We report that copper is (63)Cu-enriched by ∼0.4‰ and sulfur is (32)S-enriched by ∼1.5‰ in the blood of patients compared with that of control subjects. As expected, HCC patients have more copper in red blood cells and serum compared with control subjects. However, the isotopic signature of this blood extra copper burden is not in favor of a dietary origin but rather suggests a reallocation in the body of copper bound to cysteine-rich proteins such as metallothioneins. The magnitude of the sulfur isotope effect is similar in red blood cells and serum of HCC patients, implying that sulfur fractionation is systemic. The (32)S-enrichment of sulfur in the blood of HCC patients is compatible with the notion that sulfur partly originates from tumor-derived sulfides. The measurement of natural variations of stable isotope compositions, using techniques developed in the field of Earth sciences, can provide new means to detect and quantify cancer metabolic changes and provide insights into underlying mechanisms.

  3. Microbial sulfur metabolism evidenced from pore fluid isotope geochemistry at Site U1385

    Science.gov (United States)

    Turchyn, Alexandra V.; Antler, Gilad; Byrne, David; Miller, Madeline; Hodell, David A.

    2016-06-01

    At Site U1385, drilled during IODP Expedition 339 off the coast of Portugal on the continental slope, high-resolution sulfate concentration measurements in the pore fluids display non-steady-state behavior. At this site there is a zone of sulfate reduction in the uppermost seven meters of sediment, followed by a 38-meter interval where sulfate concentrations do not change, and finally sulfate concentrations are depleted to zero between 45 and 55 meters below seafloor. Below the sulfate minimum zone, there is abundant methane, suggesting that the lower sulfate consumption zone is coupled to anaerobic methane oxidation. We analyze pore water samples from IODP Site U1385 for sulfur and oxygen isotope ratios of dissolved sulfate, as well as the sulfur isotope composition of sedimentary pyrite. The sulfur isotopes in pore fluid sulfate display similar non-steady-state behavior similar to that of the sulfate concentrations, increasing over the uppermost zone of sulfate reduction and again over the lower zone of sulfate-driven anaerobic methane oxidation. The oxygen isotopes in sulfate increase to the 'apparent equilibrium' value in the uppermost zone of sulfate reduction and do not change further. Our calculations support the idea that sulfite to sulfide reduction is the limiting step in microbial sulfate reduction, and that the isotope fractionation expressed in the residual pore water sulfate pool is inversely proportional to the net sulfate reduction rate. The sulfur isotope composition of pyrite acquires one value in the uppermost sediments, which may be overprinted by a second value in the deeper sediments, possibly due to iron release during anaerobic methane oxidation or iron diffusion from a higher zone of bacterial iron reduction. Our results have implications for modeling the sulfur isotope composition of the pyrite burial flux in the global biogeochemical sulfur cycle.

  4. Sulfur and strontium isotopic compositions of carbonate and evaporite rocks from the late Neoproterozoic–early Cambrian Bilara Group (Nagaur-Ganganagar Basin, India): Constraints on intrabasinal correlation and global sulfur cycle

    Digital Repository Service at National Institute of Oceanography (India)

    Mazumdar, A.; Strauss, H.

    Sulfur and strontium isotope ratios are presented for carbonate and evaporite rocks from the late Neoproterozoic and early Cambrian Bilara and Hanseran Evaporite Groups, NW India. The sulfur isotopic compositions of trace sulfate in carbonate rocks...

  5. Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

    Science.gov (United States)

    Shaheen, Robina; Abaunza, Mariana M; Jackson, Teresa L; McCabe, Justin; Savarino, Joël; Thiemens, Mark H

    2014-08-19

    Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.

  6. Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

    Science.gov (United States)

    Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

    2017-06-01

    Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope

  7. Bacterial Disproportionation of Elemental Sulfur Inferred from a Field Study of Stable-Isotope Fractionations between Elemental Sulfur and Pyrite

    Science.gov (United States)

    Hardisty, D.; Pratt, L. M.; Olyphant, G. A.; Bell, J.; Johnson, A.

    2011-12-01

    Elemental sulfur (ES) is a common product of pyrite oxidation during acid mine drainage (AMD), but bacterial disproportionation of ES has not previously been inferred in acidic environments. Pore water profiles were collected seasonally within a coal-mine waste deposit, Minnehaha, in Southwest Indiana that has been abandoned for over 30 years. Geochemical characterization and modeling were used to assess how the interactions between the sulfur and iron cycle are affected by seasonally dynamic hydrologic conditions. Pore waters were collected seasonally and concentrations of Fe-species and sulfur isotopic compositions of sulfate were determined. Additionally, a sediment core was collected and used for sequential extraction and isotopic characterization of solid-phase sulfur species including elemental sulfur (δ34Ses), pyrite (δ34Spy), acid-volatile sulfides, water-soluble sulfates, and acid-soluble sulfates. The dominant disulfide phase was found to be pyrite through x-ray diffraction of an additional sediment core. Sulfur isotope fractionations between δ34Spy and δ34Ses (Δ34Ses-py) of up to -33% are inferred to indicate bacterial disproportionation of ES in the presence of a non-limiting sulfide 'scrub' Fe(III). The initial isotopic composition, following formation from pyrite oxidation, is inferred from δ34Spy, found to be ≈ 8.75% at the study site. Although ES has previously been found to accumulate in acidic Fe(III)-rich pore waters, ES is typically assumed to account for less than 1% of the oxidized sulfur pool and measurements of the ES isotopic composition are often neglected during field studies of acid AMD. The pore waters at Minnehaha were seasonally suboxic with sharp transitions from Fe(III)- to Fe(II)- dominated conditions near the phreatic surface. It is hypothesized that the sulfide product of ES disproportionation, fractionated by up to -8.6%, is immediately re-oxidized to ES near the redox gradient via reaction with Fe(III). Sulfide re

  8. The minor sulfur isotope composition of Cretaceous and Cenozoic seawater sulfate

    Science.gov (United States)

    Masterson, A. L.; Wing, Boswell A.; Paytan, Adina; Farquhar, James; Johnston, David T.

    2016-06-01

    The last 125 Myr capture major changes in the chemical composition of the ocean and associated geochemical and biogeochemical cycling. The sulfur isotopic composition of seawater sulfate, as proxied in marine barite, is one of the more perplexing geochemical records through this interval. Numerous analytical and geochemical modeling approaches have targeted this record. In this study we extend the empirical isotope record of seawater sulfate to therefore include the two minor sulfur isotopes, 33S and 36S. These data record a distribution of values around means of Δ33S and Δ36S of 0.043 ± 0.016‰ and -0.39 ± 0.15‰, which regardless of δ34S-based binning strategy is consistent with a signal population of values throughout this interval. We demonstrate with simple box modeling that substantial changes in pyrite burial and evaporite sulfate weathering can be accommodated within the range of our observed isotopic values.

  9. Improved analytical techniques of sulfur isotopic composition in nanomole quantities by MC-ICP-MS.

    Science.gov (United States)

    Yu, Tsai-Luen; Wang, Bo-Shian; Shen, Chuan-Chou; Wang, Pei-Ling; Yang, Tsanyao Frank; Burr, George S; Chen, Yue-Gau

    2017-10-02

    We propose an improved method for precise sulfur isotopic measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in conjunction with a membrane desolvation nebulization system. The problems of sulfur loss through the membrane desolvation apparatus are carefully quantified and resolved. The method overcomes low intrinsic sulfur transmission through the instrument, which was initially 1% when operating at a desolvation temperature of 160 °C. Sulfur loss through the membrane desolvation apparatus was resolved by doping with sodium. A Na/S ratio of 2 mol mol(-1) produced sulfur transmissions with 98% recovery. Samples of 3 nmol (100 ng) sulfur achieved an external precision of ±0.18‰ (2 SD) for δ(34)S and ±0.10‰ (2 SD) for Δ(33)S (uppercase delta expresses the extent of mass-independent isotopic fractionation). Measurements made on certified reference materials and in-house standards demonstrate analytical accuracy and reproducibility. We applied the method to examine microbial-induced sulfur transformation in marine sediment pore waters from the sulfate-methane transition zone. The technique is quite versatile, and can be applied to a range of materials, including natural waters and minerals. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Sulfur Isotopic Fractionation During Vacuum Ultraviolet Photolysis of SO2: Implication for Meteorites and Early Earth

    Science.gov (United States)

    Chakraborty, S.; Jackson, T. L.; Rude, B.; Ahmed, M.; Thiemens, M. H.

    2016-12-01

    Several sulfur bearing gas phase species existed in the solar nebula, including H2S, SO2, SiS, OCS, CS2, CS, NS and SO as a consequence of multiple available chemical valence states (S2- to S6+). Sulfur directly condensed into refractory phases in the solar nebula under reducing conditions. Mass independent (MI) sulfur isotopic compositions have been measured in chondrules and organics from chondritic meteorites. Large 33S excesses in sulfides from achondrite meteoritic groups have also been found suggesting that refractory sulfide minerals condensed from a nebular gas with an enhanced carbon to oxygen ratio. Photochemical reactions in the early solar nebula have been inferred to be a leading process in generating MI sulfur compositions. Previously, we have reported wavelength dependent mass-independent sulfur isotopic compositions (with a varying degree in D33S and D36S) in the product elemental sulfur during vacuum ultraviolet (VUV) photodissociation of H2S. Recently we performed photodissociation of SO2 experiments in the wavelength region 98 to 200 nm at low pressures (0.5 torr) using the VUV photons from the Advanced Light Source Synchrotron in a differentially pumped reaction chamber. To our knowledge, this is the first ever experiment to determine the isotopic fractionation in VUV photodissociation of SO2. At VUV energy region, SO2 is mostly predissociative. The measured sulfur isotopic compositions in the product elemental sulfur are MI and dependent on the wavelength. These new results support the previous finding from photodissociation of other di- and tri-atomic molecules (CO, N2, H2S) that predissociative photodissociation produces MI isotopic products and is a quantum mechanically driven selective phenomenon. These new results are useful because (i) they are important in interpreting meteoritic data and decipher sulfur chemistry in the early nebula which is indicative of the redox condition of the nebula (ii) SO2 photolysis in the atmosphere of early

  11. Sulfur isotopic composition and source identification of atmospheric environment in central Zhejiang,China

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Sulfur dioxide and sulfate aerosols in the atmosphere are significant factors leading to acidification of the atmospheric environment and worsening the pollution of acid deposition. Because of the "fingerprint" characteristics of the stable sulfur isotopic composition, sulfur isotope has been widely adopted in environmental researches concerning sulfur cycle and source identification. In this study, the atmospheric environment of Jinhua City, central Zhejiang Province, was continuously monitored, and the sulfur isotopic composition of SO2 and sulfate aerosols in the atmosphere was analyzed. The results indicate that the variation of δ34S values for SO2 ranges from 1.0‰ to 7.5‰, and annual average is 4.7‰±2.3‰, whereas that of sulfate aerosols ranges from 6.4‰ to 9.8‰,and annual average is 8.1‰±1.0‰. The δ 34S values for SO2 have significant seasonal variations, which are 7.0‰ in winter and 3.3‰ in summer. These variations cannot be attributed to a single factor, and we suggest a temperature-dependent isotope equilibrium fractionation and elevated biogenic sulfur emissions of isotopically light S in summer may be the main controlling mechanisms. Furthermore, we also discuss the δ 34S model of atmospheric SO2 oxidation to form sulfate, and suggest that heterogeneous oxidation dominates in the oxidation reactions of atmospheric SO2 in the central Zhejiang Province. We further suggest that the relative humidity in the atmosphere plays an important role in the oxidation mechanism of atmospheric SO2.

  12. Recent sedimentation in the Black Sea: New insights from radionuclide distributions and sulfur isotopes

    Science.gov (United States)

    Yücel, Mustafa; Moore, Willard S.; Butler, Ian B.; Boyce, Adrian; Luther, George W., III

    2012-08-01

    The Black Sea is the world's largest anoxic-sulfidic marine basin and has unique sedimentation conditions. Recent studies suggested that mass accumulation rates (MAR) in this environment have increased in the past century when compared to the last 2000 years (Unit 1 period). In this paper we test this hypothesis with new MAR data and further explore the relationship between the depositional pattern and pyrite-sulfur isotopic signature. Based on 15 cores sampled in 2001 and 2003, our dataset comprises radioactive isotopes (210Pb, 226Ra, 137Cs) and sulfur stable isotopes (δ34SVCDT) along with organic, inorganic carbon and pyrite-sulfur. We calculated MARs using 210Pb profiles and/or Chernobyl-derived 137Cs horizon buried in the sediment column. Our turbidite-free deep basin sediment MARs (61 to 76 g m-2 yr-1) agreed with the previous results (50-100 g m-2 yr-1) and confirm the view that MARs of the deep Black Sea basin have been increasing. A unique feature of our dataset was the presence of Chernobyl-derived radionuclides below up to 20 cm thick turbidite layers (deposited between 1986 and 2003), which enabled us to compute MARs for these coring locations. MARs were 1120±103 and 5230±125 g m-2 yr-1 for the last two decades in two turbidite-impacted western central basin cores, 20-100 times the long-term rates of the deep basin. This fast depositional pattern was reflected in the geochemical and isotopic data as well. Turbidites had isotopically heavier pyrite-sulfur compared to the Unit 1-type water column formed pyrite. This is probably because the turbidites originated from slope and transported slope pyrite isotopic signature to the deep basin. Diagenetic effects within the turbidite can make pyrite-sulfur even heavier. These tightly linked results demonstrate the importance of turbidites in recent sedimentation of the Black Sea.

  13. Primary multiple sulfur isotopic compositions of pyrite in 2.7 Ga shales from the Joy Lake sequence (Superior Province) show felsic volcanic array-like signature

    Science.gov (United States)

    Li, Jianghanyang; Zhang, Zhe; Stern, Richard A.; Hannah, Judith L.; Stein, Holly J.; Yang, Gang; Li, Long

    2017-04-01

    Multiple sulfur isotopes provide a powerful tool to study photochemical and biological processes controlling the Archean sulfur cycle and infer related atmospheric and marine environments. However, our understanding of early Earth's environment remains limited by the availability of well-preserved geological samples, as most Archean sedimentary rocks have experienced some degree of metamorphic alteration. To evaluate sulfur isotopic behavior during post-depositional processes and elucidate the sulfur cycle at 2.7 Ga, we use high-resolution in situ analytical techniques (EPMA and SIMS) to determine elemental compositions and multiple sulfur isotopic compositions of large diagenetic pyrite nodules and fine-grained secondary pyrite disseminated in quartz veins (formed during a lower greenschist metamorphic event) in shales from the 2.7 Ga Joy Lake sequence in the southwest Superior Province. Results show that trace metals and sulfur in the secondary pyrite were derived from both metamorphic fluid and pre-existing diagenetic pyrite. Diagenetic pyrite nodules could have been partially dissolved by metamorphic fluid. But the surviving nodules show elemental and isotopic features different from those of the deduced metamorphic fluid endmember, suggesting the nodules were not geochemically altered by metamorphism, and thus preserve primary isotopic signatures acquired during diagenesis. The sulfur isotopic ratios of pyrite nodules show strong variations, with decreasing δ34S values and increasing Δ33S values from cores to rims. This negative Δ33S-δ34S relationship is different from the commonly observed 'Archean reference line' defined by most Archean pyrite data, but similar to the 'felsic volcanic array'. Our observation provides a first possible case from 2.7 Ga, the age of peak crustal growth in the Archean, to support the hypothesis that photochemical pathways could be different under conditions of intense volcanic emission. This study also shows that high

  14. Multiple sulfur isotope signatures of sulfite and thiosulfate reduction by the model dissimilatory sulfate-reducer, Desulfovibrio alaskensis str. G20

    Directory of Open Access Journals (Sweden)

    William D. Leavitt

    2014-11-01

    Full Text Available Dissimilatory sulfate reduction serves as a key metabolic carbon remineralization process in anoxic marine environments. Sulfate reducing microorganisms can impart a wide range in mass-dependent sulfur isotopic fractionation. As such, the presence and relative activity of these organisms is identifiable from geological materials. By extension, sulfur isotope records are used to infer the redox balance of marine sedimentary environments, and the oxidation state of Earth’s oceans and atmosphere. However, recent work suggests that our understanding of microbial sulfate reducers (MSRs may be missing complexity associated with the presence and role of key chemical intermediates in the reductive process. This study provides a test of proposed metabolic models of sulfate reduction by growing an axenic culture of the well-studied MSRs, Desulfovibrio alaskensis strain G20, under electron donor limited conditions on the terminal electron acceptors sulfate, sulfite or thiosulfate, and tracking the multiple S isotopic consequences of each condition set. The dissimilatory reduction of thiosulfate and sulfite produce unique minor isotope effects, as compared to the reduction of sulfate. Further, these experiments reveal a complex biochemistry associated with sulfite reduction. That is, under high sulfite concentrations, sulfur is shuttled to an intermediate pool of thiosulfate. Site-specific isotope fractionation (within thiosulfate is very large (34ε ~ 30‰ while terminal product sulfide carries only a small fractionation from the initial sulfite (34ε < 10‰: a signature similar in magnitude to sulfate and thiosulfate reduction. Together these findings show that microbial sulfate reduction (MSR is highly sensitive to the concentration of environmentally important sulfur-cycle intermediates (sulfite and thiosulfate, especially when thiosulfate and the large site-specific isotope effects are involved.

  15. Carbon and Sulfur Isotopic Signatures of Ancient Life and Environment at the Microbial Scale: Neoarchean Shales and Carbonates

    Science.gov (United States)

    Williford, K. H.; Ushikubo, T.; Lepot, K.; Kitajima, K.; Hallmann, C.; Spicuzza, M. J.; Kozdon, R.; Eigenbrode, J. L.; Summons, R. E.; Valley, J. W.

    2015-01-01

    An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of delta(sup 13)C, delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS delta(sup 13)C measurement of organic matter is identified. Small (2-3 microns) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-micron domains of kerogen in a single approx. 0.5 cu cm sample of the approx. 2.7 Ga Tumbiana Formation have delta(sup 13)C = -52.3 +/- 0.1per mille and -34.4 +/- 0.1per mille, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the approx. 2.6 Ga Jeerinah Formation and the approx. 2.5 Ga Mount McRae Shale is systematically 13C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Delta(sup 33)S and more extreme spatial gradients in Delta(sup 33)S and Delta(sup 36)S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of delta(sup 34)S, Delta(sup 33)S, and Delta(sup 36)S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation

  16. Carbon and sulfur isotopic signatures of ancient life and environment at the microbial scale: Neoarchean shales and carbonates.

    Science.gov (United States)

    Williford, K H; Ushikubo, T; Lepot, K; Kitajima, K; Hallmann, C; Spicuzza, M J; Kozdon, R; Eigenbrode, J L; Summons, R E; Valley, J W

    2016-03-01

    An approach to coordinated, spatially resolved, in situ carbon isotope analysis of organic matter and carbonate minerals, and sulfur three- and four-isotope analysis of pyrite with an unprecedented combination of spatial resolution, precision, and accuracy is described. Organic matter and pyrite from eleven rock samples of Neoarchean drill core express nearly the entire range of δ(13) C, δ(34) S, Δ(33) S, and Δ(36) S known from the geologic record, commonly in correlation with morphology, mineralogy, and elemental composition. A new analytical approach (including a set of organic calibration standards) to account for a strong correlation between H/C and instrumental bias in SIMS δ(13) C measurement of organic matter is identified. Small (2-3 μm) organic domains in carbonate matrices are analyzed with sub-permil accuracy and precision. Separate 20- to 50-μm domains of kerogen in a single ~0.5 cm(3) sample of the ~2.7 Ga Tumbiana Formation have δ(13) C = -52.3 ± 0.1‰ and -34.4 ± 0.1‰, likely preserving distinct signatures of methanotrophy and photoautotrophy. Pyrobitumen in the ~2.6 Ga Jeerinah Formation and the ~2.5 Ga Mount McRae Shale is systematically (13) C-enriched relative to co-occurring kerogen, and associations with uraniferous mineral grains suggest radiolytic alteration. A large range in sulfur isotopic compositions (including higher Δ(33) S and more extreme spatial gradients in Δ(33) S and Δ(36) S than any previously reported) are observed in correlation with morphology and associated mineralogy. Changing systematics of δ(34) S, Δ(33) S, and Δ(36) S, previously investigated at the millimeter to centimeter scale using bulk analysis, are shown to occur at the micrometer scale of individual pyrite grains. These results support the emerging view that the dampened signature of mass-independent sulfur isotope fractionation (S-MIF) associated with the Mesoarchean continued into the early Neoarchean, and that the connections

  17. Isotope determination of sulfur by mass spectrometry in soil samples

    Directory of Open Access Journals (Sweden)

    Alexssandra Luiza Rodrigues Molina Rossete

    2012-12-01

    Full Text Available Sulphur plays an essential role in plants and is one of the main nutrients in several metabolic processes. It has four stable isotopes (32S, 33S, 34S, and 36S with a natural abundance of 95.00, 0.76, 4.22, and 0.014 in atom %, respectively. A method for isotopic determination of S by isotope-ratio mass spectrometry (IRMS in soil samples is proposed. The procedure involves the oxidation of organic S to sulphate (S-SO4(2-, which was determined by dry combustion with alkaline oxidizing agents. The total S-SO4(2- concentration was determined by turbidimetry and the results showed that the conversion process was adequate. To produce gaseous SO2 gas, BaSO4 was thermally decomposed in a vacuum system at 900 ºC in the presence of NaPO3. The isotope determination of S (atom % 34S atoms was carried out by isotope ratio mass spectrometry (IRMS. In this work, the labeled material (K2(34SO4 was used to validate the method of isotopic determination of S; the results were precise and accurate, showing the viability of the proposed method.

  18. Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

    DEFF Research Database (Denmark)

    Habicht, K S; Canfield, D E

    1997-01-01

    Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate...... concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S...... sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying...

  19. Source of arsenic-bearing pyrite in southwestern Vermont, USA: sulfur isotope evidence.

    Science.gov (United States)

    Mango, Helen; Ryan, Peter

    2015-02-01

    Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ(34)S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to >2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from -5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in (34)S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ(34)S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ(34)S values.

  20. In situ Nd isotopic measurement of natural geological materials by LA-MC-ICPMS

    Institute of Scientific and Technical Information of China (English)

    YANG YueHeng; SUN JinFeng; XIE LieWen; FAN HongRui; WU FuYuan

    2008-01-01

    Using newly determined Sm isotopic abundances for correcting the isobaric interference of 144Sm on 144Nd and the established mass bias relationship between Sm and Nd, a series of in situ Nd isotopic measurements were conducted for relatively high Nd concentrations of natural geological materials, including apatite, titanite, monazite and perovskite on a Neptune multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS), coupled to a 193 nm ArF excimer laser ablation system. The results show that Ce has no significant influence on the precision and accuracy of Nd isotopic analyses for LREE-enriched geological minerals and that our approach is efficient in obtaining reliable 143Nd/144Nd and 147Sm/144Nd ratios for those materials with Sm/Nd<1 (147Sm/144Nd<0.6). When combined with trace element and U-Pb isotope data, the in situ Nd isotopic data can provide important information on geological processes.

  1. Regional source identification of atmospheric aerosols in Beijing based on sulfur isotopic compositions

    Science.gov (United States)

    Lianfang, Wei; Pingqing, Fu; Xiaokun, Han; Qingjun, Guo; Yele, Sun; Zifa, Wang

    2016-04-01

    65 daily PM2.5 (aerosol particle with aerodynamic diameter less than 2.5 μm) samples were collected from an urban site in Beijing in four months representing the four seasons between September 2013 and July 2014. Inorganic ions, organic/elemental carbon and stable sulfur isotopes of sulfate aerosols were analyzed systematically. The "fingerprint" characteristics of the stable sulfur isotopic composition, together with trajectory clustering modeled by HYSPLIT-4 and potential source contribution function (PSCF), were employed for identifying potential regional sources. Results obviously exhibited the distinctive seasonality for various aerosol speciation associated with PM2.5 in Beijing with sulfate, nitrate, ammonium, organic matter, and element carbon being the dominant species. Elevated chloride associated with higher concentration of organics were found in autumn and winter, due to enhanced coal combustion emissions. The δ34S values of Beijing aerosol samples ranged from 2.94‰ to 10.2‰ with an average value of 6.18±1.87‰ indicating that the major sulfur source is direct fossil fuel burning-related emissions. Owning to a temperature-dependent fractionation and elevated biogenic sources of isotopically light sulfur in summer, the δ34S values had significant seasonal variations with a winter maximum ( 8.6‰)and a summer minimum ( 5.0‰). The results of trajectory clustering and the PSCF method demonstrated that higher concentrations of sulfate with lower sulfur isotope ratios ( 4.83‰) were associated with air masses from the south, southeast or east, whereas lower sulfate concentrations with higher δ34S values ( 6.69‰) when the air masses were mainly from north or northwest. These results suggested two main different kinds of regional coal combustion sources contributed to the pollution in Beijing.

  2. Sulfur- and oxygen-isotopes in sediment-hosted stratiform barite deposits

    Science.gov (United States)

    Johnson, C.A.; Emsbo, P.; Poole, F.G.; Rye, R.O.

    2009-01-01

    Sulfur- and oxygen-isotope analyses have been obtained for sediment-hosted stratiform barite deposits in Alaska, Nevada, Mexico, and China to examine the environment of formation of this deposit type. The barite is contained in sedimentary sequences as old as Late Neoproterozoic and as young as Mississippian. If previously published data for other localities are considered, sulfur- and oxygen-isotope data are now available for deposits spanning a host-rock age range of Late Neoproterozoic to Triassic. On a ??34S versus ??18O diagram, many deposits show linear or concave-upward trends that project down toward the isotopic composition of seawater sulfate. The trends suggest that barite formed from seawater sulfate that had been isotopically modified to varying degrees. The ??34S versus ??18O patterns resemble patterns that have been observed in the modern oceans in pore water sulfate and water column sulfate in some anoxic basins. However, the closest isotopic analog is barite mineralization that occurs at fluid seeps on modern continental margins. Thus the data favor genetic models for the deposits in which barium was delivered by seafloor seeps over models in which barium was delivered by sedimentation of pelagic organisms. The isotopic variations within the deposits appear to reflect bacterial sulfate reduction operating at different rates and possibly with different electron donors, oxygen isotope exchange between reduction intermediates and H2O, and sulfate availability. Because they are isotopically heterogeneous, sediment-hosted stratiform barite deposits are of limited value in reconstructing the isotopic composition of ancient seawater sulfate.

  3. A comprehensive sulfur and oxygen isotope study of sulfur cycling in a shallow, hyper-euxinic meromictic lake

    Science.gov (United States)

    Gilhooly, William P.; Reinhard, Christopher T.; Lyons, Timothy W.

    2016-09-01

    Mahoney Lake is a permanently anoxic and sulfidic (euxinic) lake that has a dense plate of purple sulfur bacteria positioned at mid-water depth (∼7 m) where free sulfide intercepts the photic zone. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and the water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within an aquatic environment with extremely high sulfide concentrations (>30 mM). Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S > 50‰) are consistent with sulfate reduction in both the sediments and the anoxic water column. Given the high sulfide concentrations of the lake, sulfur disproportionation is likely inoperable or limited to a very narrow zone in the chemocline, and therefore the large instantaneous fractionations are best explained by the microbial process of sulfate reduction. Pyrite extracted from the sediments reflects the isotopic composition of water column sulfide, suggesting that pyrite buried in the euxinic depocenter of the lake formed in the water column. The offset between sulfate and dissolved sulfide decreases at the chemocline (δ34SSO4-H2S = 37‰), a trend possibly explained by elevated sulfate reduction rates and inconsistent with appreciable disproportionation within this interval. Water column sulfate exhibits a linear response in δ18OSO4-δ34SSO4 and the slope of this relationship suggests relatively high sulfate reduction rates that appear to respond to seasonal changes in the productivity of purple sulfur bacteria. Although photosynthetic activity within the microbial plate influences the δ18OSO4-δ34SSO4 relationship, the biosignature for photosynthetic sulfur bacteria is restricted to the oxic/anoxic transition zone and is apparently minor relative to the more prevalent process of

  4. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

    Science.gov (United States)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  5. Early inner solar system origin for anomalous sulfur isotopes in differentiated protoplanets.

    Science.gov (United States)

    Antonelli, Michael A; Kim, Sang-Tae; Peters, Marc; Labidi, Jabrane; Cartigny, Pierre; Walker, Richard J; Lyons, James R; Hoek, Joost; Farquhar, James

    2014-12-16

    Achondrite meteorites have anomalous enrichments in (33)S, relative to chondrites, which have been attributed to photochemistry in the solar nebula. However, the putative photochemical reactions remain elusive, and predicted accompanying (33)S depletions have not previously been found, which could indicate an erroneous assumption regarding the origins of the (33)S anomalies, or of the bulk solar system S-isotope composition. Here, we report well-resolved anomalous (33)S depletions in IIIF iron meteorites (solar system (solar system S-isotope composition was chondritic (consistent with IAB iron meteorites, Earth, Moon, and Mars). The range of mass-independent sulfur isotope compositions may reflect spatial or temporal changes influenced by photochemical processes. A tentative correlation between S isotopes and Hf-W core segregation ages suggests that the two systems may be influenced by common factors, such as nebular location and volatile content.

  6. Atmospheric oxygen levels in the precambrian: a review of isotopic and geological evidence

    Science.gov (United States)

    Lambert, I. B.; Donnelly, T. H.

    1991-12-01

    The significant change in the sulfur isotope record in the early Proterozoic implies global scale oxidation of the previously reduced and sulfate-poor hydrosphere. Changes in the nature/abundance of uranium, iron and manganese deposits are consistent with the evolution of significant oxygen levels in the atmosphere in this period. It is suggested that global oxidation occurred in the early Proterozoic as a result of widespread development of sedimentary environments favourable for the proliferation of phytosynthetic organisms, coupled with steadily decreasing availability of ferrous iron, an important oxygen buffer, because of generally declining igneous and hydrothermal activity. There is a predominance of positive δ34S values for sulfides in Proterozoic carbonaceous strata and sediment-hosted mineral deposits, although the uncommonly preserved evaporitic sulfate deposits do not provide evidence of unusual 34S-enrichment in contemporaneous seawater. These data can be explained in terms of a supercontinent on which there was extensive sedimentation in major intracratonic troughs and platforms. This model is consistent with geological and palaeomagnetic data for this era. In the many sedimentary basins which had only occasional, or no, access to the open ocean, variably 34S-enriched sulfides accumulated by high rates and high degrees of biological sulfate reduction, and also by hydrothermal processes. Pyrite in Proterozoic open marine strata should have had mainly variable negative δ34S values, but few examples of such sequences occur in the geological record for this era. Late Proterozoic carbonates (ca. 900-600 m.y.) from different regions are characterised by mainly positive δ13C values. These are explained as the result of long-term global oceanic anoxia, which may have been a function of prolonged crustal stability preceding continental dispersion around the Proterozoic-Cambrian boundary. Significant rises in atmospheric oxygen levels would have resulted

  7. Determination of uranium isotopes in environmental samples by anion exchange in sulfuric and hydrochloric acid media.

    Science.gov (United States)

    Popov, L

    2016-09-01

    Method for determination of uranium isotopes in various environmental samples is presented. The major advantages of the method are the low cost of the analysis, high radiochemical yields and good decontamination factors from the matrix elements, natural and man-made radionuclides. The separation and purification of uranium is attained by adsorption with strong base anion exchange resin in sulfuric and hydrochloric acid media. Uranium is electrodeposited on a stainless steel disk and measured by alpha spectrometry. The analytical method has been applied for the determination of concentrations of uranium isotopes in mineral, spring and tap waters from Bulgaria. The analytical quality was checked by analyzing reference materials.

  8. Sulfur isotope analyses of individual aerosol particles in the urban aerosol at a central European site (Mainz, Germany

    Directory of Open Access Journals (Sweden)

    B. Winterholler

    2008-05-01

    Full Text Available Sulfur isotope analysis of atmospheric aerosols is a well established tool for identifying sources of sulfur in the atmosphere, estimating emission factors, and tracing the spread of sulfur from anthropogenic sources through ecosystems. Conventional gas mass spectrometry averages the isotopic compositions of several different types of sulfur aerosol particles, and therefore masks the individual isotopic signatures. In contrast, the new single particle technique presented here determines the isotopic signature of the individual particles.

    Primary aerosol particles retain the original isotopic signature of their source. The isotopic composition of secondary sulfates depends on the isotopic composition of precursor SO2 and the oxidation process. The fractionation with respect to the source SO2 is −9‰ for homogeneous and +16.5‰ for heterogeneous oxidation. The sulfur isotope ratio of secondary sulfate particles can therefore be used to identify the oxidation pathway by which this sulfate was formed. With the new single particle technique, different types of primary and secondary sulfates were first identified based on their chemical composition, and then their individual isotopic signature was measured separately. Our samples were collected in Mainz, Germany, in an urban environment. Secondary sulfates (ammonium sulfate, gypsum, mixed sulfates and coatings on silicates or organic aerosol dominated sulfate loadings in our samples. Comparison of the chemical and isotopic composition of secondary sulfates showed that the isotopic composition was homogeneous, independent of the chemical composition. This is typical for particles that derive from in-cloud processing. The isotopic composition of the source SO2 of secondary sulfates was calculated based on the isotopic composition of particles with known oxidation pathway and showed a strong dependence on wind direction. The contribution of heterogeneous

  9. Antiquity and evolutionary status of bacterial sulfate reduction: sulfur isotope evidence.

    Science.gov (United States)

    Schidlowski, M

    1979-09-01

    The presently available sedimentary sulfur isotope record for the Precambrian seems to allow the following conclusions: (1) In the Early Archaean, sedimentary delta 34S patterns attributable to bacteriogenic sulfate reduction are generally absent. In particular, the delta 34S spread observed in the Isua banded iron formation (3.7 x 10(9) yr) is extremely narrow and coincides completely with the respective spreads yielded by contemporaneous rocks of assumed mantle derivation. Incipient minor differentiation of the isotope pattersn notably of Archaean sulfates may be accounted for by photosynthetic sulfur bacteria rather than by sulfate reducers. (2) Isotopic evidence of dissimilatory sulfate reduction is first observed in the upper Archaean of the Aldan Shield, Siberia (approximately 3.0 x 10(9) yr) and in the Michipicoten and Woman River banded iron formations of Canada (2.75 x 10(9) yr). This narrows down the possible time of appearance of sulfate respirers to the interval 2.8--3.1 x 10(9) yr. (3) Various lines of evidence indicate that photosynthesis is older than sulfate respiration, the SO4(2-) Utilized by the first sulfate reducers deriving most probably from oxidation of reduced sulfur compounds by photosynthetic sulfur bacteria. Sulfate respiration must, in turn, have antedated oxygen respiration as O2-respiring multicellular eucaryotes appear late in the Precambrian. (4) With the bulk of sulfate in the Archaean oceans probably produced by photosynthetic sulfur bacteria, the accumulation of SO4(2-) in the ancient seas must have preceded the buildup of appreciable steady state levels of free oxygen. Hence, the occurrence of sulfate evaporites in Archaean sediments does not necessarily provide testimony of oxidation weathering on the ancient continents and, consequently, of the existence of an atmospheric oxygen reservoir.

  10. Variations of sulfur and carbon isotopes in seawater during the Doushantuo stage in late Neoproterozoic

    Institute of Scientific and Technical Information of China (English)

    ZHANG Tonggang; CHU Xuelei; ZHANG Qirui; FENG Lianjun; HUO Weiguo

    2003-01-01

    Successive analyses of sulfur and carbon isotopic compositions of carbonates strata in the Doushantuo Formation in the Yangtze area were accomplished through a method of extracting trace sulfate from carbonates. Sulfur and carbon isotopic compositions of coeval seawater were estimated from the samples that show the least diagenetic alteration. A high-resolution age curve of sulfur isotopes in seawater sulfates was obtained in the Doushantuo stage, which reflects thetrend of variation in seawater sulfur isotopes after the Neoproterozoic snowball Earth event. Similar characteristics of variation in carbon isotopes were observed in the coeval carbonates. A large positive δ34S excursion over +20‰ occurs in ancient seawater sulfates in the early Doushantuo stage. Simultaneously, the δ13C values in ancient seawater carbonates exhibit a positive excursion up to10‰. The maximum δ34S and δ13C values are +46.4‰ and +6.9‰, respectively. In the middle Doushantuo stage, the range of variation in δ34S values of seawater is relatively narrow, but δ13C values are quite high. Then, δ34S values of seawater become oscillating, and the same occurs in δ13C values. Negative excursions in δ34S and δ13C values occur simultaneously at the end of the Doushantuo stage, and the minimum δ34S and δ13C values dropped down to -10.1‰ and -5.7‰, respectively. The characteristics of variations in the sulfur and carbon isotopes of ancient seawater imply strong changes in oceanic environment that became beneficial to inhabitation and propagation of organism. The organic productivity and burial rate of organic carbon once reached a quite high level during the Doushantuo stage. However, the state of environment became unstable after the global glaciation. The global climate and environment possibly were fluctuating and reiterating. The negative excursions in δ34S and δ13C values occurring at the end of the Doushantuo stage may represent a global event, which might be related to

  11. Biogeochemistry of sulfur in the Vienna Woods: Study of sulfur stable isotope ratios by MC-ICP-MS as indicator of biogeochemical S cycling

    Science.gov (United States)

    Hanousek, Ondrej; Berger, Torsten W.; Prohaska, Thomas

    2014-05-01

    Sulfur entering forest ecosystems originates mainly from combustion of fossil fuels. This source of sulfur has been strongly (by more than 95 %) reduced in last decades and recently, higher sulfur output (in soil solution or stream water) than sulfur input (in rain water) in an ecosystem was registered in many monitored forest ecosystems. This unbalance may be caused by weathering of sulfur-bearing rocks, desorption of sulfur adsorbed in soil in the past or (re)mineralization of organic sulfur compounds. This 'negative' balance leads to mobilization of base cations along with SO42- and as such to an acidification of soils. As hypothesis, δ34S/32S depletion in stream water will be observed if a considerable proportion of atmospherically deposited sulfate is cycled through the organic S pool. Rain water and soil solutions samples were collected for this study at 3 sites (beech stands) in the Vienna Woods, Austria twice a month from May 2010 to April 2012. Due to the expected sulfate concentration gradient with respect to the distance from a tree, sampling was carried out at 5 intervals from a stem. The sulfur concentration in the samples was determined by ion chromatography. Sulfur isotope ratios (δ34S/32SV CDT) were analyzed by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in edge-resolution mode. The method was validated using IAEA-S-1 and IAEA-S-2 isotopic certified reference materials. The combined standard uncertainty of the measurement (uc = 0.10 %, k = 1) proves the suitability of the developed method. The concentration of sulfur in rain water showed expected behavior, with a seasonal maximum in winter months, in contrast to the corresponding δ34S/32SV CDT isotope ratios, where no or low seasonal trends were observed. The sulfur isotope ratios in soil solution samples show a dependence on the distance from a tree stem and the sampling depth with lower δ34S/32SV CDT ratios as compared to the precipitation. The measured isotopic

  12. Multiple sulfur isotope evidence for massive oceanic sulfate depletion in the aftermath of Snowball Earth

    Science.gov (United States)

    Sansjofre, Pierre; Cartigny, Pierre; Trindade, Ricardo I. F.; Nogueira, Afonso C. R.; Agrinier, Pierre; Ader, Magali

    2016-07-01

    The terminal Neoproterozoic Era (850-542 Ma) is characterized by the most pronounced positive sulfur isotope (34S/32S) excursions in Earth's history, with strong variability and maximum values averaging δ34S~+38‰. These excursions have been mostly interpreted in the framework of steady-state models, in which ocean sulfate concentrations do not fluctuate (that is, sulfate input equals sulfate output). Such models imply a large pyrite burial increase together with a dramatic fluctuation in the isotope composition of marine sulfate inputs, and/or a change in microbial sulfur metabolisms. Here, using multiple sulfur isotopes (33S/32S, 34S/32S and 36S/32S ratios) of carbonate-associated sulfate, we demonstrate that the steady-state assumption does not hold in the aftermath of the Marinoan Snowball Earth glaciation. The data attest instead to the most impressive event of oceanic sulfate drawdown in Earth's history, driven by an increased pyrite burial, which may have contributed to the Neoproterozoic oxygenation of the oceans and atmosphere.

  13. Sulfur and oxygen isotope geochemistry of acid mine drainage--the polymetallic sulfide deposit "himmelfahrt fundgrube" in Freiberg (Germany).

    Science.gov (United States)

    Haubrich, F; Tichomirowa, M

    2002-06-01

    We investigated physical, chemical and isotope (S, O) parameters of sulfate from acid mine drainage from the polymetallic sulfide ore deposit Freiberg (Gennany), which was mined for more than eight hundred years. Two main groups of water were distinguished: 1. Flowing mine water with sulfate concentrations of less than 9,000 mg/l and pH values higher than 3.2, 2. Pore water in weathered low grade ores and pools with sulfate concentrations higher than 9000mg/l and pH values below 3.2. The sulfur and oxygen isotope composition of sulfate from flowing mine waters reflects mixing of sulfate from two sulfur sources: a) atmospheric sulfur from precipitation and b) sulfate formed as a result of sulfide oxidation processes. Sulfur isotope values of mine water sulfate were used to estimate the contribution of sulfate derived through oxidation of sulfides. The sulfur isotope composition of pore water sulfate and precipitated sulfate (jarosite) from weathered low grade ore samples is identical to the sulfur isotope composition of primary sulfides. The oxygen isotope composition of pore water sulfate from low grade ore samples indicates that the oxidation process proceeds relatively slowly in 02-depleted waters, probably without significant microbial catalysis.

  14. Sulfur isotope geochemistry of ore and gangue minerals from the Silesian-Cracow Mississippi Valley-type ore district, Poland

    Science.gov (United States)

    Leach, D.L.; Vets, J.G.; Gent, C.A.

    1996-01-01

    Studies of the sulfur isotopic composition of ore and gangue minerals from the Silesian-Cracow Zn-Pb district were conducted to gain insights into processes that controlled the location and distribution of the ore deposits. Results of this study show that minerals from the Silesian-Cracow ore district have the largest range of sulfur isotope compositions in sulfides observed from any Mississippi Valley-type ore district in the world. The ??34S values for sulfide minerals range from +38 to -32 per mil for the entire paragenetic sequence but individual stages exhibit smaller ranges. There is a well developed correlation between the sulfur isotope composition and paragenetic stage of ore deposition. The first important ore stage contains mostly positive ??34S values, around 5 per mil. The second stage of ore formation are lower, with a median value of around -5 to -15 per mil, and with some values as low as -32 per mil. Late stage barite contains isotopically heavy sulfur around +32 per mil. The range in sulfur isotope compositions can be explained by contributions of sulfur from a variety of source rocks together with sulfur isotope fractionations produced by the reaction paths for sulfate reduction. Much of the variation in sulfur isotope compositions can be explained by bacterial reduction of sedimentary sulfate and disequilibrium reactions by intermediate-valency sulfur species, especially in the late-stage pyrite and sphalerite. Organic reduction of sulfate and thermal release of sulfur from coals in the Upper Silesian Coal Basin may have been important contributors to sulfur in the ore minerals. The sulfur isotopic data, ore mineral textures, and fluid inclusion data, are consistent with the hypothesis that fluid mixing was the dominant ore forming mechanism. The rather distinct lowering of ?? 34S values in sulfides from stage 2 to stage 3 is believed to reflect some fundamental change in the source of reduced sulfur and/or hydrology of the ore

  15. Sulfur Isotope Fractionation Due to SO2 Photolysis in the Atmosphere

    Science.gov (United States)

    Lyons, J. R.; Blackie, D.; Stark, G.; Pickering, J.

    2012-12-01

    The discovery of unusual (i.e. mass-independent) sulfur isotope fractionation (or MIF) in Archean and Paleoproterozoic sedimentary rocks has promised to yield insights into the rise of O2 and the nature of the sulfur cycle on ancient Earth [1], but interpretation has been hampered by the lack of a clear mechanism for the sulfur isotope signature. Proposed MIF mechanisms include SO2 photolysis [1-4], atmospheric S3 (thiozone) formation, and thermal sulfate reduction in sediments [5]. Studies focusing only on SO2 photolysis, including measurements of isotopic cross sections [6], have yielded results differing greatly from theory [4], and have resulted in improbable interpretations [7]. In addition to ancient rocks, there are sulfur isotope MIF signatures in polar ice core sulfates associated with massive Plinian eruptions over the past ~1000 years (e.g., [8]). The ice core MIF signatures differ significantly from the ancient Earth MIF signatures, suggesting a different source mechanism. SO2 photolysis can generate sulfur isotope MIF signatures in two ways: 1) self-shielding by an optically-thick column of SO2, and 2) isotope-dependent differences in absorption line intensities and widths, which are espcially important for optically-thin conditions. The MIF signatures in ice core sulfates appear to be consistent with self-shielding in an optically-thick plume, but the Archean MIF clearly is not. To address the optically-thin case, we've made high-resolution ultraviolet cross section measurements of the sulfur isotopologues of SO2 made with the UV FTS at Imperial College. We measured cross sections at 1 cm-1 spectral resolution for 32SO2, 33SO2, 34SO2 and for a 36SO2/34SO2 mixture. Incorporating these cross sections into a simple atmospheric photochemical model with a solar UV flux, we find sulfur MIF signatures for SO and S that.are consistent with the Archean pyrites. We also find that additional mass-dependent fractionation during self-shielding by 32SO2 places an

  16. Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

    Science.gov (United States)

    Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

    2016-09-01

    The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and

  17. Sulfur, carbon, hydrogen, and oxygen isotope geochemistry of the Idaho cobalt belt

    Science.gov (United States)

    Johnson, Craig A.; Bookstrom, Arthur A.; Slack, John F.

    2012-01-01

    Cobalt-copper ± gold deposits of the Idaho cobalt belt, including the deposits of the Blackbird district, have been analyzed for their sulfur, carbon, hydrogen, and oxygen isotope compositions to improve the understanding of ore formation. Previous genetic hypotheses have ranged widely, linking the ores to the sedimentary or diagenetic history of the host Mesoproterozoic sedimentary rocks, to Mesoproterozoic or Cretaceous magmatism, or to metamorphic shearing. The δ34S values are nearly uniform throughout the Blackbird dis- trict, with a mean value for cobaltite (CoAsS, the main cobalt mineral) of 8.0 ± 0.4‰ (n = 19). The data suggest that (1) sulfur was derived at least partly from sedimentary sources, (2) redox reactions involving sulfur were probably unimportant for ore deposition, and (3) the sulfur was probably transported to sites of ore for- mation as H2S. Hydrogen and oxygen isotope compositions of the ore-forming fluid, which are calculated from analyses of biotite-rich wall rocks and tourmaline, do not uniquely identify the source of the fluid; plausible sources include formation waters, metamorphic waters, and mixtures of magmatic and isotopically heavy meteoric waters. The calculated compositions are a poor match for the modified seawaters that form vol- canogenic massive sulfide (VMS) deposits. Carbon and oxygen isotope compositions of siderite, a mineral that is widespread, although sparse, at Blackbird, suggest formation from mixtures of sedimentary organic carbon and magmatic-metamorphic carbon. The isotopic compositions of calcite in alkaline dike rocks of uncertain age are consistent with a magmatic origin. Several lines of evidence suggest that siderite postdated the emplacement of cobalt and copper, so its significance for the ore-forming event is uncertain. From the stable isotope perspective, the mineral deposits of the Idaho cobalt belt contrast with typical VMS and sedimentary exhalative deposits. They show characteristics of deposit

  18. Sulfur isotopic fractionation and its implication: Sulfate formation in PM2.5 and coal combustion under different conditions

    Science.gov (United States)

    Chen, Shanli; Guo, Ziyan; Guo, Zhaobing; Guo, Qingjun; Zhang, Yanlin; Zhu, Bin; Zhang, Haixiao

    2017-09-01

    In order to exactly explore sulfur source and sulfate formation under highly polluted atmosphere, we determined δ34S values of sulfate in PM2.5 and atmospheric SO2 in Nanjing region from 1 to 23 Jan. 2014. The secondary sulfate formation mechanism was discussed based on sulfur isotopic fractionation in the process of SO2 oxidation. Meanwhile, we synchronously studied δ34S values of raw coals used locally as well as sulfur isotopic fractionation during the combustion under coal burning and smoldering. The results show that δ34S average values of SO2 and sulfate in PM2.5 were 1.5‰ and 5.1‰, respectively. δ34S values of sulfate in PM2.5 were consistent with those of coals widely used in Nanjing region and Northern China, indicating coal combustion was an important sulfur source for PM2.5. Sulfur isotopic fractionation factors ranged from 1.0014 to 1.0075, implying that SO2 heterogeneous and homogeneous oxidation were coexisting during the formation of the secondary sulfate. The contribution of SO2 heterogeneous oxidation to sulfate varied from 40.7% to 64.8% during the observation period. δ34S values of coals presented moderately positive sulfur isotopic signatures due to organic sulfur in low sulfur coals were mainly formed by plant assimilation. Besides, the negative relationship between δ34S values of coals and total sulfur contents was also found. In addition, there existed a significant sulfur isotopic fractionation effect during coal combustion. Sulfate in PM2.5 in flue gas enriched 34S, while SO2 in flue gas enriched 32S. There was presence of the difference of δ34S values in PM2.5 and SO2 in flue gas between coal burning and smoldering, which was related to coal property and combustion temperature.

  19. Matrix effects of calcium on high-precision sulfur isotope measurement by multiple-collector inductively coupled plasma mass spectrometry.

    Science.gov (United States)

    Liu, Chenhui; Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong

    2016-05-01

    Multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) has been successfully applied in the rapid and high-precision measurement for sulfur isotope ratios in recent years. During the measurement, the presence of matrix elements would affect the instrumental mass bias for sulfur and these matrix-induced effects have aroused a lot of researchers' interest. However, these studies have placed more weight on highlighting the necessity for their proposed correction protocols (e.g., chemical purification and matrix-matching) while less attention on the key property of the matrix element gives rise to the matrix effects. In this study, four groups of sulfate solutions, which have different concentrations of sulfur (0.05-0.60mM) but a constant sequence of atomic calcium/sulfur ratios (0.1-50), are investigated under wet (solution) and dry (desolvation) plasma conditions to make a detailed evaluation on the matrix effects from calcium on sulfur isotope measurement. Based on a series of comparative analyses, we indicated that, the matrix effects of calcium on both measured sulfur isotope ratios and detected (32)S signal intensities are dependent mainly on the absolute calcium concentration rather than its relative concentration ratio to sulfur (i.e., atomic calcium/sulfur ratio). Also, for the same group of samples, the matrix effects of calcium under dry plasma condition are much more significant than that of wet plasma. This research affords the opportunity to realize direct and relatively precise sulfur isotope measurement for evaporite gypsum, and further provides some suggestions with regard to sulfur isotope analytical protocols for sedimentary pore water.

  20. Sulfur-based absolute quantification of proteins using isotope dilution inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Lee, Hyun-Seok; Heun Kim, Sook; Jeong, Ji-Seon; Lee, Yong-Moon; Yim, Yong-Hyeon

    2015-10-01

    An element-based reductive approach provides an effective means of realizing International System of Units (SI) traceability for high-purity biological standards. Here, we develop an absolute protein quantification method using double isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) combined with microwave-assisted acid digestion for the first time. We validated the method and applied it to certify the candidate protein certified reference material (CRM) of human growth hormone (hGH). The concentration of hGH was determined by analysing the total amount of sulfur in hGH. Next, the size-exclusion chromatography method was used with ICP-MS to characterize and quantify sulfur-containing impurities. By subtracting the contribution of sulfur-containing impurities from the total sulfur content in the hGH CRM, we obtained a SI-traceable certification value. The quantification result obtained with the present method based on sulfur analysis was in excellent agreement with the result determined via a well-established protein quantification method based on amino acid analysis using conventional acid hydrolysis combined with an ID liquid chromatography-tandem mass spectrometry. The element-based protein quantification method developed here can be generally used for SI-traceable absolute quantification of proteins, especially pure-protein standards.

  1. High-resolution quadruple sulfur isotope analyses of 3.2 Ga pyrite from the Barberton Greenstone Belt in South Africa reveal distinct environmental controls on sulfide isotopic arrays

    NARCIS (Netherlands)

    Roerdink, D.L.; Mason, P.R.D.; Whitehouse, M.J.; Reimer, T.

    2013-01-01

    Multiple sulfur isotopes in Paleoarchean pyrite record valuable information on atmospheric processes and emerging microbial activity in the early sulfur cycle. Here, we report quadruple sulfur isotope data (32S, 33S, 34S, 36S) analyzed by secondary ion mass spectrometry from pyrite in a 3.26–3.23 Ga

  2. Research on isotope geology: Isotopes ages of volcanic rocks from Ryeongnam Massif, Korea

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Seong Cheon; Chi, Se Jung; Kim, Yoo Sook [Korea Institute of Geology Mining and Materials, Taejon (Korea, Republic of)

    1997-12-01

    Chronostratigraphy of most volcanic rocks in the Ryeongnam Massif have been undefined or mis-classified in different geological maps due to total absence of reported isotope ages. Twenty-four new isotope ages are given for age-undefined volcanic units and some related igneous bodies. Most of volcanic rocks show high [La/Yb]n ratios and LREE enrichments which are characteristics of subduction-related high-K calc-alkali volcanic rocks occurred in the active continental margin. Preliminary results on carbon and oxygen stable isotope ratios({delta}{sup 13}C=-1.7{approx}-6.2 per mil; {delta}{sup 18} O=-21.6{approx}-24.7 per mil) of druse- or phenocryst-calcite from andesitic and basaltic rocks in the southern coastal region indicate a magmatic origin. Based on new K-Ar whole-rock ages, chronological guidelines are established as follows: 1) Gayasan andesite (78{+-}4Ma) - Gurye andesitic tuff (81{+-}4Ma); 2) Gurye andesite (68{+-}4Ma) - Suncheon andesitic tuff (67{+-}3Ma) - Yeosu basaltic andesite (67{+-}3Ma) - Narodo andesite (70{+-}3Ma); 3) Taebaeg Baegbyeongsan basaltic andesite (62{+-}3Ma) - Gurye Obongsan andesite (64{+-}3Ma) - Yeosu dacite (63{+-}3Ma) - Dolsando andesite (62{+-}3Ma) - Jangheung Buyongsan andesite (65{+-}3Ma); 4) Suncheon Joryedong andesite (55{+-}2Ma) - Goheung andesite (56{+-}3Ma); 5) Taebaeg Baegbyeonsan basaltic andesite (48{+-}2Ma) - Yeosu basalt (51{+-}3Ma). Resetted age (49{+-}2Ma) of an intrusive rhyolite implies the timing of thermal alteration in the Wondong Fe-Mine of the Taebaegsan Mineralized Belt. K-Ar hornblende ages of two hornblendite stocks in the southern Jangsu suggests apparent emplacement-ages of late Triassic (210{+-}9Ma) and early Permian (274{+-}10Ma), independently. K-Ar hornblende age (1023{+-}37Ma) of the Ogbang amphibolite implies a reduction of original age due to later thermal effect probably attributed to either later intrusion or regional metamorphism. (author). 56 refs., 19 tabs., 14 figs.

  3. Source of arsenic-bearing pyrite in southwestern Vermont, USA: Sulfur isotope evidence

    Energy Technology Data Exchange (ETDEWEB)

    Mango, Helen, E-mail: helen.mango@castleton.edu [Department of Natural Sciences, Castleton State College, 233 South Street, Castleton, VT 05735 (United States); Ryan, Peter, E-mail: pryan@middlebury.edu [Department of Geology, Middlebury College, 276 Bicentennial Way, Middlebury, VT 05753 (United States)

    2015-02-01

    Arsenic-bearing pyrite is the source of arsenic in groundwater produced in late Cambrian and Ordovician gray and black slates and phyllites in the Taconic region of southwestern Vermont, USA. The aim of this study is to analyze the sulfur isotopic composition of this pyrite and determine if a relationship exists between pyrite δ{sup 34}S and arsenic content. Pyrite occurs in both sedimentary/diagenetic (bedding-parallel layers and framboids) and low-grade metamorphic (porphyroblast) forms, and contains up to > 2000 ppm As. The sulfur isotopic composition of arsenic-bearing pyrite ranges from − 5.2‰ to 63‰. In the marine environment, the sulfur in sedimentary pyrite becomes increasingly enriched in {sup 34}S as the geochemical environment becomes increasingly anoxic. There is a positive correlation between δ{sup 34}S and arsenic content in the Taconic pyrite, suggesting that uptake of arsenic by pyrite increased as the environment became more reducing. This increased anoxia may have been due to a rise in sea level and/or tectonic activity during the late Cambrian and Ordovician. Low-grade metamorphism appears to have little effect on sulfur isotope composition, but does correlate with lower arsenic content in pyrite. New groundwater wells drilled in this region should therefore avoid gray and black slates and phyllites that contain sedimentary/diagenetic pyrite with heavy δ{sup 34}S values. - Highlights: • Pyrite is the source of arsenic in groundwater in the Taconic region of Vermont, USA. • As-bearing pyrite δ{sup 34}S = – 5.2 to 63‰ with higher {sup 34}S as environment becomes more anoxic. • High sea level, tectonic activity create anoxia, with incorporation of As into pyrite. • New wells should avoid slate/phyllite containing sedimentary pyrite with heavy δ{sup 34}S.

  4. RARE ISOTOPIC SPECIES OF SULFUR MONOXIDE: THE ROTATIONAL SPECTRUM IN THE THz REGION

    Energy Technology Data Exchange (ETDEWEB)

    Lattanzi, Valerio; Cazzoli, Gabriele; Puzzarini, Cristina, E-mail: lattanzi@mpe.mpg.de [Dipartimento di Chimica “Giacomo Ciamician,” Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy)

    2015-11-01

    Many sulfur-bearing species have been detected in different astronomical environments and have allowed us to derive important information about the chemical and physical composition of interstellar regions. In particular, these species have also been shown to trace and probe hot-core environment time evolution. Among the most prominent sulfur-bearing molecules is SO, the sulfur monoxide radical, one of the more ubiquitous and abundant, which is also observed in its isotopic substituted species such as {sup 34}SO and S{sup 18}O. Due to the importance of this simple diatomic system, and in order to face the challenge of modern radioastronomical facilities, an extension to the THz range of the rare isotopologues of sulfur monoxide has been performed. High-resolution rotational molecular spectroscopy has been employed to extend the available data set of four isotopic species, SO, {sup 34}SO, S{sup 17}O, and S{sup 18}O, up to the 1.5 THz region. The frequency coverage and spectral resolution of our measurements allowed a better constraint of the molecular constants of the four species considered, specifically focusing on the two oxygen-substituted isotopologues. Our measurements were also employed in an isotopically invariant fit including all of the available pure rotational and ro-vibrational transitions for all of the SO isotopologues, thus enabling accurate predictions of the rotational transitions at higher frequencies. We also provide comparisons with recent works performed on the same system, demonstrating the quality of our experiment and the improvement of the data sets for all of the species considered. Transition frequencies for this system can now be used with confidence by the astronomical community well into the THz spectral region.

