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1.
Inorganic chlorine (i.e. chloride; Clin) is generally considered inert in soil and is often used as a tracer of soil and ground water movements. However, recent studies indicate that substantial retention or release of Clin can occur in soil, but the rates and processes responsible under different environmental conditions are largely unknown. We performed 36Cl tracer experiments which indicated that short-term microbial uptake and release of Clin, in combination with more long-term natural formation of chlorinated organic matter (Clorg), caused Clin imbalances in coniferous forest soil. Extensive microbial uptake and release of Clin occurred over short time scales, and were probably associated with changes in environmental conditions. Up to 24% of the initially available Clin within pore water was retained by microbial uptake within a week in our experiments, but most of this Clin was released to the pore water again within a month, probably associated with decreasing microbial populations. The natural formation of Clorg resulted in a net immobilization of 4% of the initial pore water Clin over four months. If this rate is representative for the area where soil was collected, Clorg formation would correspond to a conversion of 25% of the yearly wet deposition of Clin. The study illustrates the potential of two Clin retaining processes in addition to those previously addressed elsewhere (e.g. uptake of chloride by vegetation). Hence, several processes operating at different time scales and with different regulation mechanisms can cause Clin imbalances in soil. Altogether, the results of the present study (1) provide evidence that Clin cannot be assumed to be inert in soil, (2) show that microbial exchange can regulate pore water Clin concentrations and (3) confirm the controversial idea of substantial natural chlorination of soil organic matter.  相似文献   

2.
《Organic Geochemistry》2011,42(9):1076-1088
Bulk geochemical, petrographical, mineralogical and molecular compositions of unweathered, weathered and transitional zones of a Middle Jurassic fossil wood were analyzed to trace changes caused by oxidative weathering of the immature terrestrial organic matter (OM). The occurrence of such zones was confirmed by the mineral composition, showing replacement of siderite and pyrite by goethite. Vitrinite reflectance analysis of weathered and unweathered fossil wood samples revealed that weathering elevated the vitrinite reflectance values by ca. 0.1%, which should be taken into account during modeling of low maturity terrestrial OM. In the weathered part of the wood, most of the biomarkers and biomolecules were totally removed or the concentration decreased significantly. The concentration of most of the polynuclear aromatic hydrocarbons (PAHs) decreased by 50–80%, being >90% for the more reactive and less stable benzo[a]pyrene and perylene. On the other hand, several aromatic compounds, like phenanthrene and its methyl derivatives, phenyl naphthalenes, fluoranthene and oxygen-containing aromatic compounds increased in concentration in the weathered zone. This results from processes such as formation of phenyl derivatives of PAHs and their cyclization, as well as aromatization of diterpenoids and incorporation of oxygen into aromatic structures. Weathering should always be considered in studies of fossilized terrestrial OM, especially in the case of thermal maturation modeling, because it significantly decreases the OM content and total sulfur content, changes vitrinite reflectance values and alters the extract composition as a result of organic compound degradation.  相似文献   

3.
The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of DClapatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing DClapatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which DClapatite/melt and DClfluid/melt begin to increase also depends on composition. The experiments reveal that DFapatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so DFapatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.  相似文献   

4.
Subaerial exposure and oxidation of organic carbon (Corg)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial Corg oxidation are expected to shift new biomass δ13Corg composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ13Corg at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, Corg-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, Corg-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of Corg without producing a δ13C shift between acid rock drainage precipitates and shale. Moreover, 13C enrichment in inorganic carbon of precipitates does not support microbial Corg oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ34S = δ34Sshale − δ34Sprecipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ15N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of Corg, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.  相似文献   

5.
Organic carbon, sulphur, 13Corg, iron, manganese and calcium have been measured across a subsurface-weathering front in Pliocene sediments in southern Sicily. The results show an almost quantitative removal of Corg and sulphur and an increase in iron and manganese oxides over the weathering front, accompanied with a significant shift of the 13Corg to lower values. These data are among the first to support the rapid, extensive weathering of sedimentary organic matter and sulphur, a basic assumption made in global biogeochemical models on a Phanerozoic timescale.  相似文献   

6.
Major element, Rb, Sr and Sr isotope abundances were examined in an ancient (Cambrian) weathering zone in the Butler Hill Granite, Missouri. Most of the major elements behaved predictably and systematically as a result of weathering intensity. MgO and the alkalis (Na2O and K2O) show highly erratic variations in both fresh and weathered rocks, suggesting considerable initial heterogeneity in the composition of biotite and feldspar. Rb predictably follows the behaviour of K during weathering (showing erratic variations similar to K), whereas Sr follows Ca (decreasing steadily as a result of weathering intensity). A method is postulated to date ancient weathering episodes using Rb-Sr data from a sequence of fresh to highly weathered samples. Data from the Butler Hill Granite (1185 m.y.) lend support to the proposed dating technique but show that more detailed sampling of the most intensely weathered regions is needed to produce more accurate results in future studies.  相似文献   

7.
The ancient weathered crust studied occurs on the razed surfaces of various physiographic periods at different altitudes in the Sichuan red basin. A typical profile of the ancient weathered crust can be divided into three weathered belts from the surface to the basement: the clastic clay belt (Belt I), the clastic breccia-clastic clay belt (Belt II), and the clastic breccia belt (Belt III). These belts are different in clay mineral composition, reflecting varying degrees of chemical weathering. Wide variations are recognized in the abundance of chemical elements in the profile of th ancient weathered crust. In comparison with the underlying purple parent rocks, Fe2O3 > A12O3 > TiO2 > SiO2 are relatively concentrated in the ancient weathered crust, while CaO>P2O5>MnO>Na2O>MgO>K2O are relatively depleted due to leaching in order of Belt I > II > III. The extent of chemical weathering in the ancient weathered crust in the Sichuan red basin is closely related to the time of formation of the razed surface. For this reason, the contents of A12O3 and Fe2O3 or their concentration values, and the leaching amounts of CaO, MgO, K2O, Na2O, and P2O5 are higher in the ancient weathered crust at high altitudes than those at low altitudes.  相似文献   

8.
The Ordovician-Silurian transition (OST) hosted profound and frequent changes in the atmospheric-terrestrial-oceanic-climatic system (ATOCS). Previous studies have found contrasting stages for such changes, primarily based on hiatus-interrupted sections. However, the dominant driving factors and mechanisms reconciling such frequent changes remain controversial. Mercury isotopes, which undergo both mass-dependent and mass-independent fractionation, can provide critical insights into the deep-time ATOCSs, especially for those impacted by large igneous provinces (LIPs) events. Here, we build a high-resolution multi-proxy record of Hg (concentrations and isotopic compositions) combined with organic carbon isotopes (δ13Corg) and whole-rock geochemical data (including trace elements and phosphorus) from continuous cores in the Yangtze Platform, South China. Our data, combined with reported ones, indicate the occurrence of LIP eruptions against localized volcanism, and four successive, yet contrasting stages of ATOCSs during the OST. Moreover, we identified the coupling between two-pulse LIP magmatism and extreme ATOCSs, each with special pCO2, weathering rate, primary productivity, redox condition, climatic mode, and biotic evolution. For stage I, the first pulse of LIP magmatism triggered global warming, enhanced terrestrial weathering, oceanic acidification, eutrophication, anoxia, P recycling, and thereby widespread deposition of black shales. During stage II, the Hirnantian glaciation and oxygenation arose from the intense chemical weathering and black shale deposition of stage I; slashed terrestrial weathering and oceanic oxygenation facilitated CO2 accumulation. In stage III, another pulse of LIP magmatism triggered the de-glaciation, and the ATOCS was largely similar to that of stage I. This led to another round of oxygenation and positive δ13Corg excursion in stage IV. Compared with the environmental pressure by the peculiar ATOCS of each stage, their transitions might have been more devastating in triggering the prolonged Late Ordovician Mass Extinction (LOME). Moreover, limited biotic recovery was possible in the later portion of stages I and III. The multi-proxy study of continuous strata of the OST provides an excellent framework for better illuminating LIPs’ essential role in driving the “roller-coaster” behavior of the ATOCS and thus biotic crisis during the pivotal period of the OST.  相似文献   

9.
The hydrogeochemistry of groundwater in rural parts of Birbhum district, West Bengal, India, has been studied to understand the contaminants and prime processes involved in their enrichment with a focus on F? concentration. The lithological units consist of Quaternary alluviums with underlying Rajmahal basaltic rocks of Middle Jurassic age. Groundwater occurs in the alluviums, weathered residuum and fracture zone of Rajmahal rocks. Studies show elevated concentration of Cl?, SiO2, Fe and F?; excess Cl? is attributed to anthropogenic inputs, SiO2 is ascribed to high degree of weathering of silica rich host rocks, and high Fe is due to the interaction of water with Fe-rich sediments under reducing condition. The F? concentration is found high (>1.20 mg/L) mainly in water from Rajmahal rocks revealing a lithological control on F? enrichment. The weathering of silicates and ion exchange are the leading controlling processes for major ions in groundwater. The F? enrichment is due to the dissolution of F?-bearing minerals and perhaps also through anion exchange (OH? for F?) on clay minerals at high alkaline conditions; precipitation of CaCO3 favours CaF2 dissolution leading to elevated F? concentration. CaHCO3, the dominant water type, contains low F? while NaHCO3 and NaCl types exhibit high F? concentrations. Among the three spatial associations, Cluster-1 and Cluster-2 are CaHCO3 type; Cluster-3 shows NaHCO3 and NaCl waters with low Ca2+ and Mg2+ and high Na+ contents. Cluster-1 and Cluster-2 waters are, in general, drinkable barring the elevated Fe content, while Cluster-3 water is unsafe for drinking due to the high F? concentration.  相似文献   

10.
An intrabasaltic red bole horizon is studied for its weathering characteristics with respect to the underlying and overlying basalts. The study indicates that all the three units have been considerably weathered; the red bole unit, however shows some distinctive characteristics. The red boles show a higher cation exchange capacity (CEC) and lower sodium adsorption ratio (SAR) and organic carbon (OC) as compared to the weathered basalts. The lower values of Al2O3, TiO2 and Fe2O3(T) in red boles indicate their lesser weathering than the underlying and overlying basalts, which is further corroborated by the weathering intensity measured by the indices like chemical index of alteration (CIA) and statistical empirical index of chemical weathering (W). It is also evident that the red bole samples show more retention of original mafic and felsic components. While K2O exhibits an erratic behaviour, the MgO and CaO do not show much leaching in red boles. Lesser leaching and salinity in the red boles is indicated by the higher values of calcification and lower values of salinization. The SiO2–Al2O3–Fe2O3 plot indicates that red bole samples are close to the basalt field, while the weathered upper basalt is more kaolinized than the weathered lower basalt. These observations reveal that the post-formational weathering processes have least affected the original palaeoweathering characters of the red bole horizon and hence the intrabasaltic palaeosols (weathering horizons) can effectively be used to constrain the palaeoweathering and palaeoclimates during the continental flood basalt episodes in the geologic past.  相似文献   

11.
《Applied Geochemistry》2002,17(7):885-902
An ancient saprolite has developed on the Palaeoproterozoic granulite, granite gneiss and amphibolite bedrock of the Vuotso–Tankavaara area of central Finnish Lapland. The present day climatic regime in Finnish Lapland lies within the northern boreal zone and so the saprolite there can be regarded as fossil. Cores of saprolite were collected from 4 sections (42 samples) and analyzed chemically and mineralogically. In the study area, progressive weathering of the rocks has been marked by gradual enrichment in Al, Fe and Ti; and depletion of Na, K and Ca. The higher concentration of Fe(III) and water and reduced Na and Ca in weathered bedrock in the 4 sections are indicative of oxidation, hydration and leaching processes involved during weathering. The primary minerals in the saprolite are plagioclase feldspar, K-feldspar, quartz, garnet (almandine) and hornblende; the common secondary minerals are kaolinite, halloysite, and vermiculite in addition to minor amounts of sericite. Intense weathering is indicated by: (1) the presence of kaolinite and halloysite in 4 sections of different bedrock types, and (2) the comparatively lower SiO2/Al2O3 (wt.%) ratio (2.30) of weathered granulites (3 sections) as compared to fresh granulite (4.33) and that of weathered amphibolite (2.68) as compared to fresh amphibolite (3.56). In general, kaolinite and halloysite have formed through the weathering of feldspars, garnet, and biotite. Vermiculite is the most probable alteration product of biotite. The formation of kaolinite and halloysite in Finnish Lapland indicates wetter and warmer climatic conditions during the time of their formation than at present. The possible time for formation of the saprolite is early Cretaceous–early Tertiary into Middle Miocene.  相似文献   

12.
在南极格罗夫山普通球粒陨石的风化等级划分中出现了和Wlotzka(1993)标准矛盾的现象。部分普通球粒陨石的金属和陨硫铁氧化不足20%,然而硅酸盐却发生了蚀变。如果考虑金属的氧化量,这种风化程度应为W1,如果考虑硅酸盐的蚀变,这种风化程度应为W5。对于存在如此大的差异本文给出了折衷的解决办法——对金属和硅酸盐同时进行风化等级划分。金属的风化等级划分为W_m0-W_m4五个,硅酸盐风化等级划分为W_s0-W_s3四个。依据新方案,GRV 021588、021636、021772和021957等4块无法用Wlotzka(1993)标准来确定风化等级的陨石的风化等级均为W_m1-W_s1。而陨石GRV 023312的风化等级为W_m3-W_s0,其相当于Wlotzka(1993)标准中的W3。  相似文献   

13.

Shephards Discordant Zone is a 500–600 m thick interlayered sequence of deformed, altered and metamorphosed magnetite metagabbro and about 50 layers or lenses of magnetitite (> 80–90% magnetite). The sequence shows progressive magmatic fractionation upwards: Ti and Ti/Fe increase, and V, V/Ti and Cr decrease upwards in magnetite and in whole‐rock compositions. The main magnetite‐rich sequence (about 400 m thick) is deeply weathered, with 40 m of saprolite showing vertical zonation of weathering minerals due to progressive weathering. Magnetitites (average 1% V2O3) are resistant to weathering and show little chemical change, but magnetite gabbros (average 0.27% V2O3) are extensively weathered and show progressive loss of Ca, Na, Mg and S. Plagioclase, magnetite (1.37% V2O3), chlorite (up to 0.35% V2O3), actinolite, epidote and minor sulfides in unweathered rocks weather to kaolinite, hematite, goethite and minor vermiculite, ilmenite remaining largely unaffected. Vanadium is essentially immobile during weathering and is unaffected during weathering of magnetitites (1% V2O3), but is slightly depleted during weathering of magnetite gabbros (0.23% V2O3).  相似文献   

14.
Organic nitrogen chemistry during low-grade metamorphism   总被引：1，自引：0，他引：1  
Most of the organic nitrogen (Norg) on Earth is disseminated in crustal sediments and rocks in the form of fossil nitrogen-containing organic matter. The chemical speciation of fossil Norg within the overall molecular structure of organic matter changes with time and heating during burial. Progressive thermal evolution of organic matter involves phases of enhanced elimination of Norg and ultimately produces graphite containing only traces of nitrogen. Long-term chemical and thermal instability makes the chemical speciation of Norg a valuable tracer to constrain the history of sub-surface metamorphism and to shed light on the subsurface biogeochemical nitrogen cycle and its participating organic and inorganic nitrogen pools. This study documents the evolutionary path of Norg speciation, transformation and elimination before and during metamorphism and advocates the use of X-ray photoelectron spectroscopy (XPS) to monitor changes in Norg speciation as a diagnostic tool for organic metamorphism. Our multidisciplinary evidence from XPS, stable isotopes, traditional quantitative coal analyses, and other analytical approaches shows that at the metamorphic onset Norg is dominantly present as pyrrolic and pyridinic nitrogen. The relative abundance of nitrogen substituting for carbon in condensed, partially aromatic systems (where N is covalently bonded to three C atoms) increases exponentially with increasing metamorphic grade, at the expense of pyridinic and pyrrolic nitrogen. At the same time, much Norg is eliminated without significant nitrogen isotope fractionation. The apparent absence of Rayleigh-type nitrogen isotopic fractionation suggests that direct thermal loss of nitrogen from an organic matrix does not serve as a major pathway for Norg elimination. Instead, we propose that hot H, O-containing fluids or some of their components gradually penetrate into the carbonaceous matrix and eliminate Norg along a progressing reaction front, without causing nitrogen isotope fractionation in the residual Norg in the unreacted core of the carbonaceous matrix. Before the reaction front can reach the core, an increasing part of core Norg chemically stabilizes in the form of nitrogen atoms substituting for carbon in condensed, partially aromatic systems forming graphite-like structural domains with delocalized π-electron systems (nitrogen atoms substituting for “graphitic” carbon in natural metamorphic organic matter). Thus, this nitrogen species with