Chemical and Isotopic Characteristics of the Water and Suspended Particulate Materials in the Yangtze River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials（SPM） in the Yangtze River were investigated on the samples collected from 25 hydrological monitoring stations in the mainsteam and 13 hydrological monitoring stations in the major tributaries during 2003 to 2007. The water samples show a large variation in both δD（ 30‰ to 112‰） and δ18O（ 3.8‰ to 15.4‰） values. Both δD and δ18O values show a decrease from the river head to the Jinsha Jiang section and then increase downstream to the river mouth. It is found that the oxygen and hydrogen isotopic compositions of the Yangtze water are controlled by meteoric precipitation, evaporation, ice（and snow） melting and dam building. The Yangtze SPM concentrations show a large variation and are well corresponded to the spatial and temporal changes of flow speed, runoff and SPM supply, which are affected by the slope of the river bed, local precipitation rate, weathering intensity, erosion condition and anthropogenic activity. The Yangtze SPM consists of clay minerals, clastic silicate and carbonate minerals, heavy minerals, iron hydroxide and organic compounds. From the upper to lower reaches, the clay and clastic silicate components in SPM increase gradually, but the carbonate components decrease gradually, which may reflect changes of climate and weathering intensity in the drainage area. Compared to those of the upper crust rocks, the Yangtze SPM has lower contents of SiO2, CaO, K2 O and Na2 O and higher contents of TFe2 O3 and trace metals of Co, Ni, Cu, Zn, Pb and Cd. The ΣREE in the Yangtze SPM is also slightly higher than that of the upper crust. From the upper to lower reaches, the CaO and MgO contents in SPM decrease gradually, but the SiO2 content increases gradually, corresponding to the increase of clay minerals and decrease of the carbonates. The δ30SiSPM values（ 1.1‰ to 0.3‰） of the Yangtze SPM are similar to those of the average shale, but lower than those of the granite rocks（ 0.3‰ to 0.3‰）, reflecting the effect of silicon isotope fractionation in silicate weathering process. The δ30SiSPM values of the Yangtze SPM show a decreasing trend from the upper to the middle and lower reaches, responding to the variation of the clay content. The major anions of the river water are HCO 3, SO 4 2, Cl, NO 3, SiO 4 4 and F and the major cations include Ca2＋, Na＋, Mg2＋, K＋ and Sr2＋. The good correlation between HCO3-content and the content of Ca2＋may suggest that carbonate dissolution is the dominate contributor to the total dissolved solid（TDS） of the Yangtze River. Very good correlations are also found among contents of Cl, SO4 2, Na＋, Mg2＋, K＋and Sr2＋, indicating the important contribution of evaporite dissolution to the TDS of the Yangtze River. High TDS contents are generally found in the head water, reflecting a strong effect of evaporation in the Qinghai-Tibet Plateau. A small increase of the TDS is generally observed in the river mouth, indicating the influence of tidal intrusion. The F and NO3 contents show a clear increase trend from the upstream to downstream, reflecting the contribution of pesticides and fertilizers in the Chuan Jiang section and the middle and lower reaches. The DSi shows a decrease trend from the upstream to downstream, reflecting the effect of rice and grass growth along the Chuan Jiang section and the middle and lower reaches. The dissolved Cu, Zn and Cd in the Yangtze water are all higher than those in world large rivers, reflecting the effect of intensive mining activity along the Yangtze drainage area. The Yangtze water generally shows similar REE distribution pattern to the global shale. The δ30SiDiss values of the dissolved silicon vary from 0.5‰ to 3.7‰, which is the highest among those of the rivers studied. The δ30SiDiss values of the water in the Yangtze mainsteam show an increase trend from the upper stream to downstream. Its DSi and δ30SiDiss are influenced by multiple processes, such as weathering process, phytolith growth in plants, evaporation, phytolith dissolution, growth of fresh water diatom, adsorption and desorption of aqueous monosilicic acid on iron oxide, precipitation of silcretes and formation of clays coatings in aquifers, and human activity. The δ34SSO4 values of the Yangtze water range from 1.7‰ to 9.0‰. The SO4 in the Yangtze water are mainly from the SO4 in meteoric water, the dissolved sulfate from evaporite, and oxidation of sulfide in rocks, coal and ore deposits. The sulfate reduction and precipitation process can also affect the sulfur isotope composition of the Yangtze water. The87Sr/86Sr ratios of the Yangtze water range from 0.70823 to 0.71590, with an average value of 0.71084. The87Sr/86Sr ratio and Sr concentration are primary controlled by mixing of various sources with different87Sr/86Sr ratios and Sr contents, including the limestone, evaporite and the silicate rocks. The atmospheric precipitation and anthropogenic inputs can also contribute some Sr to the river. The δ11B values of the dissolved B in the Yangtze water range from 2.0‰ to 18.3‰, which is affected by multifactors, such as silicate weathering, carbonate weathering, evaporite dissolution, atmospheric deposition, and anthropogenic inputs.     