  5. 云南兰坪盆地云龙组硫酸盐硫同位素特征及其地质意义%Sulfur isotopic composition of sulfate and its geological significance of the Yunlong formation in the Lanping Basin, Yunnan Province

    Institute of Scientific and Technical Information of China (English)

    王立成; 刘成林; 费明明; 沈立建; 张华

    2014-01-01

    位于三江特提斯南段的兰坪盆地,发育云龙组含石膏‐石盐的蒸发岩系,这些蒸发岩系不仅对钾盐研究,而且对著名的金顶铅锌矿的成因有着重要意义。近年来,在其南端思茅盆地的研究提出了可以与云龙组相对比的勐野井组蒸发岩为新特提斯自西而东的海侵所致。那么,兰坪盆地沉积的蒸发岩是否也是来自于同时期的新特提斯海水?因此,通过系统的露头采样,本文开展了岩相学和石膏硫同位素研究。结果表明,兰坪金顶、小盐井、拉井和河西乡原生石膏样品δ34 S值在12.6‰~17.6‰之间,且主要集中在13‰~15‰范围内,几乎没有受到细菌还原作用的影响。这与思茅盆地勐野井组下段硬石膏、老挝他曲盆地含钾盐塔贡组基底硬石膏和泰国坷叻盆地含钾盐马哈萨拉堪组基底硬石膏的硫同位素值一致。云龙组石膏硫同位素值大部分样品落于白垩纪海水δ34 S范围内,表明石膏为海相成因。根据前人古地理和古地磁资料,推断在晚白垩世时期,由于新特提斯洋的海侵,在兰坪‐思茅‐万象‐坷叻形成了相互连通的蒸发盆地系。%The Lanping Basin is situated in the south part of the Sanjiang Tethys .The Yunlong Formation in the Lanping Basin contains gypsum‐rock salts ,which is significant to origin of potash salts and Jinding Zn‐Pb deposit .Recent advances in the Simao Basin inferred that evaporates in the equivalent Mengyejing Formation originated from marine incursion of the Neo‐Tethys Ocean .Did evaporates of the Yunlong Formation originate from the Neo‐Tethys Ocean . A combined analysis of petrology and sulfur isotopic geochemistry was performed .The results show that sulfur isotope values of primary gypsum samples from Jinding ,Xiaoyanjing ,Lajing ,and Hexi are between 12 .6‰ ~17 .6‰ ,with most values in the range of 13‰ ~15‰ .These values ,which have no

  6. Multiple sulfur isotope records at the end-Guadalupian (Permian) at Chaotian, China: Implications for a role of bioturbation in the Phanerozoic sulfur cycle

    Science.gov (United States)

    Saitoh, Masafumi; Ueno, Yuichiro; Matsu'ura, Fumihiro; Kawamura, Tetsuya; Isozaki, Yukio; Yao, Jianxin; Ji, Zhansheng; Yoshida, Naohiro

    2017-03-01

    A recent study on quadruple sulfur isotopes (32S, 33S, 34S, and 36S) of sedimentary pyrite suggested that the end-Guadalupian extinction was caused by shoaling of the sulfidic deep-water. This scenario is based on the assumption that sulfur isotopic compositions of pyrite from hosting sediments were controlled by benthos activities, thus by the redox conditions of the sedimentary environments. Nonetheless, the relationship between the sulfur isotope records and redox conditions, reconstructed from litho- and bio-facies, are poorly known. In order to examine the effect of bioturbation in sediments, quadruple sulfur isotopic compositions of sedimentary pyrite from the end-Guadalupian succession in Chaotian, South China, were analyzed. Black mudstones of deep-water facies immediately below the extinction horizon have consistently high Δ33S values of ca. +0.079‰, clearly suggesting a sulfate reduction in the anoxic water column. Our new data are consistent with the emergence of a sulfidic deep-water mass prior to the end-Guadalupian extinction; the upwelling of the toxic deep-water may have contributed to the extinction. In contrast, shallow-marine bioclastic limestones with burrows deposited under oxic conditions have negative Δ33S values. This anomalous isotopic signal indicates the mixing of two distinct types of pyrite; one generated during the sulfate reduction in an open system and the other in a closed system. We interpret that bioturbation supplied sulfate in the sediments and promoted sulfate reduction and in-situ sulfide precipitation within the sediments. The negative Δ33S values of oxic sediments in Chaotian are inconsistent with the previous model and demonstrate that the sedimentary sulfur cycle associated with bioturbation was more complicated than previously thought. Our study also implies that, more generally, the role of bioturbation in increasing seawater sulfate concentration in the Phanerozoic may have been overestimated in the previous

  7. Characterization of fluid inclusions and sulfur isotopes in the Iju porphyry copper deposit, North West of Shahr-e-Babak

    Directory of Open Access Journals (Sweden)

    Malihe Golestani

    2017-07-01

    Full Text Available Introduction The Iju porphyry copper deposit is located in the southern part of the Urumieh-Dokhtar magmatic arc (Dehaj-Sarduieh belt within the Kerman copper belt (Dimitrijevic, 1973. The Porphyry Copper mineralization in the Iranian plate occurs dominantly along the Urumieh-Dokhtar arc, which has resulted from the subduction of the Arabian plate beneath the central Iran and the closure of the Neo-Tethys Ocean during the Alpine orogeny (Hassanzadeh, 1993. The Iju porphyry copper deposit with 25 million tons of ore reserves is one of the main copper deposits within the Kerman copper belt. The mining area is composed of upper Miocene volcanic and subvolcanic rocks (mineralized and barren subvolcanic rocks and quaternary deposits. Two hydrothermal alteration zones of quartz-sericite-pyrite and propylitic zones can be identified in the Iju area. The copper mineralization in the Iju deposit occurs as disseminated, stockwork and hydrothermal breccia. In the hypogene zone, the mineral paragenesis include chalcopyrite, pyrite, with minor occurrences of bornite and magnetite. This paper reports geological, mineralogical, fluid inclusion and S isotope data from the Iju deposit in order to investigate ore-bearing fluids’ characteristics and the mechanisms of ore deposition. Materials and methods Fifteen samples of syngenetic quartz+pyrite bearing veinlets within the quartz-sericite-pyrite zone were selected from different depths across the seven boreholes. Quartz was used for double-polished thin sections and pyrite was used for sulfur isotope analysis. Fluid inclusion studies were performed using the Linkam cooling and heating stage, the THMSG 600 model. The syngenetic pyrite with thermometry quartz sample was used for the sulfur isotope experiments. Stable isotope analysis was performed at the Hatch Stable Isotope Laboratory in the University of Ottawa, Canada. Results The fluid inclusions of the Iju deposit represent a wide range in the

  8. Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

    Science.gov (United States)

    Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

    2012-04-01

    Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7

  9. Sulfur and lead isotopic evidence of relic Archean sediments in the Pitcairn mantle plume

    Science.gov (United States)

    Delavault, Hélène; Chauvel, Catherine; Thomassot, Emilie; Devey, Colin W.; Dazas, Baptiste

    2016-11-01

    The isotopic diversity of oceanic island basalts (OIB) is usually attributed to the influence, in their sources, of ancient material recycled into the mantle, although the nature, age, and quantities of this material remain controversial. The unradiogenic Pb isotope signature of the enriched mantle I (EM I) source of basalts from, for example, Pitcairn or Walvis Ridge has been variously attributed to recycled pelagic sediments, lower continental crust, or recycled subcontinental lithosphere. Our study helps resolve this debate by showing that Pitcairn lavas contain sulfides whose sulfur isotopic compositions are affected by mass-independent fractionation (S-MIF down to Δ33S = -0.8), something which is thought to have occurred on Earth only before 2.45 Ga, constraining the youngest possible age of the EM I source component. With this independent age constraint and a Monte Carlo refinement modeling of lead isotopes, we place the likely Pitcairn source age at 2.5 Ga to 2.6 Ga. The Pb, Sr, Nd, and Hf isotopic mixing arrays show that the Archean EM I material was poor in trace elements, resembling Archean sediment. After subduction, this Archean sediment apparently remained stored in the deep Earth for billions of years before returning to the surface as Pitcairńs characteristic EM I signature. The presence of negative S-MIF in the deep mantle may also help resolve the problem of an apparent deficit of negative Δ33S anomalies so far found in surface reservoirs.

  10. Stable sulfur and oxygen isotopes as geochemical tracers of sulfate in karst waters

    Science.gov (United States)

    Sun, Jing; Kobayashi, Tatsuaki; Strosnider, William H. J.; Wu, Pan

    2017-08-01

    Karst water resources, which are extremely sensitive to mining activities, are critical for the support of human societies and ecological systems in many regions worldwide. In order to determine the sources and fate of dissolved sulfate in low-pH karst waters, hydrochemical variations of karst waters with and without acid mine drainage (AMD) impacts were investigated along with stable isotope dynamics. As expected, hydrochemical characteristics and isotopic compositions of the AMD and AMD-downstream water (ADW) were dramatically different from that of the non-AMD-impacted water (NAW). The sources of sulfur isotopes in sulfate were predominantly pyrite oxidation for the AMD and ADW, and atmospheric deposition for the NAW. Based on the general isotope-balance model, the relative proportions of sulfate oxygen derived from water and air were calculated. The mean proportion of sulfate oxygen derived from water in ADW was roughly double that of AMD. This suggests that the sulfate associated with AMD is predominantly influenced by aerobic pyrite oxidation, while that of ADW is likely affected by the dissolution of pyrite under anaerobic conditions in reservoir sediment. This observation was coincident with the noted variations of hydrochemical characteristics and was supported by principal component analysis. These results provide a better understanding of how stable isotopes of sulfate and water can be used to track mining contamination in karst aquifers, which could benefit remediation planning for these distinctive systems.

  11. Sulfur chemistry and isotopic ratios in the starburst galaxy NGC 253

    CERN Document Server

    Martín, S; Mauersberger, R; Henkel, C; García-Burillo, S

    2004-01-01

    Based on observations of the most abundant sulfur-bearing molecules (H2S, CS, NS, SO, H2CS, OCS, and SO2) carried out with the IRAM 30m telescope and SEST, we present the first analysis of the sulfur chemistry of an extragalactic source, the nuclear region of the starburst galaxy NGC 253. This is the first time that H2S and, tentatively, H2CS are detected towards the nucleus of a starburst galaxy. Source averaged fractional abundances of these molecules are a few 10^-9, except for CS and OCS which are more abundant (10^-8). Sulfur isotopic ratios, 32S/34S~8+-2 and 34S/33S>9, are measured through observations of 13CS, C34S, and C33S. A comparison with the observed relative abundances towards different prototypical Galactic sources suggests that the chemical composition of NGC 253 is similar to that found towards the molecular clouds complexes like Sgr B2 in the nuclear region of the Milky Way. The large overabundance of OCS compared to the predictions of time-dependent sulfur chemistry models supports the idea...

  12. Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico

    Science.gov (United States)

    Jimenez, A.

    2012-04-01

    Sulfur isotope study of the Velardeña skarn (Zn-Pb), Durango, Mexico Abigail Jimenez-Franco1*, Pura Alfonso Abella2, Carles Canet3, Eduardo González-Partida4 1 Posgrado en Ciencias de la Tierra, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 2 Departament d'Enginyeria Minera i Recursos Naturals, Universitat Politècnica de Catalunya, Av de Les Bases de Manresa 61-73, 08242 Manresa. 3Instituto de Geofísica, Universidad Nacional Autónoma de México, Ciudad Universitaria, Delegación Coyoacán, 04510 México D.F., Mexico 4Centro de Geociencias, Universidad Nacional Autónoma de México, Campus Juriquilla, Boulevard Juriquilla 3001, 76230 Santiago de Querétaro, Qro., Mexico The Velardeña mining district is located in north-eastern part of the state of Durango, in northern of Mexico. The ore deposit is a lead-zinc, garnet-rich skarn developed at the contact between granite porphyry dikes (Eocene) and well-laminated limestones with interbedded chert (Albian-Cenomanian). A study of sulfur isotopes has been carried out in various sulfide minerals of the ores of Velardeña, in order to: (a) constrain the possible sources of sulfur and, therefore, better understand the sulfide mineralizing processes, and (b) to estimate the temperature of the ore-forming stage of the skarn. Sulfur isotope analyses were performed in 21 pure fractions of sulfide minerals of the ore mineralization (pyrite, chalcopyrite, sphalerite and galena). The mineral separation was performed using a series of sieves, and the purity of the samples was verified under a binocular microscope. Isotopic analyses were done on a Finnigan MAT Delta C flow elemental analyzer coupled to a TC-EA, according with the method of Giesemann et al. (1974). The δ34S values of the analyzed sulfides range mostly between -0.6 and +2.6 ‰ (relative to the CDT standard). These values are indicative of a magmatic source of sulfur. A single analysis falls

  13. 湖北江陵凹陷古新统沙市组四段硫酸盐硫同位素组成及其地质意义%Sulfur Isotopic Composition of Sulfate and Its Geological Significance of Member 4 of Palaeocene Shashi Formation in Jiangling Depression of Hubei Province

    Institute of Scientific and Technical Information of China (English)

    王春连; 刘成林; 徐海明; 王立成; 沈立建

    2013-01-01

    The sulphur isotope of anhydrite and glauberite in Member 4 of Palaeocene Shashi Formation in Jiangling depression changes between 25.2‰-32.6‰,which is much higher than the sulphur isotope of synchronism sea water (20‰).Through the study of strontium isotope in evaporate in Member 4 of Palaeocene Shashi Formation and the comparison analysis of Mg,Ca,Sr,Ba content and Sr/Ba,Mg/Ca ratio,the authors propose that lake basin of Jiangling depression is closed continental salt lake facies.Primary glauberite,typically warm facies saline minerals,is widely developed in this formation.The Fe2O3/FeO ratio represents drought climate.This feature reveals that Palaeocene Shashi Formation of south Jiangling depression in Jianghan basin is drought and warm paleoclimate.In drought and warm paleoclimate condition,because of the low supply rate of sulphate deposites,the sedimentary environment at that time is closed to sulfate.Through the study of main trace element,including Fe,Mn,Al,Mg,Ca,Ni,V,Co,Cu and Fe/Mn,(Fe+Al)/(Ca+Mg),w(V+Ni+Mn),V/(V+Ni),Ni/Co,Cu/Zn ratio,it reveals that the environment of Member 4 of Shashi Formation is anoxic and reducing environment under wave base of lake basin,which is relative deep layered lake for years.A lot of anaerobic bacteria lived in this anoxic sedimentary environment.Under hypergene condition (≤50℃),anaerobic bacteria reduced SO2/4-to H2S,which reacted with metal ion to form sulfide or escaped from the system.In addition,the continental environment at that time is relative closed to sulfate.This cyclicprocess caused the high sulphur isotope value of anhydrite and glauberite,which was also the most important sulfur isotope fractionation process in the study area.%江汉盆地江陵凹陷古新统沙市组四段硬石膏和钙芒硝中硫同位素组成为25.2‰~32.6‰,远远高于同时期海水硫同位素(20‰).结合研究区古新统沙四段蒸发岩87 Sr/86 Sr研究,借助Mg、Ca、Sr、Ba等元素及其Mg/Ca、Sr/Ba,认

  14. Isotopically labeled sulfur compounds and synthetic selenium and tellurium analogues to study sulfur metabolism in marine bacteria

    Directory of Open Access Journals (Sweden)

    Nelson L. Brock

    2013-05-01

    Full Text Available Members of the marine Roseobacter clade can degrade dimethylsulfoniopropionate (DMSP via competing pathways releasing either methanethiol (MeSH or dimethyl sulfide (DMS. Deuterium-labeled [2H6]DMSP and the synthetic DMSP analogue dimethyltelluriopropionate (DMTeP were used in feeding experiments with the Roseobacter clade members Phaeobacter gallaeciensis DSM 17395 and Ruegeria pomeroyi DSS-3, and their volatile metabolites were analyzed by closed-loop stripping and solid-phase microextraction coupled to GC–MS. Feeding experiments with [2H6]DMSP resulted in the incorporation of a deuterium label into MeSH and DMS. Knockout of relevant genes from the known DMSP demethylation pathway to MeSH showed in both species a residual production of [2H3]MeSH, suggesting that a second demethylation pathway is active. The role of DMSP degradation pathways for MeSH and DMS formation was further investigated by using the synthetic analogue DMTeP as a probe in feeding experiments with the wild-type strain and knockout mutants. Feeding of DMTeP to the R. pomeroyi knockout mutant resulted in a diminished, but not abolished production of demethylation pathway products. These results further corroborated the proposed second demethylation activity in R. pomeroyi. Isotopically labeled [2H3]methionine and 34SO42−, synthesized from elemental 34S8, were tested to identify alternative sulfur sources besides DMSP for the MeSH production in P. gallaeciensis. Methionine proved to be a viable sulfur source for the MeSH volatiles, whereas incorporation of labeling from sulfate was not observed. Moreover, the utilization of selenite and selenate salts by marine alphaproteobacteria for the production of methylated selenium volatiles was explored and resulted in the production of numerous methaneselenol-derived volatiles via reduction and methylation. The pathway of selenate/selenite reduction, however, proved to be strictly separated from sulfate reduction.

  15. Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products.

    Science.gov (United States)

    Boulyga, Sergei F; Heilmann, Jens; Heumann, Klaus G

    2005-08-01

    Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different 34S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured 34S/32S isotope ratio of the isotope-diluted sample remained constant-a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 microg g(-1) ('sulfur-free' premium gasoline) to 10.4 mg g(-1) (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 microg g(-1) and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level.

  16. Isotope dilution ICP-MS with laser-assisted sample introduction for direct determination of sulfur in petroleum products

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F.; Heilmann, Jens; Heumann, Klaus G. [Johannes Gutenberg-University Mainz (Germany). Institute of Inorganic Chemistry and Analytical Chemistry

    2005-08-01

    Inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with direct laser-assisted introduction of isotope-diluted samples into the plasma, using a laser ablation system with high ablation rates, was developed for accurate sulfur determinations in different petroleum products such as 'sulfur-free' premium gasoline, diesel fuel, and heating oil. Two certified gas oil reference materials were analyzed for method validation. Two different {sup 34}S-enriched spike compounds, namely, elementary sulfur dissolved in xylene and dibenzothiophene in hexane, were synthesized and tested for their usefulness in this isotope dilution technique. The isotope-diluted sample was adsorbed on a filter-paper-like material, which was fixed in a special holder for irradiation by the laser beam. Under these conditions no time-dependent spike/analyte fractionation was only observed for the dibenzothiophene spike during the laser ablation process, which means that the measured {sup 34}S/{sup 32}S isotope ratio of the isotope-diluted sample remained constant - a necessary precondition for accurate results with the isotope dilution technique. A comparison of LA-ICP-IDMS results with the certified values of the gas oil reference materials and with results obtained from ICP-IDMS analyses with wet sample digestion demonstrated the accuracy of the new LA-ICP-IDMS method in the concentration range of 9.2 {mu}g g{sup -1} ('sulfur-free' premium gasoline) to 10.4 mg g{sup -1} (gas oil reference material BCR 107). The detection limit for sulfur by LA-ICP-IDMS is 0.04 {mu}g g{sup -1} and the analysis time is only about 10 min, which therefore also qualifies this method for accurate determinations of low sulfur contents in petroleum products on a routine level. (orig.)

  17. Controls on stable sulfur isotope fractionation during bacterial sulfate reduction in Arctic sediments

    DEFF Research Database (Denmark)

    Bruchert, V.; Knoblauch, C.; Jørgensen, BB

    2001-01-01

    Sulfur isotope fractionation experiments during bacterial sulfate reduction were performed with recently isolated strains of cold-adapted sulfate-reducing bacteria from Arctic marine sediments with year-round temperatures below 2 degreesC. The bacteria represent quantitatively important members...... parts per thousand and 8 parts per thousand above 25 degreesC, respectively. In absence of significant differences in sulfate reduction rates in the high and low temperature range, respectively, we infer that different genera of sulfate-reducing bacteria dominate the sulfate-reducing bacterial community...

  18. Constraints from sulfur isotopes on the origin of gypsum at concrete/claystone interfaces

    Science.gov (United States)

    Lerouge, Catherine; Claret, Francis; Tournassat, Christophe; Grangeon, Sylvain; Gaboreau, Stéphane; Boyer, Bernard; Borschnek, Daniel; Linard, Yannick

    Two in situ concrete/claystone interfaces were sampled at the laboratory level in the Andra Meuse/Haute Marne (France) Underground Research Laboratory (URL) in order to study five years of interactions between Callovian-Oxfordian (COx) claystone and two cementitious materials (concrete bottom slab and shotcrete on the walls of the main gallery), with a specific focus on sulfur. Combined mineralogical, chemical and sulfur isotopic investigations were carried out to define the degree of the perturbation of the sulfur system in the claystone and in both the cementitious materials. At both interfaces, results show that the main perturbation on the claystone side is the formation of scarce μm-sized gypsum, the sulfur content of which is essentially derived from pyrite oxidation. The distribution of gypsum is highly correlated with the fissure network of the damaged zone due to excavation of the gallery. Its presence is also often associated with a loss of cohesion of the concrete/claystone interface. Due to the small amounts of gypsum and its μm-size, measurements were performed by ion microprobe. Adaptations were needed on account of the reactivity of gypsum and sulfates in general under the beam. The use of ion microprobe analysis provided evidence of high local isotopic heterogeneity that could be attributed to kinetic fractionation effects. Some analyses suggest a minor contribution of dissolved sulfates in pore water of claystone and possibly of concrete. The perturbation on the concrete side is marked by a significant increase in the bulk sulfur content within three millimeters of the interface with the claystone, showing a sulfur gradient from claystone to concrete. The main objective of this work was to define the extent of the chemical and mineralogical perturbations, taking into account in situ URL conditions, i.e. hydrodynamic conditions (shotcrete sprayed on the gallery walls and subjected to ventilation of the galleries), damaged zone of claystone induced

  19. Geochemistry, geochronology, mineralogy, and geology suggest sources of and controls on mineral systems in the southern Toquima Range, Nye County, Nevada; with geochemistry maps of gold, silver, mercury, arsenic, antimony, zinc, copper, lead, molybdenum, bismuth, iron, titanium, vanadium, cobalt, beryllium, boron, fluorine, and sulfur; and with a section on lead associations, mineralogy and paragenesis, and isotopes

    Science.gov (United States)

    Shawe, Daniel R.; Hoffman, James D.; Doe, Bruce R.; Foord, Eugene E.; Stein, Holly J.; Ayuso, Robert A.

    2003-01-01

    Geochemistry maps showing the distribution and abundance of 18 elements in about 1,400 rock samples, both mineralized and unmineralized, from the southern Toquima Range, Nev., indicate major structural and lithologic controls on mineralization, and suggest sources of the elements. Radiometric age data, lead mineralogy and paragenesis data, and lead-isotope data supplement the geochemical and geologic data, providing further insight into timing, sources, and controls on mineralization. Major zones of mineralization are centered on structural margins of calderas and principal northwest-striking fault zones, as at Round Mountain, Manhattan, and Jefferson mining districts, and on intersections of low-angle and steep structures, as at Belmont mining district. Paleozoic sedimentary rocks, mostly limestones (at Manhattan, Jefferson, and Belmont districts), and porous Oligocene ash-flow tuffs (at Round Mountain district) host the major deposits, although all rock types have been mineralized as evidenced by numerous prospects throughout the area. Principal mineral systems are gold-silver at Round Mountain where about 7 million ounces of gold and more than 4 million ounces of silver has been produced; gold at Gold Hill in the west part of the Manhattan district where about a half million ounces of gold has been produced; gold-mercury-arsenic-antimony in the east (White Caps) part of the Manhattan district where a few hundred thousand ounces of gold has been produced; and silver-lead-antimony at Belmont where more than 150,000 ounces of silver has been produced. Lesser amounts of gold and silver have been produced from the Jefferson district and from scattered mines elsewhere in the southern Toquima Range. A small amount of tungsten was produced from mines in the granite of the Round Mountain pluton exposed east of Round Mountain, and small amounts of arsenic, antimony, and mercury have been produced elsewhere in the southern Toquima Range. All elements show unique

  20. Quantitative Reconstruction of Sulfur Deposition Using a Mixing Model Based on Sulfur Isotope Ratios in Tree Rings.

    Science.gov (United States)

    Ishida, Takuya; Tayasu, Ichiro; Takenaka, Chisato

    2015-11-01

    Quantification of sulfur (S) deposition is critical to deciphering the environmental archive of S in terrestrial ecosystems. Here we propose a mixing model that quantifies S deposition based on the S isotope ratio (δS) in tree rings. We collected samples from Japanese cedar ( D. Don) stumps from two sites: one near Yokkaichi City (YOK), which is well known for having the heaviest S air pollution in the world, and one at Inabu-cho (INA) in central Japan, which has been much less affected by air pollution. The δS profiles at both sites are consistent with S air pollution and contributions of anthropogenic S. The minimum value in YOK is lower than the δS values of anthropogenic S or any other possible source. Because the δS in the tree rings is affected by fractionation in the forest ecosystems, we used a mixing model to account for the isotope effects and to distinguish the sources of S. Based on the model results, we infer that the peak of S emissions at YOK occurred sometime between the late 1960s and early 1970s (489 mmol m yr). This estimated value is comparable with the highest reported values in Europe. This is the first quantitative estimate of anthropogenic input of S in forest systems based on δS in tree rings. Our results suggest that tree ring data can be used when monitoring stations of atmospheric S are lacking and that estimates of S deposition using δS in tree rings will advance our understanding of the local-scale S dynamics and the effect of human activities on it.

  1. The ecophysiology of sulfur isotope fractionation by sulfate reducing bacteria in response to variable environmental conditions

    Science.gov (United States)

    Leavitt, W.; Bradley, A. S.; Johnston, D. T.; Pereira, I. A. C.; Venceslau, S.; Wallace, C.

    2014-12-01

    Microbial sulfate reducers (MSR) drive the Earth's biogeochemical sulfur cycle. At the heart of this energy metabolism is a cascade of redox transformations coupling organic carbon and/or hydrogen oxidation to the dissimilatory reduction of sulfate to sulfide. The sulfide produced is depleted in the heavier isotopes of sulfur relative to sulfate. The magnitude of discrimination (fractionation) depends on: i) the cell-specific sulfate reduction rate (csSRR, Kaplan & Rittenberg (1964) Can. J. Microbio.; Chambers et al. (1975) Can. J. Microbio; Sim et al. (2011) GCA; Leavitt et al. (2013) PNAS), ii) the ambient sulfate concentration (Harrison & Thode (1958) Research; Habicht et al. (2002) Science; Bradley et al. in review), iii) both sulfate and electron donor availability, or iv) an intrinsic physiological limitation (e.g. cellular division rate). When neither sulfate nor electron donor limits csSRR a more complex function relates the magnitude of isotope fractionation to cell physiology and environmental conditions. In recent and on-going work we have examined the importance of enzyme-specific fractionation factors, as well as the influence of electron donor or electron acceptor availability under carefully controlled culture conditions (e.g. Leavitt et al. (2013) PNAS). In light of recent advances in MSR genetics and biochemistry we utilize well-characterized mutant strains, along with a continuous-culture methodology (Leavitt et al. (2013) PNAS) to further probe the fractionation capacity of this metabolism under controlled physiological conditions. We present our latest findings on the magnitude of S and D/H isotope fractionation in both wild type and mutant strains. We will discuss these in light of recent theoretical advances (Wing & Halevy (2014) PNAS), examining the mode and relevance of MSR isotope fractionation in the laboratory to modern and ancient environmental settings, particularly anoxic marine sediments.

  2. Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA

    Science.gov (United States)

    Ellis, Geoffrey S.; Said-Ahamed, Ward; Lillis, Paul G.; Shawar, Lubna; Amrani, Alon

    2017-01-01

    , which cannot be determined from other bulk geochemical parameters. Moreover, when combined with additional geochemical and geologic evidence, the sulfur isotopic composition of OSCs in oils can help to identify the source of sulfate for TSR alteration in petroleum reservoirs.

  3. Measurements of radioactive and stable sulfur isotopes at Mt. Everest and its geochemical implications

    Science.gov (United States)

    Lin, M.; Thiemens, M. H.; Zhang, Q.; Li, C.; Kang, S.; Hsu, S. C.; Zhang, Z.; Su, L.

    2015-12-01

    The Himalayas were recently identified as a global hotspot for deep stratosphere-to-troposphere transport (STT) during spring [1]. Although STT transport in this region may play a vital role in tropospheric chemistry, the hydrological cycle and aquatic ecosystems in Asia, there is no direct measurement of a specific chemical stratospheric tracer to verify and evaluate its possible impact. Here, cosmogenic 35S tracer (half-life: ~87 days) produced in the stratosphere was measured for the first time in surface snow and river runoff samples collected at Mt. Everest in April 2013 using a low-noise liquid scintillation spectroscopy [2]. Strikingly, we find extraordinarily high concentrations of 35S in these samples (>10 times higher than the southern Tibetan Plateau), verifying the Himalayas as a gateway of springtime STT. In light of this, two studies were conducted: a) Measurements of 35SO2 and 35SO42- at the southern Tibetan Plateau reveals that the oxidative life time of SO2 is reduced to 2.1 days under the influence of aged stratospheric air masses from the Himalayas. A concept box model for estimating the influence of STT on surface O3 using 35S tracer is proposed. b) Quadruple stable sulfur isotopes in a sediment core (~250 years) from the Gokyo Lake (the world's highest freshwater lake) [3] near Mt. Everest are being measured to investigate the possible impact of STT on sulfur budget at the Himalayas. The absence of sulfide suggests that bacterial sulfate reduction may be negligible in this lake. Enrichment of uranium (EF ≈ 10) in 20th century samples highlights the impact of atmospheric deposition. S-isotope sulfate anomalies are not found (∆33S and ∆36S ≈ 0‰), implying that sulfate in this lake may be mainly contributed by eolian dust or derived from rock. This is also supported by the low enrichments of most trace elements (EF ≈ 1). Rare earth elements will be used to assist in identifying the potential sources and interpreting the variation of

  4. Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits, Cantabria, Spain

    Science.gov (United States)

    Pašava, Jan; Tornos, Fernando; Chrastný, Vladislav

    2014-10-01

    We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ66Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from -0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ34S = +6.6 and stage 2 has δ34S = -0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light 66Zn-depleted signatures with δ66Zn values from -0.80 to -0.01 per mil (mostly between -0.80 and -0.24 per mil) and δ34S values from +10.7 to +15.7 per mil without any relationship between the δ66Zn and δ34S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250-320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH2S > mZn2+ as a result of change in pH, T, and Zn predominant species. The light δ66Zn

  5. Fractionation of Sulfur Isotopes by Desulfovibrio vulgaris Mutants Lacking Periplasmic Hydrogenases or the Type I Tetraheme Cytochrome c3

    Science.gov (United States)

    Sim, M.; Ono, S.; Bosak, T.

    2012-12-01

    A large fraction of anaerobic mineralization of organic compounds relies on microbial sulfate reduction. Sulfur isotope fractionation by these microbes has been widely used to trace the biogeochemical cycling of sulfur and carbon, but intracellular mechanisms behind the wide range of fractionations observed in nature and cultures are not fully understood. In this study, we investigated the influence of electron transport chain components on the fractionation of sulfur isotopes by culturing Desulfovibrio vulgaris Hildenborough mutants lacking hydrogenases or type I tetraheme cytochrome c3 (Tp1-c3). The mutants were grown both in batch and continuous cultures. All tested mutants grew on lactate or pyruvate as the sole carbon and energy sources, generating sulfide. Mutants lacking cytoplasmic and periplasmic hydrogenases exhibited similar growth physiologies and sulfur isotope fractionations to their parent strains. On the other hand, a mutant lacking Tp1-c3 (ΔcycA) fractionated the 34S/32S ratio more than the wild type, evolving H2 in the headspace and exhibiting a lower specific respiration rate. In the presence of high concentrations of pyruvate, the growth of ΔcycA relied largely on fermentation rather than sulfate reduction, even when sulfate was abundant, producing the largest sulfur isotope effect observed in this study. Differences between sulfur isotope fractionation by ΔcycA and the wild type highlight the effect of electron transfer chains on the magnitude of sulfur isotope fractionation. Because Tp1-c3 is known to exclusively shuttle electrons from periplasmic hydrogenases to transmembrane complexes, electron transfers in the absence of Tp1-c3 should bypass the periplasmic hydrogen cycling, and the loss of reducing equivalents in the form of H2 can impair the flow of electrons from organic acids to sulfur, increasing isotope fractionation. Larger fractionation by ΔcycA can inform interpretations of sulfur isotope data at an environmental scale as well

  6. Sulfur Isotope Fractionation in Magmatic Systems:Models of Rayleigh Distillation and Selective Flux

    Institute of Scientific and Technical Information of China (English)

    郑永飞

    1990-01-01

    The effect of Rayleigh distillation by outgassing of SO2 and H2S on the isotopic composition of sulfur remaining in silicate melts is quantitatively modelled.A threshold mole fraction of sulfur in sulfide component of the melts is reckoned to be of critical importance in shifting the δ34S of the melts mith respect to the original magmas.The partial equilibrium fractionation in a magmatic system is evaluated by assuming that a non-equilibrium flux of sulfur occurs between magmatic volatiles and the melts,while an equilibrium fractionation is approached between sulfate and sulfide within the melts.The results show that under high fo2 conditions,the sulfate/sulfide ratio in a melt entds to increase,and the δ34S value of sulfur in a solidified rock might then be shifted in the positive direction.This may either be due to Rayleigh outgassing in case the mole fraction of sulfide is less than the threshold,or due to a unidirectional increase in δ34S value of the sulfate with decreaing temperature,Conversely,at low fo2,the sulfate/sulfide ratio tends to decrease and the δ34S value of total sulfur could be driven in the negative direction,either because of the Rayleigh outgassing in case the mole fraction of sulfide is greater than the threshold,or because of a unidirectional decrease inδ34S value of the sulfide.To establish isotopic equilibrium between sulfate and sulfide,the HM,QFM or WM buffers in the magmatic system are suggested to provide the redox couple that could simultaneously reduce the sulfate and oxidize the sulfide.CaO present in the silicatte Melts is also called upon to participate in the chemical equilibrium between sulfate and sulfide,Consequently,the δ34S value of an igneous rock could considerably deviate from that of its original magma due to the influence of oxygen fugacity and temperature at the time of magma solidification.

  7. Patterns of mortality among South Florida Manatees: Evidence from oxygen, sulfur and deuterium stable isotopes

    Science.gov (United States)

    MacAvoy, S. E.; Bacalan, V.; Kazantseva, M.; Rhodes, J.; Kim, K.

    2012-12-01

    The Florida manatee (Trichechus manatus latirostris) is an endangered marine mammal whose coastal habitat has been heavily altered by human development. Sources of mortality include anthropogenic and environmental causes. Necropsies were completed on 75 deceased individuals, and tissues, including bone samples, were collected for later analysis. This study investigates the utility of manatee bone stable oxygen (δ18O), sulfur (δ34S) and deuterium (δD) for determining where the animals lived (which may not be where they where their bodies were recovered), and the relative importance of marine versus freshwater for the individual animals. The isotopes can provide a "geochemical map" showing the distribution of mortality, aiding in the evaluation of geographical patterns in mortality. The δ18O signatures of the bones ranged from 14 to 18.5‰, with no significant difference between male and female mean values. δ18O significantly decreased with increasing latitude (p=.0016), a trend positively correlated with coastal Florida seawater δ18O literature values obtained from the NASA Global Seawater Oxygen-18 Database (http://data.giss.nasa.gov/o18data/) and the EAIA stable isotope database (http://www.univie.ac.at/cartography/project/wiser/). Bone δ34S indicated the influence of marine versus coastal freshwater dietary sources on the animals. Most individuals showed 34S-depleted signatures, which indicated a non-marine sulfur source; however some individuals clearly had taken up marine sulfate (mean 4.9 ± 3.7‰, range 0.8 to 13.8‰). Deuterium values were not available at the time this abstract was written, however we hypothesize that those values will co-vary with δ18O. We conclude that manatee diets are based on both marine and freshwater sources, but freshwater sources exert more influence. Marine water and manatee δ18O co-vary with latitude, suggesting that stable oxygen isotopes may be useful indicators of the latitude where manatees lived.

  8. Isotope geology of the bakircay porphyry copper prospect, northern turkey

    Science.gov (United States)

    Taylor, R. P.

    1981-10-01

    Isotopic data for the Bakircay granodiorite porphyry, MediaObjects/126_2005_BF01798964_f1.tif give a Late Eocene age for the development of the porphyry copper system. They suggest a close temporal and genetic relationship between igneous and hydrothermal activity, and indicate that magmatic-hydrothermal fluids produced potassic alteration and that meteoric fluids enriched in radiogenic87Sr were responsible for propylitic alteration. The granodiorite porphyry is petrologically similar to porphyry copper-related intrusions from island arc and continental margin settings, which form a group with initial87Sr/86Sr ratios of less than 0. 7043, representing magmas produced in tectonic environments lacking any important component of old (i. e. Precambrian) continental material.

  9. Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

    Science.gov (United States)

    Fiege, Adrian; Holtz, François; Shimizu, Nobumichi; Mandeville, Charles W.; Behrens, Harald; Knipping, Jaayke L.

    2014-01-01

    Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H2O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities (fO2) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure (P) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate (r) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, tA) at the final P and quenched rapidly from 1030 °C to room temperature (T).The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor αg-m.No detectable effect of r and tA on αg-m was observed. However, SIMS data revealed a remarkable increase of αg-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of fO2 on αg-m (or Δ34Sg–m) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope

  10. Sulfur isotope dynamics in two central european watersheds affected by high atmospheric deposition of SO x

    Science.gov (United States)

    Novák, Martin; Kirchner, James W.; Groscheová, Hana; Havel, Miroslav; Černý, Jiří; Krejčí, Radovan; Buzek, František

    2000-02-01

    Sulfur fluxes and δ34S values were determined in two acidified small watersheds located near the Czech-German border, Central Europe. Sulfur of sulfate aerosol in the broader region (mean δ 34S of 7.5‰ CDT) was isotopically heavier than sulfur of airborne SO 2 (mean δ 34S of 4.7‰). The annual atmospheric S deposition to the Jezeřı´ watershed decreased markedly in 1993, 1994, and 1995 (40, 33, and 29 kg/ ha · yr), reflecting reductions in industrial S emissions. Sulfur export from Jezeří via surface discharge was twice atmospheric inputs, and increased from 52 to 58 to 85 kg/ha · yr over the same three-year period. The δ 34S value of Jezeřı´ streamflow was 4.5 ± 0.3‰, intermediate between the average atmospheric deposition (5.4 ± 0.2‰) and soil S (4.0 ± 0.5‰), suggesting that the excess sulfate in runoff comes from release of S from the soil. Bedrock is not a plausible source of the excess S, because its S concentration is very low (release of soil S accounted for 64 ± 33% of sulfate S in Jezeřı´ discharge. Approximately 30% of total sulfate S in the discharge were organically cycled. At Načetı´n, the same sequence of δ34S IN > δ34S OUT > δ34S SOIL was observed. The seasonality found in atmospheric input (higher δ 34S in summer, lower δ 34S in winter) was preserved in shallow (10 cm) soil water (4.8 ± 0.2‰) were intermediate between those of atmospheric input (5.9 ± 0.3‰) and Nac̆etín soils (2.4 ± 0.1‰), again suggesting that remobilization of soil S accounts for a significant fraction (roughly 40 ± 10%) of the S in soil water at Načetı´n. The inventories of soil S at both of these sites are legacies of more intense atmospheric pollution during previous decades, and are large enough (740 and 1500 kg S/ha at Jezeřı´ and Načetı´n, respectively) to supply significant sulfur fluxes to runoff for several more decades. The ongoing release of this stored soil S may significantly delay the recovery of water quality

  11. Simultaneous Analysis of Nitrogen, Carbon and Sulfur Stable Isotopes and Concentrations in Organics and Soils

    Science.gov (United States)

    Mambelli, S.; Brooks, P. D.; Sutka, R.; Hughes, S.; Finstad, K. M.; Pakes, M. J.; Dawson, T. E.

    2014-12-01

    To date, analysis of diet, food web complexities, biogeochemical cycles, and ecosystem functioning have largely focused on using variation in carbon (C) and nitrogen (N) stable isotope ratios. This is because a great deal is understood about what leads to this variation and because the dual stable isotope analysis of these two elements using continuous flow isotope ratio mass spectrometry (IRMS) is now commonplace. However, the aforementioned studies may all greatly benefit from the additional information one can get from also having sulfur (S) stable isotopes ratio data. Until very recently the analysis of δ34S has traditionally required an additional and often more difficult analytical procedure. Here, we report on the development of a new method that simultaneously analyzes the elemental and isotopic composition of N, C and S in a single sample. The new commercially available instrument includes a modified NCS elemental analyzer in line with an IRMS outfitted with 100 volt AD converters for wide dynamic range. We tested, and modified, this instrument to achieve maximum accuracy and precision for the isotopic measurements of all three elements. We found that the original design needed improvements to achieve our goals by: a) including a component (originally designed for trapping water) as buffer to reduce S memory and obtain reliable δ34S analysis; b) adding an external furnace for complete reduction of nitrogen oxides to N2 gas for accurate δ15N; c) adding a magnesium perchlorate water trap immediately after the reduction tube to minimize any water condensation that could also influence S memory. We analyzed a selection of organic materials and soils with approximately a 1:2 standards versus unknowns ratio per run. Using this NCS set-up, the precision of the N and C isotopic measurements was comparable to the one usually attained in NC mode alone (standard deviation of ± 0.13 δ15N in the range 30 to 400 µg N, and of ± 0.12 δ13C in the range 0.20 to 4 mg

  12. Sulfur isotope systematics of microbial mats in shallow-sea hydrothermal vents, Milos Island, Greece

    Science.gov (United States)

    Gilhooly, W. P.; Fike, D. A.; Amend, J. P.; Price, R. E.; Druschel, G.

    2011-12-01

    Milos is an island arc volcano venting submarine magmatic fluids directly into overlying seawater. Our study sites are located in an extensive shallow-water hydrothermal vent field less than 200 m offshore of Paleochori Bay in 5 m water depth. The vent fluids are highly sulfidic (> 3mM), at high-temperature (50-115C), and acidic (pH 5). The seafloor vent features include large patches (> 1 m2) of white microbial mats, patches of yellow elemental sulfur, and sediments stained orange by arsenic sulfides. The microbial communities that populate the shallow-sea hydrothermal vents stand in stark contrast to other nearshore environments typically found at wave base and within the photic zone. We explore sulfur isotope patterns along sharp environmental gradients established between ambient seawater and the efflux of vent fluids in the effort to better understand resource exploitation by microbial mat communities living in extreme conditions. Pore water samples, push-cores, biofilms, and water column samples were collected by SCUBA along sampling transects radiating out from the center of white mats into background sediments. We analyzed these samples for δ34S of dissolved sulfate, sulfide, elemental sulfur, and mineral sulfides (iron monosulfides and pyrite). Free gas sulfides collected directly from vents had δ34S values ranging +2.1 to +2.8%. Pore water sulfide, collected from below white mats with δ34S values ranging +1.9 to +2.9%, was isotopically similar to free gas samples. High pore water sulfate concentrations (8-25 mM) coupled with 34S-enriched pore water sulfides are not geochemical signatures indicative of dissimilatory sulfate reduction (where δ34Ssulfide <<0%). The δ34S of pore water sulfates collected across one dive site show a mixing trend, ranging from +18% in the center, +20% mid-transect, and +21% in sediments outside of the mat. This trend may be caused by oxidation of vent sulfides by entrained seawater (δ34S = +21.2%). We continue to target

  13. Sulfur Isotope Trends in Archean Microbialite Facies Record Early Oxygen Production and Consumption

    Science.gov (United States)

    Zerkle, A.; Meyer, N.; Izon, G.; Poulton, S.; Farquhar, J.; Claire, M.

    2014-12-01

    The major and minor sulfur isotope composition (δ34S and Δ33S) of pyrites preserved in ~2.65-2.5 billion-year-old (Ga) microbialites record localized oxygen production and consumption near the mat surface. These trends are preserved in two separate drill cores (GKF01 and BH1-Sacha) transecting the Campbellrand-Malmani carbonate platform (Ghaap Group, Transvaal Supergroup, South Africa; Zerkle et al., 2012; Izon et al., in review). Microbialite pyrites possess positive Δ33S values, plotting parallel to typical Archean trends (with a Δ33S/δ34S slope of ~0.9) but enriched in 34S by ~3 to 7‰. We propose that these 34S-enriched pyrites were formed from a residual pool of sulfide that was partially oxidized via molecular oxygen produced by surface mat-dwelling cyanobacteria. Sulfide, carrying the range of Archean Δ33S values, could have been produced deeper within the microbial mat by the reduction of sulfate and elemental sulfur, then fractionated upon reaction with O2 produced by oxygenic photosynthesis. Preservation of this positive 34S offset requires that: 1) sulfide was only partially (50­­-80%) consumed by oxidation, meaning H2S was locally more abundant (or more rapidly produced) than O2, and 2) the majority of the sulfate produced via oxidation was not immediately reduced to sulfide, implying either that the sulfate pool was much larger than the sulfide pool, or that the sulfate formed near the mat surface was transported and reduced in another part of the system. Contrastingly, older microbialite facies (> 2.7 Ga; Thomazo et al., 2013) appear to lack these observed 34S enrichments. Consequently, the onset of 34S enrichments could mark a shift in mat ecology, from communities dominated by anoxygenic photosynthesizers to cyanobacteria. Here, we test these hypotheses with new spatially resolved mm-scale trends in sulfur isotope measurements from pyritized stromatolites of the Vryburg Formation, sampled in the lower part of the BH1-Sacha core. Millimeter

  14. Minor Sulfur Isotope Constraints on the composition of Earth's Archean atmosphere

    Science.gov (United States)

    Claire, M.

    2016-12-01

    Minor sulfur isotope anomalies in the sedimentary record are direct recorders of ancient chemical reactions that occurred in the atmosphere, and therefore form the most direct proxy for Archean atmospheric composition. The mere presence of mass-independently fractionated sulfur isotopes (MIF-S) in the rock record has resolved nearly a century's worth of debate by constraining atmospheric oxygen to trace levels prior to 2.4 billion years ago, and indirectly indicates the presence of a dominant reducing gas, likely H2 or CH4. The MIF-S database has grown substantially in the past decade, and reveals complex time- and facies-dependent changes in MIF-S magnitudes. The structure within the sedimentary MIF-S record suggests that constraints beyond this simple "on-off" switch for atmospheric O2 are possible once we understand the mechanisms that generate and preserve the signal in the rock record. Recently, I proposed an initial quantitative framework for predictions of atmospheric MIF-S [1], but concluded that new measurements of MIF-S generation mechanisms were needed to provide robust constraints. Since then, identification of MIF-S arising from SO2 photoexcitation [2], and updated absorption cross-sections for SO2 and SO [3-4] provide critical new ground-truth on all 4 isotopes of sulfur. Furthermore, breakthroughs in coupled photochemical-climate modeling have enabled better predictions of UV transparency within hazy atmospheres [5] such as those that might have dominated in the Archean [6-8]. I will present 1-D photochemical modeling results based on these new fundamental constraints, in comparison with MIF-S data from the Archean, to interpret the steady-state composition of the Archean atmosphere and time-dependent perturbations to it. In particular, Δ36S/Δ33S resulting from perturbations to atmospheric species will be discussed as a key tool for constraining the composition of the reducing atmosphere. [1] Claire et al. (2014) GCA; [2] Whitehill et al., PNAS

  15. Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis.

    Science.gov (United States)

    Chakraborty, Subrata; Jackson, Teresa L; Ahmed, Musahid; Thiemens, Mark H

    2013-10-29

    Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models.

  16. Sulfur isotopic fractionation in vacuum UV photodissociation of hydrogen sulfide and its potential relevance to meteorite analysis

    Science.gov (United States)

    Chakraborty, Subrata; Jackson, Teresa L.; Ahmed, Musahid; Thiemens, Mark H.

    2013-01-01

    Select meteoritic classes possess mass-independent sulfur isotopic compositions in sulfide and organic phases. Photochemistry in the solar nebula has been attributed as a source of these anomalies. Hydrogen sulfide (H2S) is the most abundant gas-phase species in the solar nebula, and hence, photodissociation of H2S by solar vacuum UV (VUV) photons (especially by Lyman-α radiation) is a relevant process. Because of experimental difficulties associated with accessing VUV radiation, there is a paucity of data and a lack of theoretical basis to test the hypothesis of a photochemical origin of mass-independent sulfur. Here, we present multiisotopic measurements of elemental sulfur produced during the VUV photolysis of H2S. Mass-independent sulfur isotopic compositions are observed. The observed isotopic fractionation patterns are wavelength-dependent. VUV photodissociation of H2S takes place through several predissociative channels, and the measured mass-independent fractionation is most likely a manifestation of these processes. Meteorite sulfur data are discussed in light of the present experiments, and suggestions are made to guide future experiments and models. PMID:23431159

  17. Sulfur isotope evidence for penetration of MVT fluids into igneous basement rocks, southeast Missouri, USA

    Science.gov (United States)

    Shelton, K. L.; Burstein, I. B.; Hagni, R. D.; Vierrether, C. B.; Grant, S. K.; Hennigh, Q. T.; Bradley, M. F.; Brandom, R. T.

    1995-08-01

    Previous studies of galena and sphalerite from Paleozoic MVT deposits in the Viburnum Trend, southeast Missouri documented large variations in δ34S values throughout the ore-forming event. The present study of Cu-Fe-sulfides reveals a similar δ34S variation that reflects two end-member sulfur reservoirs whose relative importance varied both temporally and spatially. More 34S-enriched sulfides (δ34S approaching 25‰) indicate introduction of sulfur from basinal sedimentary sources, whereas more 32S-enriched sulfides (δ34S Precambrian, igneous-hosted FeCu mineralization in southeast Missouri (West and Central Domes of Boss-Bixby) were investigated to elucidate their relationship to Cu-rich MVT orebodies hosted nearby within the overlying Cambrian Bonneterre Dolomite. Mineralization at Boss-Bixby is composed of an early phase of iron oxide deposition followed by Cu-Fe-sulfides. The Central Dome is faulted and its mineralization is more fracture-controlled than the typically podiform ores of the West Dome. The δ34S values of West Dome sulfides are 0.9 to 6.5‰ and pyrite-chalcopyrite indicate a temperature of 525° ± 50 °C. These data indicate an igneous source of sulfur during Precambrian ore deposition. In contrast, δ34S values of Central Dome sulfides are 9.4 to 20.0‰ and pyrite-chalcopyrite indicate temperatures of 275° ± 50 °C. Similar δ34S values are obtained for chalcopyrite from the overlying MVT deposits. We speculate that deeply circulating, basin-derived MVT fluids mobilized sulfur and copper from the underlying igneous basement and redeposited them in overlying Curich MVT orebodies, as well as overprinting earlier Precambrian sulfides of the Central Dome with a later, Paleozoic MVT sulfur isotope signature. Many models for MVT fluid circulation in the Midcontinent region of North America assume that igneous basement rocks are an impermeable boundary, but in southeast Missouri, evidence exists for structurally controlled MVT fluid movement

  18. Formation of black and white smokers in the North Fiji Basin: Sulfur and lead isotope constraints

    Science.gov (United States)

    Kim, J.; Lee, I.; Lee, K.; Yoo, C.; Ko, Y.

    2004-12-01

    The hydrothermal chimneys were recovered from 16o50¡_S triple junction area in the North Fiji Basin. The chimney samples are divided into three groups according to their mineralogy and metal contents; 1) Black smoker, 2) White smoker, 3) Transitional type. Black smoker chimneys are mainly composed of chalcopyrite and pyrite, and are enriched in high temperature elements such as Cu, Co, Mo, and Se. White smoker chimneys consist of sphalerite and marcasite with trace of pyrite and chalcopyrite, and are enriched in low temperature elements (Zn, Cd, Pb, As, and Ga). Transitional chimneys show intermediate characteristics in mineralogy and composition between black and white smokers. Basaltic rocks sampled from the triple junction show wide variation in geochemistry. Trace elements composition of basaltic rocks indicates that the magma genesis in the triple junction area was affected by mixing between N-MORB and E-MORB sources. The sulfur and lead isotope compositions of hydrothermal chimneys show distinct differences between the black and white smokers. Black smokers are depleted in 34S (Øä34S = +0.4 to +4.8) and are low in lead isotope composition (206Pb/204Pb = 18.082 to 18.132; 207Pb/204Pb = 15.440 to 15.481; 208Pb/204Pb = 37.764 to 37.916) compared to white smoker and transitional chimneys (Øä34S = +2.4 to +5.6; 206Pb/204Pb = 18.122 to 18.193; 207Pb/204Pb = 15.475 to 15.554; 208Pb/204Pb = 37.882 to 38.150). The heavier sulfur isotopic fractionation in white smoker can be explained by boiling of hydrothermal fluids and mixing with ambient seawater. The lead isotope compositions of the hydrothermal chimneys indicate that the metal in black and white smokers come from hydrothermal reaction with N-MORB and E-MORB, respectively. Regarding both black and white smoker are located in the same site, the condition of phase separation of hydrothermal fluid that formed white smokers might result from P-T condition of high temperature reaction zone below the hydrothermal

  19. Characterization of sulfur deposition over the period of industrialization in Japan using sulfur isotope ratio in Japanese cedar tree rings taken from stumps.

    Science.gov (United States)

    Ishida, Takuya; Tayasu, Ichiro; Takenaka, Chisato

    2015-07-01

    We characterized the sulfur deposition history over the period of industrialization in Japan based on the sulfur isotope ratio (δ(34)S) in tree rings of Japanese cedar (Cryptomeria japonica D. Don) stumps. We analyzed and compared δ(34)S values in the rings from two types of disk samples from 170-year-old stumps that had been cut 5 years earlier (older forest stand) and from 40-year-old living trees (younger forest stand) in order to confirm the validity of using stump disks for δ(34)S analysis. No differences in δ(34)S values by age were found between the sample types, indicating that stump disks can be used for δ(34)S analysis. The δ(34)S profile in tree rings was significantly correlated with anthropogenic SO2 emissions in Japan (r = -0.76, p tree rings serve as a record of anthropogenic sulfur emissions. In addition, the values did not change largely from pre-industrialization to the 1940s (+4.2 to +6.1‰). The values before the 1940s are expected to reflect the background sulfur conditions in Japan and, thus, disks containing rings formed before the 1940s contain information about the natural environmental sulfur, which is useful for biogeochemical studies.

  20. Mercury bioaccumulation in estuarine fishes: Novel insights from sulfur stable isotopes

    Science.gov (United States)

    Willacker, James J.; Eagles-Smith, Collin A.; Ackerman, Joshua T.

    2017-01-01

    Estuaries are transitional habitats characterized by complex biogeochemical and ecological gradients that result in substantial variation in fish total mercury concentrations (THg). We leveraged these gradients and used carbon (δ13C), nitrogen (δ15N), and sulfur (δ34S) stable isotopes to examine the ecological and biogeochemical processes underlying THg bioaccumulation in fishes from the San Francisco Bay Estuary. We employed a tiered approach that first examined processes influencing variation in fish THg among wetlands, and subsequently examined the roles of habitat and within-wetland processes in generating larger-scale patterns in fish THg. We found that δ34S, an indicator of sulfate reduction and habitat specific-foraging, was correlated with fish THg at all three spatial scales. Over the observed ranges of δ34S, THg concentrations in fish increased by up to 860% within wetlands, 560% among wetlands, and 291% within specific impounded wetland habitats. In contrast, δ13C and δ15N were not correlated with THg among wetlands and were only important in low salinity impounded wetlands, possibly reflecting more diverse food webs in this habitat. Together, our results highlight the key roles of sulfur biogeochemistry and ecology in influencing estuarine fish THg, as well as the importance of fish ecology and habitat in modulating the relationships between biogeochemical processes and Hg bioaccumulation.

  1. Mercury Bioaccumulation in Estuarine Fishes: Novel Insights from Sulfur Stable Isotopes.

    Science.gov (United States)

    Willacker, James J; Eagles-Smith, Collin A; Ackerman, Joshua T

    2017-02-21

    Estuaries are transitional habitats characterized by complex biogeochemical and ecological gradients that result in substantial variation in fish total mercury concentrations (THg). We leveraged these gradients and used carbon (δ(13)C), nitrogen (δ(15)N), and sulfur (δ(34)S) stable isotopes to examine the ecological and biogeochemical processes underlying THg bioaccumulation in fishes from the San Francisco Bay Estuary. We employed a tiered approach that first examined processes influencing variation in fish THg among wetlands, and subsequently examined the roles of habitat and within-wetland processes in generating larger-scale patterns in fish THg. We found that δ(34)S, an indicator of sulfate reduction and habitat specific-foraging, was correlated with fish THg at all three spatial scales. Over the observed ranges of δ(34)S, THg concentrations in fish increased by up to 860% within wetlands, 560% among wetlands, and 291% within specific impounded wetland habitats. In contrast, δ(13)C and δ(15)N were not correlated with THg among wetlands and were only important in low salinity impounded wetlands, possibly reflecting more diverse food webs in this habitat. Together, our results highlight the key roles of sulfur biogeochemistry and ecology in influencing estuarine fish THg, as well as the importance of fish ecology and habitat in modulating the relationships between biogeochemical processes and Hg bioaccumulation.

  2. Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2012-01-01

    Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

  3. Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

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    P. Hoppe

    2012-06-01

    Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals

  4. Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

    Directory of Open Access Journals (Sweden)

    P. Hoppe

    2012-01-01

    Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~ 60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917 ± 0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096 ± 0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~ 40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012 ± 0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals resulted in a very distinct fractionation factor of α34 = 1.085 ± 0.013. The

  5. Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

    Science.gov (United States)

    Eldridge, D. L.; Guo, W.; Farquhar, J.

    2016-12-01

    We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30-40H2O clusters spanning the range of sulfur oxidation state (Sn, n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34β values based on major isotope (34S/32S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values (x/34κ = ln(xβ)/ln(34β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds (33/34κ ≈ 0.5148-0.5159, 36/34κ ≈ 1.89-1.90 from T ⩾ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit (33/34κT→∞ = 0.51587 ± 0.00003 and 36/34κT→∞ = 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO3-T(aq)/SO2(g, aq), SO2(aq)/SO2(g), H2S(aq)/H2S(g), H2S(aq)/HS-(aq), SO42-(aq)/H2ST(aq), S2O32-(aq) (intramolecular), and S2O32-(aq)/H2ST(aq), and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO3-T/SO32- major isotope (34S/32S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O3

  6. Recycling of water, carbon, and sulfur during subduction of serpentinites: A stable isotope study of Cerro del Almirez, Spain

    Science.gov (United States)

    Alt, Jeffrey C.; Garrido, Carlos J.; Shanks, Wayne C.; Turchyn, Alexandra; Padrón-Navarta, José Alberto; López Sánchez-Vizcaíno, Vicente; Gómez Pugnaire, María Teresa; Marchesi, Claudio

    2012-01-01

    We use the concentrations and isotope compositions of water, carbon, and sulfur in serpentinites and their dehydration products to trace the cycling of volatiles during subduction. Antigorite serpentinites from the Cerro del Almirez complex, Spain, contain 9–12 wt.% H2O and 910 ± 730 ppm sulfur, and have bulk δ18O values of 8.6 ± 0.4‰, δD = − 54 ± 5‰, and δ34S = 5.0‰, consistent with serpentinization at temperatures of ~ 200 °C by seawater hydrothermal fluids in a seafloor setting. The serpentinites were dehydrated to chlorite–harzburgite (olivine + orthopyroxene + chlorite) at 700 °C and 1.6–1.9 GPa during subduction metamorphism, resulting in loss of water, and sulfur. The chlorite–harzburgites contain 5.7 ± 1.9 wt.% H2O, and have bulk δ18O = 8.0 ± 0.9‰, and δD = − 77 ± 11‰. The rocks contain 650 ± 620 ppm sulfur having δ34S = 1.2‰. Dehydration of serpentinite resulted in loss of 5 wt.% H2O having δ18O = 8–10‰ and δD = − 27 to − 65‰, and loss of 260 ppm sulfur as sulfate, having δ34S = 14.5‰. The contents and δ13C of total carbon in the two rock types overlap, with a broad trend of decreasing carbon contents and δ13C from ~ 1300 to 200 ppm and − 9.6 to − 20.2‰. This reflects mixing between reduced carbon in the rocks (210 ppm, δ13C ≈ − 26‰) and seawater-derived carbonate (δ13C ≈ − 1‰). Our results indicate: 1) Serpentinized oceanic peridotites carry significant amounts of isotopically fractionated water, carbon and sulfur into subduction zones; 2) Subduction of serpentinites to high P and T results in loss of water, and sulfur, which can induce melting and contribute to 18O, D, and 34S enrichments and oxidation of the sub-arc mantle wedge; and 3) Isotopically fractionated water, carbon, and sulfur in serpentinite dehydration products are recycled deeper into the mantle where they can contribute to isotope heterogeneities and may be significant for volatile budgets of the deep Earth.

  7. Genetic relationships between swamp microenvironment and sulfur distribution of the Late Paleozoic coals in North China

    Institute of Scientific and Technical Information of China (English)

    汤达祯; 杨起; 周春光; 康西栋; 刘大锰; 黄文辉

    2001-01-01

    The genetic relationships between microenvironment of the Late Paleozoic peat-forming swamp and the sulfur contents of coal in North China have been studied by using coal-facies parameters involving gelification degree, tissue preservation index, vegetation index, transportation index, groundwater influence index, water medium indicator and swamp type index, etc. Among the various controlling factors of swamp microenvironment, swamp water medium elaborates a dominant action to sulfur accumulation in the marine-influenced coals; while coal-forming plant type, hydrodynamic state and water covering depth are more important to sulfur accumulation in the fresh water-influenced coals. Geological fractionation of sulfur isotopes reflects that sulfur accumulation experienced multi-stages evolution. Pyrite sulfurs formed earlier than organic sulfur and the sulfur isotopic d 34Sp shows lower values than organic sulfur isotopic d 34So. In the brine-influenced coals, sulfur accumulation processed relatively a long time span, the distribution of sulfur isotopes dispersed,and the coals are provided with high sulfur contents. In the fresh-water-influenced coals, sulfur accumulation occurred mainly at the syngenetic-penesyngenetic stage and the early diagenetic stage, and the total sulfur is lower and mainly composed of organic sulfur.

  8. Sulfur and oxygen isotopic systematics of the 1982 eruptions of El Chichón Volcano, Chiapas, Mexico

    Science.gov (United States)

    Rye, R.O.; Luhr, J.F.; Wasserman, M.D.

    1984-01-01

    Thermometers based on sulfur and oxygen isotopic compositions of anhydrite, pyrrhotite, titanomagnetite, and plagioclase crystals from fresh pumices of the 1982 eruptions of El Chichón Volcano indicate a pre-eruption temperature of 810 ± 40°C, confirming textural evidence that the anhydrite precipitated directly from the melt. The isotopic composition of sulfate leached from fresh ashfall samples shows it to be a mixture of anhydrite microphenocrysts and adsorbed sulfate derived from oxidized sulfur (SO2) in the eruption plume. The leachate data show no evidence for rapid oxidation of significant amounts of H2S in the eruption cloud even though the fugacity ratio of H2S/SO2 in the gas phase of the magma was >400. This may indicate kinetic inhibition of H2S to SO2 conversion in the eruption cloud. Prior to eruption, the magma contained an estimated 2.6 wt. % sulfur (as SO3). The estimated δ 34S of the bulk magma is 5.8‰. Such a high value may reflect assimilation of 34S-enriched evaporites or the prior loss of 34S-depleted H2S to a fluid or gas phase during formation of a small prophyry-type hydrothermal system or ore deposit. In either case, the original magma must have been very sulfur rich. It is likely that the initial high sulfur content of the magma and at least some of its 34S enrichment reflects involvement of subducted volcanogenic massive sulfides deposits during Benioff-zone partial melting. Isotopic data on mineralized, accidental lithic fragments support the possible development of a porphyry-type system at El Chichón.

