Historical variations in the stable isotope composition of mercury in a sediment core from a riverine lake: Effects of dams,pulp and paper mill wastes,and mercury from a chlor-alkali plant     

《Applied Geochemistry》2016

The Wabigoon River (Ontario, Canada) was affected by dams starting in 1898 and was polluted with pulp and paper mill wastes starting in 1913 and mercury from a chlor-alkali plant from 1962 to 1975. A dated sediment core from a riverine lake was analysed to investigate resultant changes in the biogeochemistry of mercury as revealed by variations in mercury isotope ratios and sediment chemistry. A total mercury maximum formed by the mercury pollution coincided with minimums in the δ-values of the ¹⁹⁸Hg/²⁰²Hg, ¹⁹⁹Hg/²⁰²Hg, ²⁰⁰Hg/²⁰²Hg, and ²⁰¹Hg/²⁰²Hg ratios, and the δ-values decreased in the order δ²⁰¹Hg > δ²⁰⁰Hg > δ¹⁹⁹Hg > δ¹⁹⁸Hg. Thus, mass-dependent fractionation caused depletion in lighter isotopes, implying evaporation of Hg(0) and pollution of the atmosphere as well as the river-lake system. Concurrently, mass-independent fractionation caused ¹⁹⁹Hg enrichment, possibly reflecting an independently documented upsurge in methylmercury production, and ²⁰¹Hg depletion, suggesting removal of methylmercury with anomalously high ²⁰¹Hg/¹⁹⁹Hg ratios by aquatic organisms and accumulation of ²⁰¹Hg-depleted inorganic Hg(II) in sediments. The δ²⁰¹Hg/δ¹⁹⁹Hg ratio rose abruptly when mercury pollution began, reflecting the resultant increase in methylmercury production, and remained high but gradually declined as the pollution abated, paralleling trends shown by methylmercury in aquatic organisms. The δ²⁰¹Hg/δ¹⁹⁹Hg ratio of pre-1962 background mercury increased ca. 1898 and ca. 1913–1929, suggesting accelerated methylmercury production due to stimulation of microbial activities by the damming of the river and the input of pulp and paper mill wastes, respectively. Other variations were linked to economic and technological factors that affected pulp and paper manufacture.  相似文献   

黔中茶店桥地下河流域不同水体硫酸盐浓度特征及来源识别   总被引：8，自引：0，他引：8  

任坤  潘晓东  兰干江  焦友军  曾洁  孟小军  庞园 《地质学报》2016,90(8):1922-1932

茶店桥地下河位于西南岩溶区,流域内"三水"转换迅速,地下水是当地的重要饮用水源。本文对流域内雨水、地表水、地下水中的SO_4~(2-)浓度进行了测试,利用氘(δD_(H_2O))、氧(δ~(18) O_(H_2O))同位素示踪地表水、地下水补给来源,用硫酸盐硫(δ~(34)S_(SO4))、氧(δ~(18) O_(SO4))同位素探讨了地表水、地下水中SO_4~(2-)的来源,并计算了地下河出口河水中不同SO_4~(2-)来源的贡献比例。结果表明:1不同水体中SO_4~(2-)浓度大小顺序为地表水地下水雨水,与邻近区域相比,茶店桥地下河流域雨水、地表水、地下水呈现富集SO_4~(2-)的特征。2地表水、地下水的主要补给来源为大气降水,硫酸不仅和HCO_3~-共同参与了流域内碳酸盐岩的溶解,也参与了雨水中含钙镁颗粒物的溶解。3地表水δ~(34)S_(SO4)、δ~(18) O_(SO4)值分别介于-12.98‰~-10.19‰和-0.54‰~+9.13‰之间,地下水δ~(34)S_(SO4)、δ~(18) O_(SO4)值分别介于-14.32‰~+16.58‰和+2.81‰~+14.35‰之间,SW02的SO_4~(2-)主要来源于大气降水,SW01、SW03、GW02、GW03、GW06主要来源于煤层,GW05主要来源于石膏,GW01、GW04为混合输入源。4地下河出口河水中大气降水带来的SO_4~(2-)贡献比例为13%,煤层硫化物氧化的贡献比例为40%,石膏溶解的贡献比例为47%。  相似文献   

