Cretaceous–Neogene basin control on the formation of uranium deposits in South China: evidence from geology,mineralization ages,and H–O isotopes

ABSTRACT

The South China Uranium Province (SCUP) contains the largest number of discovered uranium deposits in China. This province includes seven uranium mineralization belts, at Wuyishan, Taoshan–Zhuguang, Chenzhou–Qinzhou, Gan–Hang, Xixia–Luzong, Mufushan–Hengshan, and Xuefengshan–Jiuwandashan. The uranium deposits can be classified according to their ore-hosting rocks into four general types: granite-, volcanic-, black-shale-, and sandstone-related. These uranium deposits crop out at the peripheries of Cretaceous–Neogene (K–N) redbed basins or are connected to the basins by NE–SW- to NNE–SSW-trending regional faults. Most of the volcanic-related uranium deposits were formed during the mid-Cretaceous (118 to 88 Ma); granite-related deposits have a wider range of ages from 124 to 11 Ma; the black-shale-related deposits have ages of 120 to 7 Ma; sandstone-related deposits yield ages of 111 to 22.5 Ma. As such, these four types of uranium deposits in South China have similar ages, irrespective of location, and are similar in age to K–N redbed basins in this region. δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values of the volcanic-related uranium deposits generally range from – 105.9‰ to – 38.0‰ and – 11.1‰ to +5.3‰, respectively. The black-shale-related uranium deposits yield δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values of – 74.5‰ to – 33.0‰ and – 4.4‰ to 9.3‰, respectively. However, the granite-related uranium deposits have a much wider range of δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values from – 104.4‰ to – 23.1‰ and – 9.4‰ to +7.3‰, respectively. H–O isotopic compositions of the SCUP ore-forming fluids are similar to those of basinal fluids, again demonstrating the link between the uranium deposits and the basins. The spatial–temporal relationships and fluid isotopic similarities between the K–N basins and uranium mineralization indicate that the uranium deposits of the SCUP are genetically related to the K–N redbed basins, and are unconformity-related uranium deposits.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

Mid- to lower-crustal architecture of the northern Lachlan and southern Thomson orogens: evidence from O–Hf isotopes

Abstract

The nature of the substrate below the northern Lachlan Orogen and the southern Thomson Orogen is poorly understood. We investigate the nature of the mid- to lower-crust using O and Lu–Hf isotope analyses of zircons from magmatic rocks that intrude these regions, and focus on the 440–410 Ma time window to minimise temporal effects while focussing on spatial differences. Over the entire region, weighted mean δ¹⁸O values range from 5.5 to 9.8‰ (relative to VSMOW, Vienna Standard Mean Oceanic Water), and weighted mean ?Hf_t range from ?8.8 to +8.5. In the northern Lachlan Orogen and much of the southern Thomson Orogen, magmatic rocks with unradiogenic ?Hf_t (～?7 to ?4) and elevated δ¹⁸O values (～9 to 10‰) reflect a supracrustal source component that may be common to both orogens. Magmatic rocks intruding the Warratta Group in the western part of the Thomson Orogen also have unradiogenic ?Hf_t (～?9 to ?6) but more subdued δ¹⁸O values (～7‰), indicating a distinct supracrustal source component in this region. Some regions record radiogenic ?Hf and mantle-like δ¹⁸O values, indicative of either a contribution from arc-derived rocks or a direct mantle input. In the northeast Lachlan Orogen Hermidale Terrane, magmatic rocks record mixing of the supracrustal source component with input from a infracrustal or mantle source component (?Hf_t as high as +8.5, δ¹⁸O values as low as 5.5‰), possibly of Macquarie Arc affinity. Samples in the west-southwestern Thomson Orogen also record some evidence of radiogenic input (?Hf_t as high as ?0.5, δ¹⁸O values as low as 6.4‰), possibly from the Mount Wright Arc of the Koonenberry Belt. Overall, our results demonstrate a strong spatial control on isotopic compositions. We find no isotopic differences between the bulk of the Lachlan Orogen and the bulk of the Thomson Orogen, and some indication of similarities between the two.     