  9. Sulfur and oxygen isotopic systematics of the 1982 eruptions of El Chichón Volcano, Chiapas, Mexico

    Science.gov (United States)

    Rye, R. O.; Luhr, J. F.; Wasserman, M. D.

    1984-12-01

    Thermometers based on sulfur and oxygen isotopic compositions of anhydrite, pyrrhotite, titanomagnetite, and plagioclase crystals from fresh pumices of the 1982 eruptions of El Chichón Volcano indicate a pre-eruption temperature of 810 ± 40°C, confirming textural evidence that the anhydrite precipitated directly from the melt. The isotopic composition of sulfate leached from fresh ashfall samples shows it to be a mixture of anhydrite microphenocrysts and adsorbed sulfate derived from oxidized sulfur (SO 2) in the eruption plume. The leachate data show no evidence for rapid oxidation of significant amounts of H 2S in the eruption cloud even though the fugacity ratio of H 2S/SO 2 in the gas phase of the magma was >400. This may indicate kinetic inhibition of H 2S to SO 2 conversion in the eruption cloud. Prior to eruption, the magma contained an estimated 2.6 wt. % sulfur (as SO 3). The estimated δ 34S of the bulk magma is 5.8‰. Such a high value may reflect assimilation of 34S-enriched evaporites or the prior loss of 34S-depleted H 2S to a fluid or gas phase during formation of a small prophyry-type hydrothermal system or ore deposit. In either case, the original magma must have been very sulfur rich. It is likely that the initial high sulfur content of the magma and at least some of its 34S enrichment reflects involvement of subducted volcanogenic massive sulfides deposits during Benioff-zone partial melting. Isotopic data on mineralized, accidental lithic fragments support the possible development of a porphyry-type system at El Chichón.

  10. Geology and reconnaissance stable isotope study of the Oyu Tolgoi porphyry Cu-Au system, South Gobi, Mongolia

    Science.gov (United States)

    Khashgerel, B.-E.; Rye, R.O.; Hedenquist, J.W.; Kavalieris, I.

    2006-01-01

    The Oyu Tolgoi porphyry Cu-Au system in the South Gobi desert, Mongolia, comprises five deposits that extend over 6 km in a north-northeast-oriented zone. They occur in a middle to late Paleozoic are terrane and are related to Late Devonian quartz monzodiorite intrusions. The Hugo Dummett deposits are the northernmost and deepest, with up to 1,000 m of premineral sedimentary and volcanic cover rock remaining. They are the largest deposits discovered to date and characterized by high-grade copper (>2.5% Cu) and gold (0.5-2 g/t) mineralization associated with intense quartz veining and several phases of quartz monzodiorite intruded into basaltic volcanic host rocks. Sulfide minerals in these deposits are zoned outward from a bornite-dominated core to chalcopyrite, upward to pyrite ?? enargite and covellite at shallower depth. The latter high-sulfidation-state sulfides are hosted by advanced argillic alteration mineral associations. This alteration is restricted mainly to dacitic ash-flow tuff that overlies the basaltic volcanic rock and includes ubiquitous quartz and pyrophyllite, kaolinite, plus late dickite veins, as well as K alunite, Al phosphate-sulfate minerals, zunyite, diaspore, topaz, corundum, and andalusite. A reconnaissance oxygen-hydrogen and sulfur isotope study was undertaken to investigate the origin of several characteristic alteration minerals in the Oyu Tolgoi system, with particular emphasis on the Hugo Dummett deposits. Based on the isotopic composition of O, H, and S (??18O(SO4) = 8.8-20.1???, ??D = -73 to -43???, ??34S = 9.8-17.9???), the alunite formed from condensation of magmatic vapor that ascended to the upper parts of the porphyry hydrothermal system, without involvement of significant amounts of meteoric water. The isotopic data indicate that pyrophyllite (??18O = 6.5-10.9???, ??D = -90 to -106???) formed from a magmatic fluid with a component of meteoric water. Muscovite associated with quartz monzodiorite intrusions occurs in the core

  11. Use of isotopic sulfur to determine whitebark pine consumption by Yellowstone bears: a reassessment

    Science.gov (United States)

    Schwartz, Charles C.; Teisberg, Justin E.; Fortin, Jennifer K.; Haroldson, Mark A.; Servheen, Christopher; Robbins, Charles T.; van Manen, Frank T.

    2014-01-01

    Use of naturally occurring stable isotopes to estimate assimilated diet of bears is one of the single greatest breakthroughs in nutritional ecology during the past 20 years. Previous research in the Greater Yellowstone Ecosystem (GYE), USA, established a positive relationship between the stable isotope of sulfur (δ34S) and consumption of whitebark pine (Pinus albicaulis) seeds. That work combined a limited sample of hair, blood clots, and serum. Here we use a much larger sample to reassess those findings. We contrasted δ34S values in spring hair and serum with abundance of seeds of whitebark pine in samples collected from grizzly (Ursus arctos) and American black bears (U. americanus) in the GYE during 2000–2010. Although we found a positive relationship between δ34S values in spring hair and pine seed abundance for grizzly bears, the coefficients of determination were small (R2 ≤ 0.097); we failed to find a similar relationship with black bears. Values of δ34S in spring hair were larger in black bears and δ34S values in serum of grizzly bears were lowest in September and October, a time when we expect δ34S to peak if whitebark pine seeds were the sole source of high δ34S. The relationship between δ34S in bear tissue and the consumption of whitebark pine seeds, as originally reported, may not be as clean a method as proposed. Data we present here suggest other foods have high values of δ34S, and there is spatial heterogeneity affecting the δ34S values in whitebark pine, which must be addressed.

  12. Platinum stable isotope analysis of geological standard reference materials by double-spike MC-ICPMS

    DEFF Research Database (Denmark)

    Creech, John Benjamin; Baker, J. A.; Handler, M. R.

    2014-01-01

    We report a method for the chemical purification of Pt from geological materials by ion-exchange chromatography for subsequent Pt stable isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using a Pt-Pt double-spike to correct for instrumental mass bias...... (Creech et al., 2013, J. Anal. At. Spectrom. 28, 853-865). The reproducibility in natural samples is evaluated by processing multiple replicates of four standard reference materials, and is conservatively taken to be ca. ±0.088 (2sd). Pt stable isotope data for the full set of reference materials have....... Double-spiking of samples was carried out prior to digestion and chemical separation to correct for any mass-dependent fractionation that may occur due to incomplete recovery of Pt. Samples were digested using a NiS fire assay method, which pre-concentrates Pt into a metallic bead that is readily...

  13. Isotopic chronology and geological events of Precambrian complex in Taihangshan region

    Institute of Scientific and Technical Information of China (English)

    刘树文; 梁海华; 赵国春; 华永刚; 简安华

    2000-01-01

    There are five major geological events in Precambrian complex, Taihangshan region determined by researching into geology and isotopic chronology of the complex. Basaltic magma erupted and quartz-dioritic to tonalitic magma intruded in earlier neo-Archaean, which formed horn-blende-plagiogneiss of Fuping gneiss complex and metamorphic mafic rock enclaves in TTG gneiss complex. Granulite fades metamorphism and emplacement of biotite-plagiogneiss occurred in late neo-Archaean. Extension and uplifting from the end of neo-Archaean to Paleoproterozoic era formed Chengnanzhuang large extensional deformation zones and metamorphic mafic veins emplaced into the deformation zones. Remobilization of Precambrian complex and tectonic uplifting in late Paleoproterozoic era formed Longquanguan ductile shear zone and emplacement of Nanying gneiss. Occurrence of regional granite pegmatite at the end of Paleoproterozoic era means the end of the Luliang movement.

  14. Isotopic chronology and geological events of Precambrian complex in Taihangshan region

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    There are five major geological events in Precambrian complex, Taihangshan region determined by researching into geology and isotopic chronology of the complex. Basaltic magma erupted and quartz-dioritic to tonalitic magma intruded in earlier neo-Archaean, which formed hornblende-plagiogneiss of Fuping gneiss complex and metamorphic mafic rock enclaves in TTG gneiss complex. Granulite facies metamorphism and emplacement of biotite-plagiogneiss occurred in late neo-Archaean. Extension and uplifting from the end of neo-Archaean to Paleoproterozoic era formed Chengnanzhuang large extensional deformation zones and metamorphic mafic veins emplaced into the deformation zones. Remobilization of Precambrian complex and tectonic uplifting in late Paleoproterozoic era formed Longquanguan ductile shear zone and emplacement of Nanying gneiss. Occurrence of regional granite pegmatite at the end of Paleoproterozoic era means the end of the Lliang movement.

  15. Isotope geochronology of Dapingzhang spilite-keratophyre formation in Yunnan Province and its geological significance

    Institute of Scientific and Technical Information of China (English)

    钟宏; 胡瑞忠; 叶造军; 涂光炽

    2000-01-01

    On the basis of the geological field investigations and isotope geochronological studies the Sm-Nd isochron age (513 Ma?0 Ma), Rb-Sr isochron age (511 Ma? Ma) and K-Ar age (312-317 Ma) of the Dapingzhang spilite-keratophyre formation in Yunnan Province are presented. From these geochronological data it is evidenced that this suite of volcanic rocks was formed in the Cambrian and the parent magma was derived from a depleted mantle, which was influenced by crustal contamination and/or seawater hydrothermal alteration. During the Late Carboniferous the volcanic rocks experienced relatively strong geological reworking. This study provides geochronological evidence for the occurrence of Cambrian volcanic rocks in the Sanjiang (three-river) area.

  16. Isotope geochronology of Dapingzhang spilite-keratophyre formation in Yunnan Province and its geological significance

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    On the basis of the geological field investigations and isotope geochronological studies the Sm-Nd isochron age (513 Ma±40 Ma),Rb-Sr isochron age (511 Ma±8 Ma) and K-Ar age (312-317 Ma) of the Dapingzhang spilite-keratophyre formation in Yunnan Province are presented.From these geochronological data it is evidenced that this suite of volcanic rocks was formed in the Cambrian and the parent magma was derived from a depleted mantle,which was influenced by crustal contamination and/or seawater hydrothermal alteration.During the Late Carboniferous the volcanic rocks experienced relatively strong geological reworking.This study provides geochronological evidence for the occurrence of Cambrian volcanic rocks in the Sanjiang (three-river) area.

  17. The geological, isotopic, botanical, invertebrate, and lower vertebrate contexts for aripithecus ramidus

    Energy Technology Data Exchange (ETDEWEB)

    Woldegabriel, Giday [Los Alamos National Laboratory; Ambrose, Stanley H [UNIV OF ILLINOIS; Barboni, Doris [CEREGE, FRANCE; Bonneffille, Raymond [CEREGE, FRANCE; Bremond, Laurent [MONTPELLIER, FRANCE; Currie, Brian [MIAMI UNIV, OXFORD, OHIO; Degusta, David [STANFORD UNIV.; Hart, William K [MIAMI UNIV, OXFORD, OHIO; Murray, Alison M [UNIV OF ALBERTA; Renne, Paul R [UC/BERKELEY; Jolly - Saad, M C [NANTERRE, FRANCE; Stewart, Kathlyn M [CANADA; White, Tim D [UC/BERKELEY

    2009-01-01

    Sediments containing Ardipithecus ramidus were deposited 4.4 million years ago on an alluvial floodplain in Ethiopia's western Afar rift. The Lower Aramis Member hominid-bearing unit, now exposed across a >9-kilometer structural arc, is sandwiched between two volcanic tuffs that have nearly identical {sup 40}Ar/{sup 39}Ar ages. Geological data presented here, along with floral, invertebrate, and vertebrate paleontological and taphonomic evidence associated with the hominids, suggest that they occupied a wooded biotope over the western three-fourths of the paleotransect. Phytoliths and oxygen and carbon stable isotopes of pedogenic carbonates provide evidence of humid cool woodlands with a grassy substrate.

  18. Sulfur isotope studies of the Stillwater Complex and associated rocks, Montana

    Science.gov (United States)

    Zientek, M.L.; Ripley, E.M.

    1990-01-01

    The stillwater Complex in south-central Montana is a late Archean layered, ultramafic to mafic intrusion emplaced into middle to late Archean metagraywacke, metashale, and iron-formation. Sulfide minerals are concentrated near the base of the intrusion in some chromitite layers, podiform pegmatoids, discontinuous discordant pods or pipes, and numerous thin, stratiform layers. This investigation focuses on the isotopic composition of sulfur in metamorphosed sedimentary rocks. Stillwater-associated sills and dikes, sulfide accumulations near the base of the complex, and platinum-group element-enriched sulfide mineralization that constitutes the J-M reef and the Picket Pin deposit. The ??34S values for 233 samples analyzed in this study have a mean of 0.4 per mil, a standard deviation of 1.7, and a maximum and minimum of -3.8 and 7.8 per mil, respectively. Despite the very narrow range of values, analysis of variance calculations confirms that the data comprise three statistically distinct groups. -from Authors

  19. Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion (SPICE) in the Jiangnan Basin, South China

    Institute of Scientific and Technical Information of China (English)

    Yang Peng; Yongbo Peng; Xianguo Lang; Haoran Ma; Kangjun Huang; Fangbing Li; Bing Shen

    2016-01-01

    ABSTRACT:Global occurrences of Steptoean Positive Carbon Isotope Excursion (SPICE) during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon (δ13C) and organic carbon (δ13Corg) isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate (CAS, δ34SCAS) and pyrite (δ34Spyrite), unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰increase inδ13Ccarb of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions inδ34SCAS andδ34Spyrite have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound (VOSC, such as methanethiol and dimethyl sulfide) formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of 32S from continental margins to open oceans, elevatingδ34S of seawater sulfate in continental margins. A simple box model indicates that about 35%to 75%of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

  20. The influence of sulfur and hair growth on stable isotope diet estimates for grizzly bears.

    Science.gov (United States)

    Mowat, Garth; Curtis, P Jeff; Lafferty, Diana J R

    2017-01-01

    Stable isotope ratios of grizzly bear (Ursus arctos) guard hair collected from bears on the lower Stikine River, British Columbia (BC) were analyzed to: 1) test whether measuring δ34S values improved the precision of the salmon (Oncorhynchus spp.) diet fraction estimate relative to δ15N as is conventionally done, 2) investigate whether measuring δ34S values improves the separation of diet contributions of moose (Alces alces), marmot (Marmota caligata), and mountain goat (Oreamnos americanus) and, 3) examine the relationship between collection date and length of hair and stable isotope values. Variation in isotope signatures among hair samples from the same bear and year were not trivial. The addition of δ34S values to mixing models used to estimate diet fractions generated small improvement in the precision of salmon and terrestrial prey diet fractions. Although the δ34S value for salmon is precise and appears general among species and areas, sulfur ratios were strongly correlated with nitrogen ratios and therefore added little new information to the mixing model regarding the consumption of salmon. Mean δ34S values for the three terrestrial herbivores of interest were similar and imprecise, so these data also added little new information to the mixing model. The addition of sulfur data did confirm that at least some bears in this system ate marmots during summer and fall. We show that there are bears with short hair that assimilate >20% salmon in their diet and bears with longer hair that eat no salmon living within a few kilometers of one another in a coastal ecosystem. Grizzly bears are thought to re-grow hair between June and October however our analysis of sectioned hair suggested at least some hairs begin growing in July or August, not June and, that hair of wild bears may grow faster than observed in captive bears. Our hair samples may have been from the year of sampling or the previous year because samples were collected in summer when bears were

  1. An evaporite-based high-resolution sulfur isotope record of Late Permian and Triassic seawater sulfate

    Science.gov (United States)

    Bernasconi, Stefano M.; Meier, Irene; Wohlwend, Stephan; Brack, Peter; Hochuli, Peter A.; Bläsi, Hansruedi; Wortmann, Ulrich G.; Ramseyer, Karl

    2017-05-01

    Variations in the sulfur isotope composition of dissolved marine sulfate through time reflect changes in the global sulfur cycle and are intimately related to changes in the carbon and oxygen cycles. A large shift in the sulfur isotope composition of sulfate at the Permian/Triassic boundary has been recognized for long time and a number of studies were carried out to understand the causes and significance of this shift. However, data for the Middle and Late Triassic are very sparse and the stratigraphic evolution of the sulfur isotope composition of seawater is poorly constrained due to the small number of samples analyzed and/or due to the limited stratigraphic intervals studied. Moreover, in the last few years the Triassic timescale has significantly changed due to a wealth of new radiometric and stratigraphic data. In this study we show that for the Late Permian and the Triassic it is possible to obtain a precise reconstruction of the evolution of the sulfur cycle, for parts of it at sub-million year resolution, by analyzing exclusively gypsum and anhydrite deposits. We base our reconstruction on new data from the Middle and Late Triassic evaporites of Northern Switzerland and literature data from evaporites from Germany, Austria, Italy and the Middle East. We propose a revised correlation between the well-dated marine Tethyan sections in northern Italy and the evaporites from Northern Switzerland and from the Germanic Basin calibrated to the newest radiometric absolute age scale. This new correlation allows for a precise dating of the evaporites and constructing a composite sulfur isotope evolution of seawater sulfate from the latest Permian (Lopingian Epoch) to the Norian. We show that a rapid positive shift of approximately 24‰ at the Permian-Triassic boundary can be used to constrain seawater sulfate concentrations in the range of 2-6 mM, thus higher than previous estimates but with less rapid changes. Finally, we discuss two possible evolution scenarios

  2. Archean Mass-independent Fractionation of Sulfur Isotope:New Evidence of Bedded Sulfide Deposits in the Yanlingguan-Shihezhuang area of Xintai, Shandong Province

    Institute of Scientific and Technical Information of China (English)

    LI Yanhe; HOU Kejun; WAN Defang; YUE Guoliang

    2008-01-01

    Multiple sulfur isotope ratios (34S/33S/32S) of Archean bedded sulfides deposits were measured in the Yanlingguan Formation of the Taishan Group in Xintai, Shandong Province, East of China; δ33S =-0.7‰ to 3.8‰,δ34S = 0.1‰-8.8‰, △33S = -2.3‰ to -0.7‰ The sulfur isotope compositions show obvious mass-independent fractionation (MIF) signatures. The presence of MIF of sulfur isotope in Archean sulfides indicates that the sulfur was from products of photochemical reactions of volcanic SO2 induced by solar UV radiation, implying that the ozone shield was not formed in atmosphere at that time, and the oxygen level was less than 10-5PAL (the present atmosphere level). The sulfate produced by photolysis of SO2 with negative △33S precipitated near the volcanic activity center; and the product of element S with positive △33S precipitated far away from the volcanic activity center. The lower △33S values of sulfide (-2.30‰ to-0.25‰) show that Shihezhuang was near the volcanic center,and sulfur was mostly from sulfate produced by photolysis. The higher △33S values (-0.5‰ to-2‰)indicate that Yanlingguan was far away from the volcanic center and that some of sulfur were from sulfate, another from element S produced by photolysis. The data points of sulfur isotope from Yanlingguan are in a line parallel to MFL (mass dependent fractionation line) on the plot of δ34S-δ33S,showing that the volcanic sulfur species went through the atmospheric cycle into the ocean, and then mass dependent fractionation occurred during deposition of sulfide. The data points of sulfur isotope from Shihezhuang represent a mix of different sulfur source.

  3. Theoretical prediction for several important equilibrium Ge isotope fractionation factors and geological implications

    Science.gov (United States)

    Li, Xuefang; Zhao, Hui; Tang, Mao; Liu, Yun

    2009-09-01

    This study estimates equilibrium fractionation factors in the Ge isotope system, including the dominant aqueous Ge(OH) 4 and GeO(OH) 3- species in seawater, Ge-bearing organic complexes (e.g. Ge-catechol, Ge-oxalic acid and Ge-citric acid), and Ge in quartz- (or opal-), albite-, K-feldspar-, olivine- and sphalerite-like structures. Estimations are based on Urey model (or Bigeleisen-Mayer equation) and high level quantum chemistry calculations. All calculations are made at B3LYP/6-311 + G(d,p) theory level. Solvation effects are treated by explicit solvent model ("water-droplet" method), and mineral structures are simulated using cluster models, in which the clusters are cut from the X-ray structures of those minerals. In addition, a number of different conformers are used for aqueous complexes in order to reduce the possible errors coming from the differences of configurations in solution. The "salt effect" on GeO(OH) 3-(aq) species is also carefully evaluated. We estimate the accuracy of these fractionation calculations at about ± 0.3‰. Excitedly, very large isotope fractionations are found between many Ge isotope systems. The Ge-containing sulfides (e.g. sphalerite) can extremely enrich light Ge isotopes (more than 10‰) compared with 4-coordinated Ge-O compounds (e.g. Ge(OH) 4(aq) or quartz). The fractionations between Ge(OH) 4(aq) and 6-coordinated Ge-bearing organic complexes can be also up to 4‰ at 25 °C. These results give a good explanation for the experimental observations of Rouxel et al. (2006). It also suggests a great potential for broad application of Ge isotope method in various geological systems.

  4. Rare Isotope Insights into Supereruptions: Rare Sulfur and Triple Oxygen Isotope Geochemistry of Stratospheric Sulfate Aerosols Absorbed on Volcanic Ash Particles

    Science.gov (United States)

    Bindeman, I. N.; Eiler, J.; Wing, B.; Farquhar, J.

    2006-12-01

    We present analyses of stable isotopic ratios of 17O/16O, 18O/16O, 34S/32S, and 33S/32S, 36S/32S of sulfate leached from volcanic ash of a series of well-known volcanic eruptions. This list covers much of the diversity of sizes and the character of volcanic eruptions. Particular emphasis is paid to the Lava Creek Tuff of Yellowstone and we present wide geographic sample coverage for this unit. This global dataset spans a significant range in δ34S, δ18O, and Δ17O of sulfate (29, 30 and 3.3 permil respectively) with oxygen isotopes recording mass-independent fractionation and sulfur isotopes exhibiting mass-dependent behavior. These ranges are defined by the isotopic compositions of products of large caldera forming eruptions. Proximal ignimbrites and coarse ash typically do not contain sulfate. The presence of sulfate with Δ17O > 0.2 permil is characteristic of small distal ash particles, suggesting that sulfate aerosols were scavenged after they underwent atmospheric photochemical reactions. Additionally, sediments that embed ash layers either do not contain sulfate or contain minor sulfate with Δ17O near 0 permil, suggesting that the observed sulfate in ash is of volcanic origin. Mass-dependent sulfur isotopic compositions suggest that sulfate-forming reactions did not involve photolysis of SO2, unlike the situation inferred for some pre-2.3 Ga sulfates or hypothesized to occur during the formation of sulfate associated with plinian eruptions that pierce the ozone layer. However, sulfate in the products of caldera-forming eruptions display a large δ34S range and fractionation relationships that do not follow equilibrium slopes of 0.515 and 1.90 for 33S/32S vs. 34S/32S and 36S/32S vs. 34S/32S, respectively. This implies that the sulfur isotopic characteristics of these sulfates were not set by a single stage, high-temperature equilibrium process in the volcanic plum. The data presented here are consistent with a single stage kinetic fractionation of sulfur

  5. Sulfur Isotopic Compositions of Individual Aerosol Particles from Below and Within Stratocumulus Clouds over the Southeast Pacific Ocean During VOCALS

    Science.gov (United States)

    Bose, M.; Anderson, J. R.; Twohy, C. H.; Williams, P.

    2012-12-01

    The VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-Rex) was a large multi-national field experiment that collected data and samples from a region of the southeast Pacific with the world's largest stratocumulus cloud systems. Samples examined here are residues of cloud droplets and ambient particles from below the clouds collected during flights of the NCAR C-130 off the coast of Chile. Selected samples were studied using scanning electron microscopy (SEM) and secondary ion mass spectrometry (SIMS) in order to contribute to the understanding of the source of non-sea-salt sulfate in this region. Particles in the size range from 0.2 to 1μm diameter on holey and lacey carbon were characterized by SEM combined with energy dispersive spectrometry (EDS), thus identifying sulfur-containing particles. Subsequently, sulfur ion imaging of identified sea salt, ammonium sulfate and sodium sulfate particles was done with the Cameca Ametek NanoSIMS 50L at Arizona State University. A electrons were collected simultaneously at high mass resolution (m/Δm>10000). Each measurement typically consists of 5 to 8 frames (~5.4 min/frame). NIST barium sulfate and ammonium sulfate particles were used as isotopic standards. Preliminary analyses on a small pool of VOCALS individual particles show a wide range in sulfur isotopic compositions (δ34S = -56 to +41‰). In addition, the in-cloud particles are enriched in 32S, while the ambient particles exhibit 34S excesses. Isotopic data on a large inventory of particles is being currently acquired, which will be presented at the meeting. Data will be used to investigate sulfur sources (marine vs. continental) and the processing of aerosols through sulfate formation.

  6. Use of sulfur and nitrogen stable isotopes to determine the importance of whitebark pine nuts to Yellowstone grizzly bears

    Science.gov (United States)

    Felicetti, L.A.; Schwartz, C.C.; Rye, R.O.; Haroldson, M.A.; Gunther, K.A.; Phillips, D.L.; Robbins, C.T.

    2003-01-01

    Whitebark pine (Pinus albicaulis) is a masting species that produces relatively large, fat- and protein-rich nuts that are consumed by grizzly bears (Ursus arctos horribilis). Trees produce abundant nut crops in some years and poor crops in other years. Grizzly bear survival in the Greater Yellowstone Ecosystem is strongly linked to variation in pine-nut availability. Because whitebark pine trees are infected with blister rust (Cronartium ribicola), an exotic fungus that has killed the species throughout much of its range in the northern Rocky Mountains, we used stable isotopes to quantify the importance of this food resource to Yellowstone grizzly bears while healthy populations of the trees still exist. Whitebark pine nuts have a sulfur-isotope signature (9.2 ?? 1.3??? (mean ?? 1 SD)) that is distinctly different from those of all other grizzly bear foods (ranging from 1.9 ?? 1.7??? for all other plants to 3.1 ?? 2.6??? for ungulates). Feeding trials with captive grizzly bears were used to develop relationships between dietary sulfur-, carbon-, and nitrogen-isotope signatures and those of bear plasma. The sulfur and nitrogen relationships were used to estimate the importance of pine nuts to free-ranging grizzly bears from blood and hair samples collected between 1994 and 2001. During years of poor pine-nut availability, 72% of the bears made minimal use of pine nuts. During years of abundant cone availability, 8 ?? 10% of the bears made minimal use of pine nuts, while 67 ?? 19% derived over 51% of their assimilated sulfur and nitrogen (i.e., protein) from pine nuts. Pine nuts and meat are two critically important food resources for Yellowstone grizzly bears.

  7. Stable carbon, nitrogen and sulfur isotopes in non-carbonate fractions of cold-seep carbonates

    Science.gov (United States)

    Feng, Dong; Peng, Yongbo; Peckmann, Jörn; Roberts, Harry; Chen, Duofu

    2017-04-01

    Sulfate-driven anaerobic oxidation of methane (AOM) supports chemosynthesis-based communities and limits the release of methane from marine sediments. This process promotes the formation of carbonates close to the seafloor along continental margins. The geochemical characteristics of the carbonate minerals of these rocks are increasingly understood, questions remain about the geochemical characteristics of the non-carbonate fractions. Here, we report stable carbon, nitrogen and sulfur isotope patterns in non-carbonate fractions of seep carbonates. The authigenic carbonates were collected from three modern seep provinces (Black Sea, Gulf of Mexico, and South China Sea) and three ancient seep deposits (Marmorito, northern Italy, Miocene; SR4 deposit of the Lincoln Creek Formation and Whiskey Creek, western Washington, USA, Eocene to Oligocene). The δ13C values of non-carbonate fractions range from ˜-25‰ to -80‰ VPDB. These values indicate that fossil methane mixed with varying amounts of pelagic organic matter is the dominant source of carbon in these fractions. The relatively small offset between the δ34S signatures of the non-carbonate fractions and the respective sulfide minerals suggests that locally produced hydrogen sulfide is the main source of sulfur in seep environments. The δ15N values of the non-carbonate fractions are generally lower than the corresponding values of deep-sea sediments, suggesting that organic nitrogen is mostly of a local origin. This study reveals the potential of using δ13C, δ15N, δ34S values to discern seep and non-seep deposits. In cases where δ13Ccarbonate values are only moderately low due to mixing processes and lipid biomarkers have been erased in the course of burial, it is difficult to trace back AOM owing to the lack of other records. This problem is even more pronounced when authigenic carbonate is not available in ancient seep environments. Acknowledgments: The authors thank BOEM and NOAA for their years' support

  8. Fire and brimstone: the microbially mediated formation of elemental sulfur nodules from an isotope and major element study in the paleo-Dead Sea.

    Directory of Open Access Journals (Sweden)

    Tom Bishop

    Full Text Available We present coupled sulfur and oxygen isotope data from sulfur nodules and surrounding gypsum, as well as iron and manganese concentration data, from the Lisan Formation near the Dead Sea (Israel. The sulfur isotope composition in the nodules ranges between -9 and -11‰, 27 to 29‰ lighter than the surrounding gypsum, while the oxygen isotope composition of the gypsum is constant around 24‰. The constant sulfur isotope composition of the nodule is consistent with formation in an 'open system'. Iron concentrations in the gypsum increase toward the nodule, while manganese concentrations decrease, suggesting a redox boundary at the nodule-gypsum interface during aqueous phase diagenesis. We propose that sulfur nodules in the Lisan Formation are generated through bacterial sulfate reduction, which terminates at elemental sulfur. We speculate that the sulfate-saturated pore fluids, coupled with the low availability of an electron donor, terminates the trithionate pathway before the final two-electron reduction, producing thionites, which then disproportionate to form abundant elemental sulfur.

  9. Fire and brimstone: the microbially mediated formation of elemental sulfur nodules from an isotope and major element study in the paleo-Dead Sea.

    Science.gov (United States)

    Bishop, Tom; Turchyn, Alexandra V; Sivan, Orit

    2013-01-01

    We present coupled sulfur and oxygen isotope data from sulfur nodules and surrounding gypsum, as well as iron and manganese concentration data, from the Lisan Formation near the Dead Sea (Israel). The sulfur isotope composition in the nodules ranges between -9 and -11‰, 27 to 29‰ lighter than the surrounding gypsum, while the oxygen isotope composition of the gypsum is constant around 24‰. The constant sulfur isotope composition of the nodule is consistent with formation in an 'open system'. Iron concentrations in the gypsum increase toward the nodule, while manganese concentrations decrease, suggesting a redox boundary at the nodule-gypsum interface during aqueous phase diagenesis. We propose that sulfur nodules in the Lisan Formation are generated through bacterial sulfate reduction, which terminates at elemental sulfur. We speculate that the sulfate-saturated pore fluids, coupled with the low availability of an electron donor, terminates the trithionate pathway before the final two-electron reduction, producing thionites, which then disproportionate to form abundant elemental sulfur.

  10. Sulfur isotope composition of metasomatised mantle xenoliths from the Bultfontein kimberlite (Kimberley, South Africa): Contribution from subducted sediments and the effect of sulfide alteration on S isotope systematics

    Science.gov (United States)

    Giuliani, Andrea; Fiorentini, Marco L.; Martin, Laure A. J.; Farquhar, James; Phillips, David; Griffin, William L.; LaFlamme, Crystal

    2016-07-01

    Sulfur isotopes are a powerful geochemical tracer in high-temperature processes, but have rarely been applied to the study of mantle metasomatism. In addition, there are very limited S isotope data on sub-continental lithospheric mantle (SCLM) material. For cratonic regions, these data are restricted to sulfide inclusions in diamonds. To provide new constraints on the S isotope composition of the SCLM and on the source(s) of mantle metasomatic fluids beneath the diamondiferous Kimberley region (South Africa), we investigated the S isotope systematics of five metasomatised mantle xenoliths from the Bultfontein kimberlite. Pentlandite and chalcopyrite in these xenoliths were analysed by in situ secondary-ion mass spectrometry (SIMS), with bulk-rock material measured by gas source isotope ratio mass spectrometry techniques. Based on previous studies, the xenoliths experienced different types of metasomatism to one another at distinct times (∼180 and ∼90-80 Ma). Contained pentlandite grains show variable alteration to heazlewoodite (i.e. Ni sulfide) + magnetite. The in situ S isotope analyses of pentlandite exhibit a relatively restricted range between -5.9 and - 1.4 ‰δ34 S (compared to VCDT), with no statistically meaningful differences between samples. Chalcopyrite only occurs in one sample and shows δ34 S values between -5.4 and - 1.0 ‰. The bulk-rock Ssulfide isotope analyses vary between -3.4 and + 0.8 ‰δ34 S. Importantly, the only sample hosting dominantly fresh sulfides shows a bulk-rock δ34 S value consistent with the mean value for the sulfides, whereas the other samples exhibit higher bulk 34S/32S ratios. The differences between bulk-rock and average in situδ34 S values are directly correlated with the degree of sulfide alteration. This evidence indicates that the elevated 34S/32S ratios in the bulk samples are not due to the introduction of heavy S (commonly as sulfates) and are best explained by isotopic fractionation coupled with the removal

  11. Sulfur isotope budget (32S, 33S, 34S and 36S) in Pacific-Antarctic ridge basalts: A record of mantle source heterogeneity and hydrothermal sulfide assimilation

    Science.gov (United States)

    Labidi, J.; Cartigny, P.; Hamelin, C.; Moreira, M.; Dosso, L.

    2014-05-01

    To better address how Mid-Ocean Ridge Basalt (MORB) sulfur isotope composition can be modified by assimilation and/or by immiscible sulfide fractionation, we report sulfur (S), chlorine (Cl) and copper (Cu) abundances together with multiple sulfur isotope composition for 38 fresh basaltic glasses collected on the Pacific-Antarctic ridge. All the studied glasses - with the exception of 8 off-axis samples - exhibit relatively high Cl/K, as the result of pervasive Cl-rich fluid assimilation. This sample set hence offers an opportunity to document both the upper mantle S isotope composition and the effect of hydrothermal fluids assimilation on the S isotope composition of erupted basalts along segments that are devoid of plume influence.

  12. Two series of copper-gold deposits in the middle and lower reaches of the Yangtze River area (MLYRA) and the hydrogen, oxygen, sulfur and lead isotopes of their ore-forming hydrothermal systems

    Institute of Scientific and Technical Information of China (English)

    周涛发; 袁峰; 岳书仓; 赵勇

    2000-01-01

    Based on studies on the geological characteristics of the copper-gold deposits in the middle and lower reaches of the Yangtze River area (MLYRA) and their hydrogen, oxygen, sulfur and lead isotope compositions, it is concluded that there existed two series of copper-gold deposits. They are evolutional products of two ore-forming hydrothermal systems in different geodynamic settings and geological era. Series I is stratiform or stratabound copper-gold deposits. These deposits were formed by submarine exhalation and sedimentation of hydrothermal solutions in Her-cynian tensional tectonic environment after bot brine ascending along contemporaneous faults and exhaled into the sea-floor. Series II consists of copper-gold deposits related to medium and acidic magmatic intrusions. Their mineralizations took place in Yanshanian in a tensional or a transitional period to the tensional tectonic environment from the composite of the tethys tectonic regime and the Paleo-Pacific ocean tectonic regime, as well as in

  13. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

  14. Sulfur isotopic characteristics of volcanic products from the September 2014 Mount Ontake eruption, Japan

    National Research Council Canada - National Science Library

    Ikehata, Kei; Maruoka, Teruyuki

    2016-01-01

    .... Ontake eruption were investigated. The volcanic ash samples were found to be composed of altered volcanic fragments, alunite, anhydrite, biotite, cristobalite, gypsum, ilmenite, kaolin minerals, native sulfur, orthopyroxene...

  15. The elemental and isotopic composition of sulfur and nitrogen in Chinese coals

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, H.Y.; Liu, C.Q. [Chinese Academy of Sciences, Guiyang (China). Inst. of Geochemistry

    2011-01-15

    Coal combustion is an important atmospheric pollution source in most Chinese cities, so systematic studies on sulfur and nitrogen in Chinese coals are needed. The sulfur contents in Chinese coals average 0.9 {+-} 1.0%, indicating that most Chinese coals are low in sulfur. A nearly constant mean {delta}{sup 34}S value is observed in low sulfur (TS < 1) Chinese coals of different ages (D, P-1, T-3 and J{sup 3}). High sulfur Chinese coals (OS > 0.8%), often found at late Carboniferous and late Permian in southern China, had two main sulfur sources (original plant sulfur and secondary sulfur). The wide variety of {delta}{sup 34}S values of Chinese coals (-15 parts per thousand to +50 parts per thousand) is a result of a complex sulfur origin. The delta N-15 values of Chinese coals ranged from -6 parts per thousand to +4 parts per thousand, showing a lack of correlation with coal ages, whereas nitrogen contents are higher in Paleozoic coals than in Mesozoic coals. This may be related to their original precursor plant species: high nitrogen pteridophytes for the Paleozoic coals and low nitrogen gymnosperms for the Mesozoic coals. Different to {delta}{sup 34}S values, Chinese coals showed higher {delta} {sup 15}N values in marine environments than in freshwater environments.

  16. Transboundary transport of anthropogenic sulfur in PM2.5 at a coastal site in the Sea of Japan as studied by sulfur isotopic ratio measurement

    Energy Technology Data Exchange (ETDEWEB)

    Inomata, Yayoi, E-mail: inomata@acap.asia [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Ohizumi, Tsuyoshi [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Niigata Prefectural Institute of Public Health and Environmental Sciences, 314-1, Sowa, Niigata, Niigata 950-2144 (Japan); Take, Naoko; Sato, Keiichi [Asia Center for Air Pollution Research, 1182, Sowa, Niigata, Niigata 950-2144 (Japan); Nishikawa, Masataka [National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki 305-8506 (Japan); Tokyo University of Science, 12-1, Ichigaya Funakawara, Shinjuku, Tokyo 162-0826 (Japan)

    2016-05-15

    Sulfur isotopic ratios (δ{sup 34}S) in size separated aerosol particles (PM2.5 and coarse particles) were measured at Niigata-Maki facing the Sea of Japan. Non-sea salt δ{sup 34}S (δ{sup 34}S{sub nss}) in PM2.5 showed seasonal variations with relatively high values in winter (1.0–3.9‰ in spring, 2.8–4.5‰ in summer, 1.3–4.5‰ in autumn, 3.7–5.7‰ in winter). Taking into consideration air mass transport routes, δ{sup 34}S{sub nss} in the air masses which originated in the Asian continent and were transported over the Sea of Japan to the monitoring sites were higher than those values for air masses which were transported over the Japanese islands after leaving the Asian continent for each season. Considering that the δ{sup 34}S{sub nss} in sulfuric acid derived from domestic emissions in Japan are lower than those of δ{sup 34}S{sub nss} in coal, the lower δ{sup 34}S{sub nss} for the air mass transported over the Japanese islands suggest that sulfuric acid in PM2.5 modified the δ{sup 34}S{sub nss} due to aerosol mixing with sulfuric acid in Japan. Material balance calculations suggested that the relative contribution of transboundary transport in winter was also higher than for other seasons (40–75% in spring, 51–63% in summer, 45–73% in autumn, and 53–81% in winter). In particular, the contribution to the air masses which were transported directly from the Asian continent was relatively large (75% in spring, 59% in autumn, 78% in winter) in comparison with that for the air masses which were transported over Japan. - Highlights: • δ{sup 34}Snss in PM2.5 is effective to estimate contribution of anthropogenic sulfur. • δ{sup 34}Snss have characterized with seasonal variation with high values in winter. • The contribution of transboundary transport is 39-81% at the site facing to the Sea of Japan. • δ{sup 34}Snss in PM2.5 are modified during transport with mixing of domestic sources. • Map of δ{sup 34}S distribution originated

  17. The precise measurement of Tl isotopic compositions by MC-ICPMS: Application to the analysis of geological materials and meteorites

    Energy Technology Data Exchange (ETDEWEB)

    Rehkaemper, M. [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Geological Sciences]|[Univ. Muenster (Germany). Zentrallabor fuer Geochronologie; Halliday, A.N. [Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Geological Sciences]|[ETH Zuerich (Switzerland). Inst. for Isotope Geology and Mineral Resources

    1999-03-01

    The precision of Tl isotopic measurements by thermal ionization mass spectrometry (TIMS) is severely limited by the fact that Tl possesses only two naturally occurring isotopes, such that there is no invariant isotope ratio that can be used to correct for instrumental mass discrimination. In this paper the authors describe new chemical and mass spectrometric techniques for the determination of Tl isotopic compositions at a level of precision hitherto unattained. Thallium is first separated from the geological matrix using a two-stage anion-exchange procedure. Thallium isotopic compositions are then determined by multiple-collector inductively coupled plasma-mass spectrometry with correction for mass discrimination using the known isotopic composition of Pb that is admixed to the sample solutions. With these procedures they achieve a precision of 0.01--0.02% for Tl isotope ratio measurements in geological samples and this is a factor of {ge}3--4 better than the best published results by TIMS. Results are discussed for five terrestrial samples and for the C3V chondrite Allende.

  18. SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Johnson, Matthew Stanley

    2013-01-01

    Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores...... plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ(33)S/δ(34)S and Δ(36)S/Δ(33)S found in glacial samples. We are able to identify the process controlling...

  19. Isotopic Investigation of Geologic and Anthropogenic Controls on Nutrient Loading in Malibu Creek Watershed, California

    Science.gov (United States)

    Harrison, M.; Hibbs, B. J.

    2015-12-01

    The upper portion of the Malibu Creek Watershed exposes the Monterey-Modelo Formation, a Miocene marine mudstone. This formation has been thought to contribute high concentrations of orthophosphate and nitrate to streams via groundwater leaching and baseflow. However, our recent studies suggest that high concentrations of orthophosphate and nitrate may be dominated by dry weather runoff of imported water (tap and recycled water) from watering of urban landscapes. Our study investigates El Camino Real Creek, a tributary in the Malibu Creek Watershed that traverses Monterey-Modelo Formation strata and is fed predominantly by dry weather runoff. From an initial input at a storm drain where dry weather runoff flows consistently, hydrochemical parameters range from 1.86 to 4.66 mg/L NO3-N and 1.06 to 2.28 mg/L PO4 that decrease to concentrations ranging from 0.15 to 0.59 mg/L NO3-N and 0.40 to 0.87 mg/L PO4 where El Camino Real Creek converges with Las Virgenes Creek. The decrease in nutrient content downstream is due to the transformational processes denitrification, vegetation uptake, and mixing with groundwater baseflow containing lower nutrient content. The average water isotope values for the imported (tap and recycled) endmembers are -9.1‰ δ18O and -73‰ δD. The average water isotope values for the samples collected at the storm drain range from -6.0‰ to -8.0‰ δ18O and -56‰ to -68‰ δD while isotope values downstream range from -6.0‰ to -6.3‰ δ18O and -47‰ to -48‰ δD. Stable isotopes of hydrogen and oxygen show mixing of imported water with local groundwater downstream, which demonstrates that nutrients in this creek are not strictly dominated by geologic sources. To further understand the nutrient changes and mixing percentages of imported and local water sources, diurnal studies are being conducted with the integration of nitrate isotopes to help understand the nutrient dynamics in El Camino Real Creek.

  20. Sulfur isotope analysis of cinnabar from Roman wall paintings by elemental analysis/isotope ratio mass spectrometry--tracking the origin of archaeological red pigments and their authenticity.

    Science.gov (United States)

    Spangenberg, Jorge E; Lavric, Jost V; Meisser, Nicolas; Serneels, Vincent

    2010-10-15

    The most valuable pigment of the Roman wall paintings was the red color obtained from powdered cinnabar (Minium Cinnabaris pigment), the red mercury sulfide (HgS), which was brought from mercury (Hg) deposits in the Roman Empire. To address the question of whether sulfur isotope signatures can serve as a rapid method to establish the provenance of the red pigment in Roman frescoes, we have measured the sulfur isotope composition (δ(34)S value in ‰ VCDT) in samples of wall painting from the Roman city Aventicum (Avenches, Vaud, Switzerland) and compared them with values from cinnabar from European mercury deposits (Almadén in Spain, Idria in Slovenia, Monte Amiata in Italy, Moschellandsberg in Germany, and Genepy in France). Our study shows that the δ(34)S values of cinnabar from the studied Roman wall paintings fall within or near to the composition of Almadén cinnabar; thus, the provenance of the raw material may be deduced. This approach may provide information on provenance and authenticity in archaeological, restoration and forensic studies of Roman and Greek frescoes.

  1. Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

    Science.gov (United States)

    Muller, Élodie; Philippot, Pascal; Rollion-Bard, Claire; Cartigny, Pierre

    2016-07-01

    Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ˜+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between -1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non-33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere.

  2. Multiple Sulfur Isotopes and Sulfur/Selenium Ratios as Tracers for the Subsurface Biosphere in Altered Oceanic Basalts in the Western Pacific

    Science.gov (United States)

    Rouxel, O. J.; Ono, S.; Alt, J.; Rumble, D.

    2006-05-01

    Alteration of oceanic crust by seawater is one of the most important processes controlling the global fluxes of elements and microbes likely play a significant role in this process. However, the study of the extent and nature of an active biosphere in the oceanic basement is currently limited due to technical difficulties involved in identifying indigenous microbes. Here, we report S isotope compositions of secondary sulfides in ~170 Ma altered basalt from ODP Site 801 in the western Pacific to assess the potential presence of microbial sulfate reduction within the basaltic oceanic crust. In-situ ion microprobe and bulk rock S isotope analyses show large variations of δ34S values ranging from -45‰ to 1‰. Low δ34S values are consistent with the coupled effects of bacterial reduction of seawater sulfate and disproportionation of S-intermediate species as observed in sedimentary environments. These low and variable δ34S values, together with bulk rock S concentrations ranging from 0.02% up to 1.28% are consistent with a net addition of reduced sulfur in some sections of the crust and constitute clear evidence for microbial activity in basaltic ocean crust. Preliminary results of high-precision multiple-sulfur isotope analyses (33S/32S, and 36S/32S) show at least two generations of secondary pyrite in altered basalt. One is mass- dependent with seawater sulfate, consistent with microbial sulfate reduction under low metabolic rate. Another set of data are consistent with either mixing of these sulfate-derived sulfides with basaltic primary sulfide or with partial oxidation-reprecipitation origin. Since Se substitutes for S in sulfides, S/Se ratios coupled to S isotopes provide further constraints on the source of S (whether remobilization of basaltic sulfide or seawater sulfate). Bacterial sulfate reduction is expected to produce a negative relationship between δ34S and S/Se composition of altered basalt since the S/Se ratio of seawater (~1.6x107) differs

  3. An Analysis of Sulfur Content and Multiple Sulfur Isotope Fractionation of Tephra Deposits at Valles Caldera, New Mexico: Variations over the Course of Two Caldera-Forming Eruptions

    Science.gov (United States)

    Campbell, M. E.; Wing, B. A.; Stix, J.

    2010-12-01

    analyses for the LBT and UBT high-silica rhyolite ignimbrite samples are relatively moderate, varying from 3.5 to 4.3‰. Whole rock sulfur concentrations range from only 4 mg S/kg rock to 393 mg S/kg rock. Measured δ34S values and their corresponding whole rock sulfur concentrations are broadly inversely correlated, and are most simply interpreted as a series of degassing events that enriched the residual Valles magma in isotopically-heavy S. The S profiles of the LBT and UBT erupted products show similar trends: from the early plinian through to the late plinian units, S contents decrease and δ34S values increase, then plateau at the ignimbrite. Both profiles start out with δ34S values near 0‰, indicative of a relatively primitive, mafic source for the S in the Valles complex, and perhaps for the caldera-forming eruptions themselves.

  4. Oxygen isotope systematics of gem corundum deposits in Madagascar: relevance for their geological origin

    Science.gov (United States)

    Giuliani, Gaston; Fallick, Anthony; Rakotondrazafy, Michel; Ohnenstetter, Daniel; Andriamamonjy, Alfred; Ralantoarison, Théogène; Rakotosamizanany, Saholy; Razanatseheno, Marie; Offant, Yohann; Garnier, Virginie; Dunaigre, Christian; Schwarz, Dietmar; Mercier, Alain; Ratrimo, Voahangy; Ralison, Bruno

    2007-02-01

    The oxygen isotopic composition of gem corundum was measured from 22 deposits and occurrences in Madagascar to provide a gemstone geological identification and characterization. Primary corundum deposits in Madagascar are hosted in magmatic (syenite and alkali basalt) and metamorphic rocks (gneiss, cordieritite, mafic and ultramafic rocks, marble, and calc-silicate rocks). In both domains the circulation of fluids, especially along shear zones for metamorphic deposits, provoked in situ transformation of the corundum host rocks with the formation of metasomatites such as phlogopite, sakenite, and corundumite. Secondary deposits (placers) are the most important economically and are contained in detrital basins and karsts. The oxygen isotopic ratios (18O/16O) of ruby and sapphire from primary deposits are a good indicator of their geological origin and reveal a wide range of δ18O (Vienna Standard Mean Ocean Water) between 1.3 and 15.6‰. Metamorphic rubies are defined by two groups of δ18O values in the range of 1.7 to 2.9‰ (cordieritite) and 3.8 to 6.1‰ (amphibolite). “Magmatic” rubies from pyroxenitic xenoliths contained in the alkali basalt of Soamiakatra have δ18O values ranging between 1.3 and 4.7‰. Sapphires are classified into two main groups with δ18O in the range of 4.7 to 9.0‰ (pyroxenite and feldspathic gneiss) and 10.7 to 15.6‰ (skarn in marble from Andranondambo). The δ18O values for gem corundum from secondary deposits have a wide spread between -0.3 and 16.5‰. The ruby and sapphire found in placers linked to alkali basalt environments in the northern and central regions of Madagascar have consistent δ18O values between 3.5 and 6.9‰. Ruby from the placers of Vatomandry and Andilamena has δ18O values of 5.9‰, and between 0.5 and 4.0‰, respectively. The placers of the Ilakaka area are characterized by a huge variety of colored sapphires and rubies, with δ18O values between -0.3 and 16.5‰, and their origin is debated. A

  5. Platinum stable isotope analysis of geological standard reference materials by double-spike MC-ICPMS

    Science.gov (United States)

    Creech, J.B.; Baker, J.A.; Handler, M.R.; Bizzarro, M.

    2015-01-01

    We report a method for the chemical purification of Pt from geological materials by ion-exchange chromatography for subsequent Pt stable isotope analysis by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using a 196Pt-198Pt double-spike to correct for instrumental mass bias. Double-spiking of samples was carried out prior to digestion and chemical separation to correct for any mass-dependent fractionation that may occur due to incomplete recovery of Pt. Samples were digested using a NiS fire assay method, which pre-concentrates Pt into a metallic bead that is readily dissolved in acid in preparation for anion-exchange chemistry. Pt was recovered from anion-exchange resin in concentrated HNO3 acid after elution of matrix elements, including the other platinum group elements (PGE), in dilute HCl and HNO3 acids. The separation method has been calibrated using a precious metal standard solution doped with a range of synthetic matrices and results in Pt yields of ≥90% with purity of ≥95%. Using this chemical separation technique, we have separated Pt from 11 international geological standard reference materials comprising of PGE ores, mantle rocks, igneous rocks and one sample from the Cretaceous–Paleogene boundary layer. Pt concentrations in these samples range from ca. 5 ng g−1 to 4 μg g−1. This analytical method has been shown to have an external reproducibility on δ198Pt (permil difference in the 198Pt/194Pt ratio from the IRMM-010 standard) of ±0.040 (2 sd) on Pt solution standards (Creech et al., 2013, J. Anal. At. Spectrom. 28, 853-865). The reproducibility in natural samples is evaluated by processing multiple replicates of four standard reference materials, and is conservatively taken to be ca. ±0.088 (2 sd). Pt stable isotope data for the full set of reference materials have a range of δ198Pt values with offsets of up to 0.4‰ from the IRMM-010 standard, which are readily resolved with this technique. These results

  6. Quaternary Branched Alkanes: A Geologic Proxy for Biological Sulfur Oxidation in Pleistocene Coastal Sediments of California

    Science.gov (United States)

    Zinniker, D. A.; Green Nylen, N.; Moldowan, J. M.; Denisevich, P.; Ingle, J. C.

    2003-12-01

    Branched alkanes with quaternary substituted carbon atoms (QBAs) have been identified in two Pleistocene sedimentary sequences exposed along the California coastline. While these compounds have yet to be isolated from cultured microorganisms, a growing body of evidence points towards their origin as membrane components of colorless sulfur oxidizing bacteria (Kenig et al., 2002). This evidence includes an association with sulfide minerals, an association with environments or paleoenvironments with sharp sulfide:oxygen gradients, a positive correlation with the bacterial lipid diploptene, and (in this study) a positive correlation between the abundance of QBAs and the abundance of elemental sulfur in organic extracts. The wide distribution of QBAs in modern environments (deep sea hydrothermal systems, Arctic shelf sediments, and sediment traps from an oligotrophic marine site) may implicate chemoautotrophic and/or chemoorganotrophic members of the epsilon Proteobacteria as the source of QBAs. Sediments of the neritic to nonmarine Merced Formation near San Francisco and the bathyal to neritic Rio Dell Formation north of Cape Mendocino have been found to contain QBAs - predominantly 5,5-diethylalkanes and 2,2-dimethylalkanes. 5,5-diethylalkanes were identified by comparison of their spectra and elution time with published reports. 2,2-dimethylalkanes were identified through the chemical synthesis of authentic standards. In both sedimentary sequences, QBAs vary in abundance by more than two orders of magnitude over glacial-interglacial cycles. This variation appears to be crudely correlated with the abundance of elemental sulfur. In the Rio Dell Formation QBAs show an inverse correlation with the neritic benthic foraminifer biofacies as well as trace and macrofossil assemblages indicative of higher benthic oxygen concentrations. The occurrence of QBAs in shelf deposits of the lower Merced Formation supports previous interpretations that suggest a restricted basin

  7. Understanding wetland sub-surface hydrology using geologic and isotopic signatures

    Directory of Open Access Journals (Sweden)

    P. Sahu

    2009-07-01

    Full Text Available This paper attempts to utilize hydrogeology and isotope composition of groundwater to understand the present hydrological processes prevalent in a freshwater wetland, source of wetland groundwater, surface water/groundwater interaction and mixing of groundwater of various depth zones in the aquifer. This study considers East Calcutta Wetlands (ECW – a freshwater peri-urban inland wetland ecosystem located at the lower part of the deltaic alluvial plain of South Bengal Basin and east of Kolkata city. This wetland is well known over the world for its resource recovery systems, developed by local people through ages, using wastewater of the city. Geological investigations reveal that the sub-surface geology is completely blanketed by the Quaternary sediments comprising a succession of silty clay, sand of various grades and sand mixed with occasional gravels and thin intercalations of silty clay. At few places the top silty clay layer is absent due to scouring action of past channels. In these areas sand is present throughout the geological column and the areas are vulnerable to groundwater pollution. Groundwater mainly flows from east to west and is being over-extracted to the tune of 65×103 m3/day. δ18O and δD values of shallow and deep groundwater are similar indicating resemblance in hydrostratigraphy and climate of the recharge areas. Groundwater originates mainly from monsoonal rain with some evaporation prior to or during infiltration and partly from bottom of ponds, canals and infiltration of groundwater withdrawn for irrigation. Relatively high tritium content of the shallow groundwater indicates local recharge, while the deep groundwater with very low tritium is recharged mainly from distant areas. At places the deep aquifer has relatively high tritium, indicating mixing of groundwater of shallow and deep aquifers. Metals such as copper, lead, arsenic, cadmium, aluminium, nickel and chromium are also

  8. Sulfur isotope analysis of individual aerosol particles – a new tool for studying heterogeneous oxidation processes in the marine environment

    Directory of Open Access Journals (Sweden)

    B. W. Sinha

    2009-02-01

    Full Text Available Understanding the importance of the different oxidation pathways of sulfur dioxide (SO2 to sulfate is crucial for an interpretation of the climate effects of sulfate aerosols. Sulfur isotope analysis of atmospheric aerosol is a well established tool for identifying sources of sulfur in the atmosphere and assessment of anthropogenic influence. The power of this tool is enhanced by a new ion microprobe technique that permits isotope analysis of individual aerosol particles as small as 0.5 μm diameter. With this new single particle technique, different types of primary and secondary sulfates are first identified based on their chemical composition, and then their individual isotopic signature is measured. Our samples were collected at Mace Head, Ireland, a remote coastal station on the North Atlantic Ocean. Sea-salt-sulfate (10–60%, ammonium sulfate/sulfuric acid particles (15–65%, and non-sea-salt-sulfate (nss-sulfate on aged salt particles all contributed significantly to sulfate loadings in our samples.

    The isotopic composition of secondary sulfates depends on the isotopic composition of precursor SO2 and the oxidation process. The fractionation with respect to the source SO2 is poorly characterized. In the absence of conclusive laboratory experiments, we consider the kinetic fractionation of −9‰ during the gas phase oxidation of SO2 by OH as suggested by Saltzman et al. (1983 and Tanaka et al. (1994 to be the most reasonable estimate for the isotope fractionation during gas phase oxidation of SO2hom=0.991 and the equilibrium fractionation for the uptake of SO2(g into the aqueous phase and the dissociation to HSO3 of +16.5‰ measured by Eriksen (1972a to be the best approximation for the fractionation during oxidation in the aqueous phase (αhet=1.0165. The sulfur isotope ratio of secondary sulfate particles can

  9. Geological, rare earth elemental and isotopic constraints on the origin of the Banbanqiao Zn-Pb deposit, southwest China

    Science.gov (United States)

    Li, Bo; Zhou, Jia-Xi; Huang, Zhi-Long; Yan, Zai-Fei; Bao, Guang-Ping; Sun, Hai-Rui

    2015-11-01

    The newly discovered Banbanqiao Zn-Pb deposit in the southeastern part of the Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province is located on the western Yangtze Block, southwest China. Ore bodies of the Banbanqiao deposit are stratiform type, host in dolomitic limestone and dolostone of the Lower Carboniferous Dapu Formation and occur within the NNE-trending Banbanqiao anticline. More than 1.5 million tones (Mt) Zn-Pb ores at grades of 0.26-10.32 wt.% Pb and 0.81-28.8 wt.% Zn have been controlled until now. δ13CPDB and δ18OSMOW values of calcite separates range from -2.8‰ to -0.7‰ (average -1.1‰) and +14.1‰ to +17.0‰ (average +15.5‰), respectively. The δ13CPDB values are similar to those of marine carbonate rocks, but higher than those of mantle and significantly different from those of sedimentary organic matter. However, the δ18OSMOW values are among those of mantle, marine carbonate rocks and sedimentary organic matter. δ34SCDT values of sulfide separates range from +3.2‰ to +9.9‰ (average +6.5‰), unlike mantle-derived sulfur (0 ± 3‰), whilst lower than evaporites (+22‰ to +28‰) within host strata. 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values of country shale and dolostone whole-rock samples are 18.47, 15.66 and 38.70, and 18.44-18.60, 15.66-15.85 and 38.70-39.14, respectively. Sulfide separates have 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values ranging from 18.03 to 18.73, 15.65 to 15.78 and 38.15 to 39.14, respectively. These Pb isotopic data indicate a clearly crustal source of Pb in the plot of 207Pb/204Pb vs. 206Pb/204Pb. Total REE (ΣREE) contents of country shale and dolostone whole-rock samples are 2.63 ppm and 0.72-86.2 ppm with δEu values are 2.79 and 0.34-0.70, respectively. Pyrite, sphalerite, galena and calcite samples have ΣREE contents of 5.3-36.4 ppm, 0.29-3.39 ppm, 0.52 ppm and 22.0-41.1 ppm, respectively, and δEu values of 0.64-0.86, 0.94-2.86, 0.32 and 0.21-0.45, respectively. These rare earth

  10. High-resolution quadruple sulfur isotope analyses of 3.2 Ga pyrite from the Barberton Greenstone Belt in South Africa reveal distinct environmental controls on sulfide isotopic arrays

    Science.gov (United States)

    Roerdink, Desiree L.; Mason, Paul R. D.; Whitehouse, Martin J.; Reimer, Thomas

    2013-09-01

    Multiple sulfur isotopes in Paleoarchean pyrite record valuable information on atmospheric processes and emerging microbial activity in the early sulfur cycle. Here, we report quadruple sulfur isotope data (32S, 33S, 34S, 36S) analyzed by secondary ion mass spectrometry from pyrite in a 3.26-3.23 Ga sedimentary barite deposit in the Barberton Greenstone Belt, South Africa. Our results demonstrate the presence of distinct pyrite populations and reproducible isotopic arrays in barite-free and barite-rich samples. The most 34S-depleted signatures with weakly positive Δ33S/δ34S were found in disseminated pyrite in barite, whereas positive Δ33S-values with negative Δ33S/δ34S and Δ36S/Δ33S = -0.9 ± 0.2 were exclusively observed in pyrite hosted by chert, dolomite, conglomerate and breccia. We interpret these variations to be related to local redox reactions and mixing in the sulfide phase, rather than representing primary atmospheric variability alone. The strong correlation between lithology and isotopic composition indicates distinct environments of sulfide formation linked to local sulfate concentrations and fluctuating inputs from different sulfur metabolisms. Strongly 34S-depleted sulfide was formed by microbial sulfate reduction at [SO42-] > 200 μM during deposition of barite-rich sediments, whereas isotope effects were suppressed when sulfate levels decreased during deposition of terrigeneous clastic rocks. Positive Δ33S-values indicate an increased input of sulfide derived from elemental sulfur metabolisms when sulfate concentrations fell below 200 μM. Our results support an important role for local sulfate concentrations on the expression of biogenic sulfur isotope signatures in some of the oldest rocks on Earth.