Silicon isotopic composition of dissolved silicon and suspended particulate matter in the Yellow River, China, with implications for the global silicon cycle

The silicon isotopic composition of dissolved silicon and suspended particulate matter (SPM) were systematically investigated in water samples from the mainstem of the Yellow River and 4 major tributaries. The SPM content of the Yellow River varied from 1.4 to 38,560 mg/L, averaging 3568 mg/L, and the δ³⁰Si of suspended particulate matter (δ³⁰Si_SPM) varied from 0.3‰ to −0.4‰, averaging −0.02‰. The major factors affecting the SPM content and the δ³⁰Si_SPM values in the Yellow River were inferred to be the mineralogical, chemical and isotopic characteristics of the sediments from the Loess Plateau and a combination of the climate and the flow discharge of the river.The major ions in the Yellow River water were Na⁺, Ca²⁺, Mg²⁺, HCO₃⁻, SO₄²⁻ and Cl⁻. High salt concentration was observed in samples from the middle and lower reaches, likely reflecting the effects of evaporation and irrigation because the Na⁺, Mg²⁺, SO₄²⁻ and K⁺ concentrations were correlated with the Cl⁻ concentration. The dissolved Si concentration (D_Si) increased downstream, varying from 0.016 to 0.323 mM. The δ³⁰Si of dissolved Si (δ³⁰Si_Diss) varied from 0.4‰ to 2.5‰, averaging 1.28‰. The major processes controlling the D_Si and δ³⁰Si_Diss of the Yellow River are (a) the weathering of silicate rocks, (b) the formation of phytoliths in plants, (c) the evaporation of water from and the addition of meteoric water to the river system, which only affects concentrations, (d) the adsorption and desorption of aqueous monosilicic acid on iron oxide, and (e) the dissolution of phytoliths in soils.The D_Si and δ³⁰Si_Diss values of global rivers vary spatially and temporally in response to changes in climate, chemical weathering intensity and biological activity. The moderately positive δ³⁰Si_Diss values observed in the Yellow River may be attributed to the higher rates of chemical weathering and biological activities that have been observed in this catchment in comparison with those of other previously studied catchments, excluding the Yangtze River. Human activities may also potentially influence chemical weathering and biological activities and affect the D_Si and δ³⁰Si_Diss values of the major rivers of the world. Further river studies should be performed to gain a better understanding of the global Si isotope budget.     

Geochemistry and provenance of bed sediments of the large rivers in the Tibetan Plateau and Himalayan region

We investigated the geochemical characteristics of major, trace and rare earth elements and Sr–Nd isotope patterns of bed sediments from the headwaters and upper reaches of the six large rivers draining the Tibetan Plateau (the Jinsha River—Yangtze, Lancang River—Mekong, Nujiang River—Salween, Huang He—Yellow, Indus, and Yarlung Tsangpo—Brahmaputra). By using Ca/Al versus Mg/Al, La/Sc versus Co/Th, and ⁸⁷Sr/⁸⁶Sr versus ε_Nd (0) binary differentiation diagrams of provenance, some typical contributors to the different catchment sediments can be identified. In the Three-River (the Jinsha, Lancang, and Nujiang Rivers) tectonomagmatic belt, acidic–intermediate-acidic volcanic rocks are very important provenance of sediments. Carbonate rocks and Permian Emeishan basalts are dominant in the Jinsha River. The Yellow River sediments have similar geochemical characteristics with loess in catchments. The Indus and Yarlung Tsangpo Rivers sediments are mainly from ultra-K volcanic rocks and Cenozoic granitoids widely distributed in the Indus–Yarlung suture. The intensity of chemical weathering in these river catchments is evaluated by calculating the chemical indices of alteration (CIA) of sediments and comparing them with bedrocks. The CIA values of the six river sediments are from 46.5 to 69.6, closing to those of bedrocks in the corresponding catchment, which indicates relatively weak chemical weathering intensity. Lithology, climate, and topography affect the chemical weathering intensity in these river catchments.     

Water and Organic Carbon Cycles in Monsoon-driven Humid Tropics of the Western Ghats Mountain Belt,India: Insights from Stable Isotope Approach

The Western Ghats form a major mountain belt, next to the Himalayas, in controlling the flux of water and carbon to the northern Indian Ocean. This study attempts to understand the water and carbon cycles in two humid tropical river basins with its streams originating at higher altitudes of the Western Ghats, India. Water and suspended particulate matter (SPM) were collected on a monthly scale during summer monsoon season (June-September) from Swarna and Nethravati rivers draining into the Arabian Sea. For the source apportionment, samples have been measured for stable isotopes of oxygen (δ¹⁸O) and hydrogen (δ²H) in water and stable isotopes of carbon (δ¹³C_POC) in particulate organic matter (POM) at spatial scale from tributaries and main channel of rivers, and runoff water from agricultural land (dominant paddy field) and forest in the downstream region. The association between δ¹⁸O and deuterium-excess in river water and rain water shows that water in these tropical basins depicts rainout effect of marine source moisture during the onset of summer monsoon. As the monsoon intensifies, the fresher rain water replenishes older water stored previously in sub surface soil layer leading to its flushing into the river during summer monsoon season. Stable carbon isotope ratio and elemental ratio of POM (δ¹³C_POC = -27.1 ± 0.4 ‰ and C/N = 8.1 ± 1.7) in two humid tropical river water during summer monsoon season is an admixture of suspended particulates from runoff water of forest (δ¹³C_POC = - 27.82 ± 0.4 ‰) and agricultural land (δ¹³C_POC = -26.29 ± 0.4 ‰). It is found that δ¹³C_POC shows minimal variability with SPM content and C/N ratio within the same organic carbon pool. The study emphasizes the need to consider the agricultural runoff contribution to the rivers while establishing the global elemental budget and observing the global climate change.     