The δ18O of UST Quartz in Two Porphyry Deposits,China

The unidirectional solidification textures (UST) quartz is generally thought to form from fluids exsolved from shallow intrusions and/or magma chambers, but such an idea is still poorly constrained from the evidence of stable isotopes. In this study, we report for the first time the δ¹⁸O of quartz that shows UST from the Qulong Cu–Mo and the Yechangping Mo porphyry deposits in China. The analysis results show that the UST quartz samples from the Qulong deposit have δ¹⁸O values ranging from +6.2 ‰ to +7.6 ‰, which are similar to that of quartz phenocrysts (+6.7 ‰ to +7.8 ‰). In contrast, the UST quartz samples from the Yechangping porphyry Mo deposit yield a high δ¹⁸O value (+10.0 ‰). The δ¹⁸O_water value of Yechangping UST quartz (+8.5 ‰) is also higher than that of Qulong (+4.6 ‰ to +5.8 ‰). Hydrothermal biotite from potassic alteration and sericite from early phyllic alteration at Qulong have similar δ¹⁸O values to UST quartz, suggesting the involvement of magmatic fluids during this stage of deposit evolution.     

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO₃-N (74–83 mg L^?1). The δ¹⁵N-NO₃ values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ¹⁵N-NO₃ values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ¹⁵N-NO₃ and δ¹⁸O-NO₃ values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between ?4.8 and ?7.9‰ and O isotope enrichment factors varying between ?3.8 and ?4.9‰. Similar δD and δ¹⁸O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10–20 years) than in the north (20–30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.     

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.     

Paleogene paleoclimate reconstruction using oxygen isotopes from land and freshwater organisms: the use of multiple paleoproxies

Understanding past climate change is critical to the interpretation of earth history. Even though relative temperature change has been readily assessed in the marine record, it has been more difficult in the terrestrial record due to restricted taxonomic distribution and isotopic fractionation. This problem could be overcome by the use of multiple paleoproxies. Therefore, the δ¹⁸O isotopic composition of five paleoproxies (rodent tooth enamel, δ¹⁸O_Phosphate = +17.7 ± 2.0‰ n = 74 (VSMOW); fish scale ganoine δ¹⁸O_Phosphate = +19.7 ± 0.7‰ n = 20 (VSMOW); gastropod shell δ¹⁸O_Calcite = −1.7 ± 1.3‰ n = 50 (VPDB); charophyte gyrogonite δ¹⁸O_Calcite = −2.4 ± 0.5‰ n = 20 (VPDB); fish otolith δ¹⁸O_Aragonite = δ¹⁸O = −3.6 ± 0.6‰ n = 20 (VPDB)) from the Late Eocene (Priabonian) Osborne Member (Headon Hill Formation, Solent Group, Hampshire Basin, UK) were determined. Because diagenetic alteration was shown to be minimal the phosphate oxygen component of rodent tooth enamel (as opposed to enamel carbonate oxygen) was used to calculate an initial δ¹⁸O_{Local water} value of 0.0 ± 3.4‰. However, a skewed distribution, most likely as a result of the ingestion of evaporating water, necessitated the calculation of a corrected δ¹⁸O_{Local water} value of −1.3 ± 1.7‰ (n = 62). This δ¹⁸O_{Local water} value corresponds to an approximate mean annual temperature of 18 ± 1°C. Four other mean paleotemperatures can also be calculated by combining the δ¹⁸O_{Local water} value with four independent freshwater paleoproxies. The calculated paleotemperature using the fish scale thermometry equations most likely represents the mean temperature (21 ± 2°C) of the entire length of the growing season. This should be concordant with the paleotemperature calculated using the Lymnaea shell thermometry equation (23 ± 2°C). The lack of concordance is interpreted to be the result of diagenetic alteration of the originally aragonitic Lymnaea shell to calcite. The mean paleotemperature calculated using the charophyte gyrogonite thermometry equation (21 ± 2°C), on the other hand, most likely represents the mean temperature of a single month toward the end of the growing season. The fish otolith mean paleotemperature (28 ± 2°C) most likely represents the mean temperature of the warmest months of the growing season. An approximate mean annual temperature of 18 ± 1°C, in addition to a mean growing season paleotemperature of 21 ± 2°C (using fish scale only) with a warmest month temperature of 28 ± 2°C, and high associated standard deviations suggest that a subtropical to warm temperate seasonal climate existed during the deposition of the Late Eocene Osborne Member.     