  11. Geological interpretation of Eastern Cuba Laterites from an airborne magnetic and radioactive isotope survey

    Energy Technology Data Exchange (ETDEWEB)

    Batista, J.A; Blanco, J [Departamento de Geologia, Instituto Superior Minero Metalurgico de Moa, (Cuba); Perez-Flores, M.A [Centro de Investigacion Cientifica y Educacion Superior de Ensenada, Baja California (Mexico)

    2008-04-15

    In eastern Cuba area several geophysical techniques have been applied to distinguish the main geological characteristics of the laterites which are of economical importance for the extraction of iron, nickel and chrome. The geophysical measurements include an aeromagnetic survey and thorium (eTh), potassium (K) and uranium (eU) isotope measurements. The results of gamma spectrometer measurements make a distinction between laterite reservoirs. The application of the magnetic and isotope methods allowed the determination of the distribution and development of the laterite crust, as well as the determination of hydrothermal alterations affecting the laterites, which is very useful for mining exploration and exploitation. Such alterations indicate the presence of silicates, which have negative effects on the metallurgic process. It is known that laterite crust has a high content of eU and eTh. [Spanish] Se han utilizado varias tecnicas geofisicas en la region oriental de Cuba para distinguir las principales caracteristicas geologicas de las lateritas, que poseen importancia economica para la extraccion de hierro, niquel y cobalto. Las mediciones geofisicas incluyen un estudio aeromagnetico y mediciones de isotopos de torio (eTh), potasio (K) y uranio (eU). Los resultados de las mediciones espectrometricas establecen diferencias entre los yacimientos de lateritas. De la aplicacion del metodo magnetico e isotopico se determino la distribucion y desarrollo de las cortezas lateriticas, asi como la ubicacion de alteraciones hidrotermales que afectan a las lateritas, lo cual es muy util durante la exploracion y explotacion minera. Esas alteraciones indican la presencia de silicatos, que tienen un efecto negativo en el proceso metalurgico. Se conoce que las cortezas lateriticas tienen altos contenidos de eU y eTh. De los contenidos de eU y eTh se infiere que las lateritas de la region de Moa se formaron antes que las de Mayari. De estas mediciones fue posible inferir el

  12. Sulfuric acid on Europa and the radiolytic sulfur cycle

    Science.gov (United States)

    Carlson, R. W.; Johnson, R. E.; Anderson, M. S.

    1999-01-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  13. Pyrite multiple-sulfur isotope evidence for rapid expansion and contraction of the early Paleoproterozoic seawater sulfate reservoir

    Science.gov (United States)

    Scott, Clint; Wing, Boswell A.; Bekker, Andrey; Planavsky, Noah J.; Medvedev, Pavel; Bates, Steven M.; Yun, Misuk; Lyons, Timothy W.

    2014-03-01

    Earth's oxygenation is often described in terms of two unidirectional steps at the beginning and end of the Proterozoic Eon, separated by a long-lived intermediate redox state. Recent work defines a more complicated path to oxygenation, exemplified by an apparent drop in oxidation state following the early Paleoproterozoic Lomagundi carbon isotope excursion. The timing of this proposed drop in oxidation state is not well constrained, and it is not clear how it relates to redox conditions during the remainder of the Proterozoic. Here we present a study of pyrite multiple-sulfur isotopes, supported by Fe speciation and organic carbon isotopes, from early Paleoproterozoic black shales. We find evidence for the rapid expansion of the seawater sulfate reservoir during the Great Oxidation Event at ca. 2.3 Ga followed by a subsequent contraction in the size of the seawater sulfate reservoir at ca. 2.05 Ga. This scenario is consistent with the emerging view of a rise and fall in surface oxidation state during the early Paleoproterozoic. Comparison of our new data to other records of the seawater sulfate reservoir suggests that the elevated sulfate concentrations that characterize the early Paleoproterozoic did not return until the late Neoproterozoic.

  14. Weathering of the black limestone of historical monuments (Ljubljana, Slovenia): Oxygen and sulfur isotope composition of sulfate salts

    Energy Technology Data Exchange (ETDEWEB)

    Kramar, Sabina, E-mail: sabina.kramar@rescen.si [Institute for the Protection of Cultural Heritage of Slovenia, Conservation Centre, Restoration Centre, Poljanska 40, 1000 Ljubljana (Slovenia); Mirtic, Breda [University of Ljubljana, Faculty of Natural Sciences and Engineering, Department of Geology, Askerceva 12, 1000 Ljubljana (Slovenia); Knoeller, Kay [UFZ Helmholtz-Centre for Environmental Research, Department of Isotope Hydrology, Theodor-Lieser-Str. 4, 06120 Halle (Germany); Rogan-Smuc, Nastja [University of Ljubljana, Faculty of Natural Sciences and Engineering, Department of Geology, Askerceva 12, 1000 Ljubljana (Slovenia)

    2011-09-15

    Highlights: > Weathering of the black limestone on historical monuments. > Oxygen and sulfur isotope composition of sulfate salts (outdoors and indoors). > A data exhibit more scattered {delta}{sup 34}S values with respect to {delta}{sup 18}O values. - Abstract: The black limestone widely used in Slovenian monuments, particularly in the baroque architecture, is deteriorating extensively due to salt crystallization. Samples of soluble salts from two important historical monuments (in Ljubljana, Slovenia) were investigated in terms of their mineral and isotopic (S and O) compositions. Results revealed the presence of gypsum and soluble salts of the MgSO{sub 4}.nH{sub 2}O series, such as starkeyite (MgSO{sub 4}.4H{sub 2}O), pentahydrite (MgSO{sub 4}.5H{sub 2}O) and hexahydrite (MgSO{sub 4}.6H{sub 2}O). Whereas black crusts and subflorescences consisted of gypsum, efflorescences appeared to be an assemblage of gypsum and MgSO{sub 4} hydrates. Sample {delta}{sup 18}O{sub sulfate} values varied from -1.9 per mille to +5.5 per mille vs. V-SMOW and {delta}{sup 34}S{sub sulfate} values from -19.8 per mille to +3.2 per mille vs. V-CDT. The respective isotopic composition of analysed outdoor and indoor monument samples indicated different sources of contamination.

  15. Geology

    Data.gov (United States)

    Kansas Data Access and Support Center — This database is an Arc/Info implementation of the 1:500,000 scale Geology Map of Kansas, M­23, 1991. This work wasperformed by the Automated Cartography section of...

  16. Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

    Science.gov (United States)

    Ridley, William I.; Pribil, Michael; Koenig, Alan E.; Slack, John F.

    2015-01-01

    Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

  17. Oxygen and sulfur isotopes in sulfate in modern euxinic systems with implications for evaluating the extent of euxinia in ancient oceans

    Science.gov (United States)

    Gomes, Maya L.; Johnston, David T.

    2017-05-01

    Euxinic conditions, which are defined by the presence of sulfide in the water column, were common in ancient oceans. However, it is not clear how the presence of sulfide in the water column affects the balance between rates of sulfide oxidation and sulfate reduction, which plays a major role in regulating the net redox state of the ocean-atmosphere system. Euxinia could lead to higher rates of sulfide oxidation because sulfide may diffuse more rapidly into the oxic zone in solution than in sediment. Alternatively, sulfide oxidation could be inhibited by low overall availability of suitable oxidants in euxinic settings. Here, we constrain rates of sulfide oxidation versus sulfate reduction in four euxinic water columns in coastal ponds by modeling the evolution of the concentration and sulfur and oxygen isotope compositions of sulfate from post-hurricane, well-oxygenated conditions to modern, euxinic conditions. The results of the one-dimensional, depth-dependent models of water column sulfate geochemistry indicate that the fraction of sulfate reduced that is subsequently reoxidized is low (0.11-0.42) in euxinic systems relative to the modern well-oxygenated ocean (0.75-0.90). This implies that sulfide reoxidation rates are low in euxinic systems because of oxidant limitation and physical transport. Low fractional sulfide reoxidation in euxinic systems has important implications for exploring how oxygen levels in the ocean and atmosphere have changed through Earth history. We use a marine sulfate isotope box model to explore how low reoxidation rates in euxinic systems affect marine sulfate sulfur and oxygen isotope records. Model results indicate that marine sulfate sulfur and oxygen isotope compositions increase during the expansion of euxinia with patterns that are distinct from other isotopic changes to the marine sulfate reservoir. Thus, marine sulfate sulfur and oxygen isotope box models can be applied to ancient isotope records in order to evaluate the

  18. Sulfur- and lead-isotope signatures of orogenic gold mineralisation associated with the Hill End Trough, Lachlan Orogen, New South Wales, Australia

    Science.gov (United States)

    Downes, P. M.; Seccombe, P. K.; Carr, G. R.

    2008-11-01

    The Hill End Trough (HET) is a deformed middle Silurian to Early Devonian sediment-dominated rift within the northeastern Lachlan Orogen. The HET hosts the Hill End, Hargraves, Napoleon Reefs, Stuart Town and Windeyer low-sulfide orogenic gold deposits. Adjacent to the HET are the Bodangora and Gulgong gold deposits. In this study we present 91 new sulfur- and 18 new lead-isotope analyses and collate a further 25 sulfur- and 32 lead-isotopes analyses from unpublished sources for these deposits. Larger gold deposits in the HET have near 0 δ34S‰ values indicating that sulfur in these systems was sourced from a magmatic reservoir. The dominant lead isotope signature for HET-hosted deposits reflects a crustal source however some mantle-derived lead has been introduced into the HET. Sulfur- and lead-isotopic results suggest that gold was sourced from mantle-derived magmatic units beneath the HET. The study supports earlier studies at Hill End by concluding that the majority of orogenic gold mineralisation in and adjacent to the HET formed during the Early Carboniferous period.

  19. Measuring Sulfur Isotope Ratios from Solid Samples with the Sample Analysis at Mars Instrument and the Effects of Dead Time Corrections

    Science.gov (United States)

    Franz, H. B.; Mahaffy, P. R.; Kasprzak, W.; Lyness, E.; Raaen, E.

    2011-01-01

    The Sample Analysis at Mars (SAM) instrument suite comprises the largest science payload on the Mars Science Laboratory (MSL) "Curiosity" rover. SAM will perform chemical and isotopic analysis of volatile compounds from atmospheric and solid samples to address questions pertaining to habitability and geochemical processes on Mars. Sulfur is a key element of interest in this regard, as sulfur compounds have been detected on the Martian surface by both in situ and remote sensing techniques. Their chemical and isotopic composition can belp constrain environmental conditions and mechanisms at the time of formation. A previous study examined the capability of the SAM quadrupole mass spectrometer (QMS) to determine sulfur isotope ratios of SO2 gas from a statistical perspective. Here we discuss the development of a method for determining sulfur isotope ratios with the QMS by sampling SO2 generated from heating of solid sulfate samples in SAM's pyrolysis oven. This analysis, which was performed with the SAM breadboard system, also required development of a novel treatment of the QMS dead time to accommodate the characteristics of an aging detector.

  20. Sulfur isotope effects associated with protonation of HS- and volatilization of H2S

    Science.gov (United States)

    Fry, B.; Gest, H.; Hayes, J. M.

    1986-01-01

    The isotope effects associated with: (1) formation of H2S from HS- by protonation in aqueous solution; and (2) volatilization of H2S have been experimentally determined. Both isotopic distributions in closed systems at equilibrium and differential rates of volatilization of isotopic species in open systems were measured at 22 +/- 1 degrees C. It was found that, at equilibrium aqueous H2S is enriched in 34S by 2.0 - 2.7% relative to HS- and that H2S volatilized from solution is depleted in 34S by 0.5% relative to dissolved H2S. A small kinetic isotope effect accompanying volatilization of H2S was observed in the open-system experiments.

  1. In situ sulfur isotopes (δ{sup 34}S and δ{sup 33}S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Jiali [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); Hu, Zhaochu, E-mail: zchu@vip.sina.com [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); The Beijing SHRIMP Center, Institute of Geology, Chinese Academy of Geological Sciences, Beijing 102206 (China); Zhang, Wen [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); Yang, Lu [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China); National Research Council Canada, 1200 Montreal Rd., Ottawa, Ontario K1A 0R6 (Canada); Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong [State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Wuhan 430074 (China)

    2016-03-10

    The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N{sub 2} on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4–8 ml min{sup −1} nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N{sub 2} = 4 ml min{sup −1}). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d{sub 90} values of the particles in pressed powder pellets for accurate

  2. Isotopic evidence for determining the sources of dissolved organic sulfur in a forested catchment

    Science.gov (United States)

    Phil-Goo Kang; Myron J. Mitchell; Bernhard Mayer; John L. Campbell

    2014-01-01

    Understanding sulfur (S) biogeochemistry, especially in those watersheds subject to elevated levels of atmospheric S inputs, is needed for determining the factors that contribute to acidification, nutrient losses and the mobilization of toxic solutes (e.g., monomeric aluminum and methylmercury). S is found in a variety of both organic and inorganic forms undergoing a...

  3. Mineralogic, fluid inclusion, and sulfur isotope evidence for the genesis of Sechangi lead-zinc (-copper) deposit, Eastern Iran

    Science.gov (United States)

    Malekzadeh Shafaroudi, Azadeh; Karimpour, Mohammad Hassan

    2015-07-01

    The Sechangi lead-zinc (-copper) deposit lies in the Lut block metallogenic province of Eastern Iran. This deposit consists of ore-bearing vein emplaced along fault zone and hosted by Late Eocene monzonite porphyry. Hydrothermal alteration minerals developed in the wall rock include quartz, kaolinite, illite, and calcite. Microscopic studies reveal that the vein contains galena and sphalerite with minor chalcopyrite and pyrite as hypogene minerals and cerussite, anglesite, covellite, malachite, hematite, and goethite as secondary minerals. Fluorite and quartz are the dominant gangue minerals and show a close relationship with sulfide mineralization. Calculated δ34S values for the ore fluid vary between -9.9‰ and -5.9‰. Sulfur isotopic compositions suggest that the ore-forming aqueous solutions were derived from magmatic source and mixed with isotopically light sulfur, probably leached from the volcanic and plutonic country rocks. Microthermometric study of fluid inclusions indicates homogenization temperatures of 151-352 °C. Salinities of ore-forming fluids ranged from 0.2 to 16.5 wt.% NaCl equivalent. The ore-forming fluids of the Sechangi deposit are medium- to low-temperature and salinity. Fluid mixing may have played an important role during Pb-Zn (-Cu) mineralization. The key factors allowing for metal transport and precipitation during ore formation include the sourcing of magmatic fluids with high contents of metallogenic elements and the mixing of these hydrothermal fluids with meteoric waters resulting in the formation of deposit. In terms of the genetic type of deposit, the Sechangi is classified as a volcanic-subvolcanic hydrothermal-related vein deposit.

  4. Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in the city of Wuhan, central China

    Science.gov (United States)

    Li, X.; Bao, H.; Zhou, A.; Wang, D.

    2012-12-01

    Secondary atmospheric sulfate (SAS) is the oxidation product and sink for sulfur gases of biological, volcanic, and anthropogenic origins on Earth. SAS can be produced from gas-phase OH-radical oxidation and five aqueous-phase chemical reactions including aqueous-phase S (IV) oxidation reactions by H2O2, O3, oxygen catalyzed by Fe3+ and Mn2+, and methyle hydrogen peroxide and peroxyacetic acid. The tropospheric sulfur oxidation pathway is therefore determined by cloud-water pH, dissolved [Fe2+] or [Mn2+] content, S emission rate, meteorological condition, and other factors. The S isotope composition is a good tracer for the source while the O isotopes, especially the triple O isotope compositions are a good tracer for S oxidation pathway. Jerkins and Bao (2006) provided the first set of multiple stable isotope compositions (δ34S, δ18O and Δ17O) for SAS collected from bulk atmosphere in Baton Rouge in the relatively rural southern USA. Their study revealed a long-tern average Δ17O value of ~+0.7‰ for SAS, and speculated that much of the Earth mid-latitudes may have a similar average SAS Δ17O value. Additional sampling campaign at different sites is necessarily for constructing and testing models on sulfur oxidation and transport in the troposphere. A total of 33 sulfate samples were collected from bulk atmospheric deposition over a 950-day period from May 2009 to December 2011 in the city of Wuhan, Hubei Province, China. Differing from Baton Rouge, Wuhan is an industrial metropolis with a population of 9.8 million and a high particulate matter content (115 μg/m3). It also has a subtropical monsoon climate, with rainwater pH at ~5.3 year-around. The rainwater ion concentrations have seasonal variations, typically low in summer and high in winter. The anions are dominated by SO42-, at an average concentration of 8.5 mg/L. There is little sulfate contribution from sea-salt (SS) sulfate or dusts in Wuhan. The isotopic compositions for bulk atmospheric sulfate

  5. Osmium-Iridium Correlation and Osmium Isotopic Composition in Some Geological Boundaries and Meteorites

    Science.gov (United States)

    Liu, Y. Z.; Wang, J. X.; Mao, X. Y.; Chai, C. F.

    1992-07-01

    Since the pioneering study of Alvarez et al. on K/T boundary event, Ir has long been considered to be the main indicator of extraterrestrial materials in boundaries, while little work about Os and its isotopic composition have been done. In this work a sophisticated radiochemical separation procedure together with neutron activation analsis (NAA) method was established for the determination of Os in some geological boundaries (P epsilon/epsilon, K/T, D/C, O/S, P/T). Combined with our early work--determination of Ir abundances [1], the sources of boundary events were deciphered by using the Os/Ir ratios. Simultaneously ^184Os/^190Os ratios in K/T boundaries, as well as inclusions of Allende chondrite and acid-insoluble residues of iron meteorites (Nandan, Jianshi, Longchang) were determined to search for the Os isotopic composition anomalies resulted from the extrasolar components by RNAA. The results show that the Os abundances exhibit a positive correlation with the Ir abundances for overall K/T boundary samples, but only the Os/Ir ratios of K/T boundaries, with the average of 0.98 +- 0.55, are in excellent agreement with 1.01 of the solar system [2], Accordingly, it provides new evidence for an extraterrestrial source of the K/T event. The results of ^184Os/^190Os ratios, with uncertainties of less than 1%, indicate there is no remarkable ^184Os/^190Os ratio anomaly in the K/T boundary samples, which implies the impacting matter may be from the solar system not the extrasolar, while no anomaly exists in the inclusions of Allende chondrite and acid-insoluble residues of iron meteorites, which disagree with the results obtained by Goel [3]. REFERENCES [1] Chai Chifang (1988) Isotopenpraxis 24, pp. 257-272. [2] Anders E. and Grevesse N. (l989) Geochim. Cosmochim. Acta 53, 197-214. [3] Goel P.S.(1987) Proc. Indian Acad. Sci. (Earth Planet. Sci), 96, pp. 81-102.

  6. Understanding wetland sub-surface hydrology using geologic and isotopic signatures

    Directory of Open Access Journals (Sweden)

    P. K. Sikdar

    2009-04-01

    Full Text Available This paper attempts to utilize hydrogeoloy and isotope composition of groundwater to understand the present hydrological processes prevalent in a freshwater wetland, source of wetland groundwater, surface water/groundwater interaction and mixing of groundwater of various depth zones in the aquifer. This study considers East Calcutta Wetlands (ECW – a freshwater peri-urban inland wetland ecosystem located at the lower part of the deltaic alluvial plain of South Bengal Basin and east of Kolkata city. This wetland is well known over the world for its resource recovery systems, developed by local people through ages, using wastewater from the city. Geological investigations reveal that the sub-surface geology is completely blanketed by the Quaternary sediments comprising a succession of silty clay, sand of various grades and sand mixed with occasional gravels and thin intercalations of silty clay. Aquifer within the depths of 80 m to 120 m has the maximum potential to supply water. Groundwater mainly flows from east to west and is being over-extracted to the tune of 65×103 m3/day. δ18O and δD values of shallow and deep groundwater are similar indicating resemblance in hydrostratigraphy and climate of the recharge areas. Groundwater originates mainly from monsoonal rain with some evaporation prior to or during infiltration and partly from bottom of ponds, canals and infiltration of groundwater withdrawn for irrigation. Relatively high tritium content of the shallow groundwater indicates local recharge, while the deeper groundwater with very low tritium is recharged mainly from distant areas. At places the deeper aquifer has relatively high tritium, indicating mixing of groundwater of shallow and deep aquifers. Metals such as copper, lead, arsenic, cadmium, aluminum, nickel and chromium are also present in groundwater of various depths. Therefore, aquifers of wetland and surrounding urban areas which are heavily

  7. Carbon and sulfur isotopic compositions of basal Datangpo Formation, northeastern Guizhou, South China: Implications for depositional environment

    Institute of Scientific and Technical Information of China (English)

    Xi Chen; Da Li; Hong-Fei Ling; Shao-Yong Jiang

    2008-01-01

    Isotopic compositions of Mn-carbonate and organic carbon from the same individual samples and sulfur isotopic compositions of pyrites in the basal Datangpo Formation were analyzed. Highly 34S-enriched pyrites (δ34Spyrite = 31.7-59.4‰) were precipitated in relatively occlusive pore water under anoxic condition in sediments, which is consistent with the observation of large and scattered pyrite framboids. The sulfidic deep ocean was not "oxidized" in the early Datangpo interglacial interval, thus the level of seawater sulfate remained low and marine δ3.4Ssuiphate remained high. Low δ13Ccar (average - 7.4‰) and abnormal relationship between δ13Ccar and frac-tionation (Δcar-org) imply that the negative δ13Ccar excursion may have resulted from oxidation of part of a large organic carbon reservoir. High Δcar-org (average 25A‰) implicates high CO2 level in the atmosphere. Small standard deviation (1.0‰) of δ13Ccar values indicates the Mn-carbonate was precipitated near the water-sediment interface under dysoxic conditions rather than in occlusive pore water in sediments.

  8. Multiple sulfur isotope constraints on sulfate-driven anaerobic oxidation of methane: Evidence from authigenic pyrite in seepage areas of the South China Sea

    Science.gov (United States)

    Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Gong, Junli; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn

    2017-08-01

    Multiple sulfur isotope signatures and secondary ion mass spectroscopy (SIMS) sulfur isotope compositions of pyrite from two seafloor sites (DH-CL11 and HD109) in seepage areas of the South China Sea were measured in order to study isotope effects of sulfate-driven anaerobic oxidation of methane (SO4-AOM). The multiple sulfur isotopes of pyrite reveal variable ranges for both sites (δ34S: between -44.1‰ and -2.9‰ for DH-CL11 and between -43.8‰ and -1.6‰ for HD109; Δ33S: between 0.02‰ and 0.17‰ for DH-CL11 and between -0.03‰ and 0.14‰ for HD109). SIMS analysis reveals an extreme variability of δ34S values (between -50.3‰ and -2.7‰ in DH-CL11; between -50.1 and 52.4‰ in HD109) for three types of pyrite: (1) framboids, (2) zoned aggregates with radial overgrowth surrounding a framboidal core, and (3) euhedral pyrite crystals. The synchronous changes of geochemical proxies (sulfate and methane concentrations, δ34Ssulfate and δ18Osulfate, δ34Spyrite, and pyrite content) at the sulfate-methane transition zone (SMTZ) at site DH-CL11 are interpreted to be induced by SO4-AOM under steady state conditions. In contrast, pyrite content and δ34S value fluctuations throughout core HD109 suggest that the sediment at this site was affected by multiple pyritization events during diagenesis. Multiple sulfur isotope signatures of early diagenetic pyrite (i.e., with low and high δ34S values, the latter above 315 cmbsf in DH-CL11; above 70 cmbsf in HD109) in the upper sediment column suggest that organoclastic sulfate reduction (OSR) and sulfur disproportionation generated the observed isotopic signatures. In contrast to the early diagenetic 34S depleted framboids, the higher SIMS δ34S values of overgrowth and euhedral crystals suggest a late diagenetic 34S enriched pool of dissolved sulfide derived from SO4-AOM at the current and paleo-SMTZs. Interestingly, pyrite resulting from SO4-AOM in the SMTZ at site DH-CL11 reveals a distinct pattern with higher

  9. Sources and Cycling of Dissolved Organic Matter in the Sacramento - San Joaquin Delta, California, Using Carbon, Nitrogen, and Sulfur Isotopes

    Science.gov (United States)

    Silva, S. R.; Kendall, C.; Doctor, D. H.; Bergamaschi, B. A.; Fram, M. S.; Kraus, T.

    2006-12-01

    An important water quality concern of the Sacramento-San Joaquin Delta portion of the Calfed Bay-Delta restoration program is the generation of disinfection byproducts (DBP) as a result of chlorination or ozonation of San Francisco Bay Delta drinking water. One means of reducing DBPs is through monitoring and control of water sources from the various delta environments entering the California aqueduct with the objective of reducing the quantity of dissolved organic matter (DOM) and lowering the fraction with the highest DBP formation potential. The purpose of this study is to investigate the use of carbon, nitrogen, and sulfur isotopic compositions of DOM to help differentiate DOM sources and interpret seasonal variations. For this purpose, water samples collected from five general delta environments between December 1999 and June 2001 were analyzed for d13C, d15N, and d34S of DOM as well as for various chemical and optical properties. Monthly averages of d13C and d15N values for DOM retained on XAD-4 and XAD-8 resins show distinctive compositions for island drain and wetland environments throughout the year which reflect the agriculturally- related terrestrial sources of DOM from island drains, and the aquatic sources for the wetland areas. On average, the d13C values of DOM from open water (flooded island) environments, channels, and the Sacramento River water are indistinguishable from each other from spring through fall and show a progressive increase in d13C, which is likely controlled by the cycle of aquatic production through the growing season. The isotopic values from these environments diverge in the winter reflecting a change in the relative importance of the various mechanisms (sources and cycling) controlling DOM production. Sulfur isotopes show both the effects of sulfate reduction and the influence of seawater sulfate on local biota. The d13C, d15N, and d34S values show a number of correlations related to both environment and season, reflecting the

  10. Fluid inclusion and sulfur stable isotope evidence for the origin of the Ahangran Pb-Ag deposit

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    Mohammad Maanijou

    2015-10-01

    Full Text Available Introduction The Ahangaran Pb-Ag deposit is located in the Hamedan province, west Iran, 25 km southeast of the city of Malayer . . The deposit lies in the strongly folded Sanandaj-Sirjan tectonic zone, in which the ore bodies occur as thin lenses and layers. The host rocks of the deposit are Early Cretaceous carbonates and sandstones that are unconformably underlain by Jurassic rocks. Ore minerals include galena, pyrite, chalcopyrite, pyrrhotite and supergene iron oxide minerals. Gangue minerals consist of barite, dolomite, chlorite, calcite and quartz. The mineralization occurs as open-space fillings, veins, veinlets, disseminations, and massive replacements. Alteration consists of silicification, sericitization, and dolomitization. In this study, we carried out studies of mineralogy, microthermometry of fluid inclusions and sulfur isotopes to determine the source of sulfur and the physico-chemical conditions of formation. Materials and methods Seventy samples of different host rocks, alteration, and mineralization were collected from surface outcrops and different tunnels. Twenty of the samples were prepared for mineralogical studies at Tarbiat Modarres University in Tehran and 25 for petrological studies at the University of Bu-Ali Sina. Fluid-inclusion studies were done on 5 samples of quartz and calcite at Pouya Zamin Azin Company in Tehran using a Linkam THM 600 model heating-freezing stage (with a range of -196 to 480ºC. The accuracy and precision of the homogenization measurements are about ±1°C. Salinity estimates were determined from the last melting temperatures of ice, utilizing the equations by Bodnar and Vityk (1994 and for CO2 fluids using equations by Chen (1972. Nine samples of sulfides and barite were crushed and separated by handpicking under binocular microscope and powdered with agate mortar and pestle. About one gram of each sample was sent to the Stable Isotope and ICP/MS Laboratory of Queen’s University, Canada for

  11. Sulfur Isotopic Compositions of Submicrometer SiC Grains from the Murchison Meteorite

    Science.gov (United States)

    Xu, Yuchen; Zinner, Ernst; Gallino, Roberto; Heger, Alexander; Pignatari, Marco; Lin, Yangting

    2015-02-01

    We report C, Si, N, S, Mg-Al, and Ca-Ti isotopic compositions of presolar silicon carbide (SiC) grains from the SiC-rich KJE size fraction (0.5-0.8 μm) of the Murchison meteorite. One thousand one hundred thirteen SiC grains were identified based on their C and Si isotopic ratios. Mainstream, AB, C, X, Y, and Z subtypes of SiC, and X-type silicon nitride (Si3N4) account for 81.4%, 5.7%, 0.1%, 1.5%, 5.8%, 4.9%, and 0.4%, respectively. Twenty-five grains with unusual Si isotopic ratios, including one C grain, 16 X grains, 1 Y grain, 5 Z grains, and 2 X-type Si3N4 grains were selected for N, S, Mg-Al, and Ca-Ti isotopic analysis. The C grain is highly enriched in 29Si and 30Si (δ29Si = 1345‰ ± 19‰, δ30Si = 1272‰ ± 19‰). It has a huge 32S excess, larger than any seen before, and larger than that predicted for the Si/S supernova (SN) zone, providing evidence against the elemental fractionation model by Hoppe et al. Two SN models investigated here present a more satisfying explanation in terms of a radiogenic origin of 32S from the decay of short-lived 32Si (τ1/2 = 153 yr). Silicon-32 as well as 29Si and 30Si can be produced in SNe by short neutron bursts; evidence for initial 44Ti (τ1/2 = 60 yr) in the C grain is additional evidence for an SN origin. The X grains have marginal 32S excesses, much smaller than expected from their large 28Si excesses. Similarly, the Y and Z grains do not show the S-isotopic anomalies expected from their large Si isotopic anomalies. Low intrinsic S contents and contamination with isotopically normal S are the most likely explanations.

  12. SULFUR ISOTOPIC COMPOSITIONS OF SUBMICROMETER SiC GRAINS FROM THE MURCHISON METEORITE

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yuchen [Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550002 (China); Zinner, Ernst [Laboratory for Space Sciences and Physics Department, Washington University, St. Louis, MO 63130 (United States); Gallino, Roberto [Dipartimento di Fisica, Università di Torino, I-10125 Torino (Italy); Heger, Alexander [Monash Centre for Astrophysics, School of Mathematical Sciences, Monash University, Vic 3800 (Australia); Pignatari, Marco [Department of Physics, University of Basel, CH-4056 Basel (Switzerland); Lin, Yangting, E-mail: xuyuchen@mail.iggcas.ac.cn [Key Laboratory of Earth' s Deep Interior, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029 (China)

    2015-02-01

    We report C, Si, N, S, Mg-Al, and Ca-Ti isotopic compositions of presolar silicon carbide (SiC) grains from the SiC-rich KJE size fraction (0.5-0.8 μm) of the Murchison meteorite. One thousand one hundred thirteen SiC grains were identified based on their C and Si isotopic ratios. Mainstream, AB, C, X, Y, and Z subtypes of SiC, and X-type silicon nitride (Si{sub 3}N{sub 4}) account for 81.4%, 5.7%, 0.1%, 1.5%, 5.8%, 4.9%, and 0.4%, respectively. Twenty-five grains with unusual Si isotopic ratios, including one C grain, 16 X grains, 1 Y grain, 5 Z grains, and 2 X-type Si{sub 3}N{sub 4} grains were selected for N, S, Mg-Al, and Ca-Ti isotopic analysis. The C grain is highly enriched in {sup 29}Si and {sup 30}Si (δ{sup 29}Si = 1345‰ ± 19‰, δ{sup 30}Si = 1272‰ ± 19‰). It has a huge {sup 32}S excess, larger than any seen before, and larger than that predicted for the Si/S supernova (SN) zone, providing evidence against the elemental fractionation model by Hoppe et al. Two SN models investigated here present a more satisfying explanation in terms of a radiogenic origin of {sup 32}S from the decay of short-lived {sup 32}Si (τ{sub 1/2} = 153 yr). Silicon-32 as well as {sup 29}Si and {sup 30}Si can be produced in SNe by short neutron bursts; evidence for initial {sup 44}Ti (τ{sub 1/2} = 60 yr) in the C grain is additional evidence for an SN origin. The X grains have marginal {sup 32}S excesses, much smaller than expected from their large {sup 28}Si excesses. Similarly, the Y and Z grains do not show the S-isotopic anomalies expected from their large Si isotopic anomalies. Low intrinsic S contents and contamination with isotopically normal S are the most likely explanations.

  13. Elucidating microbial processes in nitrate- and sulfate-reducing systems using sulfur and oxygen isotope ratios: The example of oil reservoir souring control

    Science.gov (United States)

    Hubert, Casey; Voordouw, Gerrit; Mayer, Bernhard

    2009-07-01

    Sulfate-reducing bacteria (SRB) are ubiquitous in anoxic environments where they couple the oxidation of organic compounds to the production of hydrogen sulfide. This can be problematic for various industries including oil production where reservoir "souring" (the generation of H 2S) requires corrective actions. Nitrate or nitrite injection into sour oil fields can promote SRB control by stimulating organotrophic nitrate- or nitrite-reducing bacteria (O-NRB) that out-compete SRB for electron donors (biocompetitive exclusion), and/or by lithotrophic nitrate- or nitrite-reducing sulfide oxidizing bacteria (NR-SOB) that remove H 2S directly. Sulfur and oxygen isotope ratios of sulfide and sulfate were monitored in batch cultures and sulfidic bioreactors to evaluate mitigation of SRB activities by nitrate or nitrite injection. Sulfate reduction in batch cultures of Desulfovibrio sp. strain Lac15 indicated typical Rayleigh-type fractionation of sulfur isotopes during bacterial sulfate reduction (BSR) with lactate, whereas oxygen isotope ratios in unreacted sulfate remained constant. Sulfur isotope fractionation in batch cultures of the NR-SOB Thiomicrospira sp. strain CVO was minimal during the oxidation of sulfide to sulfate, which had δ18O SO4 values similar to that of the water-oxygen. Treating an up-flow bioreactor with increasing doses of nitrate to eliminate sulfide resulted in changes in sulfur isotope ratios of sulfate and sulfide but very little variation in oxygen isotope ratios of sulfate. These observations were similar to results obtained from SRB-only, but different from those of NR-SOB-only pure culture control experiments. This suggests that biocompetitive exclusion of SRB took place in the nitrate-injected bioreactor. In two replicate bioreactors treated with nitrite, less pronounced sulfur isotope fractionation and a slight decrease in δ18O SO4 were observed. This indicated that NR-SOB played a minor role during dosing with low nitrite and that

  14. Mineralization, geochemistry, fluid inclusion and sulfur stable isotope studies in the carbonate hosted Baqoroq Cu-Zn-As deposit (NE Anarak

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Jazi

    2015-10-01

    bacterial sulfate reduction or by nonbacterial sulfate reduction through a reaction with organic materialin the sedimentary rocks (thermochemical sulfate reduction. However, the narrow range of δ34S and positive values indicates that they were not produced by bacterial sulfate reduction.Partial thermochemical reduction of sulfates has apparently produced light sulfurvalues (~ 21‰ lighter and it has been effective inthe deposition of ore minerals. Organic matter occurs as graphite in the Baqoroq formation in proximity of Baqoroq deposit (Cherepovsky et al., 1982. Discussion Epigenetic, stratabound and discordant Cu-Zn-As mineralization in the Baqoroq deposit occurs as open space filling of upper Cretaceous rocks. Host rock is partially dolomitized by ascending warm, saline fluids. Seawater sulfates were the source of the sulfidesulfur and the sulfate in the barite. The reduced sulfur was generated by partial thermochemical reduction and it was effective inthe deposition ofthe ore minerals. Based onthe evidence of carbonate host rocks, the absence of igneous activity, the open space filling texture, mineralogy, dolomite alteration, ore geochemistry (As and Sb high content and absence of Bi, microthermometric data of ore bearing fluid and sulfur isotope values, the Baqoroq deposit is very similar to the carbonate hosted copper deposits in Africa and in particular the Tsumeb deposit in Namibia. The Baqoroqdepositmay have been produced bymetamorphicfluids during orogenyrelated to theclosureof the Neo-Tethys ocean. References Cherepovsky, N., Plyaskin, V., Zhitinev, N., Kokorin, Y., Susov, M., Melnikov, B. and Aistov, L., 1982. Report on detailed geological prospecting in Anarak area (Central Iran Nakhlak locality. Geological Survey of Iran and Technoexport Company, Tehran. Report 14, 196 pp. Jazi, M.A., Karimpour, M.H., Malekzadeh, A. and Rahimi, B., 2015. Stratigraphic, lithological and structural controls in placement of Nakhlak deposit (northeast of Esfahan. Advanced

  15. Long-term variation of the source of sulfate deposition in a leeward area of Asian continent in view of sulfur isotopic composition

    Science.gov (United States)

    Ohizumi, Tsuyoshi; Take, Naoko; Inomata, Yayoi; Yagoh, Hiroaki; Endo, Tomomi; Takahashi, Masaaki; Yanahara, Kazuki; Kusakabe, Minoru

    2016-09-01

    A large emission of air pollutants from the Asian continent has caused transboundary air pollution, especially in northeastern Asia. This paper evaluates sulfate deposition at a leeward area of Asian continent, i.e., the Nagaoka observation station located along the Sea of Japan. We have monitored atmospheric sulfate deposition and its sulfur isotopic ratio for 28 years at the station. The sulfur isotopic ratios of non-sea-salt sulfate (δ34Snss) ranged from 0.0 to +6.2‰. The isotopic ratios of local emission and Chinese coal sulfur showed negative and positive values, respectively. Several statistically significant trends were detected on the deposition of non-sea-salt sulfate (nss-SO42-) during the study period. The decrease of nss-SO42- deposition since the middle of 1980s was considered to have been caused by local anthropogenic SO2 emission that showed relatively low δ34Snss values during the period. The increase of nss-SO42- deposition from the end of 1990s to the second half of 2000s was interpreted to have been caused by the change in SO2 emission in China because the δ34Snss values increased during the period with the winter values getting closer to the averaged value of Chinese coal sulfur. The decreasing trend of nss-SO42- deposition from the middle of 2000s was likely affected by reduction of Chinese SO2 emission judging from the decrease in δ34Snss values in the period. Mass balance calculations suggested that sulfur released by coal combustion in China during 1990s contributed by about 40% of annual total sulfur deposition in Nagaoka, and its contribution increased up to 60% in the middle of 2000s. The contribution turned to decrease after that peak, which was in harmony with the temporal change of emission from China.

  16. Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

    Directory of Open Access Journals (Sweden)

    Katherine S Dawson

    2016-05-01

    Full Text Available Stable isotope probing (SIP is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS, allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S and elemental ratio (C/CN and S/CN profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

  17. Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

    Science.gov (United States)

    Dawson, K.; Scheller, S.; Dillon, J. G.; Orphan, V. J.

    2016-12-01

    Stable isotope probing (SIP) is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS), allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH) microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S) and elemental ratio (C/CN and S/CN) profiles, our analysis partitioned 2200 cellular regions of interest (ROIs) into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

  18. Sulfur isotopic compositions of individual organosulfur compounds and their genetic links in the Lower Paleozoic petroleum pools of the Tarim Basin, NW China

    Science.gov (United States)

    Cai, Chunfang; Amrani, Alon; Worden, Richard H.; Xiao, Qilin; Wang, Tiankai; Gvirtzman, Zvi; Li, Hongxia; Said-Ahmad, Ward; Jia, Lianqi

    2016-06-01

    During thermochemical sulfate reduction (TSR), H2S generated by reactions between hydrocarbons and aqueous sulfate back-reacts with remaining oil-phase compounds forming new organosulfur compounds (OSCs) that have similar δ34S values to the original sulfate. Using Compound Specific Sulfur Isotope Analysis (CSSIA) of alkylthiaadamantanes (TAs), alkyldibenzothiophenes (DBTs), alkylbenzothiophenes (BTs) and alkylthiolanes (TLs), we have here attempted to differentiate OSCs due to primary generation and those due to TSR in oils from the Tarim Basin, China. These oils were generated from Cambrian source rocks and accumulated in Cambrian and Ordovician reservoirs. Based on compound specific sulfur isotope and carbon isotope data, TAs concentrations and DBT/phenanthrene ratios, the oils fall into four groups, reflecting different extents of source rock signal, alteration by TSR, mixing events, and secondary generation of H2S. Thermally stable TAs, that were produced following TSR, rapidly dominate kerogen-derived TAs at low to moderate degrees of TSR. Less thermally stable TLs and BTs were created as soon as TSR commenced, rapidly adopted TSR-δ34S values, but they do not survive at high concentrations unless TSR is advanced and ongoing. The presence of TLs and BTs shows that TSR is still active. Secondary DBTs were produced in significant amounts, sufficient to dominate kerogen-derived DBTs, only when TSR was at an advanced extent. The difference in sulfur isotopes between (i) TLs and DBTs and (ii) BTs and DBTs and (iii) TAs and DBTs, represents the extent of TSR while the presence of TAs at greater than 20 μg/g represents the occurrence of TSR. The output of this study shows that compound specific sulfur isotopes of different organosulfur compounds, with different thermal stabilities and formation pathways, not only differentiate between oils of TSR and non-TSR origin, but can also reveal information about relative timing of secondary charge events and migration

  19. Sulfur isotopic fractionation and source appointment of PM2.5 in Nanjing region around the second session of the Youth Olympic Games

    Science.gov (United States)

    Guo, Zhaobing; Shi, Lei; Chen, Shanli; Jiang, Wenjuan; Wei, Ying; Rui, Maoling; Zeng, Gang

    2016-06-01

    Sulfur isotopic compositions (δ34S) of PM2.5 in Nanjing region were determined in order to evaluate sulfur sources of PM2.5 around the second session of the Youth Olympic Games (YOG). Meanwhile, δ34S values from different potential sources of PM2.5, such as coal combustion, vehicle exhaust, and straw burning, were synchronously measured for the first time. The results showed that PM2.5 concentrations and δ34S values were much lower during the YOG (2 August to 11 September 2014) compared to those before (6 July to 1 August 2014) and after (15 September to 20 September 2014) the YOG. δ34S values of PM2.5 were generally located in a small range of 3.5‰ to 4.6‰, suggesting a stable sulfur sources in Nanjing region around the YOG. Combining with δ34S values of potential sources and SO2, ion concentrations of PM2.5 and MODIS fire spot photos, we inferred that sulfur in PM2.5 was mainly from direct emission of coal combustion and vehicle exhaust as well as the secondary sulfate from SO2 oxidation in the atmosphere. Besides, biologic sulfur release might make a contribution to sulfur content in PM2.5. High [NO3-]/[SO42 -] ratio of PM2.5 indicated that vehicle exhaust emission was predominant over coal combustion during the YOG. In addition, we studied sulfur isotopic fractionation coefficients during SO2 oxidation to sulfate in PM2.5 and found the contribution ratio (51.3%) of SO2 homogeneous oxidation was slightly higher than that (48.7%) of SO2 heterogeneous oxidation around the YOG.

  20. Microbiological disproportionation of inorganic sulfur compounds

    DEFF Research Database (Denmark)

    Finster, Kai

    2008-01-01

    The disproportionation of inorganic sulfur intermediates at moderate temperatures (0-80 °C) is a microbiologically catalyzed chemolithotrophic process in which compounds like elemental sulfur, thiosulfate, and sulfite serve as both electron donor and acceptor, and generate hydrogen sulfide...... or phototrophic sulfide oxidizers. Investigations bridging geology and microbiology have found strong evidence for disproportionating bacteria participating in and enhancing the rate at which pyrite forms and being partly responsible for the isotopic signatures of sulfidic minerals in recent and old sediments...

  1. Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth's atmosphere.

    Science.gov (United States)

    Whitehill, Andrew R; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

    2013-10-29

    Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen ((16)O,(17)O,(18)O) and sulfur ((32)S, (33)S, (34)S, (36)S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ(33)S up to 78‰ and Δ(36)S up to 110‰, from the broadband excitation of SO2 in the 250-350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 ( (3)B1), which results from intersystem crossing from the excited singlet ( (1)A2/ (1)B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin-orbit interaction between the singlet ( (1)A2/ (1)B1) and triplet ( (3)B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for (33)SO2 and (36)SO2 for the low vibrational levels of the (1)A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems.

  2. Implications of 3.2 Ga deep seawater from sulfur isotopic analysis of barite crystals in Pilbara, Western Australia.

    Science.gov (United States)

    Miki, T.; Kiyokawa, S.; Takahata, N.; Ishida, A.; Ito, T.; Ikehara, M.; Sano, Y.

    2015-12-01

    Sulfur isotopic (δ34S) analysis is used as one of the methods of Precambrian environmental reconstruction. It has been pointed out that δ34S fluctuations of sulfate and sulfide have close relationship with rise of oxygen level and increase in biological activity of sulfate reducing bacteria. For example, the difference of δ34S between sulfate and sulfide is small in Archean while it gets larger after evolution of oxygen level and biological activity (e.g. Canfield and Farquhar, 2009).  However, evidence of δ34S difference between sulfate and sulfide in Archean is scarce. In this study, we focused on barite and pyrite occurred at the layer in the 3.2 Ga Dixon Island Formation in coastal Pilbara terrane, Western Australia.  We found pyrites in from the bottom of the Black Chert Member to the Varicolored Chert Member of the Dixon Island Formation. Particularly, we can see pyrite layers of a few millimeters thick which make an alternate layers with black chert layers in the Varicolored Chert Member. The bulk δ34S values of these layers are -10.1~+26.8‰ (Sakamoto, 2010MS) and micro-meter scale heterogeneity of δ34S can be seen in minute spherical shell pyrite which was formed at early stage of diagenesis (Miki, 2015MS).  On the other hand, barite layers are remained in the lower part of the Black Chert Member in the Dixon Island Formation. In these layers, columnar quartz crystals were representative which are considered to be a pseudomorph of barite. Such equigranular occurrences of barite are typical character in submarine hydrothermal system (Kiyokawa et al., 2006). There exist small crystals of barite (less than 200 um in diameter) which are expected to be remnants of original barite. We performed microscale sulfur isotope analyses using a NanoSIMS.  As a preliminary result, we obtained δ34S value of +3.4~+9.1‰ (n=11). These values are similar to the reported values of barite which are considered to be a hydrothermal origin in 3.47 Ga North Pole

  3. Glacial/interglacial wetland, biomass burning, and geologic methane emissions constrained by dual stable isotopic CH4 ice core records

    Science.gov (United States)

    Bock, Michael; Schmitt, Jochen; Beck, Jonas; Seth, Barbara; Chappellaz, Jérôme; Fischer, Hubertus

    2017-07-01

    Atmospheric methane (CH4) records reconstructed from polar ice cores represent an integrated view on processes predominantly taking place in the terrestrial biogeosphere. Here, we present dual stable isotopic methane records [δ13CH4 and δD(CH4)] from four Antarctic ice cores, which provide improved constraints on past changes in natural methane sources. Our isotope data show that tropical wetlands and seasonally inundated floodplains are most likely the controlling sources of atmospheric methane variations for the current and two older interglacials and their preceding glacial maxima. The changes in these sources are steered by variations in temperature, precipitation, and the water table as modulated by insolation, (local) sea level, and monsoon intensity. Based on our δD(CH4) constraint, it seems that geologic emissions of methane may play a steady but only minor role in atmospheric CH4 changes and that the glacial budget is not dominated by these sources. Superimposed on the glacial/interglacial variations is a marked difference in both isotope records, with systematically higher values during the last 25,000 y compared with older time periods. This shift cannot be explained by climatic changes. Rather, our isotopic methane budget points to a marked increase in fire activity, possibly caused by biome changes and accumulation of fuel related to the late Pleistocene megafauna extinction, which took place in the course of the last glacial.

  4. [Intraoperative methylene blue and (99m)Tc-sulfur colloid isotope tracing for sentinel node mapping in early-stage non-small cell lung cancer].

    Science.gov (United States)

    Hong, Bin; Shen, Xueyuan; Chen, Jiangyong

    2014-06-01

    To compare the accuracy of intaoperative methylene blue alone and in combination with (99m)Tc-sulfur colloid isotopic tracing for detection of sentinel lymph nodes (SLNs) in early-stage non-small cell lung cancer (NSCLC). Sixty-one patients with operable NSCLC who did not receive previous radiotherapy or chemotherapy were enrolled. Methylene blue and (99m)Tc-sulfur colloid were injected into the subserosal layer adjacent to the tumor, and SLNs were defined as those with blue staining or those containing 3 times more radioactivity than the surrounding tissue detected with a gamma probe. The SLN were removed with systematic lymph node dissection. All the removed lymph nodes were examined histopathologically with HE staining and immunohistochemistry. Methylene blue alone showed a low detection rate (60.0%) and sensitivity (58.33%) for SLNs compared with the combination of methylene blue and isotope tracing (96.15% and 92.86%, respectively). The combination of methylene blue and (99m)Tc-sulfur colloid isotopic tracing allows accurate detection of the SLNs in early-stage NSCLC.

  5. Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

    DEFF Research Database (Denmark)

    Habicht, K S; Canfield, D E

    1997-01-01

    by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate......Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate...... concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S...

  6. An experimental investigation of multiple sulfur isotope fractionations during heterogenous reactions between SO2 and activated carbon

    Science.gov (United States)

    Hamasaki, H.; Watanabe, Y.; Ohmoto, H.

    2010-12-01

    . We have recognized that the δ34S of SO2 in the system continuously decreased during the experiments from -0.6 to -1.4‰ (relative to the initial value) at 200 °C, and from -1.0 to -1.2 ‰ at 250 °C. The Δ33S of SO2 continued to decrease from 0 to -0.18 ‰ at 200 °C and 0.03 to -0.05 ‰ at 250 °C. Mass balance calculations suggest that the bulk S in activated carbon increased its δ34S value from 1.4 to 12.1 ‰ at 200 °C and 3.2 to 16.7 ‰ at 250 °C; and increased the Δ33S value from 0 to 0.18 ‰ at 200 °C and from 0.07 to 0.32 ‰ at 250 °C. Results of the sequential S extraction from the solid run products (activated C) indicate the total S content of 0.9 wt%, mostly in the forms of Cr-reductive S compounds (e.g., sulfites and polysulfides) and non Cr-reductive S compounds (e.g., organic sulfur, elemental sulfur, and sulfates). Our experimental results indicate that the adsorption of SO2, the reduction of S4+ to S0 (and/or Sx2-), and the oxidation of C0 to C4+ continued to occur during the reaction between SO2 and activated carbon at 200 °C and 250 °C, and that the redox reactions produced larger sulfur isotope effects (both in δ34S and Δ33S) compared to a simple adsorption process under our experimental conditions.

  7. Lead isotope evidence for recent uranium mobility in geological formations of Brazil: implications for radioactive waste disposal

    Energy Technology Data Exchange (ETDEWEB)

    Iyer, S.S. [Department of Physics and Astronomy, University of Calgary, Calgary (Canada); Babinski, M. [Instituto de Geociencias, Universidade de Sao Paulo, Sao Paulo (Brazil); Marinho, M.M. [Companhia Baiana de Pesquisa Mineral (CBPM), Salvador (Brazil); Barbosa, J.S.F. [Instituto de Geociencias, Universidade Federal da Bahia, Salvador (Brazil); Sato, I.M.; Salvador, V.L. [Instituto de Pesquisas Energeticas e Nucleares (CNEN/SP), Sao Paulo (Brazil)

    1999-03-01

    Lead-lead isotope data from whole rock samples are used to investigate the recent (last few million years) mobility of U and Th. The method is based on the comparison of the calculated present day U and Th concentrations required to yield the Pb isotope composition in the samples with the actual present day concentrations of U and Th obtained by direct measurement. The geological formations studied include the Neoproterozoic carbonate sediments of the Bambui Group, Archean/Paleoproterozoic granite-greenstone terrain of the Contendas-Mirante Complex and a Proterozoic ortho-gneisses hosting U deposit in Lagoa Real. All these formations are in the Sao Francisco Craton, Brazil. The data show high U mobility in the carbonate sediments and in the deformed ortho-gneisses set in a ductile shear zone. Infiltration of groundwater through fault zones seems to have facilitated the U mobility. The Pb isotope approach is a useful technique complementing U-series disequilibrium studies and may be included for site characterization studies for radioactive waste disposal. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  8. Multiple sulfur isotope and mineralogical constraints on the genesis of Ni-Cu-PGE magmatic sulfide mineralization of the Monchegorsk Igneous Complex, Kola Peninsula, Russia

    Science.gov (United States)

    Bekker, A.; Grokhovskaya, T. L.; Hiebert, R.; Sharkov, E. V.; Bui, T. H.; Stadnek, K. R.; Chashchin, V. V.; Wing, B. A.

    2016-12-01

    We present the results of a pilot investigation of multiple sulfur isotopes for the Ni-Cu-PGE sulfide mineralization of the ˜2.5 Ga Monchegorsk Igneous Complex (MIC). Base Metal Sulfide (BMS) compositions, Platinum Group Element (PGE) distributions, and Platinum Group Mineral (PGM) assemblages were also studied for different types of Ni-Cu-PGE mineralization. The uniformly low S content of the country rocks for the MIC as well as variable Sm-Nd isotope systematics and low-sulfide, PGE-rich mineralization of the MIC suggest that S saturation was reached via assimilation of silicates rather than assimilation of sulfur-rich lithologies. R-factor modeling suggests that the mixing ratio for silicate-to-sulfide melt was very high, well above 15,000 for the majority of our mineralized samples, as might be expected for the low-sulfide, PGE-rich mineralization of the MIC. Small, negative Δ33S values (from -0.23 to -0.04 ‰) for sulfides in strongly metamorphosed MIC-host rocks indicate that their sulfur underwent mass-independent sulfur isotope fractionation (MIF) in the oxygen-poor Archean atmosphere before it was incorporated into the protoliths of the host paragneisses and homogenized during metamorphism. Ore minerals from the MIC have similar Δ33S values (from -0.21 to -0.06 ‰) consistent with country rock assimilation contributing to sulfide saturation, but, also importantly, our dataset suggests that Δ33S values decrease from the center to the margin of the MIC as well as from early to late magmatic phases, potentially indicating that both local assimilation of host rocks and S homogenization in the central part of the large intrusion took place.

  9. Sulfur and oxygen isotopes in barite deposits of the western Brooks Range, Alaska, and implications for the origin of the Red Dog massive sulfide deposits

    Science.gov (United States)

    Johnson, C.A.; Kelley, K.D.; Leach, D.L.

    2004-01-01

    Sulfur and oxygen isotope analyses have been obtained for barite samples from the giant stratiform sulfide barite deposits at Red Dog in the western Brooks Range of Alaska, from stratiform barite deposits elsewhere in the Red Dog district, and from stratiform and vein and breccia barite occurrences in the central Brooks Range. Twelve of the 15 deposits studied lie within middle to Upper Mississippian black shale and chert units. The data reveal two different patterns on ?? 34S versus ??18O plots. The first, which is best illustrated by the barite deposit at Anarraaq, shows linear trends with slopes that vary with barite texture. For most samples, ??34S and ??18O values are both higher than the values characteristic of Mississippian marine sulfate. The second pattern, which is evident at the Red Dog deposits, shows no correlation between ??34S and ??18. In most samples, ??18O is below the value for Mississippian marine sulfate. Comparisons with sulfate in modern marine environments suggest a possible model for the mineralizing process. Anarraaq-type barite formed at sea-floor vents where ascending fluids carrying barium and methane encountered sulfate-bearing pore waters or bottom waters. Barite deposition was accompanied by the reduction of sulfate to H2S by means of microbially mediated anaerobic methane oxidation. Red Dog-type barite was formed in a manner similar to Anarraaq-type barite but was over-printed by a massive sulfide-forming event. Red Dog sulfides precipitated where metal-bearing hydrothermal fluids encountered pore waters that had been charged with H2S by anaerobic methane oxidation. Textural and isotopic evidence indicates that the sulfide bodies grew by consuming the available H2S and then by reductively dissolving barite. Dissolution of barite caused barium to be released to higher stratigraphic levels where it was reprecipitated on encountering sulfate. Isotopic evidence is pre sented for a link between methane venting and barite formation and

  10. In-cloud sulfate addition to single particles resolved with sulfur isotope analysis during HCCT-2010

    Directory of Open Access Journals (Sweden)

    E. Harris

    2014-01-01

    Full Text Available In-cloud production of sulfate modifies the aerosol size distribution, with important implications for the magnitude of indirect and direct aerosol cooling and the impact of SO2 emissions on the environment. We investigate which sulfate sources dominate the in-cloud addition of sulfate to different particle classes as an air parcel passes through an orographic cloud. Sulfate aerosol, SO2 and H2SO4 were collected upwind, in-cloud and downwind of an orographic cloud for three cloud measurement events during the Hill Cap Cloud Thuringia campaign in Autumn, 2010 (HCCT-2010. Combined SEM and NanoSIMS analysis of single particles allowed the δ34S of particulate sulfate to be resolved for particle size and type. The most important in-cloud SO2 oxidation pathway at HCCT-2010 was aqueous oxidation catalysed by transition metal ions (TMI catalysis, which was shown with single particle isotope analyses to occur primarily in cloud droplets nucleated on coarse mineral dust. In contrast, direct uptake of H2SO4(g and ultrafine particulate were the most important sources modifying fine mineral dust, increasing its hygroscopicity and facilitating activation. Sulfate addition to "mixed" particles (secondary organic and inorganic aerosol and coated soot was dominated by in-cloud aqueous SO2 oxidation by H2O2 and direct uptake of H2SO4(g and ultrafine particle sulfate, depending on particle size mode and time of day. These results provide new insight into in-cloud sulfate production mechanisms, and show the importance of single particle measurements and models to accurately assess the environmental effects of cloud processing.

  11. Evolution of Sulfur Isotopes and Oceanic Oxygenation Recorded in a Neoproterozoic Cap Carbonate From the Chaidam Block, China

    Science.gov (United States)

    Shen, B.; Xiao, S.; Kaufman, A.; Zhou, C.

    2006-12-01

    Neoproterozoic successions in the Chaidam Block, northwestern China, include the Hongtiegou Formation, which consists of a 20-meter thick, reddish diamictite with widespread dropstones and outsized clasts. The age of the Hongtiegou diamictite is unknown, but recent biostratigraphic correlations support a Neoproterozoic assignment. The glacial deposit is immediately overlain by a 5-meter thick carbonate of the basal Zhoujieshan Formation, which we interpret as a classic post-glacial cap carbonate. However, carbon isotope compositions of samples from this unit are near zero or slightly positive (up to ~ 2‰), which contrasts with the strongly negative (ca. -5‰) values recorded in the basal portions of most other post-glacial Neoproterozoic caps. Trace sulfate concentrations in samples of the carbonate are notably high, with an average of 366 ± 266 ppm. In the lower 2.5 meters of the Zhoujieshan cap (stage I) sulfur isotope compositions of both carbonate associated sulfate (CAS) and sulfides isolated from the same sample are indistinguishable from each other, and rise in concert by over 10% to values around +22‰. Above this level (stage II), 34S abundances of sulfides continue to increase to a peak of +27‰, but CAS values fall back to ~15‰. As a result isotopic differences between sulfides and sulfates are near zero in stage I and around 10% in stage II. The evolution of both systems in the lower half of the deposit suggests that seawater sulfate must have evolved to progressively heavier 34S compositions, and that sulfate in pore waters ¨C where sulfate reducing bacteria were active ¨C was quantitatively reduced to pyrite. This might result from the progressive distillation of sulfate from seawater by an enhanced rain of carbonate, in addition to bacterial reduction of sulfate, in the glacial aftermath. The anomalous isotope systematics of stage II are difficult to model, but might signal a new source and higher abundances of oceanic sulfate, based on

  12. Iridium, sulfur isotopes and rare earth elements in the Cretaceous-Tertiary boundary clay at Stevns Klint, Denmark

    Energy Technology Data Exchange (ETDEWEB)

    Schmitz, B.; Andersson, P.; Dahl, J.

    1988-01-01

    Microbial activity and redox-controlled precipitation have been of major importance in the process of metal accumulation in the strongly Ir-enriched Cretaceous-Tertiary (K-T) boundary clay, the Fish Clay, at Stevns Klint in Denmark. Two important findings support this view: (1) Kerogen, recovered by leaching the Fish Clay in HCl and HF, shows an Ir concentration of 1100 ppb; this represents about 50% of the Ir present in the bulk sample Fish clay. Strong organometallic complexes is the most probable carrier phase for this fraction of Ir. Kerogen separated from the K-T boundary clay at Caravaca, Spain, similarly exhibits enhanced Ir concentrations. (2) Sulfur isotope analyses of metal-rich pyrite spherules, which occur in extreme abundance (about 10% by weight) in the basal Fish Clay, give a delta/sup 34/S value of -32 per thousand. This very low value shows that sulfide formation by anaerobic bacteria was intensive in the Fish Clay during early diagenesis. Since the pyrite spherules are major carriers of elements such as Ni, Co, As, Sb and Zn, microbial activity may have played an important role for concentrating these elements. In the Fish Clay large amounts of rare earth elements have precipitated from sea water on fish scales. Analyses reveal that, compared with sea water, the Fish Clay is only about four times less enriched in sea-water derived lanthanides than in Ir. This shows that a sea-water origin is plausible for elements that are strongly enriched in the clay, but whose origin cannot be accounted for by a lithogenic precursor.

