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1.
《Applied Geochemistry》2005,20(5):961-972
The temperature dependence of the self-diffusion of HTO, 22Na+ and 36Cl− in Opalinus Clay (OPA) was studied using a through-diffusion technique, in which the temperature was gradually increased in the steady state phase of the diffusion. The measurements were done on samples from two different geological locations. The dependence of the effective diffusion coefficient on temperature was found to be of an Arrhenius type in the temperature range between 0 and 70 °C. A slight difference between the two locations could be observed. The average value of the activation energy of the self-diffusion of HTO in OPA was 21.1 ± 1.6 kJ mol−1, and 21.0 ± 3.5 and 19.4 ± 1.5 kJ mol−1 for 22Na+ and 36Cl−, respectively. The measured values for HTO are slightly higher than the values found for the bulk liquid water (HTO: 18.8 ± 0.4 kJ mol−1). This indicates that the structure of the confined water in OPA might be slightly different from that of bulk liquid water. Also for Na+ and Cl−, slightly higher values than in bulk liquid water (Na+: 18.4 kJ mol−1; Cl−: 17.4 kJ mol−1) were observed.The Stokes–Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could not be used to describe the temperature dependence of the diffusion of HTO in OPA. This additionally indicates the slightly different structure of the pore water in OPA. 相似文献
2.
《Applied Geochemistry》2005,20(8):1496-1517
Chloride concentrations were as high as 230 mg/L in water from the surface discharge of long-screened production wells in Pleasant Valley, Calif., about 100 km NW of Los Angeles. Wells with the higher Cl− concentrations were near faults that bound the valley. Depending on well construction, high-Cl−water from different sources may enter a well at different depths. For example, Cl− concentration in the upper part of some wells completed in overlying aquifers influenced by irrigation return were as high as 220 mg/L, and Cl− concentrations in water sampled within wells at depths greater than 450 m were as high as 500 mg/L. These high-Cl− waters mix within the well during pumping and produce the water sampled at the surface discharge. Changes in the major ion, minor ion, trace element, and δ34S and δ13C isotopic composition of water in wells with depth were consistent with changes resulting from SO4 reduction, precipitation of calcite, and cation exchange. The chemical and isotopic composition of high-Cl− water from deep wells trends towards the composition of oil-field production water from the study area. Chloride concentrations in oil-field production water present at depths 150 m beneath freshwater aquifers were 2200 mg/L, and Cl− concentrations in underlying marine rock were as high as 4400 mg/L. High-Cl− concentrations in water from deeper parts of wells were associated with dissolved organic C composed primarily of hydrophobic neutral compounds believed to be similar to those associated with petroleum in underlying deposits. These compounds would not be apparent using traditional sampling techniques and would not be detected using analytical methods intended to measure contamination. 相似文献
3.
A field experiment is being carried out at the Diavik diamond mine in northern Canada to investigate the influence of unsaturated flow behavior on the quality of drainage from mine waste rock piles in a region of continuous permafrost. This paper is part of a series describing processes affecting the weathering of waste rock and transport of reaction products at this site; here the focus is on unsaturated water flow and its role in mass loading. Two 15 m-high instrumented test piles have been built on 60 m by 50 m collection systems, each consisting of lysimeters and a large impermeable high-density polyethylene (HDPE) liner. Collection lysimeters are installed nearby to investigate infiltration in the upper 2 m of the waste rock. Porosity, water retention curves, and hydraulic conductivity functions are estimated from field measurements and for samples ranging in size from 200 cm3 to 16 m3. Net infiltration in 2007 is estimated to have been 37% of the rainfall for mean annual rainfall conditions. Early-season infiltration freezes and is remobilized as the waste rock thaws. Wetting fronts migrate at rates of 0.2–0.4 m d−1 in response to common rainfall events and up to 5 m d−1 in response to intense rainfall. Pore water and non-reactive solutes travel at rates of <10−2 to 3 × 10−2 m d−1 in response to common rainfall events and up to 0.7 m d−1 in response to intense rainfall. Time-varying SO4 mass loading from the base of the test piles is dictated primarily by the flow behavior, rather than by changes in solute concentrations. 相似文献
4.