Characteristics of Breccias and C-O-Sr-S Isotope Geochemistry of the Duocaima Pb-Zn Deposit in Tuotuohe, Qinghai Province: Implications for the Ore-forming Process

The Duocaima carbonate-hosted Pb-Zn deposit is a newly found large deposit in the southern area of Qinghai Province.In this paper, the characteristics, genesis, significance to Pb-Zn mineralization of the widely developed breccias, and the ore-forming process have been carefully studied based on geological documentation of drilling holes, microscopic observations of petrography and microstructure and some stable isotope measurements.Based on the compositions of the clast and matrix, the breccias can be classified into three types: limestone clasts cemented by marl; limestone clasts with fine-grained calcareous materials; and limestone clasts cemented by hydrothermal calcite.The mineralization in the first type of breccia is weak, whereas it is strong in the latter two types of breccias.According to the locations of occurrence and structural characteristics of the breccias along with the relationship between the breccias and mineralization, part of the limestone clasts that are cemented by marl and outcrop in the contact zone between the Wudaoliang Formation(Nw) and the underlying Jiushidaoban Formation(Pj) are attributed to synsedimentary fault-genetic breccia, whereas the last of the limestone clasts that are cemented by marl and developed in the Jiushidaoban Formation(Pj) are attributed to the breccia generated by karst cave collapse; the limestone clasts with fine-grained calcareous materials and the limestone clasts cemented by hydrothermal calcite are attributed to breccia formed by hydrothermal dissolution.The breccia formed by karst collapse had consistently evolved for a long period of time, while the breccias with other origins were formed around the period of mineralization(i.e., about or slightly later than 20–16 Ma).The breccia generated by karst cave collapse and hydrothermal dissolution are somewhat related; the formation of the breccia from karst cave collapse provided open space for the later mineralization and reaction between hydrothermal fluids and host rocks, and the subsequent strong dissolution by hydrothermal fluids transformed some of the breccia formed earlier by karst cave collapse.Meanwhile, carbonate host rocks with breccias and brecciaed mineralization can be a potential sign of Mississippi Valley Type(MVT) deposits and important indicators for regional mineral exploration.The δ13CV-PDB, δ18OVSMOW, and 87Sr/86 Sr values of hydrothermal calcite in the Duocaima deposit range from 4.3‰ to 7.1‰, 14.9‰ to 20.1‰, and 0.707494 to 0.708185, respectively; the δ13CV-PDB, δ18OV-SMOW, and 87Sr/86 Sr values of the host limestones of the Jiushidaoban Formation range from 3.6‰ to 5.3‰, 18.0‰ to 20.5‰, and 0.707372 to 0.707945, respectively.The δ13CV-PDB and 87Sr/86 Sr values of hydrothermal calcite and limestone are similar, indicating single sources of C and Sr in this deposit, with the likely source being the limestone of the Jiushidaoban Formation.The minor scattering of the δ18OV-SMOW values suggests that different O isotope fluids underwent the isotope exchange reaction.The C-O-Sr isotope characteristics indicate that the host limestones experienced a dissolution and precipitation process during mineralization, which is beneficial to improving the porosity of host rocks and promoting the precipitation of metal sulfides.The δ34SV-CDT value of the breccia-type mineralization sulfides ranges from-30.4‰ to-0.3‰; that is, the δ34SV-CDT value is negative with considerable variation, illustrating that during the breccia-type mineralization process, the bacteriogenic reduction of sulfates provided the vast majority of sulfur, whereas the thermochemical reduction of sulfates was relatively unimportant.The brecciation that occurred as a result of karst cave collapse was mainly generated by the dissolution of groundwater; however, the brecciation related to hydrothermal dissolution and mineralization processes were caused by mixing of different fluids.     

四川省阿坝地区地表水地球化学特征

阿坝州位于四川西北部,与青海、甘肃交界,处于高海拔地区;该地区地表水资源丰富,长江与黄河上游水系均流经该区域。通过系统性采集区内河水(76件)、井水(7件)、溪水(8件)等样品,测试水体中D与¹⁸O的丰度与微量元素含量。结果表明:①受大气降水与流经地层的影响,阿坝地区河水中D与¹⁸O的丰度均显著高于溪水、井水与自来水等介质,线性相关性表明,河水中¹⁸O的富集与硫酸盐矿物的溶解密切相关;②阿坝地区井水、自来水、溪水之间存在明显的水力联系;③对于阿坝地区而言,黄河上游河流中δD与δ¹⁸O值均高于长江上游水系河流,但两者之间差别较小,这由于同一地区水系具有相同的大气降水来源;④河水、井水、溪水等表水中微量元素呈高Ba、Zn、Cr,低As、Pb、Cd的特点,与该地区岩石样品中微量元素特征基本一致,表明该地区表水中微量元素含量主要受地质背景因素控制。     

Mineralogy and Geochemistry of Sedimentary Huntite Deposits in the Egirdir-Hoyran Lake Basin of Southern Turkey