纳米比亚欢乐谷地区白岗岩型铀矿成矿物质来源分析   总被引：3，自引：0，他引：3  

陈金勇  范洪海  王生云  顾大钊  陈东欢 《地质学报》2016,90(2):219-230

本文对纳米比亚欢乐谷地区与铀成矿关系密切的白岗岩进行了系统的主量元素、微量元素及Sr-Nd同位素研究。结果表明,矿化白岗岩具有较高的SiO_2(68.81%~76.02%,平均值73.11%),富钾,A/CNK为0.96~1.07,平均值1.01,为亚碱性系列的准铝质-弱过铝质岩石。岩石富集轻稀土[LREE/HREE=2.53~7.71;(La/Yb)_N=2.14~10.40],Eu亏损中等,高Rb/Sr比值(2.03~5.50,平均值4.36),岩石同时富集Rb、Th、U、K及Pb等大离子亲石元素,亏损Ba、Nb、Ta及Sr等元素。岩石的初始~(87)Sr/~(86)Sr比值为0.73035~0.79345,ε_(Nd)(t)值为-13.5~-17.4,晶质铀矿的ε_(Nd)(t)值为-14.8~-16.5,两阶段Nd模式年龄为2.43~2.56Ga。元素和Sr-Nd同位素地球化学特征表明矿化白岗岩是在碰撞后的伸展构造环境中形成的,主成矿期的成矿物质来源于富铀的前达马拉基底;热液叠加改造期的铀可能来源于原生铀矿物本身。  相似文献   

Secondary Ion Mass Spectrometry Bias on Isotope Ratios in Dolomite–Ankerite,Part II: δ13C Matrix Effects          下载免费PDF全文

Maciej G. Śliwiński  Kouki Kitajima  Reinhard Kozdon  Michael J. Spicuzza  John H. Fournelle  Adam Denny  John W. Valley 《Geostandards and Geoanalytical Research》2016,40(2):173-184

This study is Part II of a series that documents the development of a suite of calibration reference materials for in situ SIMS analysis of stable isotope ratios in Ca‐Mg‐Fe carbonates. Part I explored the effects of Fe²⁺ substitution on SIMS δ¹⁸O bias measured from the dolomite–ankerite solid solution series [CaMg(CO₃)₂–CaFe(CO₃)₂], whereas this complementary work explores the compositional dependence of SIMS δ¹³C bias (calibrated range: Fe# = 0.004–0.789, where Fe# = molar Fe/(Mg+Fe)). Under routine operating conditions for carbonate δ¹³C analysis at WiscSIMS (CAMECA IMS 1280), the magnitude of instrumental bias increased exponentially by 2.5–5.5‰ (session‐specific) with increasing Fe‐content in the dolomite structure, but appeared insensitive to minor Mn substitution [< 2.6 mole % Mn/(Ca+Mg+Fe+Mn)]. The compositional dependence of bias (i.e., the matrix effect) was expressed using the Hill equation, yielding calibration residual values ≤ 0.3‰ relative to CRM NBS‐19 for eleven carbonate reference materials (6‐μm‐diameter spot size measurements). Based on the spot‐to‐spot repeatability of a drift monitor material that ‘bracketed’ each set of ten sample‐spot analyses, the analytical precision was ± 0.6–1.2‰ (2s, standard deviations). The analytical uncertainty for individual sample analyses was approximated by combining the precision and calibration residual values (propagated in quadrature), suggesting an uncertainty of ± 1.0–1.5‰ (2s).  相似文献   

New Thorium Isotope Ratio Measurements in Silicate Reference Materials: A‐THO,AGV‐2, BCR‐2, BE‐N,BHVO‐2 and BIR‐1          下载免费PDF全文

Marion Carpentier  Abdelmouhcine Gannoun  Christian Pin  Olgeir Sigmarsson 《Geostandards and Geoanalytical Research》2016,40(2):239-256

A two‐step Th isolation protocol, involving micro‐columns of TRU‐Spec extraction chromatography material and AG1 resin, was evaluated. The MC‐ICP‐MS procedure included ²³²Th tailing characterisation and correction, and calibrator bracketing using an in‐house standard solution (ThS1) to correct for instrumental mass bias and Faraday cup to secondary electron multiplier relative gain. Repeated analyses of reference solutions (UCSC Th ‘A’, WUN, OU Th ‘U’, IRMM‐36) were consistent with published data. Six reference materials (A‐THO, BCR‐2, AGV‐2, BHVO‐2, BE‐N and BIR‐1) were processed. The average ²³⁰Th/²³²Th values obtained for these samples are in excellent agreement with published data. In addition, we report the first ²³⁰Th/²³²Th values for BE‐N and BIR‐1. The intermediate precisions for rock samples ranged from ± 0.24 to ± 0.49% (2 RSD) and were similar to those achieved for synthetic solutions, thereby supporting the overall validity of the chemical separation, data acquisition and reduction procedures. Counting statistics on the ²³⁰Th isotope was the most significant source of uncertainty. The intermediate precision of the mean ²³⁰Th/²³²Th for the Th‐depleted BIR‐1 (5.64 × 10^?6 ± 0.27%, 2 RSD) is in the range of the analyses of other reference materials analysed in this study.  相似文献   

Calcium Isotopic Fractionation during Ion‐Exchange Column Chemistry and Thermal Ionisation Mass Spectrometry (TIMS) Determination          下载免费PDF全文