Orogenic gold mineralization in the Amalia greenstone belt is hosted by oxide facies banded iron-formation (BIF). Hydrothermal alteration of the BIF layers is characterized by chloritization, carbonatization, hematization and pyritization, and quartz-carbonate veins that cut across the layers. The alteration mineral assemblages consist of ankerite-ferroan dolomite minerals, siderite, chlorite, hematite, pyrite and subordinate amounts of arsenopyrite and chalcopyrite. Information on the physico-chemical properties of the ore-forming fluids and ambient conditions that promoted gold mineralization at Amalia were deduced from sulfur, oxygen and carbon isotopic ratios, and fluid inclusions from quartz-carbonate samples associated with the gold mineralization.Microthermometric and laser Raman analyses indicated that the ore-forming fluid was composed of low salinity H2O-CO2 composition (~3 wt% NaCl equiv.). The combination of microthermometric data and arsenopyrite-pyrite geothermometry suggest that quartz-carbonate vein formation, gold mineralization and associated alteration of the proximal BIF wall rock occurred at temperature-pressure conditions of 300 ± 30 °C and ∼2 kbar. Thermodynamic calculations at 300 °C suggest an increase in fO2 (10−32–10−30 bars) and corresponding decrease in total sulfur concentration (0.002–0.001 m) that overlapped the pyrite-hematite-magnetite boundary during gold mineralization. Although hematite in the alteration assemblage indicate oxidizing conditions at the deposit site, the calculated low fO2 values are consistent with previously determined high Fe/Fe + Mg ratios (>0.7) in associated chlorite, absence of sulfates and restricted positive δ34S values in associated pyrite. Based on the fluid composition, metal association and physico-chemical conditions reported in the current study, it is confirmed that gold in the Amalia fluid was transported as reduced bisulfide complexes (e.g., Au(HS)2−). At Amalia, gold deposition was most likely a combined effect of increase in fO2 corresponding to the magnetite-hematite buffer, and reduction in total sulfur contents due to sulfide precipitation during progressive fluid-rock interaction.The epigenetic features coupled with the isotopic compositions of the ore-forming fluid (δ34SΣS = +1.8 to +2.3‰, δ18OH2O = +6.6 to +7.9‰, and δ13CΣC = −6.0 to −7.7‰ at 300–330 °C) are consistent with an externally deep-sourced fluid of igneous signature or/and prograde metamorphism of mantle-derived rocks. 相似文献
5.
Sediment samples (213 sites) collected from the tectonic-active continental margin, offshore southwestern Taiwan were analyzed for grain sizes, organic carbon, nitrogen and carbon isotopic composition to obtain mass accumulation rate of terrestrial organic carbon and carbon budget to evaluate fate of terrestrial organic carbon from small mountainous rivers on the continental margin offshore southwestern Taiwan. Terrestrial organic carbon accumulation rates range from 0.29 to 45.6 g C m−2 yr−1 with a total accumulation budget of 0.063 Mt yr−1, which accounts for less than 13% of total river particulate organic carbon loads exported from the adjacent rivers, the Gaoping (a.k.a., Kaoping), Erhjen and Tsengwen rivers. This low burial efficiency of terrestrial organic carbon demonstrated that a majority of river-borne particles together with organic materials was moved away from the study area.For the river-borne particles from the Gaoping river, a pair of depocenters in the upper slope flanking the Gaoping submarine canyon are the locations where the maximum TCorg accumulation rate were observed which hold up to 45% (0.016 Mt yr−1) of the calculated accumulation found in the study region. On the other hand, the occurrence of higher-fraction terrestrial organic carbon in the upper and middle Gaoping submarine canyon suggests that a majority of particulate organic carbon of the Gaoping river was transported directly into the deep-sea basin through the Gaoping submarine canyon. Our results demonstrated that active margin with narrow shelf and slope is not an efficient sink for the large amount of terrigenous organic carbon supplied by the small rivers, but, a transient environment for these river derived particles. 相似文献
6.