The sediment-hosted huntite-magnesite deposits are located in the Egirdir-Hoyran lake basin in the Isparta Angle (southern Turkey). The deposits occur at two different localities in the region: (1) Kemersirti huntite deposit, (2) Köytepe huntite-magnesite deposit. The huntite-magnesite occurrences are found in shallow lacustrine rocks of the Miocene-Pliocene Kizilcik Formation and formed as a result of Neogene tectonic activity. Based on X-ray diffraction and scanning electron microscopic studies, the mineral assemblage of huntite deposits contains mostly huntite, less magnesite, dolomite, very little calcite, illite, simectite, brucite, and quartz in the Kemersirti area but contain huntite, magnesite, dolomite, and calcite in the Köytepe area.In the huntite and magnesite-bearing huntite samples, MgO varies from 32.70 to 37.95 wt. %, CaO from 7.83 to 15.10 w.t. %, and SiO₂ from 0.99 to 10.60 w.t. %. Ba and Sr are dominant minor elements in the deposits. Ba and Sr for huntite and magnesite bearing huntite in the study area vary from 11 to 233 ppm and from 325 to 765 ppm, respectively. As, U, Zr, V and Ce contents ranged from 11.5-146 ppm, 0.5-3.7 ppm, 1.4-13.2 ppm, 7-34 ppm, and 0.9-2.7 ppm respectively. The huntite-magnesite is characterized by relatively lower Ni (0.5-2.4 ppm) and Co (0.5-1.1 ppm) contents. The huntite and magnesite-bearing huntite occurrences have higher Ba, Sr, As, Zr, V, and U contents than those of the other elements. The d13C isotope values vary between 7.8‰ to 8.8‰ PDB for huntite+magnesite, 8.2‰ PDB for huntite, 1.4‰ PDB for magnesite+dolomite, and 4.0‰ PDB for limestone from deposits in the study area. The δ¹⁸O isotope values of the huntite deposits ranged from 30.4 to 35.5‰ SMOW for huntite+magnesite, 32.4‰ SMOW for huntite, 29.8‰ SMOW for magnesite+ dolomite, and 26.9‰ SMOW for limestone.The presence of nodular huntite and the abundance of gastropod, ostracoda and Chura shells in the carbonate units indicate that the huntite occurrences are precipitated at shallow, alkaline (8.5-9.5 pH) and lower temperature (approximately 25°C) lake conditions. The Mg⁺⁺, Ca⁺⁺ and Si⁺⁺ ions for the huntite formation were derived from the surrounding rocks such as ultrabasic rocks, dolomite, dolomitic limestone, and limestone in the Egirdir-Hoyran lake basin. Also, the C isotope ratios indicate that the CO₂ source for the huntite formations results to sedimentary basin from metamorphic CO₂, carbonate rocks, fresh water carbonates, and ground water. The source of oxygen for the huntite formation may come from marine limestone, fresh water carbonates and meteoric water.     

Geochemical Characteristics of the Upper Triassic Xujiahe Formation in Sichuan Basin, China and its Significance for Hydrocarbon Accumulation

The alternative development of coal-bearing hydrocarbon source rocks and low-porosity and low-permeability tight sandstone reservoirs of the Triassic Xujiahe Formation in the Sichuan Basin is favorable for near-source hydrocarbon accumulation. The natural gas composition of the Xujiahe Formation in the Sichuan Basin is dominated by hydrocarbon gases, of which the methane content is80.16%-98.67%. Typically, the C_2~+ content is larger than 5% in main wet gas. The dry gas is mainly distributed in the western and northern regions of the basin. The non-hydrocarbon gases mainly contain nitrogen, carbon dioxide, hydrogen, and helium, with a total content of 2%. The carbon isotope ranges of methane and its homologues in natural gas are: δ~(13)C_1 of-43.8‰ to-29.6‰, δ~(13)C_2 of-35.4‰ to-21.5‰, δ~(13)C_3 of-27.6‰ to-19.8‰,and δ~(13)C_4 of-27.7‰ to-18.8‰. δ~(13)C_3δ~(13)C_4 occurs in some natural gas with a low evolution degree; such gas is mainly coal-related gas from humic-type source rocks of the Xujiahe Formation. As for the natural gas, δ~2 H_(CH4) values ranged from-195‰ to-161‰,δ~2 H_(C2H6) values ranged from-154‰ to-120‰, and δ~2 H_(C3H8) values ranged from-151‰ to-108‰. The dry coefficient,δ~(13)C and δ~2 H_(CH4) are all positively correlated with the maturity of source rocks. The higher the maturity of source rocks is, the larger the natural gas dry coefficient is and the larger the δ~(13)C and δ~2 H_(CH_4) values are, indicative of the characteristic of near-source accumulation. The δ~2 H_(C2H6) value of natural gas is influenced by paleosalinity to a relatively large extent; the higher the paleosalinity is, the larger the δ~2 H_(C2H6) value is. The Pr/Ph value of the condensate oil ranged from 1.60 to 3.43, illustrating light oxidization-light reduction and partial-oxidization characteristics of the depositional environment of coal-bearing source rocks of the Xujiahe Formation. The natural gas light hydrocarbon(C_5-C_7) from the Xujiahe Formation presented two characteristics: the first was the relatively high aromatic hydrocarbon content(19%-32.1%), which reveals the characteristic of natural gas with humic substances of high-maturity; the second was the low content of aromatic hydrocarbon(0.4%-9.3%),reflecting water-washing during the accumulation of the natural gas. The reported research outcomes indicate a potential mechanism for natural gas accumulation in the Xujiahe Formation, which will further guide natural gas exploration in this region.     