Hong L. Zhu  Zhao F. Zhang  Gui Q. Wang  Yu F. Liu  Fang Liu  Xin Li  Wei D. Sun 《Geostandards and Geoanalytical Research》2016,40(2):185-194

Significant isotopic fractionation can occur during column chemistry and determination by mass spectrometry. Improper correction may produce uncertainties in the isotopic composition of geological samples. We investigated calcium isotopic fractionation during these two processes and set up a model to check data quality. The δ^44/40Ca_915a value of IAPSO seawater in different Ca cuts (e.g., 0–20, 20–40, 40–60, 60–80 and 80–100%) on column chemistry ranged from ~ 4‰ to 0‰. The more Ca was eluted, the lower the δ^44/40Ca_915a value of the elution was found. The isotopic fractionation of calcium on the column appeared to follow the exponential law. However, TIMS instrumental fractionation during Ca runs did not always follow the exponential law due to mixing effects from sample reservoirs on the filament. Our results show that errors could be caused if the instrumental fractionation deviates from the exponential law, especially when the fractionation degree is large. To improve the measurement uncertainty, a model is proposed to check the behaviour and degree of instrumental fractionation, which will provide a quick and reasonable verdict on the data quality of TIMS runs.  相似文献   

湖南七宝山铜多金属矿床石英斑岩时代与成因:锆石U-Pb定年及Hf同位素与稀土元素证据   总被引：1，自引：0，他引：1  

胡俊良  徐德明  张鲲  刘劲松 《大地构造与成矿学》2016,(6):1185-1199

湖南浏阳七宝山铜多金属矿床位于钦杭成矿带西段,是湘东北规模最大的铜多金属矿床。矿床的形成与区内的石英斑岩关系密切。石英斑岩内锆石具有岩浆锆石特征,LA-ICP-MS锆石U-Pb定年结果为155~153 Ma,代表其形成年龄,属晚侏罗世岩浆活动产物。岩浆锆石的~(176)Hf/~(177)Hf=0.282296~0.282603,εHf(t)=–12~–2.7,平均地壳模式年龄tDM2=1377~2056 Ma;锆石ΣREE=496~4162μg/g,(Yb/Nd)N=71.9~3133.8,HREE强烈富集,具有强烈Ce正异常(δCe=1.68~203.13)和强烈至中等Eu负异常(δEu=0.05~0.67),表明石英斑岩的岩浆源区具有明显壳源特征,来自于古元古代至中元古代地壳的部分熔融。结合岩石学研究,七宝山矿区石英斑岩的形成除了中下地壳冷家溪群或更古老的基底物质的部分熔融外,还有幔源组分加入,这一期岩浆与成矿作用与岩石圈拆离和软流圈物质上涌及随后的玄武岩底侵作用有关。  相似文献   

“海参-对虾”混养海水池塘的食物网结构及营养层级研究     

郭凯  赵文  王珊  刘保占  张鹏 《海洋学报(英文版)》2016,35(4):58-62

The food sources of aquacultured Apostichopus japonicus and the trophic levels of organisms in a sea cucumber(A. japonicus) and prawn(Penaeus japonica) polyculture system in a saltwater pond in Zhuanghe, Liaoning Province were examined using carbon and nitrogen stable isotopes. Across organisms, δ13C ranged from(–25.47±0.20)‰ to(–16.48±0.17)‰(mean±SD), and δ15N ranged from(4.23±0.49)‰ to(12.44±0.09)‰. The δ13C and δ15N contents of A. japonicus, P. japonica and Fenneropenaeus chinensis were comparatively higher than those of other organisms. Values of δ13C and δ15N revealed that P. japonica, Hemigrapsus sanguineus and Neomysis japonica comprised the largest component of the diet of A. japonicus. The mean trophic level of the organisms in this saltwater pond polyculture system was(2.75±0.08). P. japonica, A. japonicus, F. chinensis,Synechogobius hasta and Neomysis japonica were in the 3rd trophic level(2–3); jellyfish, H. sanguineus and zooplankton were in the 2nd trophic level(1–2); and Enteromorpha prolifera, benthic microalgae, periphyton and suspended matter primarily consisting of phytoplankton, bacteria and humus were in the primary trophic level(0–1).  相似文献   