A significant belt of carbonate-hosted Pb–Zn mineralization occurs in the Himalayan–Zagros collisional orogenic system. Three differing types of these Pb–Zn deposits within this belt have been identified based on variations in gangue mineral assemblages, leading to the classification of carbonate-, quartz- and fluorite-rich classes of Pb–Zn deposits. The third Pb–Zn mineralization (fluorite-rich) type is common in this orogenic system, but little research has been undertaken on it. Here, we focus on the Mohailaheng deposit, a large-sized fluorite-rich carbonate-hosted Pb–Zn deposit (> 100 Mt Pb + Zn ores with average grade of 2.18%–4.23%); the deposit is located in the Sanjiang Cenozoic thrust-fold belt, an important part of the Himalayan–Zagros collisional orogenic system and an area that formed during the early Tertiary India–Eurasia collision. The main orebodies in this deposit are stratabound and are hosted by Carboniferous limestones that are located along secondary faults associated with a regional thrust fault. The main assemblage is a sphalerite + galena + pyrite sulfide assemblage associated with a calcite + fluorite + barite + quartz + dolomite gangue assemblage. Detailed field and experimental work indicates that the deposit formed during three distinct phases of hydrothermal activity. Studies on fluid inclusion and stable isotopes of gangue minerals indicate that two dominant distinct fluids involving the deposit formation. They include (1) a low-temperature (130–140 °C), high-salinity (23–24 wt.% NaCl equivalent) basinal brine containing Na+–K+–Mg2 +–Ca2 +–Cl− ions and abnormally high SO42 − concentrations, which probably derived from Tertiary basins in the regional district, and (2) a low- to moderate-temperature (170–180 °C) and moderate- to high-salinity (19–20 wt.% NaCl equivalent) metamorphic fluid containing Na+–K+–Mg2 +–Cl––SO42 − ions and abnormally high F− and organic matter concentrations, that probably formed during regional metamorphism. Some evaporated seawaters and meteoric fluids were also identified in mixtures with these two dominant fluids. The Pb–Zn mineralization at Mohailaheng formed during three distinct stages, consistent with the regional tectonic history. The first stage involved the formation of favorable lithological and structural traps at Mohailaheng during regional thrusting, leading to the migration of compressed metamorphic waters at depth along a detachment zone, sequestering metals from sediments within the region. Basinal brines at the surface also began to infiltrate down along the secondary faults, dissolving gypsum from the underlying sediments. The second stage was associated with the cessation of thrusting and the onset of strike-slip movements along these thrust faults. Metamorphic fluids containing high concentrations of halogen ions, organic gases, and metals ascended into the structural traps at Mohailaheng along the reactivated thrust faults, causing fluorite, calcite, and some sulfide precipitation. Then, basinal brines rich in SO42 − quickly descended into the structural traps along the reactivated faults, causing reduction of SO42 − by organic matter, and producing significant amounts of H2S. The reduced sulfur then reacted with the metals in the fluids, causing significant sulfide precipitation. The third stage was associated with metal-depleted fluids, which only resulted in the precipitation of calcite from the diluted basinal brines. Combining these findings with research results on other fluorite-rich carbonate-hosted Pb–Zn deposits in the Himalayan–Zagros orogenic system suggests that this type of carbonate-hosted Pb–Zn deposits can also be classified as Mississippi Valley-type (MVT) deposits, and that the origin of the fluorite in these deposits may be related to multiple hydrothermal fluids involved in the mineralization evolution. 相似文献
7.
《Chemie der Erde / Geochemistry》2014,74(4):641-651
Groundwaters in the crystalline aquifers are the major source of drinking water in Vaniyambadi area of Vellore district. Geochemical methods in collaboration with statistical methods were applied in this industrial area to understand the natural and anthropogenic influences on groundwater quality. To accomplish this objective, groundwater samples were collected and analyzed for physicochemical parameters and the results showed a dominance in the order of Na+ > Mg2+ > Ca2+ > K+ and HCO3− > Cl− > SO42− > NO3− for anions and cations, respectively. In contrast to this anion dominance were changed to Cl− > HCO3− > SO42− > NO3− in samples collected near the tannery industries. Groundwater quality evaluation using TDS and TH suggested that 57% of the total samples are hard-brackish type, indicating its unsuitability for drinking purpose. Generally the water type is Na+Cl− to Ca2+Mg2+HCO3− type with an intermediate Ca2+Mg2+Cl−, suggesting the mixing of fresh groundwater with tannery effluent and cation exchange. Factor analysis and bivariate plots of major ions suggests that both natural and anthropogenic inputs are equally influencing the groundwater quality. Further investigations proved that silicate weathering is the dominant geogenic source of groundwater solute content, whereas tannery effluent is the anthropogenic source. Saline water mixing index (SWMI) and Cl− vs NO3− bivariate plot were employed to differentiate the tannery contamination from the other anthropogenic inputs such as agricultural fertilizers, municipal sewages, etc. This analysis shows that samples 2, 4, 8 and 9 (located within the tannery cluster) have a SWMI value greater than 1, representing the groundwater–tannery effluent mixing. This study infers that groundwater in the Vaniyambadi area is under serious threat from both natural and anthropogenic contamination. However, the controlling discharge of untreated tannery effluents must be regulated to reduce the further deterioration of this vital resource in this part of the country. 相似文献
8.
Temporal changes of As concentration in surface waters were observed in some areas of the Czech Republic. Mobilized As originates from past atmospheric deposition. To understand the factors influencing As aqueous concentration and mobility the chemistry and runoff generation of a number of brooks, springs and rivers in the central part of the Elbe River catchment, Czech Republic, were monitored. Seasonal variations of As (from 0.5 to 10.5 μg L−1), Fe (from 0.05 to 3.9 mg L−1) and DOC (dissolved organic C – from 1.2 to 17.5 mg L−1) were observed in monitored stream waters with maximum values of As and Fe in the summer months at pH values 7.6–7.8. The concentration of As in particles with a diameter < 60 μm correlates with the Fe concentration. There is no correlation between Fe and As in filtered samples (<0.45 μm). The As concentration in stream water colloids depends on an increase in DOC concentration and a decrease in ionic strength. The DOC stabilizes As in solution and reduces its re-adsorption on Fe colloids and consequently As concentration in the stream increases. 相似文献
9.