  13. Accurate determination of sulfur in gasoline and related fuel samples using isotope dilution ICP-MS with direct sample injection and microwave-assisted digestion.

    Science.gov (United States)

    Heilmann, Jens; Boulyga, Sergei F; Heumann, Klaus G

    2004-09-01

    Inductively coupled plasma isotope-dilution mass spectrometry (ICP-IDMS) with direct injection of isotope-diluted samples into the plasma, using a direct injection high-efficiency nebulizer (DIHEN), was applied for accurate sulfur determinations in sulfur-free premium gasoline, gas oil, diesel fuel, and heating oil. For direct injection a micro-emulsion consisting of the corresponding organic sample and an aqueous 34S-enriched spike solution with additions of tetrahydronaphthalene and Triton X-100, was prepared. The ICP-MS parameters were optimized with respect to high sulfur ion intensities, low mass-bias values, and high precision of 32S/34S ratio measurements. For validation of the DIHEN-ICP-IDMS method two certified gas oil reference materials (BCR 107 and BCR 672) were analyzed. For comparison a wet-chemical ICP-IDMS method was applied with microwave-assisted digestion using decomposition of samples in a closed quartz vessel inserted into a normal microwave system. The results from both ICP-IDMS methods agree well with the certified values of the reference materials and also with each other for analyses of other samples. However, the standard deviation of DIHEN-ICP-IDMS was about a factor of two higher (5-6% RSD at concentration levels above 100 mircog g(-1)) compared with those of wet-chemical ICP-IDMS, mainly due to inhomogeneities of the micro-emulsion, which causes additional plasma instabilities. Detection limits of 4 and 18 microg g(-1) were obtained for ICP-IDMS in connection with microwave-assisted digestion and DIHEN-ICP-IDMS, respectively, with a sulfur background of the used Milli-Q water as the main limiting factor for both methods.

  14. Accurate determination of sulfur in gasoline and related fuel samples using isotope dilution ICP-MS with direct sample injection and microwave-assisted digestion

    Energy Technology Data Exchange (ETDEWEB)

    Heilmann, Jens; Boulyga, Sergei F.; Heumann, Klaus G. [Johannes Gutenberg-University, Institute of Inorganic Chemistry and Analytical Chemistry, Mainz (Germany)

    2004-09-01

    Inductively coupled plasma isotope-dilution mass spectrometry (ICP-IDMS) with direct injection of isotope-diluted samples into the plasma, using a direct injection high-efficiency nebulizer (DIHEN), was applied for accurate sulfur determinations in sulfur-free premium gasoline, gas oil, diesel fuel, and heating oil. For direct injection a micro-emulsion consisting of the corresponding organic sample and an aqueous {sup 34}S-enriched spike solution with additions of tetrahydronaphthalene and Triton X-100, was prepared. The ICP-MS parameters were optimized with respect to high sulfur ion intensities, low mass-bias values, and high precision of {sup 32}S/{sup 34}S ratio measurements. For validation of the DIHEN-ICP-IDMS method two certified gas oil reference materials (BCR 107 and BCR 672) were analyzed. For comparison a wet-chemical ICP-IDMS method was applied with microwave-assisted digestion using decomposition of samples in a closed quartz vessel inserted into a normal microwave system. The results from both ICP-IDMS methods agree well with the certified values of the reference materials and also with each other for analyses of other samples. However, the standard deviation of DIHEN-ICP-IDMS was about a factor of two higher (5-6% RSD at concentration levels above 100 {mu}g g{sup -1}) compared with those of wet-chemical ICP-IDMS, mainly due to inhomogeneities of the micro-emulsion, which causes additional plasma instabilities. Detection limits of 4 and 18 {mu}g g{sup -1} were obtained for ICP-IDMS in connection with microwave-assisted digestion and DIHEN-ICP-IDMS, respectively, with a sulfur background of the used Milli-Q water as the main limiting factor for both methods. (orig.)

  15. Trace and minor element variations and sulfur isotopes in crystalline and colloform ZnS: Incorporation mechanisms and implications for their genesis

    Science.gov (United States)

    Pfaff, Katharina; Koenig, Alan; Wenzel, Thomas; Ridley, Ian; Hildebrandt, Ludwig H.; Leach, David L.; Markl, Gregor

    2011-01-01

    Various models have been proposed to explain the formation mechanism of colloform sphalerite, but the origin is still under debate. In order to decipher influences on trace element incorporation and sulfur isotope composition, crystalline and colloform sphalerite from the carbonate-hosted Mississippi-Valley Type (MVT) deposit near Wiesloch, SW Germany, were investigated and compared to sphalerite samples from 52 hydrothermal vein-type deposits in the Schwarzwald ore district, SW Germany to study the influence of different host rocks, formation mechanisms and fluid origin on trace element incorporation. Trace and minor element incorporation in sphalerite shows some correlation to their host rock and/or origin of fluid, gangue, paragenetic minerals and precipitation mechanisms (e.g., diagenetic processes, fluid cooling or fluid mixing). Furthermore, crystalline sphalerite is generally enriched in elements like Cd, Cu, Sb and Ag compared to colloform sphalerite that mainly incorporates elements like As, Pb and Tl. In addition, sulfur isotopes are characterized by positive values for crystalline and strongly negative values for colloform sphalerite. The combination of trace element contents, typical minerals associated with colloform sphalerite from Wiesloch, sulfur isotopes and thermodynamic considerations helped to evaluate the involvement of sulfate-reducing bacteria in water-filled karst cavities. Sulfate-reducing bacteria cause a sulfide-rich environment that leads in case of a metal-rich fluid supply to a sudden oversaturation of the fluid with respect to galena, sphalerite and pyrite. This, however, exactly coincides with the observed crystallization sequence of samples involving colloform sphalerite from the Wiesloch MVT deposit.

  16. Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China.

    Science.gov (United States)

    Xie, Xianjun; Ellis, Andre; Wang, Yanxin; Xie, Zuoming; Duan, Mengyu; Su, Chunli

    2009-06-01

    High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 microg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 microg/L in the basin and from 3.1 to 44 microg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals. The wide range of delta(34)S([SO4

  17. Sulfur isotope mass-independent fractionation in impact deposits of the 3.2 billion-year-old Mapepe Formation, Barberton Greenstone Belt, South Africa

    Science.gov (United States)

    van Zuilen, M. A.; Philippot, P.; Whitehouse, M. J.; Lepland, A.

    2014-10-01

    Theoretical and experimental studies have shown that atmospheric SO2 isotopologue self-shielding effects in the 190-220 nm region of the solar spectrum are the likely cause for mass independent fractionation of sulfur isotopes (S-MIF). The main products of this photochemical reaction - SO3 and S0 - typically define a compositional array of ca. Δ33S/δ34S = 0.06-0.14. This is at odds with the generally observed trend in Archean sulfides, which broadly defines an array of ca. Δ33S/δ34S = 0.9. Various explanations have been proposed, including a diminution of δ34S caused by chemical and biogenic mass-dependent fractionation of sulfur isotopes (S-MDF), mixing with photolytic products produced during felsic volcanic events, or partial blocking of the low-wavelength part of the spectrum due to the presence of reduced atmospheric gases or an organic haze. Early in Earth history large meteorite impacts would have ejected dust and gas clouds into the atmosphere that shielded solar radiation and affected global climate. It is thus likely that at certain time intervals of high meteorite flux the atmosphere was significantly perturbed, having an effect on atmospheric photochemistry and possibly leaving anomalous sulfur isotopic signatures in the rock record. Here we describe the sulfur isotopic signatures in sulfides of spherule beds S2, S3 and S4 of the Barberton Greenstone Belt, South Africa. In particular, in spherule bed S3 - and to a lesser extent S4 - a trend of ca. Δ33S/δ34S = 0.23 is observed that closely follows the expected trend for SO2-photolysis in the 190-220 nm spectral range. This suggests that an impact dust cloud (deposited as spherule beds), which sampled the higher region of the atmosphere, specifically incorporated products of SO2 photolysis in the 190-220 nm range, and blocked photochemical reactions at higher wavelengths (250-330 nm band). By implication, the generally observed Archean trend appears to be the result of mixing of different MIF

  18. Helium, lead and sulfur isotope geochemistry of the Gejiu Sn-polymetallic ore deposit and the sources of ore-forming materials

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Studies on the helium, lead and sulfur isotopic composition were performed of the Gejiu super-large Sn-polymetallic ore deposit. The results indicated that the ore-forming materials came from different sources and the deposit is a product of superimposed mineralization. The deposit is characterized by multi-source and multi-period mineralization, which experienced submarine hydrothermal deposition and Late Yanshanian magmatic hydrothermal mineralization. It is held that the Gejiu super-large Sn-polymetallic ore deposit is a multi-genesis deposit.

  19. Determination of the absolute 32S/34S ratio of IAEA-S-1 reference material and V-CDT sulfur isotope standard

    Institute of Scientific and Technical Information of China (English)

    丁悌平; 白瑞梅; 李延河; 万德芳; 邹晓秋; 张青莲

    1999-01-01

    The absolute 32S/34S ratios of IAEA-S-1 reference material and V-CDT standard are determined. For cross-checking, two sets of synthetic isotope mixtures are prepared from high purity 32S and 34S-enriched materials in different forms: the first set is prepared from BaSO4 whereas the second is prepared from Ag2S. The sulfur isotope analyses are done by using SF6 method with a MAT-251 EM mass spectrometer. The resulting 32S/34S ratio of IAEAS-1 reference material is 22.656 4±0. 006 0, and that of V-CDT is 22. 649 6±0. 006 0.

  20. Geology, fluid inclusion and sulphur isotope characteristics of the El Cobre VHMS deposit, Southern Cuba

    Science.gov (United States)

    Cazañas, Xiomara; Alfonso, Pura; Melgarejo, Joan Carles; Proenza, Joaquín Antonio; Fallick, Anthony Edward

    2008-09-01

    The El Cobre deposit is located in eastern Cuba within the volcanosedimentary sequence of the Sierra Maestra Paleogene arc. The deposit is hosted by tholeiitic basalts, andesites and tuffs and comprises thick stratiform barite and anhydrite bodies, three stratabound disseminated up to massive sulphide bodies produced by silicification and sulphidation of limestones or sulphates, an anhydrite stockwork and a siliceous stockwork, grading downwards to quartz veins. Sulphides are mainly pyrite, chalcopyrite and sphalerite; gold occurs in the stratabound ores. Fluid inclusions measured in sphalerite, quartz, anhydrite and calcite show salinities between 2.3 and 5.7 wt% NaCl eq. and homogenisation temperatures between 177 and 300°C. Sulphides from the stratabound mineralisation display δ 34S values of 0‰ to +6.0‰, whilst those from the feeder zone lie between -1.4‰ and +7.3‰. Sulphides show an intra-grain sulphur isotope zonation of about 2‰; usually, δ 34S values increase towards the rims. Sulphate sulphur has δ 34S in the range of +17‰ to +21‰, except two samples with values of +5.9‰ and +7.7‰. Sulphur isotope data indicate that the thermochemical reduction of sulphate from a hydrothermal fluid of seawater origin was the main source of sulphide sulphur and that most of the sulphates precipitated by heating of seawater. The structure of the deposit, mineralogy, fluid inclusion and isotope data suggest that the deposit formed from seawater-derived fluids with probably minor supply of magmatic fluids.

  1. Native sulfur, sulfates and sulfides from the active Campi Flegrei volcano (southern Italy): Genetic environments and degassing dynamics revealed by mineralogy and isotope geochemistry

    Science.gov (United States)

    Piochi, Monica; Mormone, Angela; Balassone, Giuseppina; Strauss, Harald; Troise, Claudia; De Natale, Giuseppe

    2015-10-01

    We investigated sulfur-bearing minerals from the Campi Flegrei caldera, southern Italy, in relation to the increase of hydrothermal activity phenomena since 2006, aimed at providing insights into the volcanic system dynamics. Mineral encrustations and muds were sampled between 2013 and 2015 at the long-standing degassing crater of the Solfatara tuff cone and its recently restless north-eastern Pisciarelli slope. Deep-seated sulfides were further separated from two drill cores (AGIP's Mofete boreholes: 1500 m and 2695 m depth). The mineral assemblage and texture of sampled encrustations were determined by X-ray diffraction, optical and scanning electron microscopy and X-ray microanalysis by energy dispersive spectrometry. Native sulfur and alunite dominate among the newly formed mineral phases. Other minerals are mostly alunogen, and locally pickeringite, potassium alum, hematite and pyrite. Mereiterite and amarillite sporadically occur. The mud pools are rich in gypsum, potassium alum and pyrite. Quartz and argillic phases, locally with analcime, are dispersed in the outcropping rocks. δ34S values were determined for shallow subsurface native sulfur (- 5.5 to 0.0‰) and alunite (- 1.7 to - 0.2‰), as well as for the deep-seated pyrite (3.3 to 7.4‰ in the depth range:1500-2695 m). δ18O values were measured for shallow native alunite (4.2 to 7.0‰). Pisciarelli alunite was finally analyzed for its 87Sr/86Sr ratio and 143Nd/144Nd ratios (0.707517 ± 6 and 0.512459 ± 6, respectively). Textural and isotopic data constrain the genesis of alunite at the expense of K-feldspars through rock alteration by hydrothermal fluids. We suggest that the caldera is a low-sulfidation system hosting acid-sulfate deposits in its active degassing area. The acid-sulfate environment developed on an argillitic facies that thins outwards and is characteristic for steam-heated and magmatic-steam environments. These environments developed in relation to the fractured settings that

  2. A STUDY ON THE GEOLOGICAL FEATURES AND GENESIS OF THE LONGSHAN Au-Sb DEPOSIT

    Institute of Scientific and Technical Information of China (English)

    HU; Xiang-zhao; YANG; Zhong-bao

    2002-01-01

    The geological features of the Longshan Au-Sb deposits are systematically described. Mineralization conditions, sources of ore materials and metallogenetic mechanism are also analysed according to sulfur, oxygen isotope composition, pyrite typomorphic features and fluid inclusion thermometry dating, The results show that it is a sedimentary metamophic hydrothermal deposit.

  3. Paleoproterozoic high-sulfidation mineralization in the Tapajós gold province, Amazonian Craton, Brazil: geology, mineralogy, alunite argon age, and stable-isotope constraints

    Science.gov (United States)

    Juliani, Caetano; Rye, Robert O.; Nunes, Carmen M.D.; Snee, Lawrence W.; Correa, Rafael H.; Monteiro, Lena V.S.; Bettencourt, Jorge S.; Neumann, Rainer; Neto, Arnaldo A.

    2005-01-01

    The Brazilian Tapajós gold province contains the first evidence of high-sulfidation gold mineralization in the Amazonian Craton. The mineralization appears to be in large nested calderas. The Tapajós–Parima (or Ventuari–Tapajós) geological province consists of a metamorphic, igneous, and sedimentary sequence formed during a 2.10 to 1.87 Ga ocean−continent orogeny. The high-sulfidation mineralization with magmatic-hydrothermal alunite is related to hydrothermal breccias hosted in a rhyolitic volcanic ring complex that contains granitic stocks ranging in age from 1.89 to 1.87 Ga. Cone-shaped hydrothermal breccias, which flare upward, contain vuggy silica and have an overlying brecciated cap of massive silica; the deposits are located in the uppermost part of a ring-structure volcanic cone. Drill cores of one of the hydrothermal breccias contain alunite, natroalunite, pyrophyllite, andalusite, quartz, rutile, diaspore, woodhouseite–svanbergite, kaolinite, and pyrite along with inclusions of enargite–luzonite, chalcopyrite, bornite, and covellite. The siliceous core of this alteration center is surrounded by advanced argillic and argillic alteration zones that grade outward into large areas of propylitically altered rocks with sericitic alteration assemblages at depth. Several occurrences and generations of alunite are observed. Alunite is disseminated in the advanced argillic haloes that envelop massive and vuggy silica or that underlie the brecciated silica cap. Coarse-grained alunite also occurs in branching veins and locally is partly replaced by a later generation of fine-grained alunite. Silicified hydrothermal breccias associated with the alunite contain an estimated reserve of 30 tonnes of gold in rock that grades up to 4.5 g t−1 Au. Seven alunite samples gave 40Ar/39Ar ages of 1.869 to 1.846 Ga, with various degrees of apparent minor Ar loss. Stable isotopic data require a magmatic-hydrothermal origin for the alunite, typical for high

  4. Isotope Trace Studies of Diffusion in Silicates and of Geological Transport Processes Using Actinide Elements

    Energy Technology Data Exchange (ETDEWEB)

    Prof. G. J. Wasserburg

    2001-01-19

    Over the past year we have competed two studies of Os concentration and isotopic composition in rivers from the Himalayan uplift and in hydrothermal fluids from the Juan de Fuca Ridge. Both of these studies have been published. We have completed a study of paleo-climate in Soreq Cave, Israel, and have expanded our studies of the transport of U-Th through riverine and estuarine environments. We are completing two studies of weathering and transport in the vadose in two very different environments--one a tropical regime with a deep laterite profile and the other a northern arboreal forest with only a thin weathering zone. We have begun a new study of U-Th in aquifers with low water velocity.

  5. Mesoproterozoic graphite deposits, New Jersey Highlands: Geologic and stable isotopic evidence for possible algal origins

    Science.gov (United States)

    Volkert, R.A.

    2000-01-01

    Graphite deposits of Mesoproterozoic age are locally abundant in the eastern New Jersey Highlands, where they are hosted by sulphidic biotite-quartz-feldspar gneiss, metaquartzite, and anatectic pegmatite. Gneiss and metaquartzite represent a shallow marine shelf sequence of locally organic-rich sand and mud. Graphite from massive deposits within metaquartzite yielded ??13C values of -26 ?? 2??? (1??), and graphite from massive deposits within biotite-quartz-feldspar gneiss yielded ??13C values of -23 ??4???. Disseminated graphite from biotite-quartz-feldspar gneiss country rock was -22 ??3???, indistinguishable from the massive deposits hosted by the same lithology. Anatectic pegmatite is graphitic only where generated from graphite-bearing host rocks; one sample gave a ??13C value of -15???. The ??34S values of trace pyrrhotite are uniform within individual deposits, but vary from 0 to 9??? from one deposit to another. Apart from pegmatitic occurrences, evidence is lacking for long-range mobilization of carbon during Grenvillian orogenesis or post-Grenvillian tectonism. The field, petrographic, and isotope data suggest that massive graphite was formed by granulite-facies metamorphism of Proterozoic accumulations of sedimentary organic matter, possibly algal mats. Preservation of these accumulations in the sedimentary environment requires anoxic basin waters or rapid burial. Anoxia would also favour the accumulation of dissolved ferrous iron in basin waters, which may explain some of the metasediment-hosted massive magnetite deposits in the New Jersey Highlands. ?? 2000 NRC.

  6. Mineralogical and sulfur isotopic characterization of the sulfur-bearing mineralization from the active degassing area of Campi Flegrei caldera (southern Italy)

    Science.gov (United States)

    Mormone, Angela; Piochi, Monica; Balassone, Giuseppina; Strauss, Harald; Troise, Claudia; De Natale, Giuseppe

    2015-04-01

    The Campi Flegrei caldera is a site of persistent hydrothermal circulation and gaseous emissions inside the Pozzuoli town and nearby the city of Napoli (Italy). The solfataric phenomena are associated with episodes of low-magnitude seismicity and vertical ground displacement since Roman times, evolving to the Monte Nuovo eruption in the 1538 AD. Pronounced geochemical anomalies, uplift rates up to 1 m/y and up to ten thousands microearthquakes per year also characterized the four most recent decades of unrest. The degassing phenomena are concentrated within the Solfatara crater, although, since 2006, the hydrothermal activity strongly increased in the Pisciarelli district, i.e. on the north-east slope of the tuff. We investigated sulfur-bearing mineral precipitates sampled from the active fumaroles both within the Solfatara and along the Pisciarelli slope. Mineral assemblage, texture and chemistry were determined for the efflorescence precipitated nearby the fumaroles and along the mud pool by x-ray diffraction, back-scattered electron microscope and electron diffuse microanalysis. δ34S compositions were also determined on separated sulfur-minerals. The new data have been compared with scattered literature data, including few existing for the previous '70 and '80 unrest episodes. Native sulfur and alunite are the main mineral phases that associate with alunogene, and, locally, pickeringite and potassium alum. Sporadically mereiterite, amarillite, and pyrite have been found as neogenesis mineralization along the outcropping rocks. The mud pool is rich in gypsum, potassium alum and pyrite. δ34S values range from -5.48 to 0.0‰, being slightly lower than previous data. The obtained results suggest that the Pisciarelli area is characterized by magmatic-hydrothermal, magmatic-steam and steam-heated environments, developed on a argillitic hydrothermal facies that thickens in correspondence of the degassing area. These environments develop and continuously evolve in

  7. Nd and Sr isotopes: implications of provenance and geological mapping; Isotopos de Nd e Sr: implicacoes de proveniencia e mapeamento geologico

    Energy Technology Data Exchange (ETDEWEB)

    Albuquerque, Marcio Fernando dos Santos; Horbe, Adriana Maria Coimbra; Dantas, Elton Luiz, E-mail: mgeoroots@gmail.com, E-mail: ahorbe@unb.br, E-mail: elton@unb.br [Universidade de Brasilia (UnB), DF (Brazil). Instituto de Geociencias

    2015-07-01

    XRD, Nd and Sr isotopes, major, minor and traces elements quantification were applied to rocks, lateritic crusts and soils from Sumauma Supergroup and Alto Tapajos Group, in order to indicate provenance of the rocks and using lateritic products as geologic mapping tool. For the rocks, the results showed sources related to provinces Tapajos Parima, Rondonia Juruena, Sunsas, Carajas and Amazonia Central. However, the incision of Cachimbo graben allowed which the Sumauma Supergroup erosion also were source for the Alto Tapajos Group, allied to contribution of volcanics from Colider Group. Lateritic crusts and soils are correlates to bedrocks, allowing the use as geologic mapping tool. (author)

  8. Re-Os isotopic data for molybdenum from Hejiangkou tungsten and tin polymetallic deposit in Chenzhou and its geological significance

    Institute of Scientific and Technical Information of China (English)

    刘德波; 杨柳; 邓湘伟; 戴雪玲; 王雄军; CHONGkhaiyuen; 杜高峰; 魏和平

    2016-01-01

    Hejiangkou W−Sn-polymetallic deposit is a newly found deposit in Xitian ore field, one of the important and large scale W−Sn-polymetallic ore fields in the middle segment of Nanling metallogenic zone. Re−Os isotope dating was used on three molybdenite samples from Hejiangkou deposit to determine the ore forming period. The result is (224.9±2.6)Ma−(225±3.1)Ma and isochron age is (225.5±3.6)Ma. The field geological observations, geochronological data and optical petrography indicated that Hejiangkou deposit underwent multi-period of superimposed mineralization. It can be differentiated into three periods composed of six mineralization stages. The first period is the initial period for hydrothermal metasomatism and metal element enrichment during Indosinian Epoch. Further enrichment, strong brittle fracturing and hydrothermal metasomatism, remobilization and superimposition happened in the second period, during early Yanshanian. It is the major mineralization period of Hejiangkou deposit and can be subdivided into four mineralization stages, namely the skarn stage, oxide stage, high-temperature sulfide stage and low-temperature sulfide stage. And the third period is the mineralization period of a porphyry-skarn system related to the emplacement of the granite porphyry dyke. As minerogenic epoch of Hejiangkou deposit is similar with Hehuaping deposit, they show the possibility of Indosinian mineralization event in Nanling metallogenic zone. It can be an important perspective in any future mineral exploration in the same metallogenic zone.

  9. Isotope and fluid inclusion studies of geological and hydrothermal processes, northern Peru

    Energy Technology Data Exchange (ETDEWEB)

    MacFarlane, A.W. [Florida International Univ., Miami, FL (United States); Prol-Ledesma, R.M. [Cd. Universitaria, Coyoacan (Mexico); Conrad, M.E. [Lawrence Berkeley Lab., CA (United States)

    1994-07-01

    Mineralization in the Hualgayoc district of northern Peru occurs in altered Miocene felsic intrusions and in mid-Cretaceous platform sedimentary rocks of the Goyllarisquizga, Inca, and Chulec formations. The ores occur both as stratiform and stratabound pyritiferous base-metal deposits (mantos), and as steeply dipping, sedimentary and intrusive rock-hosted base-metal veins. Igneous rocks in the district are affected by propylytic, sericitic-argillic, sericitic, potassic, and acid-sulfate alteration. K-Ar and Rb-Sr dating and geological evidence indicate multiple stages of intrusive activity and hydrothermal alteration, including close spatial emplacement of two or more separate Miocene magmatic-hydrothermal systems. K-Ar dates on sericite, hydrothermal biotite, and alunite indicate that the most important hydrothermal episodes in the district took place {approx}13.24 and 12.4 Ma. Other K-Ar dates on altered rocks in the district may reflect various amounts of resetting by the emplacement of the 9.05 {+-} 0.2 Ma Hualgayoc rhyodacite. A five-point Rb-Sr isochron for the San Miguel intrusion at Cerro Coymolache yields an age of 45 {+-} 3.4 Ma, which indicates much earlier magmatic activity in this area than recognized previously. Fluid inclusion and paragenetic studies reveal a clear temporal evolution of fluid temperature and chemistry in the San Agustin area at Hualgayoc. Gradually, ore formation shifted to precipitation of vein minerals in the brittle fractures as the mantos became less permeable and were sealed off. Vein formation continued from progressively cooler and more diluted fluids (down to {approx}150{degrees}C and 4.3 wt% NaCl equivalent) as the system waned. No evidence for phase separation is observed in the fluids until the very last paragenetic stage, which contributed no economic mineralization. 53 refs., 15 figs., 7 tabs.

  10. Uranium-lead dating method at the Pará-Iso isotope geology laboratory, UFPA, Belém - Brazil

    Directory of Open Access Journals (Sweden)

    Robert S. Krymsky

    2007-03-01

    Full Text Available Analytical procedures for U-Pb isotope dilution analyses at the Pará-Iso isotope geology laboratory of the Federal University of Pará (UFPA are described in detail. The procedures are applied to zircon, titanite, rutile, apatite, columbite-tantalite and whole rock. Reagent preparation and chemical processing are done in clean-room conditions. Samples are dissolved using TeflonTM microcapsules in steel jacket TeflonTM Parr InstrumentTM bomb or TeflonTM screw cap containers. U and Pb are separated using anion exchange AG 1x8 resin columns. Typical blanks for mineral sample amounts of 0.01 to 1.0 mg are less than 1 pg U and 20-30 pg Pb. Isotope analysis of the U and Pb from the same filament are carried out using a Finnigan MAT 262 mass-spectrometer in static and dynamic modes. The current analytical level is demonstrated on analyses of international standard zircon 91500 with three different 235U-205Pb and 235U-208Pb isotope tracers and whole rock standards. Results of analyses of two zircon samples are also presented.Os procedimentos analíticos para análises U-Pb por diluição isotópica no Laboratório de Geologia Isotópica (Pará-Iso da Universidade Federal do Pará (UFPA são descritos detalhadamente. Esses procedimentos são aplicados para análises de zircão, titanita, rutilo, apatita, columbita-tantalita e rocha total. A purificação dos reagentes e os procedimentos químicos são feitos em salas limpas. As amostras são dissolvidas em microcápsulas de Teflon em bombas do tipo Parr InstrumentTM. U e Pb são separados em colunas com resina de troca iônica AG 1x8. Os brancos de procedimento para amostra típica(0,01-1 mg são menores que 1 pg de U e 20-30 pg de Pb. As análises isotópicas de Pb e de U são feitas em um único filamento de Re em um espectrômetro de massa Finnigan MAT 262 nos modos estático e dinâmico. O nível analítico atual é comprovado pelas análises do padrão internacional de zircão 91500, usando tr

  11. Combined isotope and enantiomer analysis to assess the fate of phenoxy acids in a heterogeneous geologic setting at an old landfill

    DEFF Research Database (Denmark)

    Milosevic, Nemanja; Qiu, S; Elsner, M

    2013-01-01

    )propionic acid) is frequently obstructed by inconclusive evidence from redox conditions, heterogeneous geologic settings (e.g. clay till) and ambiguous parent-daughter relationships (i.e. 4-CPP may be daughter product or impurity of dichlorprop). For the first time, a combination of four methods was tested...... of dichlorprop to 4-CPP and further to phenoxypropionic acid. Combined evidence from concentrations, enantiomer ratios and isotope ratios of dichlorprop and 4-CPP confirmed their dechlorination in the hotspot and gave evidence for further degradation of 4-CPP downgradient of the hotspot. A combination of 4-CPP...... enantiomer and isotope analysis indicated different enantioselectivity and isotope fractionation, i.e. different modes of 4-CPP degradation, at different locations. This combined information was beyond the reach of any of the methods applied alone demonstrating the power of the new combined approach....

  12. Unravelling atmospheric photolysis and ocean redox chemistry from Paleoarchean pyrite : a multiple sulfur and iron stable isotope study

    NARCIS (Netherlands)

    Galić, A.

    2015-01-01

    This thesis brought together four individual studies on the geochemistry of three recently obtained drill cores from the Barberton Greenstone Belt, South Africa. These data were used to provide a synthesis of the iron and sulfur cycles in the Paleoarchean, with a particular focus on the nature and o

  13. Sulfur isotope signatures in gypsiferous sediments of the Estancia and Tularosa Basins as indicators of sulfate sources, hydrological processes, and microbial activity

    Science.gov (United States)

    Szynkiewicz, Anna; Moore, Craig H.; Glamoclija, Mihaela; Pratt, Lisa M.

    2009-10-01

    In order to reconstruct paleo-environmental conditions for the saline playa lakes of the Rio Grande Rift, we investigated sediment sulfate sources using sulfur isotope compositions of dissolved SO42- ions in modern surface water, groundwater, and SO42- precipitated in the form of gypsum sediments deposited during the Pleistocene and Holocene in the Tularosa and Estancia Basins. The major sulfate sources are Lower and Middle Permian marine evaporites (δ 34S of 10.9-14.4‰), but the diverse physiography of the Tularosa Basin led to a complex drainage system which contributed sulfates from various sources depending on the climate at the time of sedimentation. As inferred from sulfur isotope mass balance constraints, weathering of sulfides of magmatic/hydrothermal and sedimentary origin associated with climate oscillations during Last Glacial Maximum contributed about 35-50% of the sulfates and led to deposition of gypsum with δ 34S values of -1.2‰ to 2.2‰ which are substantially lower than Permian evaporates. In the Estancia Basin, microbial sulfate reduction appears to overprint sulfur isotopic signatures that might elucidate past groundwater flows. A Rayleigh distillation model indicates that about 3-18% of sulfates from an inorganic groundwater pool (δ 34S of 12.6-13.8‰) have been metabolized by bacteria and preserved as partially to fully reduced sulfur-bearing minerals species (elemental sulfur, monosulfides, disulfides) with distinctly negative δ 34S values (-42.3‰ to -20.3‰) compared to co-existing gypsum (-3.8‰ to 22.4‰). For the Tularosa Basin microbial sulfate reduction had negligible effect on δ 34S value of the gypsiferous sediments most likely because of higher annual temperatures (15-33 °C) and lower organic carbon content (median 0.09%) in those sediments leading to more efficient oxidation of H 2S and/or smaller rates of sulfate reduction compared to the saline playas of the Estancia Basin (5-28 °C; median 0.46% of organic carbon

  14. Geology and D-O-C Isotope Systematics of the Tieluping Silver Deposit,Henan,China:Implications for Ore Genesis

    Institute of Scientific and Technical Information of China (English)

    CHEN Yanjing; Franco PIRAJNO; SUI Yinghui

    2005-01-01

    The Tieluping silver deposit, which is sited along NE-trending faults within the high-grade metamorphic basement of the Xiong'er terrane, is part of an important Mesozoic orogenic-type Ag-Pb and Au belt recently discovered. Ore formation includes three stages: Early (E), Middle (M) and Late (L), which include quartz-pyrite (E),polymetallic sulfides (M) and carbonates (L), respectively. The E-stage fluids are characterized by δD=-90‰,δ13Cco2=2.0‰ and δ18O=9‰ at 373℃, and are deeply sourced; the L-stage fluids, with δD=-70‰,δ13Cco2=-1.3‰ and δ18O=-2‰, are shallow-sourced meteoric water; whereas the M-stage fluids, with δD=-109‰,δ13Cco2=0.1‰ and δ18O=2‰, are a mix of deep-sourced and shallow-sourced fluids. Comparisons of the D-O-C isotopic systematics of the Estage ore-forming fluids with the fluids derived from Mesozoic granites, Archean-Paleoproterozoic metamorphic basement and Paleo-Mesoproterozoic Xiong'er Group, show that these units cannot generate fluids with the measured isotopic composition (high δ18O and δ13C ratios and low δD ratios) characteristic of the ore-forming fluids. This suggests that the E-stage ore-forming fluids originated from metamorphic devolatilization of a carbonate-shale-chert lithological association, locally rich in organic matter, which could correspond to the Meso-Neoproterozoic Guandaokou and Luanchuan Groups, rather than to geologic units in the Xiong'er terrane, the lower crust and the mantle. This supports the view that the rocks of the Guandaokou and Luanchuan Groups south of the Machaoying fault might be the favorable sources. A tectonic model that combines collisional orogeny, metallogeny and hydrothermal fluid flow is proposed to explain the formation of the Tieluping silver deposit. During the Mesozoic collision between the South and North China paleocontinents, a crustal slab containing a lithological association consisting of carbonate-shale-chert, locally rich in organic matter (carbonaceous

  15. Petrography, sulfide mineral chemistry, and sulfur isotope evidence for a hydrothermal imprint on Musina copper deposits, Limpopo Province, South Africa: Evidence for a breccia pipe origin?

    Science.gov (United States)

    Chaumba, Jeff B.; Mundalamo, Humbulani R.; Ogola, Jason S.; Cox, J. A.; Fleisher, C. J.

    2016-08-01

    values of 0.4 and 0.7‰. The same sample also yielded a δ34Sbornite value of 0.4‰. Another Campbell Mine quartz vein sample yielded a chalcopyrite δ34S value of -0.3‰. Sulfur isotope thermometry for one Campbell Mine quartz vein sample with coexisting sulfides yielded a Δ34Schalcopyrite-bornite value of 359 °C that is consistent with the stability of this mineral pair. Thus, δ34S values from Campbell Mine are consistent with an igneous source for the sulfur. Based on a simple two-end member isotope mixing model, contamination of the sulfur by sulfur derived from granitic country rocks likely occurred at Artonvilla Mine. Based on findings from this study and by other previous investigators, it is concluded that features displayed by the Musina copper deposits are consistent with a breccia pipe origin for the Musina copper deposits.

  16. Micro-textures and in situ sulfur isotopic analysis of spheroidal and zonal sulfides in the giant Jinding Zn-Pb deposit, Yunnan, China: Implications for biogenic processes

    Science.gov (United States)

    Xue, Chunji; Chi, Guoxiang; Fayek, Mostafa

    2015-05-01

    The Jinding deposit in Yunnan, southwest China, is the largest sandstone- and conglomerate-hosted Zn-Pb deposit in the world. In this paper, we report various micro-textures of spheroidal and zonal sulfides, such as pellet-shaped and colloform aggregates of pyrite and sphalerite, from the deposit and interpret them to be possibly related to micro-colonies of sulfate reducing bacteria, probably supporting an in situ BSR hypothesis. Micro-scale sulfur isotope analysis in different parts of the spheroidal and zonal sulfide aggregates, using secondary ion mass spectrometry (SIMS), revealed δ34S (VCDT) values as low as -48.4‰ for sulfides formed in the early-main stage disseminated ores in the western part of the deposit, possibly suggesting maximum sulfur isotopic fractionation through BSR. Relatively elevated δ34S (VCDT) values (-7.7‰ to -34.8‰, mainly from -10‰ to -20‰) for the late-stage, cavity-filling ores in the eastern part of the deposit, are interpreted to be possibly related to elevated temperatures close to the hydrothermal conduit and elevated δ34S values of the remaining sulfates resulting from the preceding BSR processes. The apparent discrepancy between the low temperatures required for BSR and the high temperatures indicated by fluid inclusions (>120 °C) may be reconciled through invoking episodic influx of ore-forming hydrothermal fluids into a shallow, relatively cool environment. It is proposed that the host rocks of the Jinding deposit have not been buried to great depths (⩽1 km), which, combined with the availability of hydrocarbons in the Jinding dome (a paleo-oil and gas reservoir), provides an ideal environment for BSR. Episodic influx of metal-carrying hydrothermal fluids temporarily and locally suppressed BSR and promoted thermo-chemical sulfate reduction (TSR), resulting in deposit- and micro-scale variations of δ34S.

  17. Systematic sulfur stable isotope and fluid inclusion studies on veinlet groups in the Sarcheshmeh porphyry copper deposit: based on new data

    Directory of Open Access Journals (Sweden)

    Mohammad Maanijou

    2012-10-01

    Full Text Available Mineralization occurred by intrusion of granodioritic stock of middle Miocene in volcano–sedimenrary rocks in Sarcheshmeh of early Tertiary age. This research is based on samples of new drilled boreholes and benches of 2500m elevation. Based on mineralogy and crosscutting relationships, at least four groups of veinlets pertaining to four stages of mineralization were recognized. Sulfur isotope studies in the Sarcheshmeh porphyry copper deposit were conducted on pyrite, chalcopyrite, molybdenite and anhydrites of four groups of veinlets. The δ34S values in the sulfides and sulfates range from -2.2 to 1.27‰ and from 10.2 to 14.5 ‰, respectively. The average δ34S value in the sulfides is 1‰ and that for the sulfates is about 13‰. Considering these results, it can be concluded that the sulfides made up of a fluid that its sulfur has a magmatic origin. Also, fluid inclusions of different veinlet groups were studied, showing high temperature, high salinity and the occurrence of boiling in the mineralizing fluids. Moreover, these studies indicate presence of three types of fluids including magmatic, meteoritic and mixture of these two fluids in alteration and mineralizion processes.

  18. Sulfur and strontium isotope geochemistry of tributary rivers of Lake Biwa: implications for human impact on the decadal change of lake water quality.

    Science.gov (United States)

    Nakano, Takanori; Tayasu, Ichiro; Wada, Eitaro; Igeta, Akitake; Hyodo, Fujio; Miura, Yuuta

    2005-06-01

    To study the deterioration of the water quality in Lake Biwa, Japan, over the last 40 years, we measured the concentrations and isotopic ratios of sulfur and strontium of water in 41 inflowing rivers and one discharging river. The concentrations of SO4 and Sr of inflowing rivers at downstream sites were generally high in the southern urban area and in the eastern area, where a large agricultural plain is situated, but low in the northern and western areas, whose watersheds are mountainous and with low population density. SO4 and Sr concentrations are also lower at upstream sites, which are closer to mountainous areas. Thus, the inflowing river receives large amounts of SO4 and Sr as it flows across the plain, where human activity levels are high. The delta34S or 87Sr/86Sr values of most eastern rivers at downstream sites are lower than those of water in Lake Biwa, and values become more uniform as the proportion of the plain area in the watershed increases. River water in other areas has higher values of delta34S or 87Sr/86Sr than the lake water. This result indicates that the decadal decrease of delta34S and 87Sr/86Sr in the lake water has been caused mainly by the increased flux of SO4 and Sr from rivers in the eastern plain. We assume that in the plain, sulfur, nitrogen, and organic compounds induced by human activities generate sulfuric, nitric, and organic acids in the water, which accelerate the extraction of Sr from bedrocks, leading to the generation of Sr in the river water in the area.

  19. Sulfur and oxygen isotopic study of Paleozoic sediment-hosted Zn-Pb(-Ag-Au-Ba-F) deposits and associated hydrothermal alteration zones in the Nome Complex, Seward Peninsula, Alaska

    Science.gov (United States)

    Shanks, W.C. Pat; Slack, John F.; Till, Alison B.; Thurston, Roland; Gemery-Hill, Pamela

    2014-01-01

    Results of sulfur and oxygen isotope studies of sedimentary exhalative (SEDEX) Zn-Pb(-Ag-Au-Ba-F) deposits hosted in metamorphosed Paleozoic clastic and carbonate rocks of the Nome Complex, Seward Peninsula, Alaska, are consistent with data for similar deposits worldwide. Stable isotopic studies of the Nome Complex are challenging because the rocks have undergone Mesozoic blueschist- and greenschist-facies metamorphism and deformation at temperatures estimated from 390–490 °C. Studies of sulfur and oxygen isotopes in other areas suggest that, in the absence of chemical and mineralogical evidence for metasomatism, the principal effect of metamorphism is re-equilibration between individual minerals at the temperature of metamorphism, which commonly leads to a narrowing of the overall range of isotope values for a suite of rocks, but generally does not significantly modify the average whole rock value for that suite. Sulfur isotope studies of the stratabound and locally stratiform sulfide lenses at the Aurora Creek-Christophosen deposit, which is of possible Late Devonian-early Carboniferous age, show a large range of δ34Ssulfide values from -9.7 to 39.4‰, suggesting multiple sulfur sources and possibly complex processes of sulfide formation that may include bacterial sulfate reduction, thermochemical sulfate reduction, and Rayleigh distillation. Low δ34S values probably represent bacterial sulfide minerals remobilized from the host metasedimentary rocks either during the original seafloor mineralization or are related to a Cretaceous mineralizing event that produced Au-vein and base-metal replacement deposits; the latter process is supported by Pb isotope data. The Wheeler North deposit is similar to Aurora Creek-Christophosen but does not have negative δ34S values. It also probably formed in an euxinic sub-basin.

  20. Sulfur-33 Isotope Tracing of the Hydrodesulfurization Process: Insights into the Reaction Mechanism, Catalyst Characterization and Improvement.

    Science.gov (United States)

    Sushkevich, Vitaly L; Popov, Andrey G; Ivanova, Irina I

    2017-08-28

    The novel approach based on (33) S isotope tracing is proposed for the elucidation of hydrodesulfurization (HDS) mechanisms and characterization of molybdenum sulfide catalysts. The technique involves sulfidation of the catalyst with (33) S-isotope-labeled dihydrogen sulfide, followed by monitoring the fate of the (33) S isotope in the course of the hydrodesulfurization reaction by online mass spectrometry and characterization of the catalyst after the reaction by temperature-programmed oxidation with mass spectrometry (TPO-MS). The results point to different pathways of thiophene transformation over Co or Ni-promoted and unpromoted molybdenum sulfide catalysts, provide information on the role of promoter and give a key for the design of new efficient HDS catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Occurrence and Geological Genesis of Pyrites in Late Paleozoic Coals in North China

    Institute of Scientific and Technical Information of China (English)

    刘大锰; 杨起; 等

    2000-01-01

    The occurrence and geological genesis of pyrites in Late Paleozoic colas of North china have been systematically studied in terms of coal petrology,coal chemistry,elemental geochemistry and sulfur isotope geochemistry.The results suggest that eight types of pyrite,i.e.,framboidal,automorphic graular,oolitic,massive,homogeneous spherical,allotriomorphic,nodular,joint-and fisure-filling pyrintes can be subdivided under the microscope,Four generations of pyrite are also reconized according to the shape,size,coexisting assemblage,spacial distribution relationship with macerals,the contents of sulfur and iron.atomic S/Fe ratios and associated elements in pryites.Sulfur in Late Palozoic colas of North China is of diverse source as evidenced by sulfur isotope variations in the pyrites.The δ34S values of pyrite generated at the early stage ted to be negative,and at the late stage,positive.

  2. Changes in depth-transect redox conditions spanning the end-Permian mass extinction and their impact on the marine extinction: Evidence from biomarkers and sulfur isotopes

    Science.gov (United States)

    Kaiho, Kunio; Oba, Masahiro; Fukuda, Yoshihiko; Ito, Kosuke; Ariyoshi, Shun; Gorjan, Paul; Riu, Yuqing; Takahashi, Satoshi; Chen, Zhong-Qiang; Tong, Jinnan; Yamakita, Satoshi

    2012-08-01

    Changes in redox conditions during the Changhsingian to Griesbachian spanning the end-Permian mass extinction were recently reported based on analyses of organic molecules. We provide more precise organic-molecular data, that detail redox conditions spanning the end-Permian mass extinction at different palaeowater depths in the neritic Palaeotethys (estimated water depths: 10, 40, 100, and 200 m; Bulla, Huangzhishan, Meishan, and Chaohu sections, respectively) during this period. Here we propose that a change from occasional euxinia to anoxia in the shallow Palaeotethys occurred at the time of the mass extinction intercalated with oxic pulses. The second extinction at 0.7 myr after the main extinction was also caused by anoxia. New and published sulfur-isotope ratios (34S/32S) measured in carbonate-associated sulfate from the neritic Palaeotethys and in sulfide from pelagic central Panthalassa sediments show high values during the Changhsingian, consistent with the development of euxinia. The mass extinction coincided with a global fall in δ34S values, as well as a shift in δ13C values, indicating a global oxidation of H2S. This organic and isotopic geochemistry implies that accumulation of hydrogen sulfide in intermediate and deep waters followed by oxidation of hydrogen sulfide led to dissolved oxygen consumption, surface-water anoxia, and acidification, resulting in the end-Permian mass extinction in the seas.

  3. Coincident negative shifts in sulfur and carbon isotope compositions prior to the end-Permian mass extinction at Shangsi Section of Guangyuan, South China

    Institute of Scientific and Technical Information of China (English)

    Pengwei LI; Junhua HUANG; Min CHEN; Xiao BAI

    2009-01-01

    Sulfur isotope composition of carbonate-associated sulfate (δ3 434SCAS) and carbon isotope composition of carbonate (δ13Ccarb) were jointly investigated on the Late Permian rocks at Shangsi Section, Guanyuan, Northeast Sichuan, South China. Both δ3 4SCAS and δ13Ccarb show gradual decline trends in Late Permian strata, inferring the occurrence of the long-term variation of marine environmental conditions. Associated with the long-term variation are the two coincident negative shifts in δ3 4SCAS and δ13Ccarb, with one occurring at the boundary between Middle Permian Maokou Formation and Late Permian Wujiaping Formation and another at Middle Dalong Formation. Of significance is the second shift which clearly predates the regression and the biotic crisis at the end of Permian at Shangsi Section, providing evidence that a catastrophic event occurred prior to the biotic crisis. The frequent volcanisms indicated by the volcanic rocks or fragments, and the upwelling are proposed to cause the second negative excursion. An abrupt extreme negative δ3 4 SCAS (ca.-20‰) associated with a low relative concentration of CAS and total organic carbon without large change in δ13Ccarb is found at the end of the second shift, which might arise from the short-term oxygenation of bottom waters and sediments that resulted from the abrupt sea level drop.

  4. Appalachian basin bituminous coal: sulfur content and potential sulfur dioxide emissions of coal mined for electrical power generation: Chapter G.5 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

    Science.gov (United States)

    Trippi, Michael H.; Ruppert, Leslie F.; Attanasi, E.D.; Milici, Robert C.; Freeman, P.A.

    2014-01-01

    Data from 157 counties in the Appalachian basin of average sulfur content of coal mined for electrical power generation from 1983 through 2005 show a general decrease in the number of counties where coal mining has occurred and a decrease in the number of counties where higher sulfur coals (>2 percent sulfur) were mined. Calculated potential SO2 emissions (assuming no post-combustion SO2 removal) show a corresponding decrease over the same period of time.

  5. Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological, chemical and isotopic approach

    Science.gov (United States)

    Myron J. Mitchell; Scott W. Bailey; James B. Shanley; Bernhard. Mayer

    2008-01-01

    Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north-eastern USA. Chemical, isotopic and hydrological responses...

  6. Oxygen and sulfur isotopes in sulfate in modern euxinic systems with implications for evaluating the extent of euxinia in ancient oceans

    Science.gov (United States)

    Gomes, M. L.; Johnston, D. T.

    2015-12-01

    Variability in the fraction of biogenic sulfide that is reoxidized back to sulfate has played a role in regulating redox budgets and oxygen levels in the ocean-atmosphere system throughout Earth history. In the modern, well-oxygenated ocean, 75-90% of sulfide produced by microbial sulfate reduction is reoxidized back to sulfate. At present, the areal extent of seafloor overlain by euxinic (i.e., anoxic and sulfidic) water is very low (ancient oceans. In theory, the presence of sulfide in the water column could induce higher reoxidation rates, as the delivery of oxidants is less transport limited in solution than when the chemocline is in sediments. In order to better understand these sorts of systematics and place isotopic constraints on this cycling, we present sulfur and oxygen isotope geochemistry in four modern euxinic systems. To interpret these data, we further develop a one-dimensional, depth-dependent geochemical model to estimate sulfide reoxidation rates in euxinic systems and evaluate model results in the context of geochemical and isotopic information. From these results, we determine that the percent of sulfide that is reoxidized back to sulfate is quite low (~11-42%). Given the proximity to overlying, fully oxygenated waters, this suggests that vertical exchange is significantly muted. This is in some sense surprising, but also consistent with the observation that sulfide is indeed allowed to accumulate in the bottom waters. We explore how water column density stratification and lateral transport influence reoxidation rates in these coastal ponds. We further pursue how these results can be extrapolated to the global ocean of times past.

  7. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20102524 Chen Junming(Graduate School of Chinese Academy of Sciences,Beijing 100049,China);Zhao Ping Modeling the East Asian Climate during the Late Cretaceous(80 Ma)(Earth Science Frontiers,ISSN1005-2321,CN11-3370/P,16(6),2009,p.226-239,8 illus.,1 table,40 refs.)Key words:Upper Cretaceous,paleoclimate,Eastern AsiaIn this paper,the East Asian climate during the Late Cretaceous(80 Ma)is examined by using the Community Climate System Model Version 2(CCSM2)from the National Center for Atmospheric Research(NCAR)a

  8. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20112525Fan Qishun (Key Laboratory ofSalt Lake Resource and Chemistry,Qinghai Institute of Salt Lakes,Chinese Academy of Sciences, Xining 810008, China); Lai Zhongping Luminescence Chronology of High Lake

  9. GEOCHRONOMETRY & ISOTOPE GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>20082540 Ding Ping(Guangzhou Institute of Geochemistry,Chinese Academy of Sciences, Guangzhou 510640,China);Shen Chengde 14C Chronological Research of Ancient Forest Cosystem in Sihui,Guangdong Province (Quaternary Sciences,ISSN 1001—7410,CN 11—2708/P,27(4),2007,p.492—498,7 illus.,3 tables,23 refs.) Key words:radiocarbon dating,Guang- dong Province

  10. The fate of nitrogen and sulfur in hard-rock aquifers as shown by sulfate-isotope tracing

    Energy Technology Data Exchange (ETDEWEB)

    Pauwels, Helene, E-mail: h.pauwels@brgm.fr [BRGM, Water Division, BP 36009, 45060 Orleans Cedex 2 (France); Ayraud-Vergnaud, Virginie [BRGM, Water Division, BP 36009, 45060 Orleans Cedex 2 (France)] [CAREN-Geosciences, UMR 6118, Universite Rennes 1-CNRS, Rennes (France); Aquilina, Luc [CAREN-Geosciences, UMR 6118, Universite Rennes 1-CNRS, Rennes (France); Molenat, Jerome [CAREN-UMR INRA-Agrocampus Sol Agronomie Spatialisation, Rennes (France)] [IRD-Laboratoire d' etude des Interactions Sol-Agrosystemes-Hydrosystemes, UMR INRA-IRD-Supagro, Montpellier (France)

    2010-01-15

    Stable SO{sub 4} isotopes ({delta}{sup 34}S{sub -SO4} and {delta}{sup 18}O{sub -SO4}), and more occasionally {delta}{sup 15}N{sub -NO3} were studied in groundwater from seven hard-rock aquifer catchments. The sites are located in Brittany (France) and all are characterized by intensive agricultural activity. The purpose of the study was to investigate the potential use of these isotopes for highlighting the fate of both SO{sub 4} and NO{sub 3} in the different aquifer compartments. Nitrate-contaminated groundwater occurs in the regolith; {delta}{sup 34}S fingerprints the origin of SO{sub 4}, such as atmospheric deposition and fertilizers, and {delta}{sup 18}O{sub -SO4} provides evidence of the cycling of S within soil. The correlation between the {delta}{sup 18}O{sub -SO4} of sulfates and the {delta}{sup 15}N{sub -NO3} of nitrates suggests that S and N were both cycled in soil before being leached to groundwater. Autotrophic and heterotrophic denitrification was noted in fissured aquifers and in wetlands, respectively, the two processes being distinguished on the basis of stable SO{sub 4} isotopes. During autotrophic denitrification, both {delta}{sup 34}S{sub -SO4} and {delta}{sup 18}O{sub -SO4} decrease due to the oxidation of pyrite and the incorporation of O from the NO{sub 3} molecule in the newly formed SO{sub 4}. Within wetlands, fractionation occurs of O isotopes on SO{sub 4} in favour of lighter isotopes, probably through reductive assimilation processes. Fractionation of S isotopes is negligible as the redox conditions are not sufficiently reductive for dissimilatory reduction. {delta}{sup 34}S{sub -SO4} and {delta}{sup 18}O{sub -SO4} data fingerprint the presence of a NO{sub 3}-free brackish groundwater in the deepest parts of the aquifer. Through mixing with present-day denitrified groundwater, this brackish groundwater can contribute to significantly increase the salinity of pumped water from the fissured aquifer.

  11. Precambrian ophiolites of arabia: geologic settings, UPb geochronology, Pb-isotope characteristics, and implications for continental accretion

    Science.gov (United States)

    Pallister, J.S.; Stacey, J.S.; Fischer, L.B.; Premo, W.R.

    1988-01-01

    Disrupted ophiolites occur in linear belts up to 900 km long between microplates that collided during the late Proterozoic to form the Arabian Shield. UPb zircon ages and Pb-isotope data from these ophiolitic rocks help constrain the history of accretion of the Arabian Shield and thereby contribute to the definition of its microplates and terranes. Terranes of the central and western Arabian Shield are generally thought to represent intraoceanic island arcs that range in age from about 900 to 640 Ma; however, a region of the eastern Arabian Shield contains rocks of Early Proterozoic age and may represent an exotic continental fragment entrained between the arc complexes. Ophiolites of the Yanbu suture (northwestern shield), dated by UPb (zircon) and SmNd (mineral isochron) methods, yield model ages of 740-780 Ma. These are among the oldest well-dated rocks in the northwestern Arabian Shield. Ages from the Jabal al Wask complex overlap with ages of adjacent arc rocks. This overlap in age supports geologic and geochemical evidence that the Wask complex represents a fragment of back-arc oceanic lithosphere formed during arc magmatism. Older ages of about 780 Ma for gabbro from the Jabal Ess ophiolite suggest that the ophiolite is either a fragment of fore-arc oceanic crust or oceanic basement on which an arc was built. Gabbro samples from ophiolites of the Bir Umq suture (west-central Arabian Shield) yield zircons with ages of 820-870 Ma and $ ??1250 Ma. The 820-870 Ma dates overlap with ages of the oldest nearby arc rocks; this favors an intra-arc or near-arc paleotectonic setting. The older zircons suggest that middle or early Proterozoic crustal material, possibly derived from the Mozambique belt of Africa, was present during back- or intra-arc magmatism. Plagiogranite from the Bir Tuluhah ophiolitic complex at the nothern end of the 900 km-long Nabitah mobile belt was dated by the zircon UPb method at ??? 830 Ma. This date is in the range of the oldest dated arc

  12. Tracing oxygen variations and its biogeochemical expression during the late hauterivian Faraoni Event: A multi tracers approach using paired carbon, nitrogen, sulfur isotopes and trace metallic elements

    Science.gov (United States)

    Thomazo, Christophe; Riquier, Laurent; Martinez, Mathieu; Mathieu, Olivier

    2013-04-01

    During the Cretaceous, several occurrences of Oceanic Anoxic Event (OAE) are described in the sedimentary record. Among them, the late Hauterivian Faraoni Event has been extensively studied in several locations including Italy, Switzerland, France and Spain and interpreted as a short-lived OAE from palaeontological, sedimentological and geochemical observations. However, the biogeochemical response to water column oxygen depletion is poorly documented and mostly stands on carbon carbonates isotopes during the Faraoni event. In order to bring further insights into the biogeochemical cycles modifications during O2 variations across the Faraoni Event, we performed an integrated geochemical study including C, N and S isotopes together with paleo-redox tracers (i.e. trace metallic elements and iron speciation) on about 25 samples from the Río Argos section (S.E. Spain). δ13Ccarb increases from 1.23‰ to 1.61‰ at the base of the studied section before the Faraoni event. Maximum values, ranging between 1.21‰ and 1.73‰, are observed within this event and are followed by a rapid decrease in δ13Ccarb values down to 0.50‰ toward the top of the section. δ13Corg and TOC values show a narrow range of variations around -26.3±0.3‰ and 0.15±0.3 wt.%, respectively. Only one sample records a higher TOC content up to 1.53 wt.% at the very base of the Faraoni Event while no sensible variations can be deduced form organic carbon isotopes. Bulk sediments nitrogen isotopes have a mean value of 2.3±0.2‰ and nitrogen contents vary between 320 and 790 ppm. A noticeable δ15N excursion (i.e. 0.86‰) is observed at the very base of the Faraoni Event and is associated with the highest TOC value. Sulfur contents vary between 100 and 2480 ppm, the highest content being recorded just bellow the base of the Faraoni Event. δ34S show a wide range of variations from -44.8 to -10.1‰ on a short scale without easily recognizable stratigraphic trend. Finally, slight increases of

  13. Ni biogeochemical cycle through geological time: insights from Ni isotope variations in modern and ancient marine metallifereous deposits

    Science.gov (United States)

    Gueguen, B.; Rouxel, O.; Ponzevera, E.; Sorensen, J. V.; Toner, B.; Bekker, A.

    2011-12-01

    Studies of isotopic composition of transition metals such as Fe, Cu, Zn, and Mo as biogeochemical tracers became popular recently. Since Ni is ubiquitous in marine metallifereous deposits and its concentration in water column is coupled to that of nutrients, it has a potential as a biogeochemical tracer. Isotopic analyses were performed on a Neptune MC-ICP-MS using a double-spike correction method for instrumental mass bias. Deep-sea ferromanganese crusts have been used to establish a record of seawater over the last 60 Myr. Our results show that Fe-Mn crusts from both Atlantic and Pacific oceans are systematically enriched in heavy isotopes relative to Bulk Silicate Earth with δ60/58Ni values ranging from 0.30 to 1.80% (2se = 0.04%). In contrast, Iron Formations (IF) with ages ranging from 3.8 to 0.7 Gyr display a wider range of values with a striking negative Ni isotope excursion down to -2.46% (2se = 0.03%) in Neoproterozoic IF. Although correlation between Ni isotope compositions, Ni concentrations and BIFs ages seems to be lacking, several Ni isotope excursions to either positive or negative Ni isotope values are notable prior to 2.4 Gyr. Methanogens were likely abundant in Precambrian water column until they retreated to pore waters and local environments once the oceans were oxygenated after the Great Oxidation Event (GOE). They preferentially uptake light Ni isotopes leaving isotopically heavier Ni in oceans. Our Ni isotope record of Precambrian IF does not show a unidirectional change across the GOE implying that Ni isotope composition of the Archean oceans was not dominated by this metabolism. Preliminary Ni adsorption experiments on Fe-Mn oxy-hydroxides show a maximum fractionation factor between the mineral phase and aqueous solution of -1.00% (2se = 0.03%). Hence, isotopic variations in Fe-Mn crusts and IF cannot be simply explained by adsorption processes, but require changes in composition of either Ni sources (local or global) to seawater (e

  14. Geology, mineralization, U-Pb dating and Sr-Nd isotope geochemistry of intrusive bodies in northeast of Kashmar

    Directory of Open Access Journals (Sweden)

    Alireza Almasi

    2015-04-01

    Full Text Available Alireza Almasi1, Mohammad Hassan Karimpour1*, Khosrow Ebrahimi Nasrabadi1, Behnam Rahimi1, Urs KlÖtzli2 and Jose Francisco Santos3 Introduction The study area is located in central part of the Khaf- Kashmar-Bardeskan belt which is volcano-plutonic belt at the north of the Dorouneh fault in the north of Lut block. The north of the Lut block is affected by tectonic rotation and subduction processes which occur in the east of Iran (Tirrul et al., 1983. The magmatism of Lut block begins in Jurassic and continues in Tertiary (Aghanabati, 1995. Karimpour (Karimpour, 2006 pointed out the Khaf-Kashmar-Bardeskan belt has significant potential for IOCG type mineralization such as Kuh-e-Zar, Tannurjeh, and Sangan (Karimpour, 2006; Mazloumi, 2009. The data gathered on the I-type intrusive rocks include their field geology, petrography, U–Pb zircon dating and Sr–Nd isotope and also alteration and mineralization in the study area. Materials and methods - Preparation of 150 thin sections of rock samples for study of petrography and alteration of the intrusive rocks. - Magnetic susceptibility measuring of intrusive rocks. - U-Pb dating in zircon of I-type intrusive rocks by Laser-Ablation Multi Collector ICP-MS method. - Sr-Nd analysis on 5 samples of I-type intrusive rocks by Multi-Collector Thermal Ionization Mass Spectrometer (TIMS VG Sector 54 instrument. - Mineralography and paragenetic studies of ore-bearing quartz veins and geochemical analysis for 28 samples. - Production of the geology, alteration and mineralization maps by scale: 1:20000 in GIS. Results Oblique subduction in southern America initiated an arc-parallel fault and shear zones in the back of continental magmatic arc (Sillitoe, 2003. Because of this event, pull-apart basins were formed and high-K to shoshonitic calc-alkalineI- and A-type magmatism occur (Sillitoe, 2003. Most important deposits accompany with this magmatism are Au-Cu deposits types and Fe-Skarns (Sillitoe, 2003. We have

  15. Autotrophy of green non-sulphur bacteria in hot spring microbial mats: biological explanations for isotopically heavy organic carbon in the geological record.