扬子北缘马元铅锌矿床闪锌矿微量元素及S-Pb-He-Ar-C同位素地球化学研究   总被引：7，自引：3，他引：4  

高永宝  李侃  钱兵  李文渊  郑敏昌  ChenGuang ZHANG 《岩石学报》2016,32(1):251-263

马元铅锌矿床是近年扬子陆块北缘铅锌找矿的新突破。矿体呈层状、似层状产于碑坝隆起翼部震旦系灯影组角砾状白云岩层间构造带中,围岩蚀变很弱。矿石中硫化物以闪锌矿、方铅矿为主,中粗粒晶质结构,充填于白云岩角砾间。闪锌矿富集Cd、Ge、Ag,贫In、Tl、Se,Ga/In为6~132,Ge/In多1000,成矿温度以中-低温为主。金属硫化物ε~(34)S值相对集中,为12.9‰~19.4‰,平均为17.4‰,来自于海相硫酸盐的还原。铅同位素组成稳定,~(206)Pb/~(204)Pb为17.858~17.918:~(207)Pb/~(204)Pb为15.603~15.694;~(208)Pb/~(204)Pb为37.756~38.046,具有造山带和上地壳铅的特征,震旦系可能提供了金属成矿物质。闪锌矿中流体包裹体的~3He/~4He为0.03Ra~1.05Ra,~(40)Ar/~(36)Ar为326.1~765.1,~(38)Ar/~(36)Ar为0.183~0.204,表明成矿流体主要为地壳流体和饱和大气水(大气降水或海水)的混合。闪锌矿内流体包裹体挥发分δ~(13)C_(CH_4)值为-36.01‰~-28.80‰,δ~(13)C_(C_2H_6)值为-27.72‰~-22.44‰,δ~(13)C_(CO_2)值为-23.24‰~-9.68‰,表明有机流体参与了成矿作用。石英、方解石的H-O同位素结果表明具有海水和有机水混合的特征。可见,成矿流体具有两种流体混合的特征,一为蒸发海水与围岩反应所形成的盆地卤水,二为有机流体。推测矿区可能存在一个古油气藏,由于TSR生成一高硫气藏,为区内还原性有机流体的主要来源。当富含Pb、Zn等成矿物质的成矿流体运移至富含CH_4和H_2S的还原性流体的矿区角砾岩带时,两种流体混合,Pb、Zn等遇到H_2S发生反应而沉淀成矿,并伴生热液白云石等,形成了马元铅锌矿床。综上所述,我们认为马元矿床属MVT型铅锌矿床。  相似文献   

Subduction-related Late Cretaceous high-K volcanism in the Central Pontides orogenic belt: constraints on geodynamic implications     

Emre Aydınçakır 《Geodinamica Acta》2016,28(4):379-411

Mineral chemistry, major and trace elements, ⁴⁰Ar/³⁹Ar age and Sr–Nd–Pb isotopic data are presented for the Late Cretaceous Hamsilos volcanic rocks in the Central Pontides, Turkey. The Hamsilos volcanic rocks mainly consist of basalt, andesite and associated pyroclastics (volcanic breccia, vitric tuff and crystal tuff). They display shoshonitic and high-K calc-alkaline affinities. The shoshonitic rocks contain plagioclase, clinopyroxene, alkali feldspar, phlogopite, analcime, sanidine, olivine, apatite and titanomagnetite, whereas the high-K calc-alkaline rocks contain plagioclase, clinopyroxene, orthopyroxene, magnetite / titanomagnetite in microgranular porphyritic, hyalo-microlitic porphyritic and glomeroporphyritic matrix. Mineral chemistry data reveal that the pressure condition of the clinopyroxene crystallisation for the shoshonitic rocks are between 1.4 and 6.3 kbar corresponds to 6–18-km depth and the high-K calc-alkaline rocks are between 5 and 12 km. ⁴⁰Ar/³⁹Ar age data changing between 72 ± .5 Ma and 79.0 ± .3 Ma (Campanian) were determined for the Late Cretaceous Hamsilos volcanic rocks, contemporaneous with the subduction of the Neo-Tethyan Ocean beneath the Pontides. The studied volcanic rocks were enriched in the large-ion lithophile and light rare earth element contents, with pronounced depletion in the contents of high-field-strength elements. Chondrite-normalised rare earth element patterns (La_N/Lu_N = 6–17) show low to medium enrichment, indicating similar sources of the rock suite. Initial ⁸⁷Sr/⁸⁶Sr values vary between .70615 and .70796, whereas initial ¹⁴³Nd/¹⁴⁴Nd values change between .51228 and .51249. Initial ²⁰⁶Pb/²⁰⁴Pb values vary between 18.001 and 18.349, ²⁰⁷Pb/²⁰⁴Pb values between 15.611 and 15.629 and ²⁰⁸Pb/²⁰⁴Pb values between 37.839 and 38.427. The main solidification processes involved in the evolution of the volcanic rocks consist of fractional crystallisation, with minor amounts of crustal contamination ± magma mixing. According to geochemical evidence, the shoshonitic melts in the Hamsilos volcanic rocks were possibly derived from the low degree of partial melting of a subcontinental lithospheric mantle (SCLM), while the high-K calc-alkaline melts were derived from relatively high degree of partial melting of SCLM that was enriched by fluids and/or sediments from a subduction of oceanic crust.  相似文献