The isotopic composition of water and dissolved Sr as well as other geochemical parameters at the 2516 m deep Outokumpu Deep Drill Hole, Finland were determined. The drill hole is hosted by Palaeoproterozoic turbiditic metasediments, ophiolite-derived altered ultramafic rocks and pegmatitic granitoids. Sodium–Ca–Cl and Ca–Na–Cl-rich waters (total dissolved solids up to ca. 70 g L−1) containing significant amounts of gas, mainly CH4 (up to 32 mmol L−1), N2 (up to 10 mmol L−1), H2 (up to 3.1 mmol L−1) and He (up to 1.1 mmol L−1) discharge from fracture zones into the drill hole. This water is distinct from the shallow fresh groundwater of the area, and has an isotopic composition typical of shield brines that have been modified during long-term water–rock interaction. Based on water stable isotopes and geochemistry, the drill hole water profile can be divided into five water types, each discharging from separate fracture systems and affected by the surrounding rocks. The δ2H varies from −90‰ to −56‰ (VSMOW) and δ18O from −13.5‰ to −10.4‰ (VSMOW), plotting clearly above the Global and Local Meteoric Water Lines on a δ2H vs. δ18O diagram. The 87Sr/86Sr ratios range between 0.72423 and 0.73668. Simple two-component mixing between 2H and 18O rich end-member brine and meteoric water cannot explain the water stable isotopic composition and trends observed. Instead, hydration of silicates by ancient groundwaters recharged under different climatic conditions, warmer than at present, is the most likely mechanism to have caused the variation of the δ2H and δ18O values. Water types correlate with changes in microbial communities implying that different ecosystems occur at different depths. The different water types and microbial populations have remained isolated from each other and from the surface for long periods of time, probably tens of millions of years. 相似文献
10.
The Saishitang skarn type copper deposit, located in the southeast part of the Dulan–Ela Mountain Triassic volcanic–magmatic arc and forearc accretionary wedge, belongs to the Tongyugou–Saishitang tin–copper polymetallic ore field in West Qinling, Qinghai province. Based on the contact/crosscutting relationships, mineral associations and mineralization characteristics, hydrothermal fluid evolution can be divided into three stages: skarn (I), quartz sulfide (II) and polymetallic sulfide-bearing quartz–calcite vein (III). The quartz sulfide stage (II) can be further divided into a massive sulfide stage (II-1) and a layered sulfide stage (II-2). This paper presents detailed analysis of fluid inclusions, H–O, S and Pb isotope compositions of rock samples from each of the above three stages as well as analysis of fluid inclusions from quartz diorite. The homogenization temperature, salinity, density and pressure of fluid inclusions in quartz diorite and typical transparent minerals showed a tendency of gradual decline in these evolutionary stages. The ore-forming fluid can be classified as a Na+–Ca2 +–SO42 − Cl− system with a minor proportion of a Na+–Ca2 +–NO3− SO42 − system, which likely resulted from mixing of magmatic and formation water. The H–O isotope composition indicates that the proportion of formation water increased during the ore-forming process, and meteoric water was mixed in the late quartz–calcite vein stage. The δ34S (CDT) values (− 6.45–5.57‰) and Pb isotope compositions show that the ore-forming materials were mainly derived from magmatic fluid. Ore-forming fluid was boiling during the main ore-forming stage (II-1) due to pressure decrease. Consequently, the physical and chemical conditions (i.e., pH, Eh, fO2, fS2) changed, and metallic elements (including Cu) in the fluid could no longer exist in the form of complexes and precipitated from the fluid. According to the integrated analysis of ore features, mineral associations, alteration characteristics, ore-forming environment and fluid evolutionary process, it is concluded that the Saishitang deposit is a typical skarn deposit. 相似文献
11.