Isotope evidence for quantifying river evaporation and recharge processes in the lower reaches of the Yellow River

Evaporation and recharge are important hydrological processes in the water cycle. However, accurately quantifying these two processes of river remains to be difficult due to their spatial heterogeneity and the limitations of traditional methods. In this study, a more reliable method of stable isotopes of δ ¹⁸O and δ ²H based on the Rayleigh distillation equation and mass conservation was used to estimate the evaporation and recharge of the rivers in the lower reaches of the Yellow River, North China Plain. Comprehensive sampling campaigns including 30 surface water samples from 10 rivers, 33 groundwater samples from domestic and observation wells, and two Yellow River water samples were conducted. The results showed that the evaporation proportion of the rivers based on δ ¹⁸O and δ ²H both averaged 14.4%. The evaporation proportions in each river did not completely follow a linear increasing trend along the flow path. This phenomenon could be mainly explained by the different proportions of recharge from groundwater and Yellow River water. With closer to the Yellow river, evaporation of the rivers decreased while the recharge by the Yellow River increased. Regression equations based on δ ¹⁸O, δ ²H, and their average revealed that the evaporation proportion respectively increased by 1.02, 0.79, and 0.90% with the increase in the distance to the Yellow River per 10 km. On the contrary, the recharge proportion decreased by 7.68, 5.51, and 6.59%, respectively. In addition, using δ ¹⁸O rather than δ ²H was more reliable in studying the spatial influence of the Yellow River on evaporation and recharge. Sensitivity analysis showed that the evaporation model was most sensitive to isotopic composition, rather than to air temperature or relative humidity. The results of this study provide insights into the determination of river hydrological processes and the management of water resources.     

Nd and Sr isotopic compositions of sediments from the Yellow and Yangtze Rivers: Implications for partitioning tectonic terranes and crust weathering of the Central and Southeast China

New Nd and Sr isotope data are presented in this paper for sediments from the Yellow and Yangtze River drainage basins. The average ¹⁴³Nd/¹⁴⁴Nd isotope compositions of fine-grained sediments from two drainage basins seem similar. The T _DM^Nd ages of sediments from the two drainage basins are relatively uniform but exhibit subtle differences. This reflects the different underlying bedrocks, in association with the unique tectonic terranes that comprise central and southeastern China, including the North China Block, the Yangtze Block, the South China Block, the Tibet Plateau and the Qinling-Dabie Orogenic Belt. In contrast, there is an obvious difference in the ⁸⁷Sr/⁸⁶Sr ratios between fine-grained sediments of the Yellow and Yangtze Rivers, which actually reflects an increase in chemical weathering intensity from northwestern to southeastern China.     

黄河硫同位素组成与青藏高原隆起

黄河水的平均δ^３4ＳＯ₄^{2-值为＋８．４‰，是世界主要大河中硫同位素组成最重的河流；从上游至下游，河水的矿δ３4ＳＯ₄2-值规律性地逐渐增重，在龙门—三门峡河段达最大值。这反映了由于青藏高原隆起而引起的中国西北地区气候干燥趋势及随后出现的沙漠化、古盐湖蒸发岩的形成和黄土堆积环境对黄河水硫同位素组成的控制性影响。}     

Geochronology, Geochemistry, Whole Rock Sr-Nd and Zircon Hf-O Isotopes of the Early Neoproterozoic Volcanic Rocks in Jiangshan, Eastern Part of the Jiangnan Orogen: Constraints on Petrogenesis and Tectonic Implications