Different isotopic evolutionary trends of δ34S and δ18O compositions of dissolved sulfate in an anaerobic deltaic aquifer system

Concentration and isotope ratios (δ³⁴S_SO4 and δ¹⁸O_SO4) of dissolved sulfate of groundwater were analyzed in a very large anaerobic aquifer system under the Lower Central Plain (LCP) (25,000 km²) in Thailand. Groundwater samples were collected in two different kinds of aquifers; type 1 with a saline water contribution and type 2 lateritic aquifers with no saline water contribution. Two different isotopic compositional trends were observed: in type 1 aquifers sulfate isotope ratios range from low values (+2.2‰ for δ³⁴S_SO4 and +8.0‰ for δ¹⁸O_SO4) to high values (+49.9‰ for δ³⁴S_SO4 and +17.9‰ for δ¹⁸O_SO4); in type 2 aquifers sulfate isotope ratios range from low values (−0.1‰ for δ³⁴S_SO4 and +12.2‰ for δ¹⁸O_SO4) to high δ¹⁸O_SO4 ratios (+18.4‰) but with low δ³⁴S_SO4 ratios (<+12.9‰). Isotopic comparison with possible source materials and theoretical geochemical models suggests that the sulfate isotope variation for type 1 aquifer groundwater can be explained by two main processes. One is the contribution of remnant seawater, which has experienced dissimilatory sulfate reduction in the marine clay, into recharge water of freshwater origin. This process accounts for the high salinity groundwater. The other process, explaining for the modest salinity groundwater, is the bacterial sulfate reduction of the mixture water between high salinity water and fresh groundwater. Isotopic variation of type 2 aquifer groundwater may also be explained by bacterial sulfate reduction, with slower reduction rate than that of the groundwater with saline water effect. The origin of groundwater sulfate with low δ³⁴S_SO4 but high δ¹⁸O_SO4 is recognized as an important topic to be examined in a future investigation.     

Geology, Fluid Inclusion and Isotopic Study of the Neoproterozoic Suoi Thau Copper Deposit, Northwest Vietnam

The Sin Quyen-Lung Po district is an important Cu metallogenic province in Vietnam, but there are few temporal and genetic constraints on deposits from this belt. Suoi Thau is one of the representative Cu deposits associated with granitic intrusion. The deposit consists of ore bodies in altered granite or along the contact zone between granite and Proterozoic meta-sedimentary rocks. The Cu-bearing intrusion is sub-alkaline I-type granite. It has a zircon U-Pb age of ~776 Ma, and has subduction-related geochemical signatures. Geochemical analysis reveals that the intrusion may be formed by melting of mafic lower crust in a subduction regime. Three stages of alteration and mineralization are identified in the Suoi Thau deposit, i.e., potassic alteration; silicification and Cu mineralization; and phyllic alteration. Two-phase aqueous fluid inclusions in quartz from silicification stage show wide ranges of homogenization temperatures(140–383℃) and salinities(4.18wt%–19.13wt%). The high temperature and high salinity natures of some inclusions are consistent with a magmatic derivation of the fluids, which is also supported by the H-O-S isotopes. Fluids in quartz have δD values of –41.9‰ to –68.8‰. The fluids in isotopic equilibrium with quartz have δ~(18)O values ranging from 7.9‰ to 9.2‰. These values are just plotted in the compositional field of magmatichydrothermal fluids in the δD_(water) versus δ~(18)O_(water) diagram. Sulfide minerals have relatively uniform δ~(34)S values from 1.84‰ to 3.57‰, which is supportive of a magmatic derivation of sulfur. The fluid inclusions with relatively low temperatures and salinities most probably represent variably cooled magmatic-hydrothermal fluids. The magmatic derivation of fluids and the close spatial relationship between Cu ore bodies and intrusion suggest that the Cu mineralization most likely had a genetic association with granite. The Suoi Thau deposit, together with other deposits in the region, may define a Neoproterozoic subduction-related ore-forming belt.     