The Xiaguan Ag–Pb–Zn orefield (Neixiang County, Henan Province), hosting the Yindonggou, Zhouzhuang, Yinhulugou and Laozhuang fault-controlled lode deposits, is situated in the Erlangping Terrane, eastern Qinling Orogen. The quartz-sulfide vein mineralization is dominated by main alteration styles of silicic-, sericite-, carbonate-, chlorite- and sulfide alteration. Major Ag-bearing minerals are freibergite, argentite and native Ag. The deposits were formed by a CO2-rich, mesothermal (ca. 250–320 °C), low-density and low salinity (< 11 wt.% NaCl equiv.), Na+–Cl−-type fluid system. Trapping pressures of the carbonic-type fluid inclusions (FIs) decreased from ca. 280–320 MPa in the early mineralization stage to ca. 90–92 MPa in the late mineralization stage, indicating that the ore-forming depths had become progressively shallower. This further suggests that the metallogenesis may have occurred in a tectonic transition from compression to extension. Geological- and ore fluid characteristics suggest that the Xiaguan Ag–Pb–Zn orefield belongs to orogenic-type systems.The δ18OH2O values change from the Early (E)-stage (7.8–10.8 ‰), through Middle (M)-stage (6.0–9.4 ‰) to Late (L)-stage (− 1.5–3.3 ‰), with δD values changing from E-stage − 95 to − 46 ‰, through M-stage − 82 to − 70 ‰ to L-stage − 95 to − 82 ‰. δ13CCO2 values of the ore fluids in the E- and M-stage quartz vary between 0.1 ‰ and 0.9 ‰ (average: 0.3 ‰); δ13CCO2 values of L-stage FIs are − 0.2–0.1 ‰ in quartz and − 6.8 ‰ to − 3.5 ‰ in calcite. The H–O–C isotopic data indicate that the initial ore fluids were sourced from the underthrusted Qinling Group marine carbonates, and were then interacted with the ore-hosting Erlangping Group metasedimentary rocks. Inflow of circulated meteoric water may have dominated the L-stage fluid evolution.Sulfur (δ34S = 1.9–8.1 ‰) and lead isotopic compositions (206Pb/204Pb = 18.202–18.446, 207Pb/204Pb = 15.567–15.773 and 208Pb/204Pb = 38.491–39.089) of sulfides suggest that the ore-forming materials were mainly sourced from the ore-hosting metasedimentary strata. The stepped heating sericite 40Ar/39Ar detection suggests that the mineralization occurred in the Middle Jurassic to Early Cretaceous (ca. 187 − 124 Ma). Considering the regional tectonic evolution of the Erlangping Terrane, we propose that the Xiaguan Ag–Pb–Zn orefield was formed in a continent–continent collisional tectonic regime, in accordance with the tectonic model for continental collision, metallogeny and fluid flow (CMF). 相似文献
12.
Although the effects of biodegradation on the composition and physical properties of crude oil have been well studied, effects of in-reservoir petroleum biodegradation on molecular and isotopic compositions of crude oils are not yet clearly understood. The Alberta Basin, in western Canada, is one of the world’s largest petroleum accumulations and constitutes an ideal example of a natural suite of sequentially biodegraded oils. The basin hosts moderately to severely biodegraded petroleum, regionally distributed and in single, more or less continuous, oil columns. In this study, a series of oil samples from the Alberta heavy oil and oil sands provinces, with varying degrees of biodegradation, were analyzed to assess the impact of progressive biodegradation on the molecular and C, H, N, and S isotopic compositions of oils. The results of the molecular characterization of the hydrocarbon fraction of the studied oils show that the oils have suffered biodegradation levels from 2 to 10+ (toward the Alberta–Saskatchewan border) on the Peters and Moldowan scale of biodegradation (abbreviated PM 2 to PM 10) and from tens to hundreds on the Manco scale. Within single reservoirs, increasing biodegradation was observed from top to bottom of the oil columns at all sites studied. The whole oil stable isotopic compositions of the samples varied in the ranges δ13C = −31.2‰ to −29.0‰, δ2H = −147‰ to −133‰, δ15N = 0.3–4.7‰ and δ34S = 0.4–6.4‰. The maximum differences between δ values of samples (Δ) within single oil columns were Δ13C = 1.4‰, Δ2H = 7‰, Δ15N = 1.7‰ and Δ34S = 1.0‰. Regional variations in the isotopic compositions of oil samples from different wells (averaged values from top to bottom) were 1.2‰ for δ13C, 12‰ for δ2H, 4.1‰ for δ15N and 5.5‰ for δ34S and hence generally significantly larger variations were seen than variations observed within single oil columns, especially for N and S. It appears that even severe levels of biodegradation do not cause observable systematic variations in carbon, nitrogen or sulfur isotope composition of whole oils. This indicates that sulfur and nitrogen isotopic compositions may be used in very degraded oils as indicators for oil charge from different source rock facies. 相似文献
13.