    Science.gov (United States)

    van der Meer, M T; Schouten, S; de Leeuw, J W; Ward, D M

    2000-08-01

    Inferences about the evidence of life recorded in organic compounds within the Earth's ancient rocks have depended on 13C contents low enough to be characteristic of biological debris produced by the well-known CO2 fixation pathway, the Calvin cycle. 'Atypically' high values have been attributed to isotopic alteration of sedimentary organic carbon by thermal metamorphism. We examined the possibility that organic carbon characterized by a relatively high 13C content could have arisen biologically from recently discovered autotrophic pathways. We focused on the green non-sulphur bacterium Chloroflexus aurantiacus that uses the 3-hydroxypropionate pathway for inorganic carbon fixation and is geologically significant as it forms modern mat communities analogous to stromatolites. Organic matter in mats constructed by Chloroflexus spp. alone had relatively high 13C contents (-14.9%) and lipids diagnostic of Chloroflexus that were also isotopically heavy (-8.9% to -18.5%). Organic matter in mats constructed by Chloroflexus in conjunction with cyanobacteria had a more typical Calvin cycle signature (-23.5%). However, lipids diagnostic of Chloroflexus were isotopically enriched (-15.1% to -24.1%) relative to lipids typical of cyanobacteria (-33.9% to -36.3%). This suggests that, in mats formed by both cyanobacteria and Chloroflexus, autotrophy must have a greater effect on Chloroflexus carbon metabolism than the photoheterotrophic consumption of cyanobacterial photosynthate. Chloroflexus cell components were also selectively preserved. Hence, Chloroflexus autotrophy and selective preservation of its products constitute one purely biological mechanism by which isotopically heavy organic carbon could have been introduced into important Precambrian geological features.

  16. Geological evolution of the marine selenium cycle: Insights from the bulk shale δ82/76Se record and isotope mass balance modeling

    Science.gov (United States)

    Mitchell, Kristen; Mansoor, Sannan Z.; Mason, Paul R. D.; Johnson, Thomas M.; Van Cappellen, Philippe

    2016-05-01

    Bulk δ82/76Se values of representative marine shales from the Paleoarchean to the present day vary between approximately -3 and + 3 ‰ with only local deviations beyond this range. This muted Se isotope variability in the shale record contrasts with the relatively large fractionations associated with abiotic and microbial Se oxyanion reduction seen in experimental studies. Long-term temporal trends in the bulk shale data do not directly correlate with changes in redox conditions of the global ocean, although a minor but significant shift towards more negative formation-averaged δ82/76Se values appears to track oxygenation of the deep ocean at the end of the Proterozoic. We hypothesize that extensive δ82/76Se variability in the shale data was suppressed due to the early emergence of biological assimilatory uptake and the resulting persistence of low seawater Se concentrations, coupled with small authigenic Se outputs throughout most of geological time. In the modern ocean, Se is an essential micronutrient with a relatively short residence time of about 11,500 yrs. The marine Se cycle is dominated by assimilation into biomass and subsequent recycling in the water column and surface sediments, i.e. processes that result in only minimal isotopic fractionation. We suggest that similar processes dominated back through the geological record to Archean times. Our model shows that paleoceanographic information could in principle be extracted from proxy data on the Se isotopic composition of seawater, once isotopic differences can be readily discerned between individual sedimentary Se pools.

  17. Negligible sulfur isotope fractionation during partial melting: Evidence from Garrett transform fault basalts, implications for the late-veneer and the hadean matte

    Science.gov (United States)

    Labidi, J.; Cartigny, P.

    2016-10-01

    We report the quadruple sulfur isotope compositions, sulfur contents and speciation major and trace elements (including copper and chlorine abundances) of eleven basalts collected in the Garrett transform fault. We combine these data to discuss the absence of S isotopic fractionation along both partial melting and low-pressure fractional crystallization. The variations of K2O/TiO2 and La/SmN-ratios (respectively between 0.017 and 0.067, and between 0.31 and 0.59) suggest a range of depletion in Garrett lavas that includes ultra depleted samples (K2O/TiO2 8%) are ∼80 ppm, indistinguishable from MORBs. This requires their mantle sources, variably depleted in incompatible element, to host residual sulfide buffering the Cu content of all erupted melts. We calculate a minimum S content for the source of ultra-depleted Garrett lavas of 100 ± 40ppmS, i.e. roughly a factor of 2 below the MORB mantle source. After exclusion of a single sample with Cl/K ratio >0.1 that likely experienced hydrothermal sulfide assimilation, Garrett ITLs display homogeneous δ34 S, Δ33 S and Δ36 S values with averages of - 0.68 ± 0.08 ‰, + 0.010 ± 0.005 ‰ and - 0.04 ± 0.04 ‰, respectively (all 1σ, n = 10). The δ34 S values display no relationship with either K2O/TiO2 variations or extent sulfide fractionation. From these observations, we derive a 34S/32S fractionation factor between exsolved sulfides and sulfide dissolved in silicate melts of 1.0000 ± 0.0003. The S isotopic fractionation during partial melting can thus be considered as negligible, and both MORBs and ITLs record the 34S/32S ratio of their mantle source. The concept of sulfide melts segregating from the mantle, sinking and being added to the core during planetary differentiation was termed the 'Hadean Matte'. The segregation of sulfides from the mantle to the core during planetary differentiation could account for various geochemical features of the Earth's mantle. Based on S isotopic mass balance, we derive a

  18. Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

    Science.gov (United States)

    Franz, H. B.; Mahaffy, P. R.; Stern, J. C.; Eigenbrode, J. L.; Steele, A.; Ming, D. W.; McAdam, A. C.; Freissinet, C.; Glavin, D. P.; Archer, P. D.; Brunner, A. E.; Grotzinger,J. P.; Jones, J. H.; Leshin, L. A.; Miller, K.; Morris, R. V.; Navarro-Gonzalez, R.; Niles, P. B.; Owen, T. C.; Summons, R. E.; Sutter, B.; Webster, C. R.

    2014-01-01

    Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

  19. Carbon and oxygen isotope analysis of leaf biomass reveals contrasting photosynthetic responses to elevated CO2 near geologic vents in Yellowstone National Park

    Directory of Open Access Journals (Sweden)

    S. Sharma

    2008-09-01

    Full Text Available In this study we explore the use of natural CO2 emissions in Yellowstone National Park (YNP in Wyoming, USA to study responses of natural vegetation to elevated CO2 levels. Radiocarbon (14C analysis of leaf biomass from a conifer (Pinus contortus; lodgepole pine and an invasive, non-native herb (Linaria dalmatica; Dalmation toadflax was used to trace the inputs of vent CO2 and quantify assimilation-weighted CO2 concentrations experienced by individual plants near vents and in comparable locations with no geologic CO2 exposure. The carbon and oxygen isotopic composition and nitrogen percent of leaf biomass from the same plants was used to investigate photosynthetic responses of these plants to naturally elevated atmospheric CO2 concentrations. The coupled shifts in carbon and oxygen isotope values suggest that dalmation toadflax responded to elevated CO2 exposure by increasing stomatal conductance with no change in photosynthetic capacity and lodgepole pine apparently responded by decreasing stomatal conductance and photosynthetic capacity. Lodgepole pine saplings exposed to elevated levels of CO2 likewise had reduced leaf nitrogen concentrations compared to plants with no enhanced CO2 exposure, further suggesting that this widespread and dominant conifer down-regulated photosynthetic capacity under elevated CO2 levels near geologic vents.

  20. Carbon and oxygen isotope analysis of leaf biomass reveals contrasting photosynthetic responses to elevated CO2 near geologic vents in Yellowstone National Park

    Directory of Open Access Journals (Sweden)

    D. G. Williams

    2009-01-01

    Full Text Available In this study we explore the use of natural CO2 emissions in Yellowstone National Park (YNP in Wyoming, USA to study responses of natural vegetation to elevated CO2 levels. Radiocarbon (14C analysis of leaf biomass from a conifer (Pinus contortus; lodgepole pine and an invasive, non-native herb (Linaria dalmatica; Dalmation toadflax was used to trace the inputs of vent CO2 and quantify assimilation-weighted CO2 concentrations experienced by individual plants near vents and in comparable locations with no geologic CO2 exposure. The carbon and oxygen isotopic composition and nitrogen percent of leaf biomass from the same plants was used to investigate photosynthetic responses of these plants to naturally elevated atmospheric CO2 concentrations. The coupled shifts in carbon and oxygen isotope values suggest that dalmation toadflax responded to elevated CO2 exposure by increasing stomatal conductance with no change in photosynthetic capacity and lodgepole pine apparently responded by decreasing stomatal conductance and photosynthetic capacity. Lodgepole pine saplings exposed to elevated levels of CO2 likewise had reduced leaf nitrogen concentrations compared to plants with no enhanced CO2 exposure, further suggesting widespread and dominant conifer down-regulated photosynthetic capacity under elevated CO2 levels near geologic vents.

  1. Using a laser-based CO2 carbon isotope analyser to investigate gas transfer in geological media

    Science.gov (United States)

    Guillon, S.; Pili, E.; Agrinier, P.

    2012-05-01

    CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based CO2 carbon isotope analysis provides continuous measurement at high temporal resolution and is a promising alternative to isotope ratio mass spectrometry (IRMS). We performed a thorough assessment of a commercially available CO2 Carbon Isotope Analyser (CCIA DLT-100, Los Gatos Research) that allows in situ measurement of δ 13C in CO2. Using a set of reference gases of known CO2 concentration and carbon isotopic composition, we evaluated the precision, long-term stability, temperature sensitivity and concentration dependence of the analyser. Despite good precision calculated from Allan variance (5.0 ppm for CO2 concentration, and 0.05 ‰ for δ 13C at 60 s averaging), real performances are altered by two main sources of error: temperature sensitivity and dependence of δ 13C on CO2 concentration. Data processing is required to correct for these errors. Following application of these corrections, we achieve an accuracy of 8.7 ppm for CO2 concentration and 1.3 ‰ for δ 13C, which is worse compared to mass spectrometry performance, but still allowing field applications. With this portable analyser we measured CO2 flux degassed from rock in an underground tunnel. The obtained carbon isotopic composition agrees with IRMS measurement, and can be used to identify the carbon source.

  2. Petrographic and isotopic evidence for late-stage processes in sulfuric acid caves of the Guadalupe Mountains, New Mexico, USA

    Directory of Open Access Journals (Sweden)

    Palmer Arthur N.

    2012-07-01

    Full Text Available Caves of the Guadalupe Mountains have experienced many modifications since their final phase of sulfuric acid speleogenesis several million years ago. Petrographic and geochemical data reveal details of the change from H2SO4 to CO2-dominated reactions. The H2SO4 dissolution front acquired a coating of replacement gypsum with local pockets of anhydrite and by-products of altered clay, including Fe-Mn oxides. Alteration of bedrock beneath the gypsum produced a white micritized rind with small negative shifts in δ13C and δ18O. Solution basins contain records of the earliest post-speleogenetic processes: corroded bedrock, residual anhydrite, Fe-Mn oxides from fluctuating pH and Eh, mammillary calcite, and dolomitization. Later meteoric water removed or recrystallized much of the gypsum and early micrite, and replaced some gypsum with calcite. Mammillary crusts demonstrate fluctuating groundwater, with calcite layers interrupted by films of Fe-Mn oxides precipitated during periodic inflow of anoxic water. Condensation moisture (from local evaporation absorbs CO2 from cave air, corroding earlier features and lowering their δ13C and δ18O. Drips of condensation water deposit minerals mainly by evaporation, which increases δ18O in the speleothems while δ13C remains nearly constant. By forcing calcite precipitation, evaporation raises the Mg content of remaining water and subsequent precipitates. Dolomite (both primary and replacive is abundant. In areas of low air circulation, water on and within carbonate speleothems equilibrates with cave-air CO2, causing minerals to recrystallize with glassy textures. Fluorite on young evaporative speleothems suggests a recent release of deep-source HF gas and absorption by droplets of condensation water.

  3. A strategy for fast screening and identification of sulfur derivatives in medicinal Pueraria species based on the fine isotopic pattern filtering method using ultra-high-resolution mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Min [National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China); Zhou, Zhe [ThermoFisher Scientific China Co., Ltd, No 6 Building, 27 Xinjinqiao Road, Shanghai 201206 (China); Guo, De-an, E-mail: daguo@simm.ac.cn [National Engineering Laboratory for TCM Standardization Technology, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 501 Haike Road, Shanghai 201203 (China)

    2015-09-24

    Sulfurous compounds are commonly present in plants, fungi, and animals. Most of them were reported to possess various bioactivities. Isotopic pattern filter (IPF) is a powerful tool for screening compounds with distinct isotope pattern. Over the past decades, the IPF was used mainly to study Cl- and Br-containing compounds. To our knowledge, the algorithm was scarcely used to screen S-containing compounds, especially when combined with chromatography analyses, because the {sup 34}S isotopic ion is drastically affected by {sup 13}C{sub 2} and {sup 18}O. Thus, we present a new method for a fine isotopic pattern filter (FIPF) based on the separated M + 2 ions ({sup 12}C{sub x}{sup 1}H{sub y}{sup 16}O{sub z}{sup 32}S{sup 13}C{sub 2}{sup 18}O, {sup 12}C{sub x+2}{sup 1}H{sub y}{sup 16}O{sub z+1}{sup 34}S, tentatively named M + 2OC and M + 2S) with an ultra-high-resolution mass (100,000 FWHM @ 400 m/z) to screen sulfur derivatives in traditional Chinese medicines (TCM).This finer algorithm operates through convenient filters, including an accurate mass shift of M + 2OC and M + 2S from M and their relative intensity compared to M. The method was validated at various mass resolutions, mass accuracies, and screening thresholds of flexible elemental compositions. Using the established FIPF method, twelve S-derivatives were found in the popular medicinal used Pueraria species, and 9 of them were tentatively identified by high-resolution multiple stage mass spectrometry (HRMS{sup n}). The compounds were used to evaluate the sulfurous compounds' situation in commercially purchased Pueraria products. The strategy presented here provides a promising application of the IPF method in a new field. - Highlights: • We provide a new strategy for specifically screening of sulfurous compounds. • The fine isotopic pattern filter (FIPF) bases on separation of {sup 13}C{sub 2}+{sup 18}O and {sup 34}S. • Ultra high resolution mass (100,000 FWHM @ 400 m/z) is essential

  4. Boron isotope determinations in waters and other geological materials: analytical techniques and inter-calibration of measurements.

    Science.gov (United States)

    Tonarini, Sonia; Pennisi, Maddalena; Gonfiantini, Roberto

    2009-06-01

    The (11)B/(10)B ratio exhibits wide variations in nature; thus, boron isotopes have found numerous applications in geochemistry, hydrology, and environmental studies. The main analytical techniques used are as follows: positive thermal ionisation mass spectrometry is the most precise (about 0.2 per thousand of the boron isotope ratio), but requires complex and laborious sample preparation; negative thermal ionisation mass spectrometry is less precise (about 0.5 per thousand), but rapid and suitable for water samples, whereas total evaporation-NTIMS allows for identification of the precise boron isotope composition of marine carbonates. It is expected that multi-collection system inductively coupled plasma mass spectrometry (MC-ICPMS) will eventually combine high precision with simple analytical procedures. Secondary ion mass spectrometry and laser ablation (LA)-MC-ICPMS allow in situ determinations on solid samples, but require the availability of calibration materials which are chemically and mineralogically similar to samples. These features of boron isotope measurement techniques were confirmed by the results of the first inter-laboratory comparison of measurements, organised by the Istituto di Geoscienze e Georisorse in Pisa. Finally, two examples of boron isotope applications in groundwater investigations are reported.

  5. Role of evaporitic sulfates in iron skarn mineralization: a fluid inclusion and sulfur isotope study from the Xishimen deposit, Handan-Xingtai district, North China Craton

    Science.gov (United States)

    Wen, Guang; Bi, Shi-Jian; Li, Jian-Wei

    2017-04-01

    The Xishimen iron skarn deposit in the Handan-Xingtai district, North China Craton, contains 256 Mt @ 43 % Fe (up to 65 %). The mineralization is dominated by massive magnetite ore along the contact zone between the early Cretaceous Xishimen diorite stock and middle Ordovician dolomite and dolomitic limestones with numerous intercalations of evaporitic beds. Minor lenticular magnetite-dominated bodies also occur in the carbonate rocks proximal to the diorite stock. Hydrothermal alteration is characterized by extensive albitization within the diorite stock and extreme development of magnesian skarn along the contact zone consisting of diopside, forsterite, serpentine, tremolite, phlogopite, and talc. Magmatic quartz and amphibole from the diorite and hydrothermal diopside from the skarns contain abundant primary or pseudosecondary fluid inclusions, most of which have multiple daughter minerals dominated by halite, sylvite, and opaque phases. Scanning electron microscopy (SEM) and laser Raman spectrometry confirm that pyrrhotite is the predominant opaque phase in most fluid inclusions, in both the magmatic and skarn minerals. These fluid inclusions have total homogenization temperatures of 416-620 °C and calculated salinities of 42.4-74.5 wt% NaCl equiv. The fluid inclusion data thus document a high-temperature, high-salinity, ferrous iron-rich, reducing fluid exsolved from a cooling magma likely represented by the Xishimen diorite stock. Pyrite from the iron ore has δ34S values ranging from 14.0 to 18.6 ‰, which are significantly higher than typical magmatic values (δ34S = 0 ± 5 ‰). The sulfur isotope data thus indicate an external source for the sulfur, most likely from the evaporitic beds in the Ordovician carbonate sequences that have δ34S values of 24 to 29 ‰. We suggest that sulfates from the evaporitic beds have played a critically important role by oxidizing ferrous iron in the magmatic-hydrothermal fluid, leading to precipitation of massive

  6. Role of evaporitic sulfates in iron skarn mineralization: a fluid inclusion and sulfur isotope study from the Xishimen deposit, Handan-Xingtai district, North China Craton

    Science.gov (United States)

    Wen, Guang; Bi, Shi-Jian; Li, Jian-Wei

    2016-08-01

    The Xishimen iron skarn deposit in the Handan-Xingtai district, North China Craton, contains 256 Mt @ 43 % Fe (up to 65 %). The mineralization is dominated by massive magnetite ore along the contact zone between the early Cretaceous Xishimen diorite stock and middle Ordovician dolomite and dolomitic limestones with numerous intercalations of evaporitic beds. Minor lenticular magnetite-dominated bodies also occur in the carbonate rocks proximal to the diorite stock. Hydrothermal alteration is characterized by extensive albitization within the diorite stock and extreme development of magnesian skarn along the contact zone consisting of diopside, forsterite, serpentine, tremolite, phlogopite, and talc. Magmatic quartz and amphibole from the diorite and hydrothermal diopside from the skarns contain abundant primary or pseudosecondary fluid inclusions, most of which have multiple daughter minerals dominated by halite, sylvite, and opaque phases. Scanning electron microscopy (SEM) and laser Raman spectrometry confirm that pyrrhotite is the predominant opaque phase in most fluid inclusions, in both the magmatic and skarn minerals. These fluid inclusions have total homogenization temperatures of 416-620 °C and calculated salinities of 42.4-74.5 wt% NaCl equiv. The fluid inclusion data thus document a high-temperature, high-salinity, ferrous iron-rich, reducing fluid exsolved from a cooling magma likely represented by the Xishimen diorite stock. Pyrite from the iron ore has δ34S values ranging from 14.0 to 18.6 ‰, which are significantly higher than typical magmatic values (δ34S = 0 ± 5 ‰). The sulfur isotope data thus indicate an external source for the sulfur, most likely from the evaporitic beds in the Ordovician carbonate sequences that have δ34S values of 24 to 29 ‰. We suggest that sulfates from the evaporitic beds have played a critically important role by oxidizing ferrous iron in the magmatic-hydrothermal fluid, leading to precipitation of massive

  7. Isotope tracer studies of diffusion in silicates and of geological transport processes using actinide elements. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Wasserburg, G.J.

    1992-12-31

    The following are reported: high abundance sensitivity mass spectrometer for U-Th studies; {sup 238}U-{sup 230}Th disequilibrium in recent lavas from Iceland; water-rock interaction from U-Th studies; resonance ionization mass spectrometry of Os and Ti isotopes; and self-diffusion of Mg.

  8. Carbon isotope alteration during the thermal maturation of non-flowering plant species representative of those found within the geological record.

    Science.gov (United States)

    Smith, Andrew C; Kendrick, Christopher P; Moss-Hayes, Vicky L; Vane, Christopher H; Leng, Melanie J

    2017-01-15

    The carbon isotope (δ(13) C value) composition of fossil plant material is routinely used as a proxy of past climate and environment change. However, palaeoclimate interpretation requires assumptions about the stability of δ(13) C values in plant material during its decomposition and incorporation into sediments. Previous work on modern angiosperm species shows δ(13) C changes of several per mille during simulated decomposition experiments. However, no such tests have been undertaken on non-flowering plants, which are found extensively within the geological record. These plants have distinctly different cellulose-to-lignin ratios from those of their angiosperm counterparts, potentially creating hitherto unknown variations in the original to fossil δ(13) C signatures. To test the extent of δ(13) C change during decomposition we have subjected a number of plants, representing more basal, non-flowering plant lineages (cycads, ferns, horsetails and dawn redwood), to artificial decay using a hydrothermal maturation technique at two temperatures over periods of up to 273 hours. Subsamples were extracted every 12-16 hours and analysed for their δ(13) C and %C values using a Carlo Erba 1500 elemental analyser, and VG TripleTrap and Optima mass spectrometers. The %C values increased for all samples through the maturation process at both temperatures with the largest increases observed within the first 24 hours. Decreases in δ(13) C values were observed for all plants at 300°C and for two of the species at the lower temperature (200°C). The maximum shift in the δ(13) C value related to experimental decomposition was -0.90‰ (horsetail), indicating a preferential loss of (13) C during thermal maturation. The reduction in the δ(13) C value potentially suggests a preferential loss of isotopically heavier cellulose in relation to the isotopically lighter lignin component during maturation. The isotopic offset observed here (<0.9‰) means that palaeoclimatic

  9. Alkane distribution and carbon isotope composition in fossil leaves: An interpretation of plant physiology in the geologic past

    Science.gov (United States)

    Graham, H. V.; Freeman, K. H.

    2014-12-01

    The relative chain-length distribution and carbon-isotope composition of n-alkanes extracted from sedimentary rocks are important geochemical tools for investigating past terrestrial ecosystems. Alkanes preserved in ancient sediments are assumed to be contemporaneous, derived from the same ecosystem, and integrated from the biomass present on the landscape at the time of deposition. Further, there is an underlying assumption that ancient plants exhibited the same metabolic and physiological responses to climate conditions that are observed for modern plants. Interpretations of alkane abundances and isotopic signatures are complicated by the strong influence of phylogenetic affiliation and ecological factors, such as canopy structure. A better understanding of how ecosystem and taxa influence alkane properties, including homologue abundance patterns and leaf-lipid carbon isotope fractionation would help strengthen paleoecological interpretations based on these widely employed plant biomarkers. In this study, we analyze the alkane chain-length distribution and carbon-isotope composition of phytoleim and alkanes (d13Cleaf and d13Clipid) extracted from a selection of Cretaceous and Paleocene fossil leaves from the Guaduas and Cerrejon Formations of Colombia. These data were compared with data for the same families in a modern analogue biome. Photosynthetic and biosynthetic fractionation (∆leaf and elipid) values determined from the fossil material indicate carbon metabolism patterns were similar to modern plants. Fossil data were incorporated in a biomass-weighted mixing model to represent the expected lipid complement of sediment arising from this ecosystem and compared with alkane measurements from the rock matrix. Modeled and observed isotopic and abundance patterns match well for alkane homologs most abundant in plants (i.e., n-C27 to n-C33). The model illustrates the importance of understanding biases in litter flux and taphonomic pressures inherent in the

  10. Multiple sulfur isotope characteristics of 3.46-2.7 Ga sedimentary rocks from drill cores of the Archean Biosphere Drilling Project (Invited)

    Science.gov (United States)

    Watanabe, Y.; Ohmoto, H.

    2010-12-01

    As part of the Archean Biosphere Drilling Project (ABDP), we have determined the multiple sulfur isotope ratios and examined the mineralogical and geochemical characteristics of the sulfur-bearing minerals (e.g., pyrite, sphalerite, barite) and the host rocks (e.g., major and trace element chemistry; Corg, Ccarb and S contents; δ13Corg and δ13Ccarb) of >100 samples of sedimentary rocks from five ABDP drill cores in the Pilbara Craton, Western Australia. The total ranges of Δ33S and δ34S values of the studied samples are -0.9 to +1.2‰ and -4 to +8‰, respectively. We have found that the Δ33S and δ34S relationships show unique values depending on their depositional environment: (1) Pyrites in the 3.46 Ga Marble Bar Chert Member (ABDP #1), which were formed by submarine hydrothermal fluids, show no AIF-S (anomalously fractionated sulfur isotope) signatures: Δ33S = -0.08 to +0.08‰ and δ34S = -3.3 to +0.6‰ (n = 5). This indicates that the H2S presented in the submarine hydrothermal fluid, which was partly generated through seawater sulfate reduction by Fe2+, did not possess AIF-S signatures. (2) Pyrites in organic C-poor lacustrine shales of the 2.76 Ga Hardey Formation (ABDP #3) also show no or very little AIF-S signatures: Δ33S = -0.38 to +0.25‰ and δ34S = -2.7 to +1.9‰ (n = 18). (3) Pyrites in organic C-poor marine shales of the 2.92 Ga Mosquito Creek Formation (ABDP#5) show no or small negative AIF-S signatures: Δ33S = -0.59 to 0.19 ‰ and all positive δ34S = +1.4 to +7.7‰ (n = 24). (4) Pyrites in organic C-rich (> 1 wt%) and hydrothermally altered marine shales in the 3.46 Ga Panorama Formation (ABDP #2) show constant and small positive AIF-S signatures (+0.44 to +0.61‰) and the smallest variation in δ34S (-1.1 to +1.6‰) (n = 35). In contrast, pyrites in organic C-rich shales in the 2.72 Ga Mt. Roe Basalt show negative Δ33S = -0.50 to -0.10‰ and δ34S = -3.7 to 1.8‰ (n = 10). (5) Pyrites in stromatolitic carbonates of the 2.7 Ga

  11. Direct determination of halogens in powdered geological and environmental samples using isotope dilution laser ablation ICP-MS

    Science.gov (United States)

    Boulyga, Sergei F.; Heumann, Klaus G.

    2005-04-01

    Laser ablation inductively coupled plasma isotope dilution mass spectrometry (LA-ICP-IDMS) with a special laser ablation system for bulk analyses (LINA-Spark(TM)-Atomiser) was applied for direct determinations of chlorine, bromine, and iodine in rock and sediment samples. Special attention was focused on possible inter-halogen fractionations and analyte/spike isotope fractionations by using LA-ICP-MS and LA-ICP-IDMS, respectively. A variation of Br/Cl and I/Cl element intensity ratios by a factor of 1.3-3 was observed when changing the nebulizer gas flow rate in the range of 0.84-1.0 L min-1 and the laser power density in the range of 2-10 GW cm-2, respectively. When using an internal standard for halogen quantification in LA-ICP-MS, this inter-element fractionation can cause systematic errors, which can be avoided by applying the isotope dilution technique. However, at high laser power densities (>5.7 GW cm-2 for iodine and >4.0 GW cm-2 for bromine and chlorine) the corresponding measured isotope ratio of the isotope-diluted sample deviates significantly from the target value. Under optimised conditions concentrations in the range of 30 [mu]g g-1-16 × 103 [mu]g g-1 for chlorine, <2-140 [mu]g g-1 for bromine, and <0.1-31 [mu]g g-1 for iodine were determined by LA-ICP-IDMS in two sediment reference materials (SRM 1646, SRM 2704) and three rock reference samples (GS-N, Granite; BX-N, Bauxite; DT-N, Disthene), which have not been certified for these halogens. The sediment results agree well within the given uncertainties with indicative values by different methods and the results of the rock samples with those obtained by negative thermal ionisation isotope dilution mass spectrometry. The detection limits of LA-ICP-IDMS are 8 [mu]g g-1 for chlorine, 1.7 [mu]g g-1 for bromine, and 0.1 [mu]g g-1 for iodine.

  12. Helium and argon isotopic compositions of the Longquanzhan gold deposit in the Yishu fault zone and their geological implications

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The Longquanzhan gold deposit hosted in granitic cataclasites with mylontization of the foot wall of the main Yishui-Tangtou fault. 3He/4He ratios in fluid inclusions range from 0.14 to 0.24 R/Ra,close to those of the crust-source helium. 40Ar/36Ar ratios were measured to be 289-1811, slightly higher than those of atmospheric argon. The results of analysis of helium and argon isotopes suggested that ore-forming fluids were derived chiefly from the crust. The δ18O values of fluid inclusions from vein quartz range from -1.78‰ to 4.07‰, and the δD values of the fluid inclusions vary between -74‰ and -77‰. The hydrogen and oxygen isotope data indicated that the ore-forming fluid for the Longquanzhan gold deposit had mixed with meteoric water in the process of mineralization. This is consistent with the conclusion from the helium and argon isotope data.

  13. Stable-isotope geochemistry of the Pierina high-sulfidation Au-Ag deposit, Peru: Influence of hydrodynamics on SO42--H2S sulfur isotopic exchange in magmatic-steam and steam-heated environments

    Science.gov (United States)

    Fifarek, R.H.; Rye, R.O.

    2005-01-01

    The Pierina high-sulfidation Au-Ag deposit formed 14.5 my ago in rhyolite ash flow tuffs that overlie porphyritic andesite and dacite lavas and are adjacent to a crosscutting and interfingering dacite flow dome complex. The distribution of alteration zones indicates that fluid flow in the lavas was largely confined to structures but was dispersed laterally in the tuffs because of a high primary and alteration-induced permeability. The lithologically controlled hydrodynamics created unusual fluid, temperature, and pH conditions that led to complete SO42--H2S isotopic equilibration during the formation of some magmatic-steam and steam-heated alunite, a phenomenon not previously recognized in similar deposits. Isotopic data for early magmatic hydrothermal and main-stage alunite (??34S=8.5??? to 31.7???; ??18 OSO4=4.9??? to 16.5???; ??18 OOH=2.2??? to 14.4???; ??D=-97??? to -39???), sulfides (??34 S=-3.0??? to 4.3???), sulfur (??34S=-1.0??? to 1.1???), and clay minerals (??18O=4.3??? to 12.5???; ??D=-126??? to -81???) are typical of high-sulfidation epithermal deposits. The data imply the following genetic elements for Pierina alteration-mineralization: (1) fluid and vapor exsolution from an I-type magma, (2) wallrock buffering and cooling of slowing rising vapors to generate a reduced (H2S/SO4???6) highly acidic condensate that mixed with meteoric water but retained a magmatic ??34S???S signature of ???1???, (3) SO2 disproportionation to HSO4- and H2S between 320 and 180 ??C, and (4) progressive neutralization of laterally migrating acid fluids to form a vuggy quartz???alunite-quartz??clay???intermediate argillic???propylitic alteration zoning. Magmatic-steam alunite has higher ??34S (8.5??? to 23.2???) and generally lower ??18OSO4 (1.0 to 11.5???), ??18OOH (-3.4 to 5.9???), and ??D (-93 to -77???) values than predicted on the basis of data from similar occurrences. These data and supporting fluid-inclusion gas chemistry imply that the rate of vapor ascent for this

  14. COAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20091749 Cai Hou’an(College of Energy Geology,China University of Geosciences,Beijing 100083,China);Xu Debin SHRIMP U-Pb Isotope Age of Volcanic Rocks Distributed in the Badaohao Area,Liaoning Province and Its Significance(Coal Geology & Exploration,ISSN1001-1986,CN61-1155/P,36(4),2008,p.17-20,2 illus.,1 table,16 refs.)Key words:coal measures,volcanic rocks,U-Pb dating,LiaoningA set of andesite volcanic rocks distributes in the Badaohao area in Heishan County,Liaoning Province.It’s geological age and stratigraphy sequence relationship between the Lower Cretaceous Badaohao Formation and the volcanic rocks can not make sure till now and is influencing the further prospect for coals.Zircon

  15. Long chain n-alkanes and their carbon isotopes in lichen species from western Hubei Province: implication for geological records

    Institute of Scientific and Technical Information of China (English)

    Xianyu HUANG; Jiantao XUE; Shouyu GUO

    2012-01-01

    Five coticolous lichen samples were collected from western Hubei Province of China to analyze the long chain n-alkanes and their carbon isotope compositions.The n-alkanes range in carbon number from C17 to C33 with strong odd-over-even predominance between C21and C33.Lichens are dominated by n-C29 in the samples of Dajiuhu,Shennongjia Mountain,but by both n-C23 and n-C29 at Qizimei Mountain.This difference may result from the different environmental conditions in these two sites.The δ13C values of long chain n-alkanes in lichen samples show the signature of C3 plants.Based on compoundspecific carbon isotopic values and previous results,we state that alkane homologs > C23 mainly originate from the symbiotic fungi,while symbiotic algae only contribute trace amount of long chain alkanes.Of great interesting is the occurrence of long chain 3-methylalkanes in the Qizimei samples.These anteiso compounds range from C24 to C32,displaying obvious even-over-odd predominance.This study reveals that the association of long chain 3-methylalkanes with n-C23 alkane might be used as proxies to reconstruct the paleoecological implications of lichens in Earth history.

  16. Long chain n-alkanes and their carbon isotopes in lichen species from western Hubei Province: implication for geological records

    Science.gov (United States)

    Huang, Xianyu; Xue, Jiantao; Guo, Shouyu

    2012-03-01

    Five coticolous lichen samples were collected from western Hubei Province of China to analyze the long chain n-alkanes and their carbon isotope compositions. The n-alkanes range in carbon number from C17 to C33 with strong odd-over-even predominance between C21 and C33. Lichens are dominated by n-C29 in the samples of Dajiuhu, Shennongjia Mountain, but by both n-C23 and n-C29 at Qizimei Mountain. This difference may result from the different environmental conditions in these two sites. The δ 13C values of long chain n-alkanes in lichen samples show the signature of C3 plants. Based on compoundspecific carbon isotopic values and previous results, we state that alkane homologs >C23 mainly originate from the symbiotic fungi, while symbiotic algae only contribute trace amount of long chain alkanes. Of great interesting is the occurrence of long chain 3-methylalkanes in the Qizimei samples. These anteiso compounds range from C24 to C32, displaying obvious even-over-odd predominance. This study reveals that the association of long chain 3-methylalkanes with n-C23 alkane might be used as proxies to reconstruct the paleoecological implications of lichens in Earth history.

  17. Isotope and Chemical Methods in Support of the U.S. Geological Survey Science Strategy, 2003-2008

    Science.gov (United States)

    Rye, R.O.; Johnson, C.A.; Landis, G.P.; Hofstra, A.H.; Emsbo, P.; Stricker, C.A.; Hunt, A.G.; Rusk, B.G.

    2008-01-01

    Principal functions of the Mineral Resources Program are providing information to decision-makers related to mineral deposits on federal lands and predicting the environmental consequences of the mining or natural weathering of those deposits. Performing these functions requires that predictions be made of the likelihood of undiscovered deposits. The predictions are based on geologic and geoenvironmental models that are constructed for the various types of mineral deposits from detailed descriptions of actual deposits and detailed understanding of the processes that formed them. Over the past three decades the understanding of ore-forming processes has benefitted greatly from the integration of laboratory-based geochemical tools with field observations and other data sources. Under the aegis of the Evolution of Ore Deposits and Technology Transfer Project (EODTTP), a five-year effort that terminated in 2008, the Mineral Resources Program provided state-of-the-art analytical capabilities to support applications of several related geochemical tools.

  18. Active microbial sulfur disproportionation in the Mesoproterozoic.

    Science.gov (United States)

    Johnston, David T; Wing, Boswell A; Farquhar, James; Kaufman, Alan J; Strauss, Harald; Lyons, Timothy W; Kah, Linda C; Canfield, Donald E

    2005-12-02

    The environmental expression of sulfur compound disproportionation has been placed between 640 and 1050 million years ago (Ma) and linked to increases in atmospheric oxygen. These arguments have their basis in temporal changes in the magnitude of 34S/32S fractionations between sulfate and sulfide. Here, we present a Proterozoic seawater sulfate isotope record that includes the less abundant sulfur isotope 33S. These measurements imply that sulfur compound disproportionation was an active part of the sulfur cycle by 1300 Ma and that progressive Earth surface oxygenation may have characterized the Mesoproterozoic.

  19. Reply to Comment by Cole-dai Et Al. on "Climatic Impact of the Long-lasting Laki Eruption: Inapplicability of Mass-independent Sulfur Isotope Composition Measurements"

    Science.gov (United States)

    Schmidt, Anja; Thordarson, Thorvaldur; Oman, Luke D.; Robock, Alan; Self, Stephen

    2014-01-01

    -only" scenario [Stevenson et al., 2003]. We acknowledge that there is uncertainty on the volatile release height for Laki; however, it is worth considering that those climate model simulations that used an injection altitude between 9 km and 13 km for the Laki SO2 [Highwood and Stevenson, 2003; Oman et al., 2006a, 2006b; Schmidt et al., 2012] best match the observed temperature changes during summer of 1783 [Angell and Korshover, 1985; Brázdil et al., 2010; Briffa et al., 1998; D'Arrigo and Jacoby, 1999; Jacoby et al., 1999; Kington, 1988; Manley, 1974; Parker et al., 1992; Thordarson and Self, 2003]. Based on these model simulations, a climatic impact during the winter of 1783-1784, albeit weaker than during the climactic phases of Laki, is expected (and our argument here does not exclude the role of natural variability in contributing to the cold winter of 1783-1784 as discussed in Schmidt et al. [2012]). Therefore, we continue to argue that for high-latitude eruptions such as Laki, the applicability of sulfur isotopic measurements to interpret the climatic relevance has yet to be demonstrated. Itmay transpire that the interpretation of MIF signals for the climate-relevance of an eruption is valid and unambiguous only for short-lived explosive eruptions in the tropics. In terms of the processes producing a MIF anomaly (section 3.3 in Cole-Dai et al. [2014]), the works by Hattori et al. [2013] and Ono et al. [2013] suggest that there are remaining issues not discussed by Cole-Dai et al. [2014], for instance, self-shielding of SO2 due to high column densities typical for eruptions of Pinatubo-scale and greater, and the preservation of the MIF signature in general.

  20. Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

    Institute of Scientific and Technical Information of China (English)

    SUN Xiaoming; XUE Ting; HE Gaowen; YE Xianren; ZHANG Mei; LU Hongfeng; WANG Shengwei

    2007-01-01

    Noble gas isotopic compositions of various layers in three-layered (outer, porous and compact layers) cobalt-rich ferromanganese crusts and their basaltic and phosphorite substrates from the western Pacific Ocean were analyzed by using a high vacuum gas mass spectrum. The analytical results show that the noble gases in the Co-rich crusts have derived mainly from the ambient seawater,extraterrestrial grains such as interplanetary dust particles (IDPs) and wind-borne continental dust grains, and locally formation water in the submarine sediments, but different noble gases have different sources. He in the crusts derives predominantly from the extraterrestrial grains, with a negligible amount of radiogenic He from the eolian dust grains. Ar is sourced mainly from the dissolved air in the seawater and insignificantly from radiogenic Ar in the eolian continental dust grains or the formation water. Xe and Ne derive mainly from the seawater, with minor amounts of extraterrestrial Xe and Ne in the IDPs. Compared with the porous and outer layers, the compact layer has a relatively high 4He content and lower 3He/4He ratios, suggesting that marine phosphatization might have greatly modified the noble gas isotopic compositions of the crusts. Besides, the 3He/4He values of the basaltic substrates of the cobalt-rich crusts are very low and their R/Ra ratios are mostly <0.1 Ra, which are similar to that of phosphorite substrates (0.087 Ra), but much lower than that of fresh submarine MORB (8.75±2.14Ra) or seamount basalts (3-43 Ra), implying that the basaltic substrates have suffered strong water/rock interaction and reacted with radiogenic 4He and P-rich upwelling marine currents during phosphatization. The trace elements released in the basalt/seawater interaction might favor the growth of cobalt-rich crusts. The relatively low 3He/4He values in the seamount basalts may be used as an important exploration criterion for the cobalt-rich ferromanganese crusts.

  1. Microbial cycling, oxidative weathering, and the triple oxygen isotope consequences for marine sulfate

    Science.gov (United States)

    Johnston, D. T.; Cowie, B.; Turchyn, A. V.; Antler, G.; Gill, B. C.; Berelson, W.

    2015-12-01

    Microorganisms are responsible for most geochemical sulfur cycling in the ocean. On both modern and geological time scales, stable isotope ratios often serve as a mechanism to track conspicuous or coupled microbial processes, which in turn inform burial fluxes. The most common example of this approach is the use of sulfur isotopes in sulfate and sulfide (both aqueous and in mineral form) to track everything from rates of microbial processes through to the presence/absence of certain metabolic processes in a given environment. The use of oxygen isotope ratios in sulfate has developed in a similar fashion, providing complementary information to that of sulfur isotopes. Through our current work, we will extend the application of oxygen isotopes to include the trace stable oxygen isotope, 17O. These data are facilitated by a new laser F2 fluorination technique running at Harvard, and accompanied by the calibration of a suite of common sulfate standards. At first blush, 16O - 17O - 18O systematics should carry mass-dependent microbial fractionations with process-specific mass laws that are resolvable at the level of our analytical precision. We look to calibrate these biogeochemical effects through the integrated picture captured in marine pore water sulfate profiles, where the 18O/16O is known to evolve. In compliment, riverine sulfate (the sulfate input to the ocean) is an oxidative weathering product and is posited to carry a memory effect of tropospheric O2. Interestingly, the 17O/16O of that O2 carries a mass-independent signal reflecting the balance between stratospheric reactions and Earth surface biospheric fluxes. Through this presentation, we look to calibrate the controls on the balance between biospheric and atmospheric contributions to the marine sulfate reservoir. This is enabled by a series of isotope mass-balance models and with the ultimate goal of developing the geological triple oxygen isotope records of sulfate as a new environmental proxy for paleo

  2. Textural, compositional, and sulfur isotope variations of sulfide minerals in the Red Dog Zn-Pb-Ag deposits, Brooks Range, Alaska: Implications for Ore Formation

    Science.gov (United States)

    Kelley, K.D.; Leach, D.L.; Johnson, C.A.; Clark, J.L.; Fayek, M.; Slack, J.F.; Anderson, V.M.; Ayuso, R.A.; Ridley, W.I.

    2004-01-01

    The Red Dog Zn-Pb deposits are hosted in organic-rich mudstone and shale of the Mississippian Kuna Formation. A complex mineralization history is defined by four sphalerite types or stages: (1) early brown sphalerite, (2) yellow-brown sphalerite, (3) red-brown sphalerite, and (4) late tan sphalerite. Stages 2 and 3 constitute the main ore-forming event and are volumetrically the most important. Sulfides in stages 1 and 2 were deposited with barite, whereas stage 3 largely replaces barite. Distinct chemical differences exist among the different stages of sphalerite. From early brown sphalerite to later yellow-brown sphalerite and red-brown sphalerite, Fe and Co content generally increase and Mn and Tl content generally decrease. Early brown sphalerite contains no more than 1.9 wt percent Fe and 63 ppm Co, with high Mn (up to 37 ppm) and Tl (126 ppm), whereas yellow-brown sphalerite and red-brown sphalerite contain high Fe (up to 7.3 wt %) and Co (up to 382 ppm), and low Mn (subsea-floor hydrothermal recrystallization and coarsening of preexisting barite; (3) open-space deposition of barite, red-brown sphalerite and other sulfides in veins and coeval replacement of barite; and (4) postore sulfide deposition, including the formation of late tan sphalerite breccias. Stage 1 mineralization took place in a low-temperature environment where fluids rich in Ba mixed with pore water or water-column sulfate to form barite, and metals combined with H2S derived from bacterial sulfate reduction to form sulfides. Higher temperatures and salinities and relatively oxidized ore-stage fluids (stages 2 and 3) compared with stage 1 were probably important controls on the abundances and relative amounts of metals in the fluids and the resulting sulfide chemistry. Textural observations and isotopic data show that preexisting barite was reductively dissolved, providing a source of H2S for sulfide mineral formation. In stage 3, the continued flow of hydrothermal fluids caused thermal

  3. The Stanford-U.S. Geological Survey SHRIMP ion microprobe--a tool for micro-scale chemical and isotopic analysis

    Science.gov (United States)

    Bacon, Charles R.; Grove, Marty; Vazquez, Jorge A.; Coble, Matthew A.

    2012-01-01

    Answers to many questions in Earth science require chemical analysis of minute volumes of minerals, volcanic glass, or biological materials. Secondary Ion Mass Spectrometry (SIMS) is an extremely sensitive analytical method in which a 5–30 micrometer diameter "primary" beam of charged particles (ions) is focused on a region of a solid specimen to sputter secondary ions from 1–5 nanograms of the sample under high vacuum. The elemental abundances and isotopic ratios of these secondary ions are determined with a mass spectrometer. These results can be used for geochronology to determine the age of a region within a crystal thousands to billions of years old or to precisely measure trace abundances of chemical elements at concentrations as low as parts per billion. A partnership of the U.S. Geological Survey and the Stanford University School of Earth Sciences operates a large SIMS instrument, the Sensitive High-Resolution Ion Microprobe with Reverse Geometry (SHRIMP–RG) on the Stanford campus.

  4. Sulfur Isotope Systematics and the Link Between Fluctuating Sulfate Levels and P Recycling in a Low Sulfate, Permanently Anoxic Lake (Lake McCarrons, MN): Implications for the Precambrian Rise of Oxygen

    Science.gov (United States)

    Gomes, M. L.; Hurtgen, M. T.

    2009-12-01

    Seawater sulfate concentrations have been used to track the rise of oxygen in the Precambrian ocean-atmosphere system because the primary mode of sulfate delivery to the ocean is the oxidative weathering of sulfides on land. Ancient seawater sulfate concentrations have been inferred from the extent of sulfur (S) isotope fractionation incurred during bacterial sulfate reduction (BSR) where organisms preferentially utilize 32S (over 34S) in the process of reducing of sulfate to sulfide. Within this context, increased variability in δ34Spyrite values in Proterozoic (~2.3 Ga) sediments—along with a corresponding increase in the isotopic difference between sulfate and pyrite (Δ34S)—has been attributed to an increase in seawater sulfate concentrations (from 1 mM) and inferentially Earth-surface oxygen levels. However, most S isotope studies have been calibrated using modern marine sediments that contain sulfate-reducing bacteria that are adapted to the high concentration of sulfate in the modern ocean (~28mM). In order to better understand S isotope systematics within a low sulfate system and to improve our interpretive construct for S isotope results generated from ancient strata, we explore the magnitude of S isotope fractionations associated with microbial activity in the water column and sediments of a low sulfate (isotope difference between surface water sulfate and bottom water sulfide is ~5‰ (Δ34S) while in situ S isotope fractionations associated with BSR at the sediment-water interface approach 35‰; (3) sulfate reduction rates in the upper 3 cm of organic carbon rich sediment are ~0.1 µM cm-3 d-1, an order of magnitude lower than those recorded under higher (modern marine) sulfate concentrations; and (4) sulfate concentrations influence the efficiency of P recycling (as determined via bag incubation experiments). Here, we suggest that an increase in sulfate levels at ~2.3 Ga, as indicated by larger Δ34S values recorded in strata of this age

  5. Evolution of the magmatic-hydrothermal acid-sulfate system at Summitville, Colorado: Integration of geological, stable-isotope, and fluid-inclusion evidence

    Science.gov (United States)

    Bethke, P.M.; Rye, R.O.; Stoffregen, R.E.; Vikre, P.G.

    2005-01-01

    The Summitville Au-Ag-Cu deposit is a classic volcanic dome-hosted high-sulfidation deposit. It occurs in the Quartz Latite of South Mountain, a composite volcanic dome that was emplaced along the coincident margins of the Platoro and Summitville calderas at 22.5??0.5 Ma, penecontemporaneous with alteration and mineralization. A penecontemporaneous quartz monzonite porphyry intrusion underlies the district and is cut and overlain by pyrite-quartz stockwork veins with traces of chalcopyrite and molybdenite. Alteration and mineralization proceeded through three hypogene stages and a supergene stage, punctuated by at least three periods of hydrothermal brecciation. Intense acid leaching along fractures in the quartz latite produced irregular pipes and lenticular pods of vuggy silica enclosed sequentially by alteration zones of quartz-alunite, quartz-kaolinite, and clay. The acid-sulfate-altered rocks host subsequent covellite+enargite/luzonite+chalcopyrite mineralization accompanied by kaolinite, and later barite-base-metal veins, some containing high Au values and kaolinite. The presence of both liquid- and vapor-rich fluid inclusions indicates the episodic presence of a low-density fluid at all levels of the system. In the mineralized zone, liquid-rich fluid inclusions in healed fractures in quartz phenocrysts and in quartz associated with mineralization homogenize to temperatures between 160 and 390 ??C (90% between 190 and 310 ??C), consistent with the range (200-250 ??C) estimated from the fractionation of sulfur isotopes between coexisting alunite and pyrite. A deep alunite-pyrite pair yielded a sulfur-isotope temperature of 390 ??C, marking a transition from hydrostatic to lithostatic pressure at a depth of about 1.5 km. Two salinity populations dominate the liquid-rich fluid inclusions. One has salinities between 0 and 5 wt.% NaCl equivalent; the other has salinities of up to 43 wt.% NaCl equivalent. The occurrence of high-salinity fluid inclusions in vein

  6. Geology of Precambrian rocks and isotope geochemistry of shear zones in the Big Narrows area, northern Front Range, Colorado

    Science.gov (United States)

    Abbott, Jeffrey T.

    1970-01-01

    Rocks within the Big Narrows and Poudre Park quadrangles located in the northern Front Range of Colorado are Precambrian metasedimentary and metaigneous schists and gneisses and plutonic igneous rocks. These are locally mantled by extensive late Tertiary and Quaternary fluvial gravels. The southern boundary of the Log Cabin batholith lies within the area studied. A detailed chronology of polyphase deformation, metamorphism and plutonism has been established. Early isoclinal folding (F1) was followed by a major period of plastic deformation (F2), sillimanite-microcline grade regional metamorphism, migmatization and synkinematic Boulder Creek granodiorite plutonism (1.7 b.y.). Macroscopic doubly plunging antiformal and synformal structures were developed. P-T conditions at the peak of metamorphism were probably about 670?C and 4.5 Kb. Water pressures may locally have differed from load pressures. The 1.4 b.y. Silver Plume granite plutonism was post kinematic and on the basis of petrographic and field criteria can be divided into three facies. Emplacement was by forcible injection and assimilation. Microscopic and mesoscopic folds which postdate the formation of the characteristic mineral phases during the 1.7 b.y. metamorphism are correlated with the emplacement of the Silver Plume Log Cabin batholith. Extensive retrograde metamorphism was associated with this event. A major period of mylonitization postdates Silver Plume plutonism and produced large E-W and NE trending shear zones. A detailed study of the Rb/Sr isotope geochemistry of the layered mylonites demonstrated that the mylonitization and associated re- crystallization homogenized the Rb87/Sr 86 ratios. Whole-rock dating techniques applied to the layered mylonites indicate a probable age of 1.2 b.y. Petrographic studies suggest that the mylonitization-recrystallization process produced hornfels facies assemblages in the adjacent metasediments. Minor Laramide faulting, mineralization and igneous activity

  7. Geological and isotopic evidence for magmatic-hydrothermal origin of the Ag-Pb-Zn deposits in the Lengshuikeng District, east-central China

    Science.gov (United States)

    Wang, Changming; Zhang, Da; Wu, Ganguo; Santosh, M.; Zhang, Jing; Xu, Yigan; Zhang, Yaoyao

    2014-08-01

    The Lengshuikeng ore district in east-central China has an ore reserve of ˜43 Mt with an average grade of 204.53 g/t Ag and 4.63 % Pb + Zn. Based on contrasting geological characteristics, the mineralization in the Lengshuikeng ore district can be divided into porphyry-hosted and stratabound types. The porphyry-hosted mineralization is distributed in and around the Lengshuikeng granite porphyry and shows a distinct alteration zoning including minor chloritization and sericitization in the proximal zone; sericitization, silicification, and carbonatization in the peripheral zone; and sericitization and carbonatization in the distal zone. The stratabound mineralization occurs in volcano-sedimentary rocks at ˜100-400 m depth without obvious zoning of alterations and ore minerals. Porphyry-hosted and stratabound mineralization are both characterized by early-stage pyrite-chalcopyrite-sphalerite, middle-stage acanthite-native silver-galena-sphalerite, and late-stage pyrite-quartz-calcite. The δ34S values of pyrite, sphalerite, and galena in the ores range from -3.8 to +6.9‰ with an average of +2.0‰. The C-O isotope values of siderite, calcite, and dolomite range from -7.2 to -1.5‰ with an average of -4.4‰ (V-PDB) and from +10.9 to +19.5‰ with an average of +14.8‰ (V-SMOW), respectively. Hydrogen, oxygen, and carbon isotopes indicate that the hydrothermal fluids were derived mainly from meteoric water, with addition of minor amounts of magmatic water. Geochronology employing LA-ICP-MS analyses of zircons from a quartz syenite porphyry yielded a weighted mean 206Pb/238U age of 136.3 ± 0.8 Ma considered as the emplacement age of the porphyry. Rb-Sr dating of sphalerite from the main ore stage yielded an age of 126.9 ± 7.1 Ma, marking the time of mineralization. The Lengshuikeng mineralization classifies as an epithermal Ag-Pb-Zn deposit.

  8. Zircon U-Pb Geochronology, Hf Isotopic Composition and Geological Implications of the Neoproterozoic Huashan Group in the Jingshan Area, Northern Yangtze Block, China

    Science.gov (United States)

    Yang, Z.; Yang, K.

    2015-12-01

    In the northern Yangtze Block, a clear angular unconformity between the Mesoproterozoic sequences (e.g. Dagushi Group) and the overlying Neoproterozoic strata (e.g. Huashan Group) marks the the Jinning orogeny. A combined study of Lu-Hf isotopes and U-Pb ages for detrital zircons from Huashan Group can provide information on the crustal evolution of sedimentary provenances and the timing of the Jinning orogeny. Detrital zircons from Huashan Group have two major U-Pb age populations of about 2.0Ga, 2.65Ga, and three subordinate age groups of about 0.82Ga, 2.5Ga, 2.9Ga with minor >3.0Ga ages. The youngest five analyses yield a weighted average age of 816±9Ma, which is consistent with that of interlayered basalt (824±9Ma, Deng et al., 2013) and roughly defines the minimum depositional age of Huashan Group. Detrital zircons of Huashan Group mostly have two stage Hf isotope model ages (TDM2) between 3.0 to 3.3Ga, indicating that the northern Yangtze Block experienced significant continental crustal growth during the Paleo- to Meso-archean. Similar U-Pb ages of detrital zircons have been obtained from Precambrian sedimentary rocks in the northern Yangtze Block from previous studies (Liu et al., 2008; Guo et al., 2014 and references therein). Recently, ca. 2.65Ga A-type granites had been reported from the Kongling and Huji area, which likely record the thermally stable lithosphere (Chen et al., 2013; Zhou et al., 2015). In combination with this study, it documents the widespread 2.6-2.7Ga magmatic rocks in the northern Yangtze Block. Zhao et al. (2013) demonstrated both the ca. 850Ma tonalite and trondhjemite of the Huangling igneous complex were formed in a continental arc setting. This suggests the Miaowan-Huashan oceanic basin proposed by Bader et al. (2013) has not been closed at ca. 850Ma. This evidence, together with the depositional age of the Huashan Group, indicates the Jinning orogeny took place at 850-820 Ma. [1] Bader et al., 2013 Tectonics [2] Deng et al

  9. Evolution of Ore Deposits and Technology Transfer Project: Isotope and Chemical Methods in Support of the U.S. Geological Survey Science Strategy, 2003-2008

    Science.gov (United States)

    Rye, Robert O.; Johnson, Craig A.; Landis, Gary P.; Hofstra, Albert H.; Emsbo, Poul; Stricker, Craig A.; Hunt, Andrew G.; Rusk, Brian G.

    2010-01-01

    Principal functions of the U.S. Geological Survey (USGS) Mineral Resources Program are providing assessments of the location, quantity, and quality of undiscovered mineral deposits, and predicting the environmental impacts of exploration and mine development. The mineral and environmental assessments of domestic deposits are used by planners and decisionmakers to improve the stewardship of public lands and public resources. Assessments of undiscovered mineral deposits on a global scale reveal the potential availability of minerals to the United States and other countries that manufacture goods imported to the United States. These resources are of fundamental relevance to national and international economic and security policy in our globalized world economy. Performing mineral and environmental assessments requires that predictions be made of the likelihood of undiscovered deposits. The predictions are based on geologic and geoenvironmental models that are constructed for the diverse types of mineral deposits from detailed descriptions of actual deposits and detailed understanding of the processes that formed them. Over the past three decades the understanding of ore-forming processes has benefited greatly from the integration of laboratory-based geochemical tools with field observations and other data sources. Under the aegis of the Evolution of Ore Deposits and Technology Transfer Project (referred to hereinafter as the Project), a 5-year effort that terminated in 2008, the Mineral Resources Program provided state-of-the-art analytical capabilities to support applications of several related geochemical tools to ore-deposit-related studies. The analytical capabilities and scientific approaches developed within the Project have wide applicability within Earth-system science. For this reason the Project Laboratories represent a valuable catalyst for interdisciplinary collaborations of the type that should be formed in the coming years for the United States to meet

  10. In situ Th and U isotope determinations of low-U geological samples using laser ablation single-collector sector-field ICPMS

    Science.gov (United States)

    Mertz-Kraus, R.; Jochum, K. P.; Sharp, W. D.; Stoll, B.; Weis, U.; Andreae, M. O.

    2009-12-01

    In situ spatially resolved U-series dating of geological and biological silicates, phosphates and carbonates (e.g., bone, speleothem, coral, and pedogenic silica and carbonate), facilitates measurement of the rates of natural processes (e.g., precipitation, crystallization) during the past 500,000 years. We present a LA-ICPMS technique for precise and accurate determination of Th and U isotopic ratios applicable to samples with U concentrations as low as 0.4 µg/g. Previously, in situ U-series determinations have been done using multi-collector ICPMS. We use a single-collector sector-field ICPMS connected to a 213 Nd:YAG laser ablation system. Precision and accuracy were determined for different matrices, such as synthetic NIST SRM 612, diverse silicate MPI-DING and USGS reference glasses, 91500 zircon, and a travertine previously analyzed by TIMS.230Th and 234U (~0.00001 to 0.0001 µg/g), required laser tracks up to 1800 µm long, rastering over a 400 x 400 µm square and measurement times of 5 to 25 minutes. We applied corrections for background (tails of 232Th, 235U and 238U peaks on 230Th and 234U (0.1 to 6 cps corresponding to a proportion of 0.3 to 30 % of the measured peak for 232Th and 238U concentrations of 0.003 to 10 µg/g), instrumental mass fractionation (~1 % per atomic mass unit), and differences in element sensitivity of Th and U using the certified values of the reference glasses.230Th/238U and 234U/238U determinations varies between 1.6 and 5 % depending on the extent of peak tailing corrections. We obtained 230Th/238U = 1.65 x 10-5 and 234U/238U = 5.29 x 10-5 for BCR-2G (1.7 µg/g U, 5.9 µg/g Th) which agree within 2 % and 4 %, respectively, with TIMS values (Matthews et al., 2008). For the travertine (2.5 µg/g U, 0.003 µg/g Th) the mean values for four scans (~0.14 mg sample each) are 230Th/238U = 2.47 x 10-5 and 234U/238U = 7.49 x 10-5, within 2 % of TIMS values. Matthews K. et al. (2008), Evaluation of Solid Geologic Reference Materials for

  11. Ginseng authenticity testing by measuring carbon, nitrogen, and sulfur stable isotope compositions that differ based on cultivation land and organic fertilizer type

    National Research Council Canada - National Science Library

    Chung, Ill-Min; Lee, Taek-Jun; Oh, Yong-Taek; Ghimire, Bimal Kumar; Jang, In-Bae; Kim, Seung-Hyun

    .... Therefore, the analysis of C, N, and S stable isotope ratios in ginseng can provide a feasible method for determining ginseng authenticity depending on the cultivation land and type of fertilizer. Methods...

  12. Isotopes in heterogeneous catalysis

    CERN Document Server

    Hargreaves, Justin SJ

    2006-01-01

    The purpose of this book is to review the current, state-of-the-art application of isotopic methods to the field of heterogeneous catalysis. Isotopic studies are arguably the ultimate technique in in situ methods for heterogeneous catalysis. In this review volume, chapters have been contributed by experts in the field and the coverage includes both the application of specific isotopes - Deuterium, Tritium, Carbon-14, Sulfur-35 and Oxygen-18 - as well as isotopic techniques - determination of surface mobility, steady state transient isotope kinetic analysis, and positron emission profiling.