This paper presents the results of combined studies of geochronology, geochemistry, whole rock Sr-Nd and zircon Hf-O isotopes carried out upon the rhyodacite and ignimbrite of Shangshu village, Shangyu town and Shanghupeng village of Jiangshan City in Zhejiang Province, along the northwestern side of the Jiangshan–Shaoxing suture. SHRIMP zircon U-Pb dating of samples in the three areas yielded weighted mean 206 Pb/238 U ages of 842.8 ± 6.9 Ma and 850.0 ± 7.3 Ma, 839 ± 9 Ma and 832.2 ± 8.1 Ma, 828.3 ± 8.5 Ma and 836.9 ± 9.9 Ma, respectively. These ages are older than the volcanic rocks of the Shangshu Formation dated at around 780 Ma distributed in Fuyang City, Hangzhou City, Kaihua County, etc. The volcanic rocks generally have high SiO2(54.08–76.80 wt%) and Al2 O3(12.40–21.31 wt%), low Fe2 O3(0.68–8.92 wt%), MgO(0.29–2.49 wt%), CaO(0.12–2.86 wt%), TiO2(0.10–1.59 wt%) and P2 O5(0.01–0.39 wt%), with variable total alkalis(K2 O + Na2 O =5.42–8.29 wt%). There exists a clear negative correlation between SiO2 and P2 O5. The volcanic rocks have A/CNK ratios of 1.03–2.77 and thus are peraluminous. They are characterized by enrichment in LREE, Rb, Ba, Zr, Hf, K, Th, La, U and depletion in Nb, Sr, P, Ti, with distinct LREE and HREE fractionation of(La/Yb)N values of 5.68–11.67, and with a moderate negative Eu anomaly(Eu=0.58–0.89). Whole-rock geochemical data shows that the Jiangshan volcanic rocks are possibly I-type granitic rocks, even though they have some characteristics of AS-type granites due to the magma fractional crystallization and water-rock interaction. Zircon δ18 O values are 3.97‰–5.49‰(average 4.50‰), 2.90‰–5.21‰(average 4.32‰) for ignimbrite from Shangshu village section, and Shanghupeng village section, respectively. They are slightly lower than the average δ18 O values of igneous zircons in equilibrium with mantle magmas(5.3 ± 0.6‰(2σ)), the lower δ18 O value also demonstrating the presence of high temperature water-rock interactions. The ignimbrite rocks have positive εNd(t)(4.02, 3.37, 3.91, 4.74, 2.85, 4.39, totals from the three areas) and εNd(t)(in-situ zircon)(4.3–14.6, a weighted mean of 8.4; 6.6–12.7, a weighted mean of 9.0; 8.1–12.0, a weighted mean of 9.5, respectively, from the three areas). In conjunction with the trace element studies, they indicate that the source region of the Jiangshan volcanic rocks was mainly composed of juvenile lower crustal material, mixed with some mantle-sourced magma. Detailed elemental and isotopic data suggest that the Jiangshan volcanic rocks were formed in a continental arc setting. There is a series of ca. 860–830 Ma volcanic rocks formed in a back-arc extensional setting in the southern margin of the eastern Jiangnan Orogen, along the northwest side of the Jiangshan–Shaoxing suture. The first stage rift-related anorogenic magmatism may have occurred as early as ca. 860 Ma in the eastern Jiangnan Orogen.     

Geochemical constraints for the origin of thermal waters from western Turkey

The combined chemical composition, B and Sr isotopes, and the basic geologic setting of geothermal systems from the Menderes Massif in western Turkey have been investigated to evaluate the origin of the dissolved constituents and mechanisms of water–rock interaction. Four types of thermal water are present: (1) a Na–Cl of marine origin; (2) a Na–HCO₃ type with high CO₂ content that is associated with metamorphic rocks of the Menderes Massif; (3) a Na–SO₄ type that is also associated with metamorphic rocks of the Menderes Massif with H₂S addition; and (4) a Ca–Mg–HCO₃–SO₄ type that results from interactions with carbonate rocks at shallow depths. The Na–Cl waters are further subdivided based on Br/Cl ratios. Water from the Cumalı Seferihisar and Bodrum Karaada systems are deep circulated seawater (Br/Cl=sea water) whereas water from Çanakkale–Tuzla (Br/Cl<sea water) are from dissolution of Messinian evaporites. Good correlations between different dissolved salts and temperature indicate that the chemical composition of the thermal waters from non-marine geothermal systems is controlled by: (1) temperature dependent water–rock interactions; (2) intensification of reactions due to high dissolved CO₂ and possibly HCl gasses; and (3) mixing with overlying cold groundwater. All of the thermal water is enriched in B. The B isotopic composition (δ¹¹B=2.3‰ to 18.7‰; n=6) can indicate either leaching of B from the rocks, or B(OH)₃ degassing flux from deep sources. The large ranges in B concentrations in different rock types as well as in thermal waters from different systems suggest the water-rock mechanism. ⁸⁷Sr/⁸⁶Sr ratios of the thermal water are used to differentiate between solutes that have interacted with metamorphic rocks (⁸⁷Sr/⁸⁶Sr ratio as high as 0.719479) and carbonate rocks (low ⁸⁷Sr/⁸⁶Sr ratio of 0.707864).     

Distinguishing Cambrian from Upper Ordovician source rocks: Evidence from sulfur isotopes and biomarkers in the Tarim Basin

The reported source rocks for the abundant petroleum in the Tarim Basin, China range from Cambrian to Lower Ordovician and/or Upper Ordovician in age. However, the difference between the two groups of source rocks is not well characterized. In this study, pyrite was removed from eleven mature to over mature kerogen samples from source rocks using the method of CrCl₂ reduction and grinding. The kerogen and coexisting pyrite samples were then analyzed for δ³⁴S values. Results show that the kerogen samples from the Cambrian have δ³⁴S values between +10.4‰ and +19.4‰. The values are significantly higher than those from the Lower Ordovician kerogen (δ³⁴S of between +6.7‰ and +8.7‰), which in turn are generally higher than from the Upper Ordovician kerogen samples (δ³⁴S of between ?15.3 and +6.8‰). The associated pyrite shows a similar trend but with much lower δ³⁴S values. This stratigraphically controlled sulfur isotope variation parallels the evolving contemporary marine sulfate and dated oil δ³⁴S values from other basins, suggesting that seawater sulfate and source rock age have an important influence on kerogen and pyrite δ³⁴S values. The relatively high δ³⁴S values in the Cambrian to Lower Ordovician source rocks are associated with abundant aryl isoprenoids, gammacerane and C₃₅ homohopanes in the extractable organic matter, indicating that these source rocks were deposited in a bottom water euxinic environment with water stratification. Compared with the Upper Ordovician, the Cambrian to Lower Ordovician source rocks show abundance in C₂₈ 20R sterane, C₂₃ tricyclic terpanes, 4,23,24-trimethyl triaromatic dinosteroids and depletion in C₂₄ tetracyclic terpane, C₂₉ hopane. Thus, δ³⁴S values and biomarkers of source rock organic matter can be used for distinguishing the Cambrian and Upper Ordovician source rocks in the Tarim Basin.     