The relationship among subducted oxidized oceanic crust and oxidation state of the subarc mantle, and arc magmas is one of the important aspects to evaluate convergent margin tectonics. However details of the oxidized mass transferred from buried oceanic crust to the overlying subarc mantle wedge remain obscure. Here we investigate the Songduo eclogites from south Tibet formed by the subduction of the paleo-Tethyan oceanic crust, and identify an abrupt decrease in pyrope and increase in almandine contents from the mantle to rim of garnet grains. This is coupled with a decrease in the Fe3 + content of epidote and Fe3 +/(Fe2 ++ Fe3 +) ratios from garnet core to rim domains, as well as speciation of calcite, a new mineral phase, in the rock matrix. Minor sulfates occur only as inclusions in garnet core domains, whereas sulfides are confined to the matrix as an accessory mineral phase. Aegirine augite occurs as relics or inclusions in garnet and omphacite. These features clearly suggest that oxidized components, Fe3 + and S6 +, were reduced as Fe2 + and S2 −, respectively, at the subduction zone. Thermodynamic modeling in the P–T-log10fO2 space using updated Perplex_X programs further revealed that the Songduo eclogites experienced oxygen fugacity variation of up to 8 log10 units, with decreasing pressure. Petrological observations further suggest that the strong redox processes took place, after breaking of garnet, during the initial exhumation of the eclogites. CO2 and minor sulfur are subsequently transferred from the cold oceanic subduction zone to the overlying mantle wedge, partially released by arc volcanoes to atmosphere. Our study presents a case of C and S recycling between the Earth's exterior and interior. 相似文献
14.
《Chemical Geology》2007,236(3-4):199-216
The chemical characteristics of freshwaters draining the silicate rocks in the northern part of Okinawa Island were studied to understand solute generation processes, and to determine rates of chemical weathering and CO2 consumption. It was observed that the water chemistry is highly influenced by marine aerosols, contributing more than 60% of total solute. Significant positive correlations observed for chloride versus dissolved silica and chloride versus bicarbonate suggest a strong influence of evapotranspiration on the seasonality of solute concentration. It was also found that chemical weathering has been highly advanced in which the dominant kaolinite minerals are being gibbsitized. Carbonic acid was found to be the major chemical weathering agent, releasing greater than 80% of weathering-derived dissolved cations and silica while the remaining portion was attributed to weathering by sulfuric acid generated via oxidation of pyrite contained in the rocks. The flux of basic cations, weathering-derived silica and CO2 consumption were relatively high due to favourable climatic condition, topography and high rate of mechanical erosion. Silicate weathering rates for basic cations were estimated to be 6.7–9.7 ton km− 2 y− 1. Carbon dioxide consumed by silicate weathering was 334–471 kmol km− 2 y− 1 which was slightly higher than that consumed by carbonate weathering. In general, divalent cations (Mg and Ca) and bicarbonate alkalinity derived from carbonate dissolution were higher than those from silicate weathering. As a consequence, the evolution of chemical species in the freshwaters of northern area of Okinawa Island to a large extent could be explained by mixing of two components, characterized by waters with Na+ and Cl− as predominant species and waters enriched with Ca2+ and HCO3−. 相似文献
15.
Pure-iron end-member hibbingite, Fe2(OH)3Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe2(OH)3Cl(s), the pure-iron end-member of hibbingite (FeII, Mg)2(OH)3Cl(s), and Fe(OH)2(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe2(OH)3Cl(s) + 3H+ ? 3 H2O + 2 Fe2+ + Cl?,the solubility constant of Fe2(OH)3Cl(s) at infinite dilution and 25 °C has been found to be log10 K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)2(s) + 2H+ ? 2 H2O + Fe2+,the solubility constant of Fe(OH)2 at infinite dilution and 25 °C has been found to be log10 K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe2(OH)3Cl(s) and Fe(OH)2(s), the Na+–Fe2+ pair Pitzer interaction parameter θNa+/Fe2+ has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)2(s) to Fe2(OH)3Cl(s). Additionally, when Fe2(OH)3Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations. 相似文献
16.