Identifying the Sources of Solutes in Karst Groundwater in Chongqing,China: a Combined Sulfate and Strontium Isotope Approach

Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are impacted by both natural environment and people. Therefore, the study of hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. In this paper, thirty?five representative karst groundwater samples were collected from different aquifers (limestone and dolomite) and various land use types in Chongqing to trace the sources of solutes and relative hydrochemical processes. Hydrogeochemical types of karst groundwater in Chongqing were mainly of the Ca?HCO3 type or Ca (Mg)?HCO3 type. However, some hydrochemical types of karst groundwater were the K+Na+Ca?SO4 type (G25 site) or Ca?HCO3+SO4 type (G26 and G14 site), indicating that the hydrochemistry of these sites might be strongly influenced by anthropogenic activities or unique geological characteristics. The dissolved Sr concentrations of the studied groundwater ranged from 0.57 to 15.06 μmmol/L, and the 87Sr/86Sr varied from 0.70751 to 0.71627. The δ34S?SO42? fell into a range of ?6.8‰?21.5‰, with a mean value of 5.6‰. The variations of both 87Sr/86Sr and Sr values of the groundwater samples indicated that the Sr element was controlled by the weathering of limestone, dolomite and silicate rock. However, the figure of 87Sr/86Sr vs. Sr2+/[K++Na+] showed that the anthropogenic inputs also obviously contributed to the Sr contents. For tracing the detailed anthropogenic effects, we traced the sources of solutes collected karst groundwater samples in Chongqing according to the δ34S value of potential sulfate sources. The variations of both δ34S and 1/SO42? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sul?de mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) have contributed to solutes in karst groundwater. The influence of oxidation of sul?de mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread.     

A stable isotope study of serpentinization and metamorphism in the Highland Border Suite,Scotland, U.K.

$\text{D}\text{H}$ and ${}^{18}\text{O}{}^{16}\text{O}$ ratios have been measured for whole-rock samples and mineral separates from the mafic and ultramatic rocks of the Cambro-Ordovician Highland Border Suite. The H- and O- isotopic compositions of these rocks record individual stages in a relatively complex 500 Myr old hydrothermal/metamorphic history. Lizardite serpentinites (δD ～ ? 105‰; δ¹⁸O ～ + 6.2‰) record a premetamorphic history and indicate that parent harzburgites, dunites, and pyroxenites were serpentinized through low-temperature interaction with meteoric waters during cooling. The other rocks of the Highland Border Suite record subsequent interaction with metamorphic fluids. Amphibolite facies hornblende schists were produced through thrust-related (dynamothermal) metamorphism of spilitic pillow lavas. During dehydration, D-enriched fluids were driven off from the spilites thus leaving the hornblende schists to equilibrate with a relatively D-depleted internal fluid reservoir (δD ～ ? 45‰). The expelled D-enriched fluids may have mixed with more typical Dalradian metamorphic waters which then exchanged with the remaining mafic rocks and lizardite serpentinites during greenschist facies regional metamorphism to produce antigorite serpentinites (δD ～ ? 62‰; δ¹⁸O ～ + 8‰) and greenschist metaspilites (δD ～ ? 57‰; δ¹⁸O ～ + 7.3‰) with similar H- and O-isotopic compositions. Serpentinites which have been only partially metamorphosed show intermediate H-isotopic compositions between that of metamorphic antigorite (δD ～ ? 62‰) and non-metamorphic lizardite δD ～ ? 105‰) end members.     

Geochemistry and modification of oilfield brines in surface pits in Northern Kuwait