  13. Geochemical evidence for cryptic sulfur cycling in salt marsh sediments

    DEFF Research Database (Denmark)

    Mills, Jennifer V.; Antler, Gilad; Turchyn, Alexandra V.

    2016-01-01

    investigate sulfur cycling in salt marsh sediments from Norfolk, England where we observe high ferrous iron concentrations with no depletion of sulfate or change in the sulfur isotope ratio of that sulfate, but a 5‰ increase in the oxygen isotope ratio in sulfate, indicating that sulfate has been through...

  14. Using High-Frequency Infrared Carbon and Sulfur Analyzer to Measure Carbon and Sulfur in Geological Samples%利用高频红外碳硫分析仪测定地质样品中碳、硫

    Institute of Scientific and Technical Information of China (English)

    袁润蕾; 王敏捷; 郝胜涛

    2013-01-01

      采用高频红外分析仪利用 CO2 与 SO2 对红外线的选择性吸收这一原理,测定地质样品中 S、C。精密度采用测定国家一级标准物质,C 的 RSD% 范围从 2.47%~8.5%,S 的 RSD% 范围从 2.95%~3.9%;准确度同样采用国家一级标准物质,C 的 RE% 范围从 -3.33%~1.78%, S 的 RE% 范围从 -2.4%~4.1%,C 的最低检出限为 0.5709%,S 的最低检出限为 0.0103%。高频红外碳硫分析仪测定地质样品中 S、C 时,数据稳定,检出限低。%The experiment in this thesis determines the S and C in geological samples by HF - IRCS Analyzer , based on the selective absorption of CO2 and SO2. The precision based on national’s CRM(certified reference material). The RSD% of C ranges from 2.47% to 8.5%, and the RSD% of S ranges from 2.95% to 3.9%. The precision also based on national’s CRM(certified reference material). The RE% of C ranges from -3.33% to 1.78%, and the RE% of S ranges from -2.4% to 4.1%.The limit of detecton of C is 0.5709%, and S is 0.0103%. Using HF - IRCS Analyzer, the stability of sampled-data is good, and a low detection limit is maintained.

  15. Biogeochemical Cycles of Carbon and Sulfur

    Science.gov (United States)

    DesMarais, David J.; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    The elements carbon (C) and sulfur (S) interact with each other across a network of elemental reservoirs that are interconnected by an array of physical, chemical and biological processes. These networks are termed the biogeochemical C and S cycles. The compounds of C are highly important, not only as organic matter, but also as atmospheric greenhouse gases, pH buffers in seawater, oxidation-reduction buffers virtually everywhere, and key magmatic constituents affecting plutonism and volcanism. The element S assumes important roles as an oxidation-reduction partner with C and Fe in biological systems, as a key constituent in magmas and volcanic gases, and as a major influence upon pH in certain environments. This presentation describes the modern biogeochemical C and S cycles. Measurements are described whereby stable isotopes can help to infer the nature and quantitative significance of biological and geological processes involved in the C and S cycles. This lecture also summarizes the geological and climatologic aspects of the ancient C and S cycles, as well as the planetary and extraterrestrial processes that influenced their evolution over millions to billions of years.

  16. Biogeochemical Cycles of Carbon and Sulfur

    Science.gov (United States)

    DesMarais, David J.; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    The elements carbon (C) and sulfur (S) interact with each other across a network of elemental reservoirs that are interconnected by an array of physical, chemical and biological processes. These networks are termed the biogeochemical C and S cycles. The compounds of C are highly important, not only as organic matter, but also as atmospheric greenhouse gases, pH buffers in seawater, oxidation-reduction buffers virtually everywhere, and key magmatic constituents affecting plutonism and volcanism. The element S assumes important roles as an oxidation-reduction partner with C and Fe in biological systems, as a key constituent in magmas and volcanic gases, and as a major influence upon pH in certain environments. This presentation describes the modern biogeochemical C and S cycles. Measurements are described whereby stable isotopes can help to infer the nature and quantitative significance of biological and geological processes involved in the C and S cycles. This lecture also summarizes the geological and climatologic aspects of the ancient C and S cycles, as well as the planetary and extraterrestrial processes that influenced their evolution over millions to billions of years.

  17. Characteristics of stable isotopic compositions and its geological significances of the Yangla copper deposit, northwestern Yunnan Province%滇西北羊拉铜矿床稳定同位素特征及其地质意义

    Institute of Scientific and Technical Information of China (English)

    陈思尧; 顾雪祥; 程文斌; 章永梅; 郑硌; 彭义伟; 刘瑞萍

    2013-01-01

    The Yangla copper deposit is locate in the middle part of the Jinshajiang belt. It was formed due to the westward subduction of the Jinshajiang oceanic basin and collisional orogeny during Mid-Late Triassic. Ore bodies are typically layered or bedded and closely related to the acidic plutons. Ore bodies are trinity controlled by the pluton, stratum and structure and have obvious feature of the skarn deposit. The stable isotopic compositions of marble and various kinds of minerals in different stages have been analyzed respectively. The results show that the δ18OSMOW values of the garnet which is the major mineral of the skarn is 6.1‰, indicating that the oxygen isotopic compositions of skarn may inherit directly from the acidic plutons. The δD values of the quartz in main mineralization are varied from — 112‰ ~-77‰ and the δ180H2O values are varied from -2. 42‰ ~4. 85‰, which reflects that the main compositions of ore-forming fluids was magmatic water and accompanied with input of meteoric water. The δ13 CPDB values of — 5.1‰ ~ — 1. 7‰ and the δ18OSMOW values of 12. 7‰ ~20.1‰ for the calcite shows that the carbon and oxygen of calcite are sourced mainly from magma and less from marble. The δ13CPDB values of 3. 6‰ ~5. 0‰ and the δ18OSMOW values of 21. 2‰ -25. 4‰ for marble indicate that the marble was re-crystallized from the oceanic carbonate. And as the distance between marble and ore-body decreases, the δ13C values and δ18O values have a trend reducing constantly, which shows that during the process which the ore-forming fluids metasomatiled marble, the fluids with low δ13C values and δ18O values occurred isotope exchange with marble and made the δ13C values and δ18 0 values of marble decrease, and the nearer distance between marble and ore-body was, the more intense the isotope exchange was. The δ34S value of ore sulfides varied from -6. 9‰ ~ 2. 5‰ and were focused from - 2‰ ~ 1‰, showing that the sulfur of

  18. Iron and sulfur isotope constraints on redox conditions associated with the 3.2 Ga barite deposits of the Mapepe Formation (Barberton Greenstone Belt, South Africa)

    Science.gov (United States)

    Busigny, Vincent; Marin-Carbonne, Johanna; Muller, Elodie; Cartigny, Pierre; Rollion-Bard, Claire; Assayag, Nelly; Philippot, Pascal

    2017-08-01

    The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dissolved sulfate (SO42-), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by reducing conditions, with low oceanic sulfate concentration (gases produced by large subaerial volcanic events, and possibly SO42- produced by magmatic SO2 disproportionation in hydrothermal systems.

  19. Combined isotope and enantiomer analysis to assess the fate of phenoxy acids in a heterogeneous geologic setting at an old landfill

    DEFF Research Database (Denmark)

    Milosevic, Nemanja; Qiu, S; Elsner, M;

    2013-01-01

    Phenoxy acid herbicides and their potential metabolites represent industrial or agricultural waste that impacts groundwater and surface waters through leaching from old landfills throughout the world. Fate assessment of dichlorprop and its putative metabolite 4-CPP (2-(4-chlorophenoxy...... to assess transformation of phenoxy acids at a contaminated landfill (Risby site): analysis of (i) parent and daughter compound concentrations, (ii) enantiomer ratios (iii) compound-specific isotope analysis and (iv) enantiomer-specific isotope analysis. Additionally, water isotopes and chloride were used...

  20. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    S. Borrmann

    2012-05-01

    Full Text Available The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g. However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g → multiple steps → SOOCl2−. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32− by O3 (αseasalt = 1.0124±0.0017 at 19 °C. Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways – oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2 – which favour the heavy isotope, and

  1. Geology, S-Pb isotopes, and 40Ar/39Ar geochronology of the Zhaxikang Sb-Pb-Zn-Ag deposit in Southern Tibet: implications for multiple mineralization events at Zhaxikang

    Science.gov (United States)

    Sun, Xiang; Zheng, Youye; Pirajno, Franco; McCuaig, T. Campbell; Yu, Miao; Xia, Shenlan; Song, Qingjie; Chang, Huifang

    2017-07-01

    Several Au, Sb, Sb-Au, Pb-Zn, and Sb-Pb-Zn-Ag deposits are present throughout the North Himalaya in southern Tibet, China. The largest Sb-Pb-Zn-Ag deposit is Zhaxikang (18 Mt at 0.6 wt% Sb, 2.0 wt% Pb, 3.5 wt% Zn, and 78 g/t Ag). Zhaxikang veins are hosted within N-S trending faults, which crosscut the Early-Middle Jurassic Ridang Formation consisting of shale interbedded with sandstone and limestone deposited on a passive continental margin. Ore paragenesis indicates that Zhaxikang mineralization occurred in two main phases composed of six total stages. The initial phase was characterized by assemblages of fine-grained Mn-Fe carbonate + arsenopyrite + pyrite + sphalerite (stage 1), followed by relatively coarse-grained Mn-Fe carbonate + Fe-rich sphalerite + galena + pyrite (stage 2). The second phase was marked by assemblages of quartz + pyrite + Fe-poor sphalerite and Ag-rich galena + tetrahedrite + sericite (stage 3), quartz + Sb-Pb sulfosalt minerals mainly composed of boulangerite and jamesonite (stage 4), quartz + stibnite ± cinnabar (stage 5), and quartz ± calcite (stage 6). Sulfides of stage 2 have δ34SV-CDT of 8.4-12.0‰, 206Pb/204Pb ratios of 19.648 to 19.659, 207Pb/204Pb ratios of 15.788 to 15.812, and 208Pb/204Pb ratios of 40.035 to 40.153. Sulfides of stage 3 have similar δ34SV-CDT of 6.1-11.2‰ and relatively more radiogenic lead isotopes (206Pb/204Pb = 19.683-19.792). Stage 4 Sb-Pb sulfosalt minerals have δ34SV-CDT of 5.0-7.2‰ and even more radiogenic lead (206Pb/204Pb = 19.811-19.981). By contrast, stibnite of stage 5 has δ34SV-CDT of 4.5-7.8‰ and less radiogenic lead (206Pb/204Pb = 18.880-18.974). Taken together with the geological observations that the Pb-Zn-bearing Mn-Fe carbonate veins were crosscut by various types of quartz veins, sphalerite and galena of stage 2 underwent dissolution and remobilization, and that Sb-Pb(-Fe) sulfosalts formed at the expense of Pb from stage 2 galena and of Fe from stage 2 sphalerite, we argue that

  2. Lunar sulfur

    Science.gov (United States)

    Kuck, David L.

    Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

  3. Mass-independent sulfur of inclusions in diamond and sulfur recycling on early Earth.

    Science.gov (United States)

    Farquhar, J; Wing, B A; McKeegan, K D; Harris, J W; Cartigny, P; Thiemens, M H

    2002-12-20

    Populations of sulfide inclusions in diamonds from the Orapa kimberlite pipe in the Kaapvaal-Zimbabwe craton, Botswana, preserve mass-independent sulfur isotope fractionations. The data indicate that material was transferred from the atmosphere to the mantle in the Archean. The data also imply that sulfur is not well mixed in the diamond source regions, allowing for reconstruction of the Archean sulfur cycle and possibly offering insight into the nature of mantle convection through time.

  4. 重大地质转折期的碳、硫循环与环境演变%Variation in carbon and sulphur isotopes and environments during the critical geological transitions

    Institute of Scientific and Technical Information of China (English)

    汪建国; 陈代钊; 严德天

    2009-01-01

    碳、硫在表层储库和地质储库以不同的形式相互转换,在这个过程中都伴随着一定的同位素分馏.碳同位素的分馏主要受到光合作用以及海水溶解无机碳与大气CO_2交换的控制,而硫同位素的分馏则主要受控于硫酸盐细菌还原作用.表层储库碳、硫同位素的组成通过地质作用被很好地保存在地质储库中,因此通过对地质储库中碳、硫同位素的分析和研究,可以很好地了解地球各圈层相互作用的规律,重塑地质历史特别是重大关键转折时期的演化过程.同时文中借助一些碳、硫同位素应用实例,进一步加深理解影响碳、硫同位素组成和变化的原因,以提高对不同时期全球环境变化的认知程度.%Stable isotopes of carbon and sulphur are fractionated during cycling between surface reservoirs and geological reservoirs. The main processes that control the isotopic composition of various reservoirs are photosynthesis and equilibrium between oceanic dissolved inorganic carbon and atmospheric CO_2 for carbon, and bacterial sulphate reduction for sulphur. C-S cycling from surface reservoirs and stored in geological reservoirs provides a geological record of ancient isotopic compositions. These isotopic signals can be used to improve and refine our understanding of historical changes in global geochemical cycles through geological time, especially for some key transitional periods. A number of case studies with detailed applications of these principles have been discussed to illustrate the causes and effects of ancient global environmental change.

  5. Variations in the chemical and stable isotope composition of carbon and sulfur species during organic-rich sediment alteration: An experimental and theoretical study of hydrothermal activity at guaymas basin, gulf of california

    Science.gov (United States)

    Seewald, Jeffrey S.; Seyfried, W.E.; Shanks, Wayne C.

    1994-01-01

    at sediment-covered spreading centers. Our data show that the sulfur isotope composition of hydrothermal Sulfide minerals in Guaymas Basin can be explained by derivation of S from diagenetic sulfide and seawater sulfate. Basaltic S may also contribute to hydrothermal sulfide precipitates but is not required to explain their isotopic composition. Estimates of seawater/ sediment mass ratios based on sulfur isotopic composition of sulfide minerals and the abundance of dissolved NH3 in vent fluids range from 3-29 during hydrothermal circulation. Sources of C in Guaymas Basin hydrothermal fluids include thermal degradation of organic matter, bacteriogenic methane production, and dissolution of diagenetic carbonate. ?? 1994.

  6. Variations in the chemical and stable isotope composition of carbon and sulfur species during organic-rich sediment alteration: An experimental and theoretical study of hydrothermal activity at guaymas basin, gulf of california

    Science.gov (United States)

    Seewald, Jeffrey S.; Seyfried, William E., Jr.; Shanks, Wayne C., III

    1994-11-01

    hydrothermal systems at sediment-covered spreading centers. Our data show that the sulfur isotope composition of hydrothermal Sulfide minerals in Guaymas Basin can be explained by derivation of S from diagenetic sulfide and seawater sulfate. Basaltic S may also contribute to hydrothermal sulfide precipitates but is not required to explain their isotopic composition. Estimates of seawater/ sediment mass ratios based on sulfur isotopic composition of sulfide minerals and the abundance of dissolved NH 3 in vent fluids range from 3-29 during hydrothermal circulation. Sources of C in Guaymas Basin hydrothermal fluids include thermal degradation of organic matter, bacteriogenic methane production, and dissolution of diagenetic carbonate.

  7. Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples.

    Science.gov (United States)

    Boulyga, Sergei F; Heilmann, Jens; Prohaska, Thomas; Heumann, Klaus G

    2007-10-01

    A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for (35)Cl+ to more than 6 x 10(5) cps for (238)U+ for 1 microg of trace element per gram of coal sample. Detection limits vary from 450 ng g(-1) for chlorine and 18 ng g(-1) for sulfur to 9.5 pg g(-1) for mercury and 0.3 pg g(-1) for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis.

  8. The cycle of stable isotopes and tritium in water

    Energy Technology Data Exchange (ETDEWEB)

    Hunziker, J.C. [Inst. de Mineralogie, Lausanne (Switzerland)

    1998-12-31

    In hydrology, meteorology, climatology and environmental research natural hydrogen and oxygen isotopes of water increasingly replace radioactive or chemical tracers used in the past to track fluid paths through nature. This evolution has made possible through the network of precipitation data established since 1961 by the International Atomic Energy Agency (IAEA) in Vienna, that provides the necessary data base for the stable isotope interpretations. Evaporation and condensation and, at higher temperatures, water-rock interaction are the main mechanisms responsible for changing the isotopic ratio of water. These data provide insight into mean residence time of a water body and/or mean altitude of a catchment area. They also yield climatological information and allow the mass transfer quantification because of the temperature dependence of equilibrium fractionation. As the acquired isotopic ratio of a water is generally conserved during flow and percolation through geologic bodies, admixing of water showing different histories can easily be monitored, and when the end members are known or can be measured, mixtures can be calculated. Including isotopic measurements of certain anions, often dissolved in remarkable quantities in groundwaters e.g. nitrates, sulfates or phosphates, increases the reliability and the possibility to trace fluid paths through geologic bodies. In addition in environmental studies, oxygen, nitrogen and sulfur isotopes allow for source determination studies, again providing a possibility of quantification, which can not be obtained by any other method. Recent advances in the specific determination of organic molecules by means of GC-IRMS (gas-chromatography-isotope ratio mass spectrometry) has considerably enlarged our possibilities in detection and quantification of organic water pollution. These organic compounds (debris of macromolecules) increasingly deteriorate the quality of our drinking water; unfortunately they are normally not

  9. Triple oxygen and sulfur isotope analyses of sulfate extracted from voluminous volcanic ashes in the Oligocene John Day Formation: insight into dry climate conditions and ozone contribution to supereruptions

    Science.gov (United States)

    Workman, J.; Bindeman, I. N.; Martin, E.; Retallack, G.; Palandri, J. L.; Weldon, N.

    2014-12-01

    Large volume pyroclastic silicic eruptions emit hundreds of megatons of SO2 into the troposphere and stratosphere that is oxidized into sulfuric acid (H2SO4) by a variety of reactions with mass independent oxygen signatures (MIF), Δ17O>0. Sulfuric acid is then preserved as gypsum in parental volcanic deposits. Diagenic effects are mass dependent and can dilute, but otherwise do not affect MIF ratios. Pleistocene Yellowstone and Bishop tuffs and modern volcanic eruptions preserved under arid climate conditions in North American playa lakes, preserve small amounts of volcanic sulfate as gypsum. This gypsum's Δ17O>0, in combination with isotopic variations of δ18O, δ33S and δ34S is distinct from sedimentary sulfate and reveals its original MIF sulfate isotopic signal and the effect of super eruptions on the atmosphere, and ozone consumption in particular. We use linear algebraic equations to resolve volcanic versus sedimentary (MIF=0) sources. We have found that many large volume ignimbrites have very high initial Δ17O in volcanic sulfate that can only be acquired from reaction with stratospheric ozone. We here investigate nine thick (>2 m) ash beds ranging in age from ~33-23 Ma in the John Day Formation of central Oregon, including massive 28.6 Ma Picture Gorge tuff of newly identified Crooked River supercaldera. The 28.6 Ma Picture Gorge tuff (PGT) has the highest measured Δ17O of 3.5‰, and other tuffs (Tin Roof, Biotite, Deep Creek) have +1.3 to 3.4‰ Δ17O excesses. Sulfate from modern smaller tropospheric eruptions studied for comparison have a resolvable 0.4‰ range consistent with liquid-phase based H2O2 oxidation. The PGT is coeval with the ignimbrite flare-up in western N. America, the 28-29 Ma eruption of the 5000 km3 Fish Canyon tuff and the 28 Ma Never Summer Field eruption in Nebraska-Colorado that have the highest measured Δ17O of 6‰ (Bao et al. 2003). We speculate on the climatic/atmospheric effects of these multiple ~28 Ma supereruptions

  10. Coupled sulfur, iron and molybdenum isotope data from black shales of the Teplá-Barrandian unit argue against deep ocean oxygenation during the Ediacaran

    Science.gov (United States)

    Kurzweil, Florian; Drost, Kerstin; Pašava, Jan; Wille, Martin; Taubald, Heinrich; Schoeckle, Daniel; Schoenberg, Ronny

    2015-12-01

    The Earth's atmosphere and hydrosphere changed from an Archean anoxic to a modern oxygenated world in two major steps, the Paleoproterozoic Great Oxidation Event (2.4-2.3 billion years ago) and the Neoproterozoic Oxidation Event (0.8-0.5 billion years ago). Both events had a strong influence on the availability of redox sensitive and bio-essential metals within the ocean and are, thus, strongly linked to fundamental biological innovations and diversification. Biological diversification during the Precambrian-Cambrian transition between 555 and 540 million years ago may have been driven by ocean-atmosphere oxygenation. The exact timing and the extent of (deep) ocean oxygenation within this time period remains unresolved though. Here we present major and trace element compositions as well as Mo, S and Fe isotopic data of organic-rich black shales from the Teplá-Barrandian unit, Czech Republic. New in situ zircon U-Pb ages provide a maximum depositional age of 559.8 ± 3.8 million years. Black shales with strong metal enrichment show low δ56Fe values due to the dominance of authigenic pyrite-Fe with δ56Fe values around -0.6‰ over detrital Fe with δ56Fe values around 0.1‰. Samples with lower authigenic metal enrichment show relatively low Mo/TOC ratios and increasing δ34S values, which is interpreted to reflect basinal restriction and longer seawater renewal times. In analogy to the modern Black Sea, the accompanied depletion of basinal Moaq due to near quantitative Mo removal might have led to the preservation of the seawater δ98Mo in the respective black shales. Our best estimate for this seawater Mo isotopic composition Proterozoic black shales. The lack of higher δ98Mo values in black shales (and seawater) argues against contemporaneous Mn oxide formation in well oxygenated deep sea settings, which would preferentially adsorb isotopically light Mo leaving behind an isotopically heavy ocean. By contrast, the deep ocean might have remained ferruginous with

  11. COAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111053 Chen Jian(School of Earth and Environment,Anhui University of Science and Technology,Huainan 232001,China);Liu Wenzhong Organic Affinity of Trace Elements in Coal from No.10 Coal-Bed at Western Huagou,Guoyang(Coal Geology & Exploration,ISSN1001-1986,CN61-1155/P,38(4),2010,p.16-20,24,3 illus.,3 tables,19 refs.)Key words:coal,minor elements,Anhui Province In order to study the organic affinity of trace elements in coal from No.10 coal-bed at western Huagou,Guoyang,10 borehole samples were collected at exploration area of Huaibei mining area.The contents of 12 kinds of trace elements were determined by the inductively coupled plasma mass spectrometry(ICP-MS),the total organic carbon(TOC)of coal was determined by LECO carbon and sulfur analyzer,and the organic affinity of trace elements were deduced from the correlations between contents and TOCs.The results showed that the contents of V,Cr,Co,Ni,Mo,Cd,Sb,Pb and Zn were lower than

  12. Geochemical Characteristics and Geological Significance of the Tawangshan gold deposit in Dongfang City, Hainan Province

    Directory of Open Access Journals (Sweden)

    Xiong Ying

    2016-01-01

    Full Text Available The Tawangshan gold deposit is located in the southwest of the Gezhen ductile shear zone in southwestern Hainan Island. Major, trace and rare earth element characteristics of the least altered granites and altered granite ores, as well as the oxygen and hydrogen isotopic features of the quartz, the sulfur and lead isotopic features of the pyrites, galena from this deposit were systematically studied. The altered granite ores content of Fe2O3/(Fe2O3+FeO ranges from 0.409 to 0.410, showing strong magma reducibility. REE characteristics of the granite ores are similar to those of the least altered granites, indicating a close relationship between the mineralization and granite. Hydrogen and oxygen analysis results show that the content of 18OSMOW ranges from 7.7‰ to 16.3‰, δ18OH2O ranges from 1.0‰ to 6.8‰, suggesting that the ore-forming fluid was the dual nature of the metamorphic and magmatic hydrothermal. The compositions of sulfur isotope and lead isotope imply that the metallogenic materials of the deposit derived from the deep magma mixing with the shell source material contamination. Ore deposit geological features reflect the obvious characteristics of magmatic hydrothermal and porphyritic granite is mineralized rocks, implying the deposit was formed in the post-collisional extensional tectonic setting.

  13. Sulfur Earth

    Science.gov (United States)

    de Jong, B. H.

    2007-12-01

    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  14. Authigenic sulfide minerals and their sulfur isotopes in sediments of the northern continental slope of the South China Sea and their implications for methane flux and gas hydrate formation

    Institute of Scientific and Technical Information of China (English)

    PU XiaoQiang; ZHONG ShaoJun; YU WenQuan; TAO XiaoWan

    2007-01-01

    This is a report of the study of the authigenic sulfide minerals and their sulfur isotopes in a sediment core (NH-1) collected on the northern continental slope of the South China Sea, where other geophysical and geochemical evidence seems to suggest gas hydrate formation in the sediments. The study has led to the findings: (1) the pyrite content in sediments was relatively high and its grain size relatively large compared with that in normal pelagic or hemipelagic sediments; (2) the shallowest depth of the acid volatile sulfide (AVS) content maximum was at 437.5 cm (>2 μmol/g), which was deeper than that of the authigenic pyrite content maximum (at 141.5-380.5 cm); (3) δ34S of authigenic pyrite was positive (maximum: +15‰) at depth interval of 250-380 cm; (4) the positive δ34S coincided with pyrite enrichment. Compared with the results obtained from the Black Sea sediments by Jorgensen and coworkers, these observations indicated that at the NH-1 site, the depth of the sulfate-methane interface (SMI) would be or once was at about 437.5-547.5 cm and the relatively shallow SMI depth suggested high upward methane fluxes. This was in good agreement with the results obtained from pore water sulfate gradients and core head-space methane concentrations in sediment cores collected in the area. All available evidence suggested that methane gas hydrate formation may exist or may have existed in the underlying sediments.

  15. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20041200 Peng Yujing (Regional Geology and Mineral Resources Survey of Jilin Province, Changchun, Jilin); Chen Erzhen A Preliminary Study on the Ore -Forming Geologic Events (Jilin Geology, ISSN 1001-2427, CN22-1099/P, 22(3), 2003, p. 1 -11, 23, 1 illus. , 38 refs. ) Key words: geological eventAn ore - forming geologic event, as a

  16. Atmospheric influence of Earth's earliest sulfur cycle

    Science.gov (United States)

    Farquhar; Bao; Thiemens

    2000-08-01

    Mass-independent isotopic signatures for delta(33)S, delta(34)S, and delta(36)S from sulfide and sulfate in Precambrian rocks indicate that a change occurred in the sulfur cycle between 2090 and 2450 million years ago (Ma). Before 2450 Ma, the cycle was influenced by gas-phase atmospheric reactions. These atmospheric reactions also played a role in determining the oxidation state of sulfur, implying that atmospheric oxygen partial pressures were low and that the roles of oxidative weathering and of microbial oxidation and reduction of sulfur were minimal. Atmospheric fractionation processes should be considered in the use of sulfur isotopes to study the onset and consequences of microbial fractionation processes in Earth's early history.

  17. Formation of Apollo 16 impactites and the composition of late accreted material: Constraints from Os isotopes, highly siderophile elements and sulfur abundances

    Science.gov (United States)

    Gleißner, Philipp; Becker, Harry

    2017-03-01

    Fe-Ni metal-schreibersite-troilite intergrowths in Apollo 16 impact melt rocks and new highly siderophile element (HSE) and S abundance data indicate that millimeter-scale closed-system fractional crystallization processes during cooling of impactor-derived metal melt droplets in impact-melts are the main reason for compositional variations and strong differences in abundances and ratios of HSE in multiple aliquots from Apollo 16 impact melt rocks. Element ratios obtained from linear regression of such data are therefore prone to error, but weighted averages take into account full element budgets in the samples and thus represent a more accurate estimate of their impactor contributions. Modeling of solid metal-liquid metal partitioning in the Fe-Ni-S-P system and HSE patterns in impactites from different landing sites suggest that bulk compositions of ancient lunar impactites should be representative of impact melt compositions and that large-scale fractionation of the HSE by in situ segregation of solid metal or sulfide liquid in impact melt sheets most likely did not occur. The compositional record of lunar impactites indicates accretion of variable amounts of chondritic and non-chondritic impactor material and the mixing of these components during remelting of earlier ejecta deposits. The non-chondritic composition appears most prominently in some Apollo 16 impactites and is characterized by suprachondritic HSE/Ir ratios which increase from refractory to moderately volatile HSE and exhibit a characteristic enrichment of Ru relative to Pt. Large-scale fractional crystallization of solid metal from sulfur and phosphorous rich metallic melt with high P/S in planetesimal or embryo cores is currently the most likely process that may have produced these compositions. Similar materials or processes may have contributed to the HSE signature of the bulk silicate Earth (BSE).

  18. The Role of Organic Matter in the Formation of High-Grade Al Deposits of the Dopolan Karst Type Bauxite, Iran: Mineralogy, Geochemistry, and Sulfur Isotope Data

    Directory of Open Access Journals (Sweden)

    Somayeh Salamab Ellahi

    2017-06-01

    Full Text Available Mineralogical and geochemical analyses of the Dopolan karstic bauxite ore were performed to identify the characteristics of four bauxite horizons, which comprise from top to bottom, bauxitic kaolinite, diaspore-rich bauxite, clay-rich bauxite, and pyrite-rich bauxite. Diaspore, kaolinite, and pyrite are the main minerals; böhmite, muscovite, rutile, and anatase are the accessory minerals. The main minerals of the Dopolan bauxite deposit indicate slightly acidic to alkaline reducing conditions during bauxitization. Immobile elements (Nb, Ta, Zr, Hf, and rare earth elements are enriched in the diaspore-rich horizon, which also has the highest alumina content, whereas redox sensitive elements (e.g., Cr, Cu, Ni, Pb, Zn, Ag, U, and V are enriched in the lowest horizon of pyrite-rich bauxite. The presence of a high content of organic matter was identified in different horizons of bauxitic ore from wet chemistry. The presence of organic matter favored Fe bioleaching, which resulted in Al enrichment and the formation of diaspore-rich bauxite. The leached Fe2+ reacted with the hydrogen sulfur that was produced due to bacterial metabolism, resulting in the formation of the pyrite-rich horizon towards the bottom of the Dopolan bauxite horizons. Biogeochemical activity in the Dopolan bauxitic ore was deduced from the reducing environment of bauxitization, and the deposition of framboidal and cubic or cubic/octahedral pyrite crystals, with large negative values of δ34S of pyrite (−10‰ to −34‰ and preserved fossil cells of microorganisms.

  19. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    20152392 Geng Shufang(Institute of Geology,Chinese Academy of Geological Sciences,Beijing 100037,China);Liu Ping Deep Geological Structure Constraints on Shallow Geology and Mineralization:A Study in the Land and Sea Areas of East China(Marine Geology&Quaternary Geology,ISSN0256-1492,CN37-1117/P,34(6),2014,p.49-61,8illus.,13refs.,with English abstract)

  20. New sequential separation procedure for Sr, Nd and Pb isotope ratio measurement in geological material using MC-ICP-MS and TIMS

    Digital Repository Service at National Institute of Oceanography (India)

    Makishima, A.; Nath, B.N.; Nakamura, E.

    A new 3-step sequential separation chemistry for Sr, Nd and Pb from silicate samples, which is suitable for isotope analysis by MC-ICP-MS as well as TIMS, has been developed. The chemistry is designed to minimize the number of evaporation steps...

  1. Final Report: Fundamental Research on the Fractionation of Carbon Isotopes during Photosynthesis, New Interpretations of Terrestrial Organic Carbon within Geologic Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Jahren, A. Hope [Univ. of Hawaii, Honolulu, HI (United States); Schubert, Brian A. [Univ. of Louisiana, Lafayette, LA (United States)

    2017-08-02

    The goal for the current grant period (2013 – 2016) was to quantify the effect of changing atmospheric carbon dioxide concentration (pCO2) on published terrestrial carbon isotope excursion events. This work supported four scientists across multiple career stages, and resulted in 5 published papers.

  2. Geological evolution of the marine selenium cycle : Insights from the bulk shale δ82/76Se record and isotope mass balance modeling

    NARCIS (Netherlands)

    Mitchell, Kirsten|info:eu-repo/dai/nl/304823791; Mansoor, Sannan Z.; Mason, Paul R D|info:eu-repo/dai/nl/304829331; Johnson, Thomas M.; Van Cappellen, Philippe|info:eu-repo/dai/nl/304829366

    2016-01-01

    Bulk δ82/76Se values of representative marine shales from the Paleoarchean to the present day vary between approximately -3 and +3‰ with only local deviations beyond this range. This muted Se isotope variability in the shale record contrasts with the relatively large fractionations associated with a

  3. Geochemistry, geology, and isotopic (Sr, S, and B) composition of evaporites in the Lake St. Martin impact structure: New constraints on the age of melt rock formation

    Science.gov (United States)

    Leybourne, Matthew I.; Denison, Rodger E.; Cousens, Brian L.; Bezys, Ruth K.; Gregoire, D. Conrad; Boyle, Dan R.; Dobrzanski, Ed

    2007-03-01

    We report new Sr, S, and B isotopic data for evaporites (gypsum, anhydrite), carbonates, melt rocks, gneisses, and groundwaters recovered in and around the Lake St. Martin (LSM) impact structure, Interlake Region, Manitoba, Canada. The LSM meteorite impacted Devonian to Ordovician carbonates and sandstones of the eastern Williston Basin, resulting in partial melting of underlying Superior Province (~2.5 Ga) gneisses of the Canadian Shield. Overlying the LSM melt rocks are red beds and evaporites (anhydrite/gypsum/glauberite) previously inferred to have been deposited during the Jurassic. The 87Sr/86Sr (lowest values cluster at 0.70836) and δ 34SCDT (+23.7 +/- 0.9‰) of the evaporites, combined with B isotope compositions of associated groundwaters (δ 11BNBS951 = +25 to +28‰), are consistent with evaporite deposition within the impact structure near the edge of an ocean-connected salina. The establishment of a marine origin for the evaporites offers a method of age assignment using the secular variation of S and Sr isotopes in seawater. Comparison of Sr and S isotope results with the seawater curves precludes Jurassic deposition for the evaporites or correlation with Watrous and Amaranth formation evaporites, previously considered correlative with those at LSM. The lowest Sr and mean of S isotope values from the LSM evaporites are similar to seawater in the latest Devonian, consistent with conodonts recovered from carbonate breccia overlying melt rocks, and we suggest this as an alternative age of the evaporites. Data presented here preclude a Jurassic age for the evaporites and therefore for the impact event.

  4. Zircon U-Pb geochronology, Sr-Nd-Hf isotopic composition and geological significance of the Late Triassic Baijiazhuang and Lvjing granitic plutons in West Qinling Orogen

    Science.gov (United States)

    Duan, Meng; Niu, Yaoling; Kong, Juanjuan; Sun, Pu; Hu, Yan; Zhang, Yu; Chen, Shuo; Li, Jiyong

    2016-09-01

    The Qinling Orogen was a consequence of continental collision of the South China Craton with the North China Craton in the Triassic and caused widespread granitoid magmatism. However, the petrogenesis of these granitoids remains controversial. In this paper, we choose the Baijiazhuang (BJZ) and Lvjing (LJ) plutons in the West Qinling Orogen for a combined study of the zircon U-Pb geochronology, whole-rock major and trace element compositions and Sr-Nd-Hf isotopic characteristics. We obtained zircon crystallization ages of 216 Ma and 212 Ma for the BJZ and the LJ plutons, respectively. The granitoid samples from both plutons have high K2O metaluminous to peraluminous compositions. They are enriched in large ion lithophile elements (LILEs), light rare earth elements (LREEs) and depleted in high field-strength elements (HFSEs) with significant negative Eu anomalies. The BJZ samples have initial Sr isotopic ratios of 0.7032 to 0.7078, εNd(t) of - 10.99 to - 8.54 and εHf (t) of - 10.22 to - 6.41. The LJ granitoids have initial Sr isotopic ratios of 0.7070 to 0.7080, εNd(t) of - 5.37 to - 4.58 and εHf(t) of - 3.64 to - 1.78. The enriched isotopic characteristics of the two plutons are consistent with their source being dominated by ancient continental crust. However, two BJZ samples show depleted Sr isotope compositions, which may infer possible involvement of mantle materials. Mantle-derived melt, which formed from partial melting of mantle wedge peridotite facilitated by dehydration of the subducted/subducting Mianlue ocean crust, provide the required heat for the crustal melting while also contributing to the compositions of these granitoids. That is, the two granitic plutons are magmatic responses to the closure of the Mianlue ocean basin and the continental collision between the Yangtze and South Qinling crustal terranes.

  5. Development of an accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals) in coal samples

    Energy Technology Data Exchange (ETDEWEB)

    Boulyga, Sergei F. [University of Natural Resources and Applied Life Sciences, Department of Chemistry, Division of Analytical Chemistry-VIRIS Laboratory, Vienna (Austria); Johannes Gutenberg-University, Institute of Inorganic Chemistry and Analytical Chemistry, Mainz (Germany); Heilmann, Jens; Heumann, Klaus G. [Johannes Gutenberg-University, Institute of Inorganic Chemistry and Analytical Chemistry, Mainz (Germany); Prohaska, Thomas [University of Natural Resources and Applied Life Sciences, Department of Chemistry, Division of Analytical Chemistry-VIRIS Laboratory, Vienna (Austria)

    2007-10-15

    A method for the direct multi-element determination of Cl, S, Hg, Pb, Cd, U, Br, Cr, Cu, Fe, and Zn in powdered coal samples has been developed by applying inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) with laser-assisted introduction into the plasma. A sector-field ICP-MS with a mass resolution of 4,000 and a high-ablation rate laser ablation system provided significantly better sensitivity, detection limits, and accuracy compared to a conventional laser ablation system coupled with a quadrupole ICP-MS. The sensitivity ranges from about 590 cps for {sup 35}Cl{sup +} to more than 6 x 10{sup 5} cps for {sup 238}U{sup +} for 1 {mu}g of trace element per gram of coal sample. Detection limits vary from 450 ng g{sup -1} for chlorine and 18 ng g{sup -1} for sulfur to 9.5 pg g{sup -1} for mercury and 0.3 pg g{sup -1} for uranium. Analyses of minor and trace elements in four certified reference materials (BCR-180 Gas Coal, BCR-331 Steam Coal, SRM 1632c Trace Elements in Coal, SRM 1635 Trace Elements in Coal) yielded good agreement of usually not more than 5% deviation from the certified values and precisions of less than 10% relative standard deviation for most elements. Higher relative standard deviations were found for particular elements such as Hg and Cd caused by inhomogeneities due to associations of these elements within micro-inclusions in coal which was demonstrated for Hg in SRM 1635, SRM 1632c, and another standard reference material (SRM 2682b, Sulfur and Mercury in Coal). The developed LA-ICP-IDMS method with its simple sample pretreatment opens the possibility for accurate, fast, and highly sensitive determinations of environmentally critical contaminants in coal as well as of trace impurities in similar sample materials like graphite powder and activated charcoal on a routine basis. (orig.)

  6. Lead and sulfur isotopes of Guarn Halfaya and Bou Grine deposits associated to salt dome cap rocks (Diapirs zone, Northern Tunisia): sources of metals and genetic model

    Science.gov (United States)

    Jemmali, N.; Souissi, F.; Carranza, E. J. M.; Vennemann, T. W.

    2012-04-01

    The Pb-Zn ores districts at Guarn Halfaya and Bou Grine are hosted mainly by the dolostones in the contact breccias between Triassic and Upper Cretaceous and by Upper Cretaceous limestones. The mineralization occurs as lenticular, impregnations, substitutions, replacements, stratiform, vein, dissemination, and stockwork. A complex polymetallic sulfide assemblage typifies the main ore stage, dominated by sphalerite and galena, pyrite with minor chalcopyrite, arsenopyrite, and sulfosalt (grey copper). Limestone, barite and celestite dominate the gangue, with lesser calcite. Barite and celestite intergrown with main ore-stage sulfides of Oum Edeboua has δ34S values of 12.7 to 15.0 ‰, consistent with the derivation of sulfate from Triassic evaporites form the study area (12.8reduction (TSR) of Triassic sulfates at depth. However, the presence of bacterial relics suggests involvement of bacterially-mediated sulfate reduction (BSR). The lead isotope composition is homogeneous with 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratio ranging between from 18.723 to 18.783, 15.667 to 15.685, and 38.806 to 38.889, respectively, and plot between the upper crust and orogene curves of Zartman and Doe (1981) which imply involvement of a well-mixed multi-source reservoir of Pb at depth. The syn-diagenetic mineralization in the Bahloul Formation and the calculate of model age suggest a Late Cretaceous age, correspond to a NE-SW to ENE-WSS regional extensional tectonic events, which likely favored migration of mineralizing fluids and eventual deposition at Guarn Halfaya and Bou Grine.

  7. Recharge Area on the Slopes of Volcano Based on Geological Setting, Content of Deuterium and Oxygen Isotopes of Groundwater Chemistry: Case Study on the Slopes of Salak Mountain, West Java

    Directory of Open Access Journals (Sweden)

    Hendarmawan

    2011-09-01

    Full Text Available Indonesian is huge areas that have the highest precipitation in the world, therefore water deficit of groundwater is often happened at anywhere. This study was related to determination of recharge area with approached by combining geological setting, stable isotopes and chemical content of groundwater. Case study was carried out at surrounding the Cicurug area, Sukabumi Prefecture, West Java Province. The area is the slopes of Salak Mountain that have elevation of 400 until 1,200 m mean sea level (msl. While, much groundwater supplies industry activities on elevation 450-500 m msl. Based on data and result analysis of the studies, the recharge areas was not around peak of mountain or near, but water infiltrated on elevation of 700-800 m msl for groundwater exploited by industries. Therefore, the accurate determination of recharge area becomes a key for the groundwater sustainability.

  8. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20140958 Mei Huicheng(No.915GeologicalBrigade,Jiangxi Bureau of Geology and Mineral Resources,Nanchang 330002,China);Li Zhongshe Geological Features and Causes of the Huihuang Geotherm in Xiushui,Jiangxi Province(Journal of Geological Hazards and

  9. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20090700 Chen Anshu(Tianjin Institute of Geology and Mineral Resources,China Geological Survey,Tianjin 300170,China);Li Xiaoguang 1:250 000-Scale Regional Geological Map Spatial Database(Geological Survey and Research,ISSN1672-4135,CN12-1353/P,31(1),2008,p.64-69,2 illus.,2 tables,5 refs.)

  10. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20140805Fan Baocheng(Xi’an Center of Geological Survey,China Geology Survey,Xi’an710054,China);Meng Guanglu The Geological Evolution and Metallization of TalasKalatawu Block in Northern Tianshan,Kyrgyzstan(Northwestern Geology,ISSN1009-6248,CN61-1149/P,46(2),2013,p.54-

  11. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20071510 Chen Ge(No.282 Geological Par- ty,Geological Bureau of Sichuan Nuclear In- dustry,Deyang,Sichuan 618000)Assess- ment of Geological Hazards in the Sichuan Sector of the Nanchong-Wanzhou 500 KV Transmisson Line Engineering(Acta Geolog- ica Sichuan,ISSN 1006-0995,CN 51- 1273/P,26(2),2006,p.88-93,2 tables) Key words:geologic hazards,construction field,Sichuan Province Possibility of inducing and intensifying geological hazards by the Nanhong- Wanzhou 500 KV transmission line engineer- ing,geological hazards which probably occur

  12. Circulation patterns and geothermometry of some Italian spring systems by sulfate isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Cortecci, G. (Univ. of Pisa, Italy); Bertrami, R.; Ceccarelli, A.; Campbell, A. (ed.)

    1980-01-01

    Sulfur and oxygen isotopes of sulfates and waters in springs emerging in the Monti Vulsini and Monti Sabatini areas (Latium, Italy) have been applied to the evaluation of the hydrological situation and temperature conditions at depth. These areas belong to the pre-Apennine belt of geothermal interest, where an intense volcanic activity of Quaternary age occurred. Using results of studies on other Italian geothermal fields and the interpretation of the available geological, geophysical, and geochemical data, a model was advanced for the hydrology of this area.

  13. Isotopic and hydrogeochemical characterization of high-altitude karst aquifers in complex geological settings. The Ordesa and Monte Perdido National Park (Northern Spain) case study

    Energy Technology Data Exchange (ETDEWEB)

    Lambán, L.J., E-mail: javier.lamban@igme.es [Geological Survey of Spain (IGME) (Spain); Jódar, J., E-mail: jorge.jodar@upc.edu [Department of Geotechnical Engineering and Geosciences, Technical University of Catalonia (UPC), Barcelona (Spain); Custodio, E., E-mail: emilio.custodio@upc.edu [Department of Geotechnical Engineering and Geosciences, Technical University of Catalonia (UPC), Barcelona (Spain); Soler, A., E-mail: albertsoler@ub.edu [Grup de Mineralogia Aplicada i Medi Ambient, Departament Cristal lografia Mineralogia i Dipòsits Minerals, Facultat de Geologia, Universitat de Barcelona (UB) (Spain); Sapriza, G., E-mail: g.sapriza@usask.ca [Global Institute for Water Security, National Hydrology Research Centre (Canada); Soto, R., E-mail: r.soto@igme.es [Geological Survey of Spain (IGME) (Spain)

    2015-02-15

    The Ordesa and Monte Perdido National Park, located in the Southern Pyrenees, constitutes the highest karst system in Western Europe. No previous studies regarding its geochemical and isotopic groundwater characterization are available in this area. This work presents the results of field and sampling campaigns carried out between July 2007 and September 2013. The groundwater presents high calcium bicarbonate contents due to the occurrence of upper Cretaceous and lower Paleocene–Eocene carbonate materials in the studied area. Other relevant processes include dissolution of anhydrite and/or gypsum and incongruent dissolution of Mg-limestone and dolomite. The water stable isotopes (δ{sup 18}O, δ{sup 2}H) show that the oceanic fronts from the Atlantic Ocean are responsible for the high levels of precipitation. In autumn, winter, and spring, a deuterium excess is found in the recharge water, which could be related to local atmospheric transport of low-altitude snow sublimation vapour and its later condensation on the snow surface at higher altitude, where recharge is mostly produced. The recharge zones are mainly between 2500 m and 3200 m a.s.l. The tritium content of the water suggests short groundwater transit times. The isotopic composition of dissolved sulphate points to the existence of regional fluxes mixed with local discharge in some of the springs. This work highlights the major role played by the altitude difference between the recharge and discharge zones in controlling the chemistry and the vertical variability of the isotopic composition in high-altitude karst aquifers. - Highlights: • Environmental tracers are essential to study complex alpine karst aquifers. • The long presence of snow controls the deuterium excess in groundwater. • Seasonal δD content in springs depends on gap between recharge and discharge points. • The first hydrogeological characterization of the Ordesa National Park is presented. • Sulphate content in springs comes

  14. Near Surface Leakage Monitoring for the Verification and Accounting of Geologic Carbon Sequestration Using a Field Ready {sup 14}C Isotopic Analyzer

    Energy Technology Data Exchange (ETDEWEB)

    Marino, Bruno

    2014-04-14

    Results for the development of a field ready multi-isotopic analyzer for {sup 12}CO{sub 2}, {sup 13}CO{sub 2} and {sup 14}CO{sub 2} and applications for carbon capture and storage (CCS) containment performance are described. A design goal of the field platform was to provide isotopic data with a high data rate, a standardized reference baseline and acceptable precision (e.g., ~ ±50 per mil D{sup 14}CO{sub 2}) for detection and quantification of fossil-fuel CO{sub 2} CCS leakage scenarios. The instrument platform was not designed to replace high precision accelerator mass spectrometry. An additional goal was to combine project scale isotopic data and associated fluxes with unique financial instruments linking CCS containment performance to a publicly traded security providing project revenue to stakeholders. While the primary goals of the project were attained additional work is needed for the instrument platform and deployment within a full scale CCS site that was not available during the project timeframe.

  15. The Vein-type Zn-(Pb, Cu, As, Hg mineralization at Fedj Hassène orefield, North-Western Tunisia: Mineralogy, Trace Elements, Sulfur Isotopes and Fluid Inclusions

    Directory of Open Access Journals (Sweden)

    Bejaoui, J.

    2011-06-01

    Full Text Available The Fedj Hassène district is localized at the edge of the Tuniso-Algerian border 10 km of Ghardimaou area. It consists of a Zn-Pb vein type with minor amounts of Cu-As-Hg. The total Zn reserves are about 370.000t. The mineralization occurs within subparallel fractures to the Ain El Kohla ESE-WNW fault. Host rocks consist of limestones and marly limestones of the Middle Turonian. In the principal lode of Fedj Hassène, the mineralization occurs as vein filling of massive and brecciated brown sphalerite and minor galena ore with gangue. Other trace minerals are pyrite, chalcopyrite, orpiment, realgar, smithsonite and cerussite. LA-ICP-MS analyses in sphalerites show mean contents of 0,84 wt% Fe, 0,14 wt% Cd and 0,02 wt% Mn Ore. Fluid inclusions study in calcite and sphalerite reveals one mineralizing fluid characterized by an average salinity 23% wt NaCl with decreasing homogenisation temperature. In fact the temperature shows decrease from sphalerite to calcite. The fluid density that corresponds to trapping pressure ranges between 1.00 g/cm3 and 1.11 g/cm3 and pressure close to 200 bars. Microthermometric data in fluid inclusion hosted by gangue mineral presented by calcite show an average temperature of formation around 194°C. These inclusions homogenized to the liquid phase between 156°C and 210°C and salinities values ranging from 22 to 28 wt% NaCl and an average around 23% wt NaCl. The δ34S (VCDT values of sphalerite are in the range of + 4,6‰ to 6,4‰ (average=5,6‰. Thermochemical reduction of Triassic sulfate by reaction with hydro-carbons is the most probable source for the heavy and the narrow range of the ?34S values. Mineralogical, geochemical of trace elements, fluid inclusions and sulfur isotopes studies allow to include the vein-type ore field of Fedj Hassène in the polymetallic (Pb-Zn-As-Hg vein mineralization of the nappe zone in northern Tunisia and north eastern Algeria

  16. Biologically produced sulfur

    NARCIS (Netherlands)

    Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

    2003-01-01

    Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are stabil

  17. Salinization of the Upper Colorado River - Fingerprinting Geologic Salt Sources

    Science.gov (United States)

    Tuttle, Michele L.W.; Grauch, Richard I.

    2009-01-01

    Salt in the upper Colorado River is of concern for a number of political and socioeconomic reasons. Salinity limits in the 1974 U.S. agreement with Mexico require the United States to deliver Colorado River water of a particular quality to the border. Irrigation of crops, protection of wildlife habitat, and treatment for municipal water along the course of the river also place restrictions on the river's salt content. Most of the salt in the upper Colorado River at Cisco, Utah, comes from interactions of water with rock formations, their derived soil, and alluvium. Half of the salt comes from the Mancos Shale and the Eagle Valley Evaporite. Anthropogenic activities in the river basin (for example, mining, farming, petroleum exploration, and urban development) can greatly accelerate the release of constituents from these geologic materials, thus increasing the salt load of nearby streams and rivers. Evaporative concentration further concentrates these salts in several watersheds where agricultural land is extensively irrigated. Sulfur and oxygen isotopes of sulfate show the greatest promise for fingerprinting the geologic sources of salts to the upper Colorado River and its major tributaries and estimating the relative contribution from each geologic formation. Knowing the salt source, its contribution, and whether the salt is released during natural weathering or during anthropogenic activities, such as irrigation and urban development, will facilitate efforts to lower the salt content of the upper Colorado River.

  18. The oxygen isotope evolution of seawater: A critical review of a long-standing controversy and an improved geological water cycle model for the past 3.4 billion years

    Science.gov (United States)

    Jaffrés, Jasmine B. D.; Shields, Graham A.; Wallmann, Klaus

    2007-07-01

    Controversy over the oxygen isotope composition of seawater began in the 1950's, since which time there has been no agreement over whether the oxygen isotope composition of the oceans has changed over time. Resolving this uncertainty would allow the δ18O values of demonstrably well preserved marine authigenic precipitates to be used to reconstruct surface climate trends back to early Archean times and would help towards a more quantitative description of Earth's global water cycle on geological time scales. Isotopic studies of marine carbonate and silica reveal a trend of increasing δ18O values with decreasing age since the Archean. This trend has been interpreted by some to reflect a progressive increase in seawater δ18O through time; however, it is generally accepted on the basis of ophiolite studies and theoretical considerations that seawater δ18O cannot change significantly because of the buffering effects of ocean crust alteration at mid-ocean ridges. As a result many alternative interpretations have been proposed, including meteoric alteration; warmer paleoclimates; higher seawater pH; salinity stratification and biased sampling. Here we review these interpretations in the light of an updated compilation of marine carbonate δ18O from around the world, covering the Phanerozoic and Precambrian rock records. Recent models of the geological water cycle demonstrate how long-term trends in chemical weathering and hydrothermal circulation can indeed influence the O-isotope composition of the global ocean to the extent necessary to explain the carbonate δ18O trend, with residual variation attributed to climatic fluctuations and post-depositional alteration. We present the further development of an existing model of the geological water cycle. In the model, seawater δ18O increased from about - 13.3‰ to - 0.3‰ over a period of 3.4 Ga, with average surface temperatures fluctuating between 10 °C to 33 °C, which is consistent with known biological

  19. Sm-Nd ISOTOPIC AGE OF LAMPROPHYRES IN THE GEZHEN GOLD-BEARING SHEAR ZONE ON HAINAN ISLAND AND ITS GEOLOGICAL IMPLICATIONS

    Institute of Scientific and Technical Information of China (English)

    XU De-ru; LIANG Xin-quan; CHEN Guang-hao; HUANG Zhi-long

    2002-01-01

    Sm-Nd isotopic compositions of eight lamprophyre samples, which come from the Gezhen gold-bearing shear zone on western Hainan Island, are measured. The Sm-Nd isochron age is 495.98±13.14 Ma, (143Nd/144Nd) 0=0.512094, εNd(t) ranges from +1.80 to +2.00 and TDM from 982 Ma to 1196 Ma (average: 1060 Ma). The authors point out that the whole-rock Sm-Nd isochron age (495.98 ± 13.14 Ma) really represents the petrogenetic age of lamprophyre and the time of magmatism during subsequent subduction.

  20. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141243Chen Ge(Hangzhou Research Institute of Petroleum Geology,PetroChina,Hangzhou 310023,China);Si Chunsong Study on Sedimentary Numerical Simulation Method of Fan Delta Sand Body(Journal of Geology,

  1. Engineering Geology.

    Science.gov (United States)

    Ivey, John B.

    1983-01-01

    Engineering geology activities in government and the private sector are highlighted. Also highlighted are conferences in this field, awards presented at conferences (including an award to an undergraduate geology student), and a new publication "Geotechnology in Massachusetts." (JN)

  2. 云南兰坪盆地西缘脉状铜多金属矿床硫、铅同位素组成及成矿示踪%Sulfur and lead isotope compositions and tracing of copper deposits on the western border of the Lanping Basin, Yunnan Province

    Institute of Scientific and Technical Information of China (English)

    张锦让; 温汉捷

    2012-01-01

    云南兰坪盆地西缘脉状铜多金属矿床主要赋存于由砂岩、粉砂岩和页岩组成的碎屑岩建造中.为了查明兰坪盆地西缘脉状铜多金属矿床成矿物质来源,对盆地西缘四个典型脉状铜多金属矿床(科登涧、连城、金满和水泄)的硫、铅同位素的组成进行了分析和对比研究.结果表明,这些矿床的铅同位素组成总体变化较小,且大部分落在盆地沉积地层铅范围内,金满、连城铜矿床可能有部分深源铅的加入.硫同位素特征表明,兰坪盆地西缘脉状铜多金属矿床的硫主要来源于地层硫酸盐的还原作用,其中金满铜矿床和连城铜钼多金属矿床可能有深源硫的混入.各矿床硫同位素不同的特点,除反映各矿床源区硫同位素组成的差异外,可能还与各矿床成矿时不同的物理化学条件(温度、氧逸度、pH值和离子强度等)差异有关.%A large number of vein-type Cu-polymetallic deposits were developed on the western border of the Lanping Basin in western Yunnan Province, which constituted an important Cu-polymetallic mineralization belt. These deposits are hosted in clastic rocks (sandstone, siltite and argillite) of Mesozoic and Cenozoic formation. In order to trace source of ore-forming materials of these deposits, four representative deposits (Jinman, Shuixie, Kedengjian and Liancheng) were selected to analyze sulfur and lead isotopic compositions. Pb isotopic compositions show very narrow variations and mostly fall within the range of the sedimentary rock lead, suggesting that lead in these vein-type Cu-polymetallic deposits is mostly derived from the basement of the basin. However, the Jinman and Liancheng deposits may have deep sources of lead with different Pb isotopic composition. Sulfur isotope analysis show that the reduced sulfur of these vein-type Cu-polymetallic deposits mainly come from the strata sulfate. However, like Pb isotopes, the Jinman and Liancheng deposits have more

  3. 江西省兴源冲铜矿床同位素地球化学特征及成矿机制探讨%Carbon, oxygen and sulfur isotopic geochemistry and metallogenic mechanism of Xingyuanchong copper deposit in Jiangxi Province

    Institute of Scientific and Technical Information of China (English)

    刘婷; 刘成东; 严兆彬; 陈益平; 吴旭铃; 凡秀君

    2013-01-01

    The Xingyuanchong copper deposit of Huangmao area is located in the west segment of the South Jiuling large copper polymetallic ore concentration area.In combination with the metallogenic characteristics of the ore deposit,the authors mainly studied stable isotopes of the ores to probe into the sources of metallogenic materials and metallogenic mechanism of the deposit.δ13 CVPDB values of carbonates in this area vary in the range of -5.4‰~1.9‰,0.6‰ on average,whereas δ18OsMow values range from 9.0‰ to 13.8‰,10.9‰ on average,indicating that carbonates were mainly marine carbonates.The δ18O-δ13C diagram shows that carbon in the region probably came from the deep earth,and experienced metamorphism at high temperatures and alteration at low temperatures.Except two higher values of δ34S,most δ34S values in this deposit vary in the range of 1.0‰ ~6.2‰ ; in comparison with other similar deposits,sulfur of this deposit is characterized by submarine exhalation sedimentation and hydrothermal superimposition.In combination with isotopic data and geological setting,it is proposed that the ore-forming processes of the Xingyuanchong copper deposit could be divided into two stages.At the first stage,submarine volcanic sediments or protore layers were formed in Mesoproterozoic.At the second stage,the pre-existing protores were altered by the hydrothermal fluids and dynamic metamorphism mainly derived from Jinning orogenic period in Late Proterozoic.%兴源冲铜矿床地处九岭南缘铜多金属大型矿集区西段的黄茅地区.文章在成矿地质特征的基础上,通过对矿石进行稳定同位素地球化学研究,重点分析了成矿物质来源,探讨了矿床成矿机制.碳、氧同位素分析结果表明,矿区碳酸盐岩δ13 CVPDB为-5.4‰~ 1.9‰,平均为0.6‰,δ18 OSMOW变化范围为9.0‰~13.9‰,平均为10.9‰,主要为海相碳酸盐岩,碳、氧同位素图解表明碳可能主要来源于深部,且受高温变质作

  4. Sulfur metabolism in phototrophic sulfur bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2008-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

  5. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2016-01-01

    20160639Cai Wutian(Center for Hydrogeology a nd Environmental Geology Survey,China Geological Survey,Baoding071051,China)Several Issues on Contaminated Sites(Hydrogeology and Engineering Geology,ISSN1000-3665,CN11-2202/P,42(1),2015,p.123

  6. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20142560Hu Hongxia(Regional Geological and Mineral Resources Survey of Jilin Province,Changchun 130022,China);Dai Lixia Application of GIS Map Projection Transformation in Geological Work(Jilin Geology,ISSN1001-2427,CN22-1099/P,32(4),2013,p.160-163,4illus.,2refs.)

  7. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>20081307 Cao Xiping(Geological Museum of China,Beijing 100034)Discussion on the Digitization of Geological Specimen Information and Digital Geological Museum Construction(Acta Geoscientica Sinica,ISSN1006-3021,CN11-3474/P,28(2),2007,p.205-208,1 illus.,1 table,4 refs.)

  8. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    20152086 Liu Lei(Shandong Zhengyuan Geo-logical Exploration Institute,China Metallurgical Geology Bureau,Jinan 250101,China)Comparison of Gridding Effect of MapGIS Software(Contributions to Geology and Mineral Resources Research,ISSN1001-1412,CN12

  9. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20091383 Cui Yiwen(First Geology and Mineral Resources Prospecting Team of Qinghai Province,Ping’an 810600,China);Zhang Liling Quaternary Three-Dimensional Model of Geological Structures of Changchun City(Jilin Geology,ISSN1001-2427,CN22 -1099/P,27(2),2008,p.125-130,10 illus.,4 tables,14 refs.,with English abstract)

  10. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20132393 Lü Guxian(Institute of Geomechanics,Chinese Academy of Geological Sciences,Beijing 100081,China);Li Xiuzhang Research and Development of Orefield Geology(Geology and Prospecting,ISSN0495-5331,CN11-2043/P,48(6),2012,p.1143-1150,3illus.,1table,46refs.)Key words:study of mineral deposit

  11. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2015-01-01

    20150901Dai Chuangu(Guizhou Academy of Geologic Survey,Guiyang550005,China);Zheng Qiqian Geological Background Study of Metallogenic in Haixi-Yanshan Tectonic Cycle in Guizhou Province(Guizhou Geology,ISSN1000-5943,CN52-1059/P,31(2),2014,p.82-88,3illus.,2tables,13refs.)Key words:metallogenesis,metallogenic area,

  12. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2016-01-01

    20160938Gao Xiaowei(Wuhan Center of Geo-logical Survey,China Geological Survey,Wuhan 430223,China);Wu Xiurong Two Types of Terrain and Regional Mineralization in Sumatra,Indonesia(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,34

  13. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2016-01-01

    20160276Jiang Hanbing(Xi’an Institute of Geology and Mineral Resources,Xi’an710054,China);Yang Hequn The Metallogenic Series Family of Geological Formation in Dunhuang Metallogenetic Belt(Northwestern Geology,ISSN1009-6248,CN61-1149/P,48(1),2015,p.63-71,2illus.,2tables,28refs.)