Geochemical records of the sediments and their significance in Dongping Lake Area,the lower reach of Yellow River,North China

Dongping Lake area, located in the lower reaches of Yellow River, is an ideal place to study the changes of modern river and lake sedimentary environment. The sediment samples of Dawen River, Yellow River, and Dongping Lake were collected, and the major elements, trace elements and organic matter geochemical composition of the samples were analyzed. Cluster analysis, characteristic element ratio method and graphic method were used to explore the geochemical characteristics of sediments and their environmental implication. The results show that the contents of SiO_2, Na_2O, TiO_2 and Zr in sediments of Dawen River and Yellow River are relatively high, and the contents of iron and manganese oxides, organic matter, CaO, P_2O_5 and Sr in lake sediments are relatively high. That reveals the differences of sedimentary environments between the rivers and the lake. The contents of Sr and Zr in Dawen River are affected by the rapid migration of clastic materials in the upstream carbonate source area during the flood season; the δCe,ΣREE and REE's ratios in the sediments of the Yellow River reflect the influence of the Loess source; and the distribution of elements changes along the flow direction during the flood season. The characteristics of p H, element composition and LREE HREE fractionation of the lake sediments indicate that the sediment source is complex, and the lake environment is affected by the flood season. The study shows that the geochemical content and its variation characteristics of sediments effectively reveal the sedimentary environment, material composition and characteristics of flood season of rivers and the lake in the study area.     

Dolomitization by hypersaline reflux into dense groundwaters as revealed by vertical trends in strontium and oxygen isotopes: Upper Muschelkalk,Switzerland

The Trigonodus Dolomit is the dolomitized portion of the homoclinal ramp sediments of the Middle Triassic Upper Muschelkalk in the south‐east Central European Basin. Various dolomitizing mechanisms, followed by recrystallization, have been previously invoked to explain the low δ¹⁸O, high ⁸⁷Sr/⁸⁶Sr, extensive spatial distribution and early nature of the replacive matrix dolomites. This study re‐evaluates the origin, timing and characteristics of the dolomitizing fluids by examining petrographic and isotopic trends in the Trigonodus Dolomit at 11 boreholes in northern Switzerland. In each borehole the ca 30 m thick unit displays the same vertical trends with increasing depth: crystal size increase, change from anhedral to euhedral textures, ultraviolet‐fluorescence decrease, δ¹⁸O_VPDB decrease from ?1·0‰ at the top to ?6·7‰ at the base and an ⁸⁷Sr/⁸⁶Sr increase from 0·7080 at the top to 0·7117 at the base. Thus, dolomites at the top of the unit record isotopic values similar to Middle Triassic seawater (δ¹⁸O_VSMOW = 0‰; ⁸⁷Sr/⁸⁶Sr = 0·70775) while dolomites at the base record values similar to meteoric groundwaters from the nearby Vindelician High (δ¹⁸O_VSMOW = ?4·0‰; ⁸⁷Sr/⁸⁶Sr = >0·712). According to water–rock interaction modelling, a single dolomitizing or recrystallizing fluid cannot have produced the observed isotopic trends. Instead, the combined isotopic, geochemical and petrographic data can be explained by dolomitization via seepage‐reflux of hypersaline brines into dense, horizontally‐advecting groundwaters that already had negative δ¹⁸O and high ⁸⁷Sr/⁸⁶Sr values. Evidence for the early groundwaters is found in meteoric calcite cements that preceded dolomitization and in fully recrystallized dolomites with isotopic characteristics identical to the groundwaters following matrix dolomitization. This study demonstrates that early groundwaters can play a decisive role in the formation and recrystallization of massive dolomites and that the isotopic and textural signatures of pre‐existing groundwaters can be preserved during seepage‐reflux dolomitization in low‐angle carbonate ramps.     

Metasomatic effects related to channelled fluid streaming through deep crust: fenites and associated carbonatites (In Ouzzal Proterozoic granulites, Hoggar, Algeria)