The Baoligaomiao Formation, within the Hegenshan ophiolite-arc-accretion complex is an important segment to understand the tectonic evolution of the Central Asian Orogenic Belt (CAOB), world's largest Phanerozoic orogenic belt. In this study, we present an integrated study of zircon U-Pb isotopic ages, whole rock major-trace elements, and Sr-Nd-Pb isotopic data from the volcanic succession in the Baoligaomiao Formation. The volcanic succession can be divided into the lower sequence with zircon U-Pb ages in the range of 326.3 Ma–307.4 Ma and the upper sequence of 305.3 Ma. The succession belongs to two suites: calc-alkaline volcanics and high-Si rhyolites. The calc-alkaline volcanic rocks include basaltic andesite through andesite and dacite to rhyolite and their pyroclastic equivalents. These rocks exhibit a well-defined compositional trend from basaltic to rhyolitic magma, reflecting continuous fractional crystallization. These rocks show obvious enrichment in LILEs and LREEs and relative depletion of HFSEs, typical of subduction-related magma. The calc-alkaline rocks have low initial 87Sr/86Sr (0.7023–0.7052), positive ɛNd(t) values (2.75–4.80), and their initial Pb isotopic compositions are 17.875–18.485 of 206Pb/204Pb, 15.481–15.520 of 207Pb/204Pb and 37.467–37.764 of 208Pb/204Pb, respectively. Geochemical and isotopic results suggest that the volcanic succession represents Carboniferous subduction-related, mature, continental arc volcanism. The outcrops of high-Si rhyolites are restricted to the northern edge of the continental arc, marking a transition zone between volcanic arc and back-arc basin, where they are interbedded with the calc-alkaline rocks in the lower sequence, and the upper sequence is composed only of high-Si rhyolites. The high-Si rhyolites have high SiO2 (71.12–81.76 wt%) and varied total alkali contents (K2O + Na2O = 5.46–10.58 wt%), low TiO2 (0.06–0.27 wt%), MgO (0.09–0.89 wt%) and CaO (0.08–0.72 wt%). Based on the presence of mafic alkali phenocrysts, such as arfvedsonite and siderophyllite, high Zr/Nb ratios (> 10) and peralkalinity index (PI) near unity, the high-Si rhyolites can be classified as peralkaline comendites. The high-Si rhyolites are characterized by unusually low Sr and Ba, and high abundance of Zr, Th, Nb, HREEs and Y. They show geochemical characteristics similar to those of typical A2-type granites including their high K2O + Na2O, Nb, Zr and Y, and high ratios of FeOT/MgO, Ga/Al and Y/Nb. Our study suggests that the high-Si rhyolites were derived from discrete trachytic parent magma with fractional crystallization within shallow magma reservoirs. Their Nd-Pb isotopic characteristics are similar to those of the calc-alkaline arc rocks and are compatible with partial melting of pre-existing juvenile continental arc crust. We observe that the widespread eruptions of A2-rhyolitic magmas (305.3 Ma–303.4 Ma) following a short period of magmatic quiescence was temporally and spatially associated with voluminous intrusion of the bimodal magmas (304.3 Ma–299.3 Ma) in the pre-existing arc volcanic-plutonic belt (329 Ma–307 Ma). We envisage northward subduction and slab breakoff process resulting in an obvious change of the regional stress field to extensional setting within the Carboniferous continental arc running E-W for thousands of kilometers. Therefore, we propose the existence of an east-west-trending Carboniferous continental arc in the Hegenshan ophiolite-arc-accretion complex, with the slab breakoff event suggesting that the age of the upper sequence (305.3 ± 5.5 Ma) likely indicates the maximum age for the cessation of the northward subduction of the Hegenshan oceanic lithosphere. 相似文献
17.
The effect of fluorine on the solubilities of Mn-columbite (MnNb2O6), Mn-tantalite (MnTa2O6), zircon (ZrSiO4) and hafnon (HfSiO4) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab72Or28) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P2O5, 1.05 wt.% Li2O and 1.83 wt.% B2O3. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF3 to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb2O5] and [MnO] 1 [Ta2O5] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10− 4 (mol2/kg2), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10− 4 (mol/kg) ZrO2 and 4.04 ± 0.2 × 10− 4 (mol/kg) HfO2 for melts with 0 wt.% F to 3.81 ± 0.3 × 10− 4 (mol/kg) ZrO2 and 6.18 ± 0.04 × 10− 4 (mol/kg) HfO2 for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt. 相似文献
18.
The Quaternary Tasse basalts are exposed near the north shore of Quesnel Lake in southeastern British Columbia. They host a variety of mantle xenoliths consisting predominantly of spinel lherzolite with minor dunite and pyroxenite. Mineralogically, the xenoliths are composed of olivine, orthopyroxene, clinopyroxene and spinel characterized by forsterite (Fo87–93), enstatite (En90–92), diopside (En45–50–Wo40–45–Fs5), and Cr-spinel (6 − 11 wt.% Cr), respectively. All of the mantle xenoliths are coarse-grained and show granoblastic textures. Clinopyroxene and spinel display textural evidence for chemical reactions with percolating melts.The mantle xenoliths are characterized by restricted Mg-numbers (89 − 92) and low abundances of incompatible elements (Ba = 2 − 11 ppm; Sr = 3 − 31 ppm) and Yttrium (1 − 3 ppm). On the basis of REE patterns, the xenoliths are divided into three groups reflecting the various degrees of mantle metasomatism: (1) Group 1 consists of concave-up LREE patterns (La/Smcn = 0.48 − 1.16; Gd/Ybcn = 0.71 − 0.92); (2) Group 2 possesses flat to moderately LREE-enriched patterns (La/Smcn = 1.14 − 1.92; Gd/Ybcn = 0.87 − 1.09); and (3) Group 3 is characterized by strongly LREE-enriched patterns (La/Smcn = 1.53 − 2.45; Gd/Ybcn = 1.00 − 1.32). On MORB-normalized trace element diagrams, the majority of the xenolith samples share the enrichment of LILE (Rb, Ba, K), U, Th, Pb, Sr and the depletion of HFSE (Nb, Ta, Ti, Y) relative to REE. These geochemical characteristics are consistent with a compositionally heterogeneous subcontinental lithospheric mantle source that originated as subarc mantle wedge peridotite at a convergent plate margin.The Tasse basalts have alkaline compositions characterized by low SiO2 (44 − 46 wt.%) and high alkali (Na2O + K2O = 5.1 − 6.6 wt.%) contents. They are strongly enriched in incompatible elements (TiO2 = 2.4 − 3.1 wt.%; Ba = 580 − 797 ppm; Sr = 872 − 993 ppm) and, display OIB-like trace element patterns (La/Smn = 3.15 − 3.85; Gd/Ybn = 3.42 − 4.61). They have positive εNd (+ 3.8 to + 5.5) values, with 338 − 426 Ma depleted mantle model ages, and display uniform OIB-like Sr (87Sr/86Sr = 0.703346 − 0.703591) and Pb (206Pb/204Pb = 19.40 − 19.58; 207Pb/204Pb = 15.57 − 15.60; 208Pb/204Pb = 38.99 − 39.14) isotopic compositions. The basalts erupted discontinuously along a > 1000 km long SE-NW-trending linear belt with minimal compositional variation indicative of a homogenous mantle source. The Sr − Nd − Pb isotope and trace element systematics of the alkaline basalts suggests that they originated from partial melting of an upwelling asthenospheric mantle source. Melting of the asthenospheric mantle might have stemmed from extension of the overlying lithosphere in response to the early stages of back-arc basin opening in the Omineca and Intermontane belts. Ridge subduction beneath the Canadian Cordillera might have played an important role in the weakening of the lithospheric mantle prior to its extension. Alternatively, melting of the upwelling asthenosphere in response to the delamination of the lithospheric mantle beneath the Rocky Mountain Trench might have generated the alkaline lavas. 相似文献
19.
《Applied Geochemistry》2005,20(2):295-316
A confined aquifer system has developed in argillaceous marine and freshwater sediments of Pliocene–Holocene age in the northeastern Osaka Basin (NEOB) in central Japan. The shallow groundwater (<100 m) in the system is recharged in a northern hilly to mountainous area with dominantly Ca-HCO3 type water, which changes as it flows toward the SW to Mg-HCO3 type and then to Na-HCO3 type water. Comparison of the chemical and Sr isotopic compositions of the groundwater with those of the bulk and exchangeable components of the underground sediments indicates that elements leached from the sediments contribute negligibly to the NEOB aquifer system. Moreover, model calculations show that contributions of paleo-seawater in the deep horizon and of river water at the surface are not major factors of chemical change of the groundwater. Instead, the zonal pattern of the HCO3-dominant groundwater is caused by the loss of Ca2+ from the water as it is exchanged for Mg2+ in clays, followed by loss of Mg + Ca as they are exchanged for Na + K in clays between the Ca-HCO3 type recharge water and the exchangeable cations in the clay layers, which were initially enriched in Na+. Part of this process was reproduced in a chromatographic experiment in which Na type water with high 87Sr/86Sr was obtained from Mg type water with low 87Sr/86Sr by passing it through marine clay packed in a column. The flux of recharge water into the confined aquifer system according to this chromatographic model is estimated to be 0.99 mm/day, which is compatible with the average recharge flux to unconfined groundwater in Japan (1 mm/day). 相似文献
20.
《Comptes Rendus Geoscience》2007,339(14-15):895-906
Carbonaceous chondrites are characterized by their enrichment in organic matter, mainly represented by insoluble organic matter (IOM), which consists of small aromatic units linked by short-branched aliphatic chains. Furthermore, IOM contains organic radicals heterogeneously distributed along with diradicaloids. These chemical features discriminate IOM from terrestrial counterparts. Isotopic compositions, especially the D/H isotopic ratio, are also distinct. IOM is highly enriched in D (D/H > 350 × 10−6), and the D/H isotopic ratio is heterogeneous. The isotopic composition is the result of interstellar-like processes that could have taken place during the first ages of the protosolar nebula. Chemical structure and isotopic composition clearly show that IOM is synthesized by an abiotic process and is subsequently affected by aqueous alteration or high-temperature metamorphism on the parent body. 相似文献