Oilfield brines (produced water) are produced as a waste product daily at the gathering centers (GCs) in Kuwait oilfields. The geochemical evolution of the water produced at the GC (fresh brine) to stagnant pit water (evaporate) has been investigated in the northern fields of Kuwait, and a model is presented showing time-dependent variations. Kuwait oilfield brines are globally similar to others in other large sedimentary basins (USA, Canada), but modifications have occurred due to seawater injection practices performed episodically during the oil extraction process. Brine water chemistry changes from generally average brine chemistry (based on cations and anions) to saturated mixture of seawater, oilfield brine, and anthropogenic chemical pollutants. The objective of this study was to harmonize the database of brine waters in terms of regional identity by comparison with oilfield brines elsewhere, identify water–rock interaction, and statistically treat daily recordings from the pits in order to identify injection peaks and troughs. Laboratory analysis of major and minor cations and anions from the Rawdatayn samples gave the following concentration ranges in parts per million (ppm): (Na⁺, 11,698–203,977), (Ca²⁺, 2,216–98,514), (Mg²⁺, 1,602–28,885), (K⁺, 1,528–16,573), (Sr²⁺, 70–502), (Ba²⁺, 0.01–18.04), (Fe²⁺, 0.01–8.93), (Li⁺, 0.09–6.48), (Si²⁺, 0.00–13.18), (B³⁺, 0.05–37.45), (SO ₄ ²⁺ , 330–3100). For the Sabriyah oilfield samples, the major and minor cations and anions concentration ranges in ppm are: (Na⁺, 9,807–274,947), (Ca²⁺, 2,555–77,992), (Mg²⁺, 1,415–28,183), (K⁺, 764–19,201), (Sr²⁺, 77.84–641), (Ba²⁺, 0.15–6.76), (Fe²⁺, 0.016–38.88), (Li⁺, 0.05–6.83), (Si²⁺, 0.0195–16.84), (B³⁺, 7.17–55.33), (SO ₄ ²⁺ , 44,812–135,264). The stable isotopic analysis of five samples indicates normal trends in oxygen and hydrogen isotopes that classify the waters as “connate” which follow an evaporation trend. Carbon isotopic signatures are normal for hydrocarbon fields and average out around GC15, δ¹⁸O‰?=?1.4, δD‰?=??10, δ¹³C‰?=??3.6; while for GC23, δ¹⁸O‰?=?2.3, δD‰?=??4, δ¹³C‰?=??2.5; for GC25, δ¹⁸O‰?=??2.0, δD‰?=??14, δ¹³C‰?=??4.6; for pit1, δ¹⁸O‰?=?2.3, δD‰?=??5, δ¹³C‰?=??18.3; and for pit 2, δ¹⁸O‰?=?2.5, δD‰?=??4, δ¹³C‰?=??17.8. Carbon isotope average values for all brine samples from the GCs is?=??56 which falls within normal hydrocarbon formation water category. Data spikes coincide with injection periods at the following times (A: May–Jun, 2006), (B: Sep–Oct, 2006), (C: Jan–Feb, 2007), (D: Mar, 2007), (E: May–Jun, 2007), (F: Feb, 2006), (G: Mar–Apr, 2006) and, subsequently the decay to “normal” brine occurs over a period of several weeks. The database was large enough to apply a principal component statistical analysis (PCA). PCA and geo-statistical techniques reveal several distinct population groups. The main chemical groups in the data are as follows: plateau, spike groups, and pit evaporation group. The spike periods correlate closely with seawater injection periods (Jan–Feb, Mar–Apr, May–Jun, and Sep–Oct). The pit chemistry reveals exceptionally high evaporation processes coinciding with summer peak temperature. PCA results show distinct groupings centered around the major elements reminiscent of other oilfields, but with the added evaporation trend strongly enhanced.     

Fingerprinting groundwater salinity sources in the Gulf Coast Aquifer System,USA

Understanding groundwater salinity sources in the Gulf Coast Aquifer System (GCAS) is a critical issue due to depletion of fresh groundwater and concerns for potential seawater intrusion. The study objective was to assess sources of groundwater salinity in the GCAS using ～1,400 chemical analyses and ～90 isotopic analyses along nine well transects in the Texas Gulf Coast, USA. Salinity increases from northeast (median total dissolved solids (TDS) 340 mg/L) to southwest (median TDS 1,160 mg/L), which inversely correlates with the precipitation distribution pattern (1,370– 600 mm/yr, respectively). Molar Cl/Br ratios (median 540–600), depleted δ²H and δ¹⁸O (?24.7‰, ?4.5‰) relative to seawater (Cl/Br ～655 and δ²H, δ¹⁸O 0‰, 0‰, respectively), and elevated ³⁶Cl/Cl ratios (～100), suggest precipitation enriched with marine aerosols as the dominant salinity source. Mass balance estimates suggest that marine aerosols could adequately explain salt loading over the large expanse of the GCAS. Evapotranspiration enrichment to the southwest is supported by elevated chloride concentrations in soil profiles and higher δ¹⁸O. Secondary salinity sources include dissolution of salt domes or upwelling brines from geopressured zones along growth faults, mainly near the coast in the northeast. The regional extent and large quantities of brackish water have the potential to support moderate-sized desalination plants in this location. These results have important implications for groundwater management, suggesting a current lack of regional seawater intrusion and a suitable source of relatively low TDS water for desalination.     

Geochemical Characteristics of Deep—Seated Potassium—Rich Brine in the Middle Triassic Leikoupo Formation,Sichuan,China

Brine extremely rich in potassium, boron and bromine has been discovered from the Middle Triassic Leikoupo Formation at a depth of 4300 m in Sichuan Province. It contains ～50 g/L of K⁺, >92 g/L of Na⁺, >12 g/L of B₂O₃, >2.36 g/L of Br^? and ～0.030 g/L of I⁺. The solid precipitates during evaporation at 25°C include KB₅O₈·4H₂O, K₂B₄O₇·3H₂O, MgCl₂·6H₂O and KMgCl₃·6H₂O. The brine ranges from 2.2‰ to 2.8‰ (SMOW) in δ¹⁸O, ? 38‰ – ? 53‰ (SMOW) in δD, 15.6‰ in δ³⁴S, and 13.5‰–15.1‰ in δ¹¹B. These data, particularly the isotopic composition of boron, indicate that the brine has a composite derivation from marine and nonmarine brines and dissolved marine evaporites in the Triassic system.     

Mixed Oceanic and Freshwater Depositional Conditions for Beachrocks of Northeast Brazil: Evidence from Carbon and Oxygen Isotopes

Holocene beachrocks of Northeast Brazil are composed predominantly of quartz (90%) with minor carbonate fragments (6% algal detritus) and feldspars (4%). The cement shows three textural varieties: (1) calciferous, surrounding siliciclastic grains; (2) micritic, with an acicular fringe; and (3) cryptocrystalline calcite in pores. Sandstone structures and composition show evidence of submerged and low-energy beaches. Cement is formed by ～20 mol% MgCO₃; the δ¹³C in cement ranges from ?1.3‰ to +3.5‰ PDB and δ¹⁸O varies from ?2.1 to +1.2‰_PDB. The cement was precipitated under high CO₂ pressure, as a result of the interaction of CaCO_3^? saturated seawater and nonsaturated groundwater, in a beach environment.     

Genesis of the Bangbu Orogenic Gold Deposit,Tibet: Evidence from Fluid Inclusion,Stable Isotopes,and Ar-Ar Geochronology

The Bangbu gold deposit is a large orogenic gold deposit in Tibet formed during the AlpineHimalayan collision. Ore bodies(auriferous quartz veins) are controlled by the E-W-trending Qusong-Cuogu-Zhemulang brittle-ductile shear zone. Quartz veins at the deposit can be divided into three types: pre-metallogenic hook-like quartz veins, metallogenic auriferous quartz veins, and postmetallogenic N-S quartz veins. Four stages of mineralization in the auriferous quartz veins have been identified:(1) Stage S1 quartz+coarse-grained sulfides,(2) Stage S2 gold+fine-grained sulfides,(3) Stage S3 quartz+carbonates, and(4) Stage S4 quartz+ greigite. Fluid inclusions indicate the oreforming fluid was CO_2-N_2-CH_4 rich with homogenization temperatures of 170–261°C, salinities 4.34–7.45 wt% Na Cl equivalent. δ~(18)Ofluid(3.98‰–7.18‰) and low δDV-SMOW(-90‰ to-44‰) for auriferous quartz veins suggest ore-forming fluids were mainly metamorphic in origin, with some addition of organic matter. Quartz vein pyrite has δ~(34)SV-CDT values of 1.2‰–3.6‰(an average of 2.2‰), whereas pyrite from phyllite has δ~(34)SV-CDT 5.7‰–9.9‰(an average of 7.4‰). Quartz vein pyrites yield 206Pb/204 Pb ratios of 18.662–18.764, 207Pb/204 Pb 15.650–15.683, and ~(208)Pb/204 Pb 38.901–39.079. These isotopic data indicate Bangbu ore-forming materials were probably derived from the Langjiexue accretionary wedge. 40Ar/39 Ar ages for sericite from auriferous sulfide-quartz veins yield a plateau age of 49.52 ± 0.52 Ma, an isochron age of 50.3 ± 0.31 Ma, suggesting that auriferous veins were formed during the main collisional period of the Tibet-Himalayan orogen(~65–41 Ma).     

Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ³⁴S_SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ¹⁸O_SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ³⁴S_SO4 and δ¹⁸O_SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II₁) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II₂) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II₃) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ³⁴S_SO4 = 10–35‰ and δ¹⁸O_SO4 = 7–20‰), soil sulfate (δ³⁴S_SO4 = 5.9‰ and δ¹⁸O_SO4 = 5.8‰) and sewage water (δ³⁴S_SO4 = 10.0‰ and δ¹⁸O_SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II₃), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ³⁴S_SO4 and δ¹⁸O_SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es₂, the second member of the Shahejie Formation, showed values of δ¹³C and δ¹⁸O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ¹³C and δ¹⁸O values than in a meteoric environment. The values of δ¹³C and δ¹⁸O preserved within the carbonates of the overlying lower Shahejie I (Es₁) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ¹³C and δ¹⁸O were controlled by salinity. The high δ¹³C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ¹³C and δ¹⁸O from carbonates in upper Es₁ ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ¹³C values resulted from biochemical fermentation. The positive δ¹³C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.     

Hydrogeochemistry and possible sulfate sources in karst groundwater in Chongqing, China

Groundwater from karst subterranean streams is among the world’s most important sources of drinking water supplies, and the hydrochemical characteristics of karst water are affected by both natural environment and people. Therefore, the study of karst groundwater hydrochemistry and its solutes’ sources is very important to ensure the normal function of life support systems. This paper focused on the major ion chemistry and sulfate isotope of karst groundwater in Chongqing for tracing the sulfate sources and related hydrochemical processes. Hydrochemical types of karst groundwater in Chongqing were mainly of the Ca-HCO₃ type or Ca(Mg)-HCO₃ type. However, some hydrochemical types were the K + Na + Ca-SO₄ type (G25 site) or Ca-HCO₃ + SO₄ type (G26 and G14 sites), indicating that the hydrochemistry of these sites may be strongly influenced by anthropogenic activities or unique geological characteristics. The δ³⁴S-SO₄ ^2? of collected karst groundwater sample fell into a range of ?6.8 to 21.5 ‰, with a mean value of 5.6 ‰. In dolomite aquifer, the δ³⁴S-SO₄ ^2? value ranges from ?4.3 to 11.0 ‰, and in limestone aquifer, it ranged from ?6.8 to 21.5 ‰. The groundwater samples from different land use types showed distinctive δ³⁴S-SO₄ ^2? value. The δ³⁴S-SO₄ ^2? value of groundwater samples had range of ?6.8 to 16.7 ‰ (mean 4.0 ‰, n = 11) in cultivated land areas, 1.5–21.5 ‰ (mean 7.2 ‰, n = 20) in forested land areas, and ?4.3 to 0.8 ‰ (mean ?1.7 ‰, n = 2) in coalmine areas. The δ³⁴S-SO₄ ^2? values of groundwater samples collected from factory area and town area were 2.2 and 9.9 ‰, respectively. According to the δ³⁴S information of potential sulfate sources, this paper discussed the possible sulfate sources of collected karst groundwater samples in Chongqing. The variations of both δ³⁴S and 1/SO₄ ^2? values of the groundwater samples indicated that the atmospheric acid deposition (AAD), dissolution of gypsum (GD), oxidation of sulfide mineral (OS) or anthropogenic inputs (SF: sewage or fertilizer) contributed to sulfate in karst groundwater. The influence of oxidation of sulfide mineral, atmospheric acid deposit and anthropogenic inputs to groundwater in Chongqing karst areas was much widespread. For protecting, sustaining, and utilizing the groundwater resources, the sewage possibly originating from urban, mine or industrial area must be controlled and treated, and the use of fertilizer should be limited.     

Stable isotope geochemistry of magnesite from Holocene salt lake deposits,Taoudenni, Mali

Stable isotope data (δ¹⁸O, δ¹³C) were obtained for magnesite (MgCO₃) from Holocene salt lake deposits of the Taoudenni–Agorgott basin, Mali, in which it is the only carbonate mineral present. The deposits have a high glauberite content (Na₂Ca(SO₄)₂), representing a type of continental evaporite formation that is commonly magnesite‐bearing. Samples from seven different levels in a 5 m long sequence were analysed. δ¹⁸O_V‐PDB values are between +3.17 and +5.91‰, which is lower than might be expected for evaporitic environments, recording reduced ¹⁸O enrichment at high salinity. δ¹³C_V‐PDB values are between −1.32‰ and −4.79‰, showing an influence of carbon derived from the decomposition of organic matter rather than from exchange with atmospheric CO₂. Covariance between δ¹⁸O and δ¹³C is strong for the lower part of the sequence, recording coupled ¹⁸O and ¹³C enrichment as commonly observed for closed basins. Covariance is lacking for the upper part of the sequence, with only periodic massive magnesite deposition in a more shallow lake. Copyright © 2012 John Wiley & Sons, Ltd.