The In Ouzzal granulitic unit (IOGU) consists predominantly of felsic orthogneisses most of which correspond to granitoids emplaced during the Archaean, plus metasediments, including olivine-spinel marbles, of late Archaean age. All units were metamorphosed at granulite facies during the Eburnean (2 Ga). The stable isotope signature of the marbles (δ¹³C=–0.8 to –4.2‰/PDB; δ¹⁸O = 7.9 to 18.9‰/SMOW) does not record a massive streaming of C-bearing fluids during metamorphism. Most of the isotopic variation in the marbles is explained in terms of pregranulitic features. Metasomatic transformation of granulites into layered potassic syenitic rocks and emplacement of carbonate veins and breccias occurred during retrogressive granulite facies conditions. The chemistry of these rocks is comparable with that of fenites and carbonatites with high contents of (L)REEs, Th, U, F, C, Ba and Sr but, with respect to these elements, a relative depletion in Nb, Ta, Hf, Zr and Ti. The isotopic compositions of Nd (?Nd_(T)=–6.3 to –9.9), of Sr (⁸⁷Sr/⁸⁶Sr_(T)= 0.7093–0.7104), and the O isotopic composition of metasomatic clinopyroxene (δ¹⁸O = 6.9 to 8‰), all indicate that the fluid had a strong crustal imprint. On the basis of the C isotope ratios (δ¹³C =–3.5 to –9.7‰), the fluid responsible for the crystallization of carbonates and metasomatic alteration is thought to be derived from the mantle, presumably through degassing of mantle-derived magmas at depth. Intense interaction with the crust during the upward flow of the fluid may explain its chemical and isotopic signatures. The zones of metasomatic alteration in the In Ouzzal granulites may be the deep-seated equivalents of the zones of channelled circulation of carbonated fluids described at shallower levels in the crust.     

Geological and C–O–S–Pb–Sr isotopic constraints on the origin of the Qingshan carbonate-hosted Pb–Zn deposit,Southwest China

Located in the western Yangtze Block, the Qingshan Pb–Zn deposit, part of the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province, contains 0.3 million tonnes of 9.86 wt.% Pb and 22.27 wt.% Zn. Ore bodies are hosted in Carboniferous and Permian carbonate rocks, structurally controlled by the Weining–Shuicheng anticline and its intraformational faults. Ores composed of sphalerite, galena, pyrite, dolomite, and calcite occur as massive, brecciated, veinlets, and disseminations in dolomitic limestones.

The C–O isotope compositions of hydrothermal calcite and S–Pb–Sr isotope compositions of Qingshan sulphide minerals were analysed in order to trace the sources of reduced sulphur and metals for the Pb–Zn deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from –5.0‰ to –3.4‰ and +18.9‰ to +19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid had a mixed origin of mantle, marine carbonate rocks, and sedimentary organic matter. δ³⁴S values of sulphide minerals range from +10.7‰ to +19.6‰, similar to Devonian-to-Permian seawater sulphate (+20‰ to +35‰) and evaporite rocks (+23‰ to +28‰) in Carboniferous-to-Permian strata, suggesting that the reduced sulphur in hydrothermal fluids was derived from host-strata evaporites. Ores and sulphide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.561 to 18.768, ²⁰⁷Pb/²⁰⁴Pb = 15.701 to 15.920, and ²⁰⁸Pb/²⁰⁴Pb = 38.831 to 39.641) that plot in the upper crust Pb evolution curve, and are similar to those of Devonian-to-Permian carbonate rocks. Pb isotope compositions suggest derivation of Pb metal from the host rocks. ⁸⁷Sr/⁸⁶Sr ratios of sphalerite range from 0.7107 to 0.7136 and (⁸⁷Sr/⁸⁶Sr)_200Ma ratios range from 0.7099 to 0.7126, higher than Sinian-to-Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than Proterozoic basement rocks. This indicates that the ore strontium has a mixture source of the older basement rocks and the younger cover sequence. C–O–S–Pb–Sr isotope compositions of the Qingshan Pb–Zn deposit indicate a mixed origin of the ore-forming fluids and metals.     

Geology and Isotope Geochemistry of the Yinchanggou-Qiluogou Pb-Zn Deposit, Sichuan Province, Southwest China

The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD_(H2O-SMOW) and δ~(18)O_(H2O-SMOW) values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H_2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ~(13)C_(PDB) values ranging from-6.2‰ to-4.1‰ and δ~(18)O_(SMOW) values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ~(34)S_(CDT) values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The ~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.     

Stable carbon isotopes of alkane gases from the Xujiahe coal measures and implication for gas-source correlation in the Sichuan Basin,SW China

The Upper Triassic Xujiahe Formation in the Sichuan Basin, SW China consists of a series of coal measures. The first, third and fifth members of this formation are dominated by gas prone dark mudstones and coals. The mudstones contain Type II and III kerogens with average organic carbon contents around 1.96%. These source rocks are mature in the central Sichuan and highly mature in the western Sichuan Basin, characterized by gas generation with subordinate amounts of light oil or condensate oils. The source rocks are intercalated with the sandstone dominated second, fourth and sixth members of the Xujiahe Formation, thus leading to three separate self contained petroleum systems in the region. The proven gas reserves in the Xujiahe Formation are only less than that of the Triassic Feixianguan Formation and the Xujiahe Formation has the second largest gas field (Guang’an gas field) in the basin. Gases derived from the Xujiahe Formation coals generally show a normal stable carbon isotopic trend for C₁–C₄ n-alkanes, with the highest δ¹³C₂ values among the nine gas pay zones in the basin (?20.7‰ to ?28.3‰), and δ¹³C₁ values as low as ?43.0‰ in the central Sichuan. Gas accumulations with an oil leg have also been found in the eastern and southern Sichuan where the thickness of the Xujiahe Formation is significantly reduced. Gases in these accumulations tend to show low δ¹³C₂ values (?30.0‰ to ?36.3‰), characteristic of oil prone source rocks.