  14. Precambrian ophiolites of Arabia; a summary of geologic settings, U-Pb geochronology, lead isotope characteristics, and implications for microplate accretion, Kingdom of Saudi Arabia

    Science.gov (United States)

    Pallister, John S.; Stacey, J.S.; Fischer, L.B.; Premo, W.R.

    1988-01-01

    Disrupted ophiolites occur in linear belts as much as 900 km long between micro plates that collided during the late Proterozoic to form the Arabian Shield. The U-Pb zircon ages and lead-isotope data from these ophiolitic rocks help constrain the history of accretion of the Arabian Shield and thereby contribute to the definition of its microplates and terranes. Microplates of the central and western Arabian Shield are generally thought to represent intra-oceanic island arcs that range in age from about 900 Ma to 640 Ma; however, a region of the eastern Arabian Shield contains rocks of early Proterozoic age and may represent an exotic continental fragment entrained between the arc complexes.

  15. Geochemistry of sulfur in the Florida Everglades; 1994 through 1999

    Science.gov (United States)

    Bates, Anne L.; Orem, W.H.; Harvey, J.W.; Spiker, E. C.

    2000-01-01

    In this report, we present data on the geochemistry of sulfur in sediments and in surface water, groundwater, and rainwater in the Everglades region in south Florida. The results presented here are part of a larger study intended to determine the roles played by the cycling of carbon, nitrogen, phosphorus, and sulfur in the ecology of the south Florida wetlands. The geochemistry of sulfur in the region is particularly important because of its link to the production of toxic methylmercury through processes mediated by sulfate reducing bacteria. Sediment cores were collected from the Everglades Agricultural Area (EAA), Water Conservation Areas (WCAs) 1A and 2A, from Lake Okeechobee, and from Taylor Slough in the southern Everglades. Water collection was more widespread and includes surface water from WCAs 1A, 2A, 3A, 2B, the EAA, Taylor Slough, Lake Okeechobee, and the Kissimmee River. Groundwater was collected from The Everglades Nutrient Removal Area (ENR) and from WCA 2A. Rainwater was collected at two month intervals over a period of one year from the ENR and from WCA 2A. Water was analyzed for sulfate concentration and sulfate sulfur stable isotopic ratio (34S/32S). Sediment cores were analyzed for total sulfur concentration and/or for concentrations of sulfur species (sulfate, organic sulfur, disulfides, and acid volatile sulfides (AVS)) and for their stable sulfur isotopic ratio. Results show a decrease in total sulfur content (1.57 to 0.61 percent dry weight) with depth in two sediment cores collected in WCA 2A, indicating that there has been an increase in total sulfur content in recent times. A sediment core from the center of Lake Okeechobee shows a decrease in total sulfur content with depth (0.28 to 0.08 percent dry weight). A core from the periphery of the lake (South Bay) likewise shows a decrease in total sulfur content with depth (1.00 to 0.69 percent dry weight), however, the overall sulfur content is greater than that near the center at all depths

  16. Geochemical evidence for cryptic sulfur cycling in salt marsh sediments

    DEFF Research Database (Denmark)

    Mills, Jennifer V.; Antler, Gilad; Turchyn, Alexandra V.

    2016-01-01

    to represent the salt marsh sediments suggests that the uptake rate of sulfate during this cryptic sulfur cycling is similar to the uptake rate of sulfate during the fastest microbial sulfate reduction that has been measured in the natural environment. The difference is that during cryptic sulfur cycling, all...... investigate sulfur cycling in salt marsh sediments from Norfolk, England where we observe high ferrous iron concentrations with no depletion of sulfate or change in the sulfur isotope ratio of that sulfate, but a 5‰ increase in the oxygen isotope ratio in sulfate, indicating that sulfate has been through...... a reductive cycle replacing its oxygen atoms. This cryptic sulfur cycle was replicated in laboratory incubations using 18O-enriched water, demonstrating that the field results do not solely result from mixing processes in the natural environment. Numerical modeling of the laboratory incubations scaled...

  17. ECONOMIC GEOLOGY (5)GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20071202 Bai Fu(Second Prospecting Insti- tute of Geology and Mineral Resources of the Gansu Bureau of Geology and Mineral Re- sources,Lanzhou 730020,China);Ma Genxi Analysis of the Occurrence of the Geother- mal Resources in Lanzhou,Gansu Province (Hydrogeology & Engineering Geology,

  18. Isotopic tracers of sources, wells and of CO{sub 2} reactivity in geological reservoirs; Tracage isotopique des sources, puits et de la reactivite du CO{sub 2} dans les reservoirs geologiques

    Energy Technology Data Exchange (ETDEWEB)

    Assayag, N

    2006-12-15

    The aim of this research works consisted in studying the behaviour of the carbonate system (dissolved inorganic carbon: DIC) following a CO{sub 2} injection (artificial or natural), in geological reservoirs. One part of the study consisted in improving an analytical protocol for the measurement of {delta} {sup 13}C DIC and DIC, using a continuous flow mass spectrometer. As a first study, we have focused our attention on the Pavin Lake (Massif Central, France). Owing to its limnologic characteristics (meromictic lake) and a deep volcanic CO{sub 2} contribution, it can be viewed as a natural analogue of reservoir storing important quantities of CO{sub 2} in the bottom part. Isotopic measurements ({delta} {sup 18}O, {delta} {sup 13}C DIC) allowed to better constrain the dynamics of the lake (stratification, seasonal variations), the magnitudes of biological activities (photosynthesis, organic matter decay, methane oxidation, methano-genesis), carbon sources (magmatic, methano-genetic), and the hydrological budgets (sub-lacustrine inputs). The second study was conducted on the Lamont-Doherty test well site (NY, USA). It includes an instrumental borehole which cuts through most of the section of the Palisades sill and into the Newark Basin sediments. Single well push-pull tests were performed: a test solution containing conservative tracers and a reactive tracer (CO{sub 2}) was injected at a permeable depth interval located in basaltic and meta sedimentary rocks. After an incubation period, the test solution/groundwater mixture was extracted from the hydraulically isolated zone. Isotopic measurements ({delta} {sup 18}O, {delta} {sup 13}C DIC) confronted to chemical data (major elements) allowed to investigate the extent of in-situ CO{sub 2}-water-rock interactions: essentially calcite dissolution and at a lesser extend silicate dissolution...and for one of the test, CO{sub 2} degassing. (author)

  19. Geochronology, geochemistry, and Sr-Nd-Hf isotopes of the early Paleozoic igneous rocks in the Duobaoshan area, NE China, and their geological significance

    Science.gov (United States)

    Wu, Guang; Chen, Yuchuan; Sun, Fengyue; Liu, Jun; Wang, Guorui; Xu, Bei

    2015-01-01

    The Duobaoshan area of northwestern Heilongjiang Province is the most important copper resource concentration region in NE China. To date, the Duobaoshan superlarge Cu-Mo deposit and the Tongshan large Cu-Mo deposit have been discovered in the Duobaoshan area. Both the deposits are hosted by granodiorites and volcanic rocks. Zircon LA-ICP-MS U-Pb dating indicates that these granodiorites emplaced approximately 479 Ma ago and that those volcanic rocks erupted between 447 and 450 Ma. The early Ordovicain granodiorites belong to the high-K to medium-K calc-alkaline series and are characterized by high Al2O3 and Sr contents, low Yb and Y contents, and relatively low Mg# values and Na2O/K2O ratios, with positive Eu or slight negative Eu anomalies (averaging 1.18). All of these geochemical characters are similar to those of the adakites generated by partial melting of a thickened lower crust in the world. Moreover, the granodiorites have low initial 87Sr/86Sr ratios (varying from 0.703474 to 0.704436), very high zircon εHf(t) and whole-rock εNd(t) values (varying from 13.0 to 16.8 and 5.27 to 5.46, respectively), and young zircon Hf and whole-rock Nd single-stage and two-stage model ages. Taking these geochemical characteristics and Sr-Nd-Hf isotope compositions together, we suggest that the early Ordovician granodiorites in the Duobaoshan area occurred in a post-collision environment and were formed by partial melting of a juvenile thickened lower crust dominated by depleted mantle-derived material. These late Ordovician volcanic rocks, which are composed of basalt, basaltic andesite, and andesite, belong to the tholeiitic or calc-alkaline series. They are generally enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs; e.g., Nb, Ta, Zr, Hf, P, and Ti), consistent with the geochemistry of igneous rocks from island arcs or active continental margins. Compared with the early Ordovician granodiorites, these volcanic rocks

  20. Chromium isotope variations

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary

    is incorporated into carbonates. Hence, ancient carbonates can potentially record the Cr isotopic composition (δ53Cr ‰) of seawater in the geological past. Reliable application and interpretation of this proxy requires a detailed knowledge about processes that fractionate Cr on the Earth’s surface...... deposited during the Early Ordovician — a time of known redox instability in ancient oceans – exhibit a significant positive Cr isotope excursion of +0.5‰. This excursion is interpreted as the reductive drawn down of dissolved Cr in seawater in response to the development of a proximal anoxic sink......, and the quantification the Cr isotope composition of major Cr fluxes into and out of ocean. This thesis adds to the current knowledge of the Cr isotope system and is divided into two studies. The focus of the first study was to determine what processes control the Cr isotopic compositionof river water and to quantify...

  1. Geological, geochronological, geochemical, and Sr-Nd-O-Hf isotopic constraints on origins of intrusions associated with the Baishan porphyry Mo deposit in eastern Tianshan, NW China

    Science.gov (United States)

    Wang, Yinhong; Xue, Chunji; Liu, Jiajun; Zhang, Fangfang

    2016-10-01

    The Baishan porphyry Mo deposit (0.72 Mt; 0.06 % Mo) is located in the interior of the eastern Tianshan orogenic belt in Xinjiang, NW China. The deposit comprises 15 orebodies that are associated with monzogranite and granite porphyry stocks and are structurally controlled by roughly EW-trending faults. Secondary ion mass spectrometry (SIMS) zircon U-Pb dating of the monzogranite and granite porphyry yielded the Middle Triassic age (228 ± 2 to 227 ± 2 Ma), which coincide with the molybdenite Re-Os model ages ranging from 226 ± 3 to 228 ± 3 Ma. The Triassic monzogranite and granite porphyry belong to high-K calc-alkaline series and are characterized by high SiO2 and Al2O3 and low MgO, TiO2, and P2O5 concentrations, with negative Eu anomalies (δEu = 0.55-0.91). The least-altered monzogranite and granite porphyry yield uniform ɛ Nd( t) values from +1.6 to +3.6, and wide (87Sr/86Sr) i ratios ranging between 0.7035 and 0.7071, indicating that they were derived from the lower crust. In situ O-Hf isotopic analyses on zircon using SIMS and laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) indicate that the δ18O and ɛ Hf( t) values of zircon from a monzogranite sample vary from 6.1 to 7.3 ‰ and +8.0 to +11.7, respectively, whereas zircon from a granite porphyry sample vary from 6.2 to 6.9 ‰ and +7.3 to +11.2, respectively. The geochemical and isotopic data imply that the primary magmas of the Baishan granite were likely derived from partial melts from the lower crust involving some mantle components. The Baishan Mo deposit and granitic emplacement were proposed to be most likely related to post-orogenic lithospheric extension and magmatic underplating. An extensional event coupled with the rising of hot mantle-derived melts triggered partial melting of the lower crust, as well as provided metals (Mo).

  2. Nature of isomerism in exotic sulfur isotopes

    CERN Document Server

    Utsuno, Yutaka; Otsuka, Takaharu; Yoshida, Tooru; Tsunoda, Yusuke

    2014-01-01

    We clarify the origin of the anomalously hindered $E2$ decay from the $4^+_1$ level in $^{44}$S that has recently been observed, performing a novel many-body analysis in the shell model. Opposed to the normal yrast states, this level is dominated by a two-quasiparticle $K=4$ intrinsic state occupying $\

  3. Geology, Petrology and O and H isotope geochemistry of remarkably 18O depleted Paleoproterozoic rocks of the Belomorian Belt, Karelia, Russia, attributed to global glaciation 2.4 Ga

    Science.gov (United States)

    Bindeman, I. N.; Serebryakov, N. S.

    2011-06-01

    This paper deals with strongly 18O-depleted (down to - 27.3‰ VSMOW) 1.9Ga Paleoproterozoic mid-grade metamorphic rocks found in the Belomorian Belt of Karelia (E. Baltic Shield). The protolith of these rocks is attributed to have been altered by glacial meltwaters during the world's first 2.4-2.3 Ga Paleoproterozoic "Slushball" glaciation, when Karelia was located near equatorial latitudes. We describe in detail three and report seven new localities with unusually depleted 18O signatures that now span 220 km across the Belomorian Belt. Hydrogen isotope ratios measured in amphibole, biotite and staurolite also display remarkably low values of - 212 to - 235‰. Isotope mapping in the three best exposed localities has allowed us to identify the world's most 18O depleted rock, located at Khitostrov with a δ 18O value - 27‰. In Khitostrov samples, zircons have normal δ 18O detrital cores and low-δ 18O metamorphic rims. Mapping demonstrates that zones of δ 18O depletion occur in a concentric pattern 100-400 m in dimension, and each locality displays significant δ 18O and δD heterogeneity on a meter to centimeter scale, characteristic of meteoric-hydrothermal systems worldwide. The zone of maximum δ 18O depletions usually has the highest concentration of metamorphic corundum, rutile, and zircon and also display doubled concentrations of insoluble trace elements (Zr, Ti, Cr, HREE). These results are explained by elemental enrichment upon mass loss during hydrothermal dissolution in pH-neutral meteoric fluid. Remarkably low-δ 18O and δD values suggest that alteration could have only happened by glacial meltwaters in a subglacial rift zone. Many localities with δ 18O depletions occur inside metamorphozed 2.4 Ga gabbro-noritic intrusions, or near their contact with Belomorian gneisses, implying that the intrusions were driving meteoric hydrothermal systems during the known 2.4 Ga episode of Belomorian rifting. Given that the isotopically-depleted localities now

  4. Global geochemical cycles of carbon, sulfur and oxygen

    Science.gov (United States)

    Walker, J. C.

    1986-01-01

    Time resolved data on the carbon isotopic composition of carbonate minerals and the sulfur isotopic composition or sulfate minerals show a strong negative correlation during the Cretaceous. Carbonate minerals are isotopically heavy during this period while sulfate minerals are isotopically light. The implication is that carbon is being transferred from the oxidized, carbonate reservoir to the reservoir of isotopically light reduced organic carbon in sedimentary rocks while sulfur is being transferred from the reservoir of isotopically light sedimentary sulfide to the oxidized, sulfate reservoir. These apparently oppositely directed changes in the oxidation state of average sedimentary carbon and sulfur are surprising because of a well-established and easy to understand correlation between the concentrations of reduced organic carbon and sulfide minerals in sedimentary rocks. Rocks rich in reduced carbon are also rich in reduced sulfur. The isotopic and concentration data can be reconciled by a model which invokes a significant flux of hydrothermal sulfide to the deep sea, at least during the Cretaceous.

  5. STRUCTURAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141912Cao Hui(State Key Laboratory for Continental Tectonics and Dynamics,Institute of Geology,Chinese Academy of Geological Sciences,Beijing 100037,China)Gravitational Collapse and Folding during Orogenesis:A Comparative Study of FIA Trends and Fold Axial Plane Traces(Geology in China,ISSN1000-3657,CN11-1167/P,40(6),2013,p.1818-1828,9illus.,35refs.,with

  6. GENERAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20071601 Yin Yanhong (Qingdao Institute of Marine Geology, Qingdao 266071, China); Sun Jiashi Discovery of Qingdao Iron Meteorite and Its Chemical Composition and Mineralogy (Marine Geology & Quaternary Geology, ISSN0256-1492, CN37-1117/P, 26(3), 2006, p.121-124, 3 illus., 2 tables, 9 refs.)Key words: iron meteorites, Shandong Province The Qingdao iron meteorite was found in May, 2004.

  7. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20070721 Dong Yaosong (National Key La-boratory of Geological Process and Mineral resources, Institute of Mathematical Geology and Remote Sensing, China University of Geosciences, Wuhan 430074, China); Yang Yanchen Mutual Compensation of Nerval Net and Characteristic Analysis in Mineral Resources Exploration (Mineral Resources and Geology, ISSN1001-5663, CN45-1174/TD, 20(1), 2006, p.1-6, 3 illus., 6 tables, 5 refs.) Key words: prospecting and exploration of mineral, neural network systems

  8. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072222 Cao Xiuding(Chengdu University of Technology,Chengdu 610059,China);Qin Guoqing General Packet Radio Service(GPRS)Technology and Its Application in Geological Hazard Monitoring(The Chinese Journal of Geological Hazard and Control,ISSN1003-8035,CN11-2852/P,17(1),2006,p.69-72,76,2 illus.,3 refs.)Key words:geologic hazards

  9. STRUCTURAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    <正>20122174 Bai Daoyuan ( Institute of Geological Survey of Hunan Province,Changsha 410011,China );Jia Baohua Neoproterozoic TectonicEvolution of the Xuefeng Orogenic Zone in Hunan Province ( Sedimentary Geology and Tethyan Geology,ISSN1009-3850,CN51-1593 / P,31 ( 3 ), 2011,p.78-87,2illus.,1 table,96refs. ) Key words:structural evolution,Neoproterozoic Era,Hunan Province This paper deals,on the basis of abundant lithogeochemical and geochronologic

  10. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20041748 Chen Liang (China University of Geosciences, Nanjing , Jiangsu); Meng Gao-tou Application of Information Model on Geological Hazards Investigating and Zoning of Counties and Cities: Taking Xianju County, Zhejiang Province as an Example (Hydroge-ology & Engineering Geology, ISSN 1000-3665, CN11-2202/P, 30(5), 2003, p. 49 - 52, 4 illus. , 2 tables, 6 refs. ) Key words: geologic hazards, information systems

  11. Geology and isotopic composition of helium, neon, xenon and metallogenic age of the Jinding and Baiyangping ore deposits, northwest Yunnan, China

    Institute of Scientific and Technical Information of China (English)

    XUE; Chunji(薛春纪); CHEN; Yuchuan(陈毓川); WANG; Denghong(王登红); YANG; Jianmin(杨建民); YANG; Weiguang(杨伟光); ZENG; Rong(曾; 荣)

    2003-01-01

    Both the Jinding and Baiyangping ore deposits developed in the Lanping basin, which is a Mesozoic-Cenozoic terrestrial clastic sedimentary basin. Their occurrences can easily lead many people to compare them with the Pb-Zn deposit hosted in sedimentary rocks, such as Mississippian Valley-, Sedex- and sandstone-type Pb-Zn deposits. However, the Lanping basin developed in the settings of strong tectonic activity of the continental crust, which could cause an effective material exchange between the lower crust and the upper mantle. The orebodies are clearly tectonically controlled without syngenetic features, which probably represents a new type of the sedimentary rock-hosted Pb-Zn deposit. The isotopic compositions of noble gases in ore-forming fluids indicate that 2%-32% of helium (3He/4He = 0.19 Ra-1.97 Ra) is derived from the mantle, 50.1% of neon (20Ne/22Ne = 10.45-10.83; 21Ne/22Ne = 0.03) from the mantle, and considerable amount of xenon (129Xe/130Xe = 5.84-6.86; 134Xe/130Xe = 2.26-2.71) from the mantle, which show that mantle fluids played an important role in the ore formation. The ore-forming age of 67-60 Ma obtained by Re-Os and 40Ar-39Ar dating methods is later than the host rock, which is coeval with the Himalayan alkali magmatism of the mantle source and mantle-crust source. In this paper, the mineralization of the Jinding and Baiyangping ore deposits is considered to be related to the mantle fluids which move upward with the magma or along the deep faults, and mix with the meteoritic brine in the crust to result in large-scale deposition.

  12. Evidence of a Neoproterozoic active continental margin - Geochemistry and isotope geology of high-grade paragneiss from the Ribeira Orogen, SE Brazil

    Science.gov (United States)

    Capistrano, G. G.; Schmitt, R. S.; Medeiros, S. R.; Fernandes, G. L. F.

    2017-08-01

    Ediacaran paragneisses from the Palmital Unit are located in a key region, between two major tectonic domains of the Ribeira Orogen (in Rio de Janeiro, SE Brazil): the Cabo Frio Tectonic Domain and the Oriental Terrane. We present here petrographic, geochemical and isotopic data in order to partially unravel the origin and tectonic nature of the protoliths from these metamorphic rocks. Litharenites interpreted as immature sediments, mostly derived from the erosion of felsic rocks (granites/rhyolites and diorites/andesites) are here described. Multi-elements patterns and trace elements ratios reinforce an upper continental crust nature for the composition of the protoliths. These were probably located close to the source area and accommodated in semi-arid climate and high topography conditions. Tectonic discrimination diagrams indicate that the Palmital basin developed in an active continental margin, corroborated by the zircon detrital spectra. The main population of detrital zircon (ca. 750-550 Ma) is partially coeval with the age of the Rio Negro continental magmatic arc, resident in the Oriental Terrane. The Palmital basin could represent a forearc environment with no oceanic crust material, but only a continuous sedimentation of turbidites derived from the arc, with gradational bedding signifying a subaqueous environment, without outside tectonic disturbances. On the other hand, TDM ages of 1.6-1.8 Ga suggest that these sediments are not juvenile, indicating also a contribution from an ancient crust. This recycled continental crust could come either from the basement of the Oriental Terrane (which was not identified yet) or from the basement of the Cabo Frio Tectonic Domain. In the last assumption the Palmital deposition would be concomitant with the initiation of continental collision and the subduction of the passive margin of the Cabo Frio Tectonic Domain towards west. This unit was subsequently metamorphosed/deformed during the ca. 540 Ma collision between

  13. Mesozoic Bimodal Volcanic Suite in Zhalantun of the Da Hinggan Range and Its Geological Significance:Zircon U-Pb Age and Hf Isotopic Constraints

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Mesozoic bimodal volcanic rocks of basaltic andesite and rhyolite are widely distributed in the Da Hinggan Range, but their petrogenetic relationships and geodynamic implications are rarely constrained. Detailed studies on doleritic and porphyry dikes in the Zhalantun area indicate that they display features of magma mixing, suggesting their coeval formation. In situ zircon U-Pb dating shows that the porphyry was emplaced in the Early Cretaceous with a 206Pb/238U age of 130±1 Ma. Zircons from the dolerite also yield an Early Cretaceous emplacement age of 124±2 Ma although some inherited zircons have been identified. These age results indicate that the Early Cretaceous was an important period of magmatism in the Da Hinggan Range. Zircons from porphyry are characterized by positive value of εHf(t) as high as 10.3±0.5 with Hf depleted mantle model age of 349-568 Ma, whereas magmatic zircons from the dolerite have εHf(t) value of 11.0±1.4 with Hf depleted mantel model age of 342-657 Ma,consistent with those from the porphyry. Considering other data on the geological evolution of this area,it is concluded that the mafic magma originated from the partial melting of Paleozoic enriched lithospheric mantle, whereas the felsic magma came from recycling of juvenile crust formed during the Paleozoic. Both of the protoliths are closely related to the subduction of the Paleo-Asian Ocean during the Paleozoic, indicating that the Paleozoic is an important period of large-scale crustal growth in the area.

  14. Dietary analysis of Late Cenozoic Mexican equids from three different geographic/geologic settings using stable carbon isotopes: Coincidences, differences and paleobiologic significance

    Science.gov (United States)

    Pérez-Crespo, Víctor Adrian; Ferrusquía-Villafranca, Ismael; Bravo-Cuevas, Víctor Manuel; Morales-Puente, Pedro; Ruiz-González, José E.

    2016-03-01

    The development of Vertebrate Paleontology in Mexico is uneven, so that there is a strong bias in favor of Neogene/Quaternary mammals largely collected in the Trans-Mexican Volcanic Belt (TMVB hereafter) and Central Plateau (CeP hereafter) Morphotectonic Provinces [MP hereafter]; however, the time is ripe for pursuing research in other than taxonomic areas. Here we investigate C3/C4 plant consumption in the equid lineage in three such provinces, which provide different geographic/geologic and paleoecologic scenarios during the Barstovian, Hemphillian and Rancholabrean times. Our results show that the Barstovian equids from Oaxaca, Sierra Madre del Sur MP Cormohipparion aff. C. quinni, Merychippus cf. M. sejunctus and Pliohippus sp. largely fed on C3 plants, which were the chief food stuff of horses in Mexico, particularly in the Southeast. On the other hand, the Hemphillian equid from Guanajuato, CeP Astrohippus stocki, was an unbalanced C3/C4 mixed feeders in favor of C4 plants, a fact that indicates a profound plant diversification due to the inception and rapid diversification of C4 plants that occurred there at this time, as it occurred in temperate North America, resulting in the differential consumption of C4 plants over that of C3 plants. Such trend prevailed until the Rancholabrean, as born out by the inferred diet for Equus conversidens and Equus sp. from Hidalgo, TMVB. Clearly then, the coeval diet change observed in Mexico and temperate North America implies a correlative vegetation change resulting in the appearance and rapid diversification of C4 plants, which largely formed the preferred food stuff of equids since the Hemphillian, although some C3 plant consumption was maintained till the Rancholabrean. It should be noted that the development of hypsodonty in equids and many artiodactyls, has long been interpreted as the adaptive mammalian response to the new feeding conditions.

  15. Genetic relationships between swamp microenvironment and sulfur distribution of the Late Paleozoic coals in North China

    Institute of Scientific and Technical Information of China (English)

    TANG; Dazhen

    2001-01-01

    [1]Yang, Q., Coal resources of China, in Move Toward Science Together, Hundreds Academicians' Series Reports on Science and Technology (Part 1) (in Chinese), Beijing: Xinhua Press, 1997, 276-286.[2]Flores, R. M., Geologic and geomorphic controls of coal development in some Tertiary rocky mountain basins, USA, Int. J. Coal Geol., 1993, 23: 43-73.[3]Hacquebard, P. A., Petrology and facies studies of the Carboniferous coals at Mabou Mines and the Port Hood, St. Rose and Sydney coalfields of Cape Breton Island, Nova Scotia, Canada, Int. J. Coal Geol., 1993, 24: 7-46.[4]Kalkreuth, W. D., McIntyre, D. J., Richardson, R. J. H., The geology, petrography and palynology of Tertiary coals from the Eureka Sound Group at Strathcona Fiord and Bache Peninsula, Ellesmere Island, Arctic Canada, Int. J. Coal Geol., 1993, 24: 75-111.[5]Price, F. T., Shieh, Y. H., Correlation between the d 34S of pyritic and organic sulfur in coal and oil shale, Chemical Geol-ogy, 1986, 58: 333-337.[6]Prosser, D. J., Daws, J. A., Fallick, A. E. et al., The occurrence and d 34S of authigenic pyrite in Middle Jurassic Brent Group sediments, Journal Petrol. Geol., 1994, 17(4): 407-428.[7]Spiker, E. C., Pierce, B. S., Bates, A. L. et al., Isotopic evidence for the source of sulfur in the Upper Freeport coal bed, west-central Pennsylvania, USA, Chemical Geology, 1994, 114: 115-130.[8]Berner, R. A., Sedimentary pyrite formation:An update, Geochim. Cosmochim. Acta, 1984, 48: 605-615.[9]Francois, R., A study of sulphur enrichment in the humic fraction of marine sediments during early diagenesis, Geochim. Cosmochim. Acta, 1987, 51: 17-27.[10]Canfield, D. E., Berner, R. A., Dissolution and pyritization of magnetite in anoxic marine sediments, Geochim. Cosmo-chim. Acta, 1987, 51: 645-660.[11]Sang, S. X., Liu, H. J., Shi, J., Study of the sulfur of the mangrove peat and its genesis in Hainandao, Geology and Explo-ration of Coalfield(in Chinese), 1993, 21(1): 12-17.

  16. Isotopic composition of sulfate accumulations, Northern Calcareous Alps, Austria

    Science.gov (United States)

    Bojar, Ana-Voica; Halas, Stanislaw; Bojar, Hans-Peter; Trembaczowski, Andrzej

    2015-04-01

    isotopic compositon of 14 sulfides as galena, sphalerite, pyrite and native sulfure were determined as well, with values ranging between -17.5 and 2.8 ‰ (CDT). For the investigated sulfates, the sulfur isotopic values show generally low values, which are characteristic for the late Permian. The broad distribution of sulfide values point toward bacterial reduction, fact also reflected by some higher isotopic values of sulfates. The oxygen values show a larger scatter from 9 to 23‰, which is even larger than that found for the Zechstein anhydrites of northern Germany, north-eastern Italian Alps or western Poland. The associated carbonates, as calcite, dolomite and magnesite are in disequilibrium with the sulfates indicating rather primary marine isotopic signature than re-equlibration with the sulfates at higher temperatures. References Leitner, C., Neubauer, F., Genser, J., Borojevic-Sostaric, B., Rantitsch, G., 2013. 40Ar/39Ar ages of recrystallization of rock-forming polyhalite in Alpine rocksalt deposits. In Jordan, F., Mark, D.F., Verati C. (eds.) Advances in 40Ar/39Ar Dating: from Archaeology to Planetary Sciences. Geological Society, London, Special Publications, 378, 207-244. Kirchner, E., 1987: Die Mineral- und Gesteinsvorkommen in den Gipslagerstätten der Lammermasse, innerhalb der Hallstattzone, Salzburg. Jahrbuch Haus der Natur. 10, 156-167. Postl, W., 1990. Enargit und Parnauit aus dem Gips- und Anhydritbergbau Tragöß-Oberort, Steiermark. In: Niedermayr, G. et al. (1990): Neue Mineralfunde aus Österreich XXXIX. Carinthia II, 180/100, 277. Tollmann, A., 1977. Geologie von Österreich. Band 1. Die Zentralalpen. Deuticke, Wien, 766 pp.

  17. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131683 Lin Wenjing(Institute of Hydrogeology and Environmental Geology,Chinese Academy of Geological Sciences,Shijiazhuang050061,China);Liu Zhiming An Estimation of HDR Resources in China’s Mainland(Acta Geoscientica Sinica,ISSN1006-3021,CN11-3474/P,33(5),2012,p.807-811,2illus.,2tables,14refs.)

  18. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131088 Fan Difu (Geological Survey of Jiangsu Province , Nanjing 210018 , China ); Xu Xueqiu Origin Study of Geothermal Field in Xiaoyangkou of Rudong County in Jiangsu (Journal of Geology , ISSN1674-3636 , CN32-1796/P , 36 (2), 2012 , p.192-197 , 3illus. , 9refs.) Key words : geothermal fields , Jiangsu Province

  19. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>20081086 Feng Wujun(Geological Research Institute,Jiangsu Oil Field Branch Company,Yangzhou 225012,Jiangsu);Cao Bing Geoheat Resources Evaluation and Target Optimization in Gaoyou Region of Jiangsu Province(Jiangsu Geology,ISSN1003-6474,CN32-1258/P,31(2),2007,p.130-13

  20. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    <正>20050726 Cheng Jiabai (Survey Team of Huabei Geological Exploration Bureau, Sanhe 065201, China); Zhao Yuanyi Prospecting Hypothesis and Verification (Contributions to Geology and Mineral Resources Research, ISSN 1001-1412, CN12-1131/P, 19(2), 2004, p. 122-129, 2 refs. , with English abstract) Key words: prospecting model

  1. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131925 Chen Ning(State Key Laboratory of Geological Hazards Prevention,Chengdu University of Technology,Chengdu 610059,China);Wang Yunsheng Features and Chains Genesis Analysis of Earthquake Geo-Hazards in Yuzi Stream of Wenchuan County(Journal of Engineering Geology,ISSN1004-9665,CN11-3249/P,20(3),2012,p.340-349,4

  2. STRUCTURAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131382 Chen Tao(Key Laboratory of Active Tectonics and Volcano,Institute of Geology,China Earthquake Administration,Beijing 100029,China);Liu Yugang The Activity Age of Tarwan Fault and Genesis of the Topographic Scarp(Seismology and Geology,ISSN0253-4967,CN11-2192/P,34(3),

  3. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20090651 Chen Boyang(Fujian Institute of Geological Survey and Research,Fuzhou 350011,China) Bio-Geochemical Characteristics of High and Low-Incidence Area of Stomach Cancer in the Coastal Area of Fujian Province(Geology of Fujian,ISSN1001-3970,CN35-1080/P,27(1),2008,p.29-36,3 tables,6 refs.)

  4. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20040862 Chen Zhihua (Faculty of Engineering, China University of Geosciences, Wuhan, Hubei); Guan Xuefeng Development of DBMS for Environmental Geologic Hazards on WebGIS (Hydrogeology & Engineering Geology, ISSN1000-3665, CN11-2202/P, 30(2), 2003, p. 20-24, 3 illus. , 9 refs. )

  5. STRUCTURAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    <正>20050576 Li Sanzhong (College of Marine Geosciences, Ocean University of China, Qingdao 266003,China) ; Zhou Lihong Cenozoic Faulting and Basin Formation in the Eastern North China Plate (Marine Geology & Quaternary Geology, ISSN 0256 - 1492, CN37 -1117/P, 24(3), 2004, p. 57-66, 5 illus. , 33 refs. ) Key words: tectonic framework, North China

  6. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20040834 Chen Yijiu (Geological Exploration Bureau of Guangdong Province, Guangzhou, Guangdong) Discussion on Natural Chornic Irradiation Environment and Pertinent Problems in Guangdong Province, China (Guangdong Geology, ISSN 1001 - 8670, CN44-1201/P, 18(1), 2003, p. 30-41, 7 tables, 1 ref. , with English abstract) Keywords: radioactivity radiation environmental pollution Guangdong Province

  7. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20131358 Li Jianzhong (State Key Laboratory of Geological Processes and Mineral Resources , School of Earth Sciences and Resources , China University of Geosciences , Beijing 100083 , China); Cui Jing Geological Application of Mult-Idimensional Data Visualization Based on Geometric Coordinate Method (Earth Science Frontiers

  8. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20142114Lin Quansheng(China University of Geosciences,Bejing 100083,China)On the Geologic Characteristics and Economic Significance of the Cambrian Lintian Group in Fujian Province(Geology of Fujian,ISSN1001-3970,CN35-1080/P,32(4),2013,p.264-273,2illus.,2tables,6refs.)

  9. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20140227Li Wenyuan(Xi’an Center of Geological Survey,CGS,Xi’an 710054,ChinaThe Continental Growth and Ore-Forming Processes(Northwestern Geology,ISSN1009-6248,CN61-1149/P,46(1),2013,p.1-10,5illus.,18refs.)

  10. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2004-01-01

    <正>20041944 Chen Yuchuan (Chinese Academy of Geological Sciences, Beijing) ; Xue Chunli Discussion on the Regional Mineralizing Pedigree of the Ore Deposits in the Northern Margin of the North China Landmass (Geological Journal of China Universities, ISSN 1006-7493, CN32-1440/P, 9(4), 2003, p. 520-535, 2 illus. , 3 tables, 43 refs. ,

  11. Solubility of Sulfur Dioxide in Sulfuric Acid

    Science.gov (United States)

    Chang, K. K.; Compton, L. E.; Lawson, D. D.

    1982-01-01

    The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.

  12. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111337 Chen Guoxu(Faculty of Earth Resources,China University of Geosciences,Wuhan 430074,China);Wu Chonglong Study on Integration of 3D Geological Modeling and Mineral Resource Exploration Mapping(Geology and Prospecting,ISSN0495-5331,CN11-2043/P,46(3),2010,p.542-546,5 illus.,19 refs.)Key words:geological modeling,digital cartography According to the workflow of traditional methods of mineral reserve estimation,the authors took mine 3D geological modeling and mineral reserve estimation mapping as a starting point to explore a new method for the integration of 3D geological modeling and mineral resource exploration mapping.In order to verify this method,the authors have applied this method to some real mines.The results show that this method can effectively solve those problems of

  13. 江西永平铜多金属矿床流体包裹体及硫同位素研究%Fluid Inclusions and Sulfur Isotope of the Yongping Copper-polymetallic Deposit in Jiangxi Province

    Institute of Scientific and Technical Information of China (English)

    陈军军; 曹殿华; 杨昔林; 邱昌容; 王训军; 阚迎松

    2016-01-01

    of fluid inclusions related to metallogensis are present in the porphyry Mo deposit: I-type gas-liquid inclusion, II-type CO2-bearing three-phase inclusion and III-type daughter-minerals bearing inclusion. Homogenization temperatures and salinities of fluid inclusions at the quartz-sulfide stage range from 202℃ to 359℃ and 4.62 wt%NaCl to 36.68 wt%NaCl. The quartz-carbonate-sulfide stage yielded homogenization temperatures of 211~318℃ and salinities of 2.07~11.47 wt%NaCl. Fluid inclusions in minerals of the skarn Cu deposit are mainly I-type gas-liquid inclusions. The homogenization temperatures and salinity of fluid inclusions at the skarn stage vary in the range of 406~486℃ and 9.21~9.89 wt%NaCl. The fluid inclusions of middle-stage have the homogenization temperatures of 137~335℃ and the salinity of 4.98~13.20 wt%NaCl. The late stage fluid has the homogenization temperatures of 89~151℃ and the salinity of 2.07~19.13 wt%NaCl. Raman microspectroscopic studies of the fluid inclusions of the skarn deposit and the porphyry deposit show that the main components are CO2 and H2O, and the ore-forming fluid belongs to the H2O-CO2-NaCl system. CH4 in the Mo fluid indicates condition of low oxygen fugacity. Therefore, Mo mineralization center is formed in the early stage of fluid evolution. Mo fluid has a higher temperature and pressure with respect to the Cu fluid at the quartz-sulfide stage. Most sulfur isotope values of the sulfides give a narrowδ34S range from –0.2‰ to +1.9‰, indicating a predominant magmatic sulfur origin. The authors hold that the Yongping copper-polymetallic deposit is a porphyry-skarn type deposit resulting from the emplacement of the Late Jurassic monzogranite intrusions. From the intrusion through the contact zone to the host rocks, the mineralization is demonstrated by zoning of Mo-Cu-W-Pb-Zn.

  14. Accumulation of atmospheric sulfur in some Costa Rican soils

    Science.gov (United States)

    Bern, Carleton R.; Townsend, Alan R.

    2013-01-01

    Sulfur is one of the macronutrient elements whose sources to terrestrial ecosystems should shift from dominance by rock-weathering to atmospheric deposition as soils and underlying substrate undergo progressive weathering and leaching. However, the nature and timing of this transition is not well known. We investigated sources of sulfur to tropical rain forests growing on basalt-derived soils in the Osa Peninsula region of Costa Rica. Sulfur sources were examined using stable isotope ratios (δ34S) and compared to chemical indices of soil development. The most weathered soils, and the forests they supported, are dominated by atmospheric sulfur, while a less weathered soil type contains both rock-derived and atmospheric sulfur. Patterns of increasing δ34S with increasing soil sulfur concentration across the landscape suggest atmospheric sulfur is accumulating, and little rock-derived sulfur has been retained. Soil sulfur, minus adsorbed sulfate, is correlated with carbon and nitrogen, implying that sulfur accumulation occurs as plants and microbes incorporate sulfur into organic matter. Only the lower depth increments of the more weathered soils contained significant adsorbed sulfate. The evidence suggests a pattern of soil development in which sulfur-bearing minerals in rock, such as sulfides, weather early relative to other minerals, and the released sulfate is leached away. Sulfur added via atmospheric deposition is retained as organic matter accumulates in the soil profile. Adsorbed sulfate accumulates later, driven by changes in soil chemistry and mineralogy. These aspects of sulfur behavior during pedogenesis in this environment may hasten the transition to dominance by atmospheric sources.

  15. ECONOMIC GEOLOGY (5)GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>20082442 Han Zaisheng(China Geological Servey,Beijing 100011,China);Ran Weiyan Exploration and Evaluation of Shal- low Geothermal Energy(Geology in China, ISSN1000—3657,CN11—1167/P,34(6), 2007,p.1115—1121,6 refs.,with English abstract) Key words:geothermal exploration, geothermal resources

  16. GENERAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2016-01-01

    20160715Lai Yongwang(State Key Laboratory of Isotope Geochemistry,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510640,China);Wang Guiqin Classification of 10Meteorites from Hami in Xinjiang:Petrology and Mineralogy

  17. Optimization of LC-DRC-ICP-MS for the speciation of selenotrisulfides with simultaneous detection of sulfur and selenium as oxides combined with determination of elemental and isotope ratios

    DEFF Research Database (Denmark)

    Sturup, S.; Bendahl, L.; Gammelgaard, B.

    2006-01-01

    A LC-DRC-ICP-MS method for the simultaneous detection of selenium and Sulfur in the selenotrisulfides selenocysteineglutathione (Cys-Se-SG) and selenodiglutathione (GS-Se-SG) is described. Both sulfur and selenium are reacted with oxygen in the dynamic reaction cell (DRC) and detected as oxides....... The selenotrisulfides were separated applying a 30 rnin gradient liquid chromatographic (LC) method with a formic acid/methanol eluent. The detection limits for sulfur (as (SO+)-S-32-O-16) and selenium (as (SeO+)-Se-80-O-16) in the chromatographic system were 4.0 and 0.2 mu g L-1 (100 and 5 ng in absolute mass units...

  18. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20111836 Gao Jian(Sichuan Institute of Geological Survey for Nuclear Industry,Chengdu 610061,China);Shi Yuzhen Feasibility Study of Exploitation of Geothermal Resource in the Lugu Lake Region,Yanyuan,Sichuan Province(Acta Geologica Sichuan,ISSN1006-0995,CN51-1273/P,30(3),2010,p.291-294,1 illus.,1 table,1 ref.,with English abstract)Key words:geothermal water,Sichuan Province20111837 He Jianhua(Geological Brigade 102,Bureau of Geolog

  19. STRUCTURAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072338 Bai Long(Guizhou Academy of Geology Survey,Guiyang,Guizhou 550005,China);Zhang Zhen Treatment of Discovery on Ductile Shear Belts in Yiwu,Xingjiang Province and Its Ore-Forming Geology Process(Guizhou Geology,ISSN1000-5943,CN52-1059/P,23(4),2006,p.286-291,295,3 illus.,9 refs.)Key words:ductile shear zones,metallogenesis,XinjiangOf ductile shear belts,deformation fabric considerably developed in Yiwu,

  20. Isotopic evidence of TSR origin for natural gas bearing high H2S contents within the Feixianguan Formation of the northeastern Sichuan Basin, southwestern China

    Institute of Scientific and Technical Information of China (English)

    ZHU Guangyou; ZHANG Shuichang; LIANG Yingbo; DAI Jinxing; LI Jian

    2005-01-01

    The northeastern area of Sichuan Basin, southwestern China, is the area with the maximal reserve of natural gas containing higher hydrogen sulphide (H2S) that has been found among the petroliferous basins of China, with the proven and controlled gas reserve of more than 200 billion cubic meters. These gas pools, with higher H2S contents averaging 9%, some 17%, are mainly distributed on structural belts of Dukouhe, Tieshanpo, Luojiazhai, Puguang, etc., while the oolitic-shoal dolomite of the Triassic Feixianguan Fm. (T1f) is the reservoir. Although many scholars regard the plentiful accumulation of H2S within the deep carbonate reservoir as the result of Thermochemical Sulfate Reduction (TSR), however, the process of TSR as well as its residual geological and geochemical evidence is still not quite clear. Based on the carbon isotopic analysis of carbonate strata and secondary calcite, etc., together with the analysis of sulfur isotopes within H2S, sulphur, gypsum, iron pyrites, etc., as well as other aspects including the natural gas composition, carbon isotopes of hydrocarbons reservoir petrology, etc., it has been proved that the above natural gas is a product of TSR. The H2S, sulphur and calcite result from the participation of TSR reactions by hydrocarbon gas. During the process for hydrocarbons being consumed due to TSR, the carbons within the hydrocarbon gas participate in the reactions and finally are transferred into the secondary calcite, and become the carbon source of secondary calcite, consequently causing the carbon isotopes of the secondary calcite to be lower (-18.2‰). As for both the intermediate product of TSR, i.e. sulfur, and its final products, i.e. H2S and iron pyrites, their sulfur elements are all sourced from the sulfate within the Feixianguan Fm. During the fractional processes of sulfur isotopes, the bond energy leads to the 32S being released firstly, and the earlier it is released, the lower δ34S values for the generated sulphide (H2S

  1. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20101802 Fang Bin (China University of Geosciences,Beijing 100083,China);Yang Yunjun Characteristics and Resource Evaluation of the Jiwa Geothermal Field in Central Qiangtang,Northern Tibet,China (Geological Bulletin of China,ISSN1671-

  2. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20112453 Li Qing (First Design and Research Institute,Ministry of Mechanical Industry, Bengbu 233000, China); Li Yixiang Application of Shallow Geothermal Energy Resources in the Hefei Area(Geology

  3. Marine geology

    Digital Repository Service at National Institute of Oceanography (India)

    Rao, V.P.; Shankar, R.

    Significant scientific contributions in Marine Geology in India during the Nineties have been highlighted in this paper. Sediment trap data collected in the Arabian Sea and Bay of Bengal have provided much understanding about annual sediment fluxes...

  4. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20112745Cheng Shurang(Geological survey of Shanxi Province,Xi’an 710065,China); Zhang Lin Grade Evaluation Based on Fuzzy Clustering and Pattern Recognition of Comprehensive Anomalies of Geophysics and

  5. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20101648 Peng Yujing (Survey of Regional Geology and Mineral Resources of Jilin Province, Changchun 130022, China); Zhai Yuchun Age Determination and Characteristics of the Late Indosinian-Yanshanian Metallogenetic Events of Jilin Province

  6. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20112330 Liu Xifang (Key Laboratory of Saline Lake Resources and Environment, Ministry of Land and Resources,Institute of Mineral Resources, Beijing 100037, China);Zheng Mianping Geological Features

  7. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    <正>20102475 Chen Shiliang(No.4 Geological Party of Fujian Province,Ningde 352100,China)A Brief Analysis on Geothermy in the Nantai Isle of Fuzhou Municipality,Fujian Province(Geology of Fujian,ISSN1001-3970,CN35-1080/P,28(4),2009,p.310-314,1 illus.,1 table,3 refs.)Key words:geothermal exploration,Fujian ProvinceBased on the geochemistry and geophysical

  8. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    <正>20122531 Hu Lingzhi ( Institute of Geological Engineering Design & Research of Beijing,Miyun 101500,China );Wang Jiankang Discussion on the Feasibility of Geothermal Resources Development and Utilization in Miyun District,Beijing ( City Geology,ISSN1007-1903,CN11-5519 / P,6 ( 3 ), 2011,p.34-35,59 ,) Key words:geothermal resources,Beijing Geothermal,as a new type of clean energy with the integrated trinity of " heat energy-mineral resource-water resource ",

  9. GEOTHERMICS GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2013-01-01

    <正>20132568 Du Guilin(Seismological Bureau of Weihai City,Weihai 264200,China);Cao Wenhai Genesis of Baoquantang Hot Spring in Weihai and Its Influence on Faulting and Seismic Activities(Marine Geology&Quaternary Geology,ISSN0256-1492,CN37-1117/P,32(5),2012,p.67-72,3illus.,2tables,18refs.)Key words:hot springs,seismicity,Shandong Province

  10. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072933 Bie Jun(Institute of Oceanology,Chinese Academy of Sciences,Qingdao 266071,China);Huang Haijun Ground Subsidence of the Modern Yellow River Delta and Its Causes(Marine Geology & Quaternary Geology,ISSN0256-1492,CN37-1117/P,28(4),2006,p.29-35,5 illus.,13 refs.,with English abstract)Key words:land subsidence,Yellow River Delta

  11. GENERAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141269 Dai Deqiu(Institute of Geology,Hunan University of Science and Technology,Xiangtan 411201,China);Chen Xinyue Contrastive of Petrography and Mineral Chemistry Characteristics among Olivine and Ca,Al-rich Assemblages(Chinese Journal of Geology,ISSN0563-5020,CN11-1937/P,48(3),2013,p.762-772,3 illus.,2 tables,25 refs.)

  12. ENVIRONMENTAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141810 Bian Yumei(Geological Environmental Monitoring Center of Liaoning Province,Shenyang 110032,China);Zhang Jing Zoning Haicheng,Liaoning Province,by GeoHazard Risk and Geo-Hazard Assessment(Journal of Geological Hazards and Environment Preservation,ISSN1006-4362,CN51-1467/P,24(3),2013,p.5-9,2 illus.,tables,refs.)

  13. GENERAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20140001Dong Shuwen(Chinese Academy of Geological Sciences,Beijing 100037,China);Li Tingdong Progress of SinoProbe-Deep Exploration in China 2008~2012(Acta Geoscientica Sinica,ISSN1006-3021,CN11-3474/P,34(1),2013,p.7-23,8illus.,69refs.)Key words:deep geology,deep seismic sounding,Continental Scientific Drilling,China SinoProbe 2008~2012,the initial phase

  14. Geology, summary

    Science.gov (United States)

    Sabins, F. F., Jr.

    1975-01-01

    Trends in geologic application of remote sensing are identified. These trends are as follows: (1) increased applications of orbital imagery in fields such as engineering and environmental geology - some specific applications include recognition of active earthquake faults, site location for nuclear powerplants, and recognition of landslide hazards; (2) utilization of remote sensing by industry, especially oil and gas companies, and (3) application of digital image processing to mineral exploration.

  15. PETROLEUM GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2012-01-01

    <正>20122476 Bao Yunjie ( Wuxi Research Institute of Petroleum Geology,SINOPEC,Wuxi 214151,China );Wang Shuyi Reservoir Diagenesis of 3rd Member of Feixianguan Formation,Jiannan Gas Field ( Petroleum Geology & Experiment,ISSN1001-6112,CN32-1151 / TE,33 ( 6 ), 2011,p.564-568,2 il-lus.,1plate,2tables,10refs. ) Key words:carbonate reservoirs,diagenesis,Chongqing,Hubei Province

  16. MATHEMATICAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072288 Hong Quan(Ningbo Institute for Engineering Investigation,Ningbo 315012,China)Design of Information Management System for Engineering Investigation Maps Based on C/S Model(The Chinese Journal of Geological Hazard and Control,ISSN1003-8035,CN11-2852/P,17(1),2006,p.86-90,2 illus.,6 refs.)Key words:information systems,engineering geological map

  17. STRUCTURAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2014-01-01

    <正>20141283 Bai Daoyuan(Hunan Institute of Geological Survey,Changsha 410016,China);Zhong Xiang Nature,Origin and Tectonic Setting of Jinzhou Basin in the South Segment of Xuefeng Orogen(Geology in China,ISSN1000-3657,CN11-1167/P,40(4),2013,p.1079-1091,10 illus.,47 refs.)Key words:foreland basins,strike-slip faults,Hunan Province

  18. COAL GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    <正>20091159 Gao Yan(No.3 Prospecting Team of Anhui Bureau of Coal Geology,Suzhou 234000,China) Effect of Depositional Environment of Coal-Bearing Stratum on Major Coal Seams in Suntan Coalmine,Anhui Province(Geology of Anhui,ISSN 1005- 6157,CN34-1111/P,18(2),2008,p.114 -117,5 illus.,1 ref.,with English abstract)

  19. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>20110164 Dong Lianhui(Xinjiang Bureau of Geology and Mineral Resources and Development,Urumqi 830000,China);Feng Jing Research for Classification of Metallogenic Unit of Xinjiang(Xinjiang Geology,ISSN1000-8845,CN65-1092/P,28(1),2010,p.1-15,1 illus.,1 table,17 refs.,with English abstract)Key words:metallogenic provinces,metallogenic belts,metallogenic area,Xinjiang

  20. ECONOMIC GEOLOGY

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    <正>20072528 Chen Yuchuan(Chinese Academy of Geological Sciences,Beijing,100037);Pei Rongfu On Minerogenetic(Metallogenetic)Series:Third Discussion(Acta Geologica Sinica,ISSN0001-5717,CN11-1951/P,80(10),2006,p.1501-1508,3illus.,1 table,57 refs.,with English abstract)Key words:metallogenic series20072529 Pei Rongfu(Institute of Mineral Resources,CAGS,Beijing 100037);Mei Yanxiong Event Geology Stimulati

  1. Lead-isotopic, sulphur-isotopic, and trace-element studies of galena from the Silesian-Cracow Zn-Pb ores, polymetallic veins from the Gory Swietokrzyskie MTS, and the Myszkow porphyry copper deposit, Poland

    Science.gov (United States)

    Church, S.E.; Vaughn, R.B.; Gent, C.A.; Hopkins, R.T.

    1996-01-01

    Lead-isotopic data on galena samples collected from a paragenetically constrained suite of samples from the Silesian-Cracow ore district show no regional or paragenetically controlled lead-isotopic trends within the analytical reproducibility of the measurements. Furthermore, the new lead-isotopic data agree with previously reported lead-isotopic results (R. E. Zartman et al., 1979). Sulfur-isotopic analyses of ores from the Silesian-Cracow district as well as from vein ore from the Gory Swietokrzyskie Mts. and the Myszkow porphyry copper deposit, when coupled with trace-element data from the galena samples, clearly discriminate different hydrothermal ore-forming events. Lead-isotopic data from the Permian and Miocene evaporite deposits in Poland indicate that neither of these evaporite deposits were a source of metals for the Silesian-Cracow district ores. Furthermore, lead-isotopic data from these evaporite deposits and the shale residues from the Miocene halite samples indicate that the crustal evolution of lead in the central and western European platform in southern Poland followed normal crustal lead-isotopic growth, and that the isotopic composition of crustal lead had progressed beyond the lead-isotopic composition of lead in the Silesian-Cracow ores by Permian time. Thus, Mesozoic and Tertiary sedimentary flysch rocks can be eliminated as viable source rocks for the metals in the Silesian-Cracow Mississippi Valley-type (MVT) deposits. The uniformity of the isotopic composition of lead in the Silesian-Cracow ores, when coupled with the geologic evidence that mineralization must post-date Late Jurassic faulting (E. Gorecka, 1991), constrains the geochemical nature of the source region. The source of the metals is probably a well-mixed, multi-cycle molasse sequence of sedimentary rocks that contains little if any Precambrian metamorphic or granitic clasts (S. E. Church, R. B. Vaughn, 1992). If ore deposition was post Late Jurassic (about 150 m. y.) or later

  2. The Vein-type Zn-(Pb, Cu, As, Hg) mineralization at Fedj Hassene ore field, North-Western Tunisia: Mineralogy, Trace Elements, Sulfur Isotopes and Fluid Inclusions; Le champ filonien a Zn-(Pb, Cu, As, Hg) du district minier de Fedj Hassene (Nord Ouest de la Tunisie): Mineralogie, Elements en traces, Isotopes du Soufre et Inclusions Fluides

    Energy Technology Data Exchange (ETDEWEB)

    Bejaouil, J.; Bouhlel, S.; Barca, D.; Braham, A.

    2011-07-01

    The Fedj Hassene district is localized at the edge of the Tuniso-Algerian border 10 km of Ghardimaou area. It consists of a Zn-Pb vein type with minor amounts of Cu-As-Hg. The total Zn reserves are about 370.000t. The mineralization occurs within sub parallel fractures to the Ain El Kohla ESE-WNW fault. Host rocks consist of limestones and marly limestones of the Middle Turonian. In the principal lode of Fedj Hassene, the mineralization occurs as vein filling of massive and brecciated brown sphalerite and minor galena ore with gangue. Other trace minerals are pyrite, chalcopyrite, orpiment, realgar, smithsonite and cerussite. LA-ICP-MS analyses in sphalerites show mean contents of 0,84 wt% Fe, 0,14 wt% Cd and 0,02 wt% Mn Ore. Fluid inclusions study in calcite and sphalerite reveals one mineralizing fluid characterized by an average salinity 23% wt NaCl with decreasing homogenisation temperature. In fact the temperature shows decrease from sphalerite to calcite. The fluid density that corresponds to trapping pressure ranges between 1.00 g/cm{sup 3} and 1.11 g/cm{sup 3} and pressure close to 200 bars. Micro thermometric data in fluid inclusion hosted by gangue mineral presented by calcite show an average temperature of formation around 194 degree centigrade. These inclusions homogenized to the liquid phase between 156 degree centigrade and 210 degree centigrade and salinities values ranging from 22 to 28 wt% NaCl and an average around 23% wt NaCl. The {delta}{sup 3}4S (VCDT) values of sphalerite are in the range of + 4,6% to 6,4% (average=5,6%). Thermochemical reduction of Triassic sulfate by reaction with hydro-carbons is the most probable source for the heavy and the narrow range of the d{delta}{sup 3}4S values. Mineralogical, geochemical of trace elements, fluid inclusions and sulfur isotopes studies allow to include the vein-type ore field of Fedj Hassene in the polymetallic (Pb-Zn-As-Hg) vein mineralization of the nappe zone in northern Tunisia and north eastern

  3. Well materials durability in case of carbon dioxide and hydrogen sulphide geological sequestration; Durabilite des materiaux de puits petroliers dans le cadre d'une sequestration geologique de dioxyde de carbone et d'hydrogene sulfure

    Energy Technology Data Exchange (ETDEWEB)

    Jacquemet, N

    2006-01-15

    The geological sequestration of carbon dioxide (CO{sub 2}) and hydrogen sulphide (H{sub 2}S) is a promising solution for the long-term storage of these undesirable gases. It consists in injecting them via wells into deep geological reservoirs. The steel and cement employed in the well casing can be altered and provide pathways for leakage with subsequent human and environmental consequences. The materials ageing was investigated by laboratory experiments in geologically relevant P-T conditions. A new experimental and analysis procedure was designed for this purpose. A numerical approach was also done. The cement and steel were altered in various fluid phases at 500 bar-120 C and 500 bar-200 C: a brine, a brine saturated with H{sub 2}S-CO{sub 2}, a mixture of brine saturated with H{sub 2}S-CO{sub 2} and of supercritical H{sub 2}S-CO{sub 2} phase, a dry supercritical H{sub 2}S-CO{sub 2} phase without liquid water. In all cases, two distinct reactions are observed: the cement carbonation by the CO{sub 2} and the steel sulfidation by the H{sub 2}S. The carbonation and sulfidation are respectively maximal and minimal when they occur within the dry supercritical phase without liquid water. The textural and porosity properties of the cement are weakly affected by all the treatments at 120 C. The porosity even decreases in presence of H{sub 2}S-CO{sub 2}. But these properties are affected at 200 C when liquid water is present in the system. At this temperature, the initial properties are only preserved or improved by the treatments within the dry supercritical phase. The steel is corroded in all cases and thus is the vulnerable material of the wells. (author)

  4. Geologic environmental study

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Chun Soo; Bae, Dae Seok; Kim, Kyung Su; Park, Byung Yoon; Koh, Young Kown; Chun, Kwan Sik; Kim, Jhin Wung

    2000-05-01

    The geoscience research works are focused on the production of geologic basic data accompanying with the technical development of geology and hydrogeologic characterization. The lithology of the Korean peninsula consists of a complex structure of 29 rock types from Archean to Quaternary. The wide distribution of Mesozoic plutonic rock is an important consideration as a potential host rock allowing flexibility of siting. The recent tectonic activities are limited to localized particular area, which can be avoided by excluding in the early stage of siting. Three rock types such as plutonic rocks, crystalline gneisses and massive volcanic rocks were suggested as the preferred host rocks for the further study on HLW disposal system. This report contains grouping of regional faults, and on the distributional characteristics of faults and fractures(zones) in terms of lithological domain and tectonical provinces. The regional groundwater regime can be grouped into 3 regimes by tectonic setting and four groundwater regions based on an altitute. Groundwaters can be grouped by their chemistry and host rocks. The origin of groundwater was proposed by isotope ({sup 1}8O, {sup 2}H, {sup 1}3C, {sup 3}4S, {sup 8}7Sr, {sup 1}5N) studies and the residence time of groundwater was inferred from their tritium contents. Based on the geochemical and isotope characteristics, the geochemical evolutions of each types of groundwater were simulated using SOLVEQ/CHILLER and PHREEQC programs.

  5. Tracing Origin of sulfur in hydrothermal system of Eastern Taiwan

    Science.gov (United States)

    Hsu, Hsiao-Yuan; You, Chen-Feng; Chung, Chuan-Hsiung; Aggarwal, Suresh Kumar

    2016-04-01

    Multiple sulfur isotope results and sulfate concentrations are reported for different hydrothermal system in many countries. However, Taiwan is a seismically active country with plenty of hot spring resources, but only a few studies discuss about sulfur isotopes of them. No exhaustive study has been done to explain the high concentration and origin of sulfur in hydrothermal system of Taiwan, and chemical reaction between sulfide and sulfate. The true sulfur speciation in geothermal waters is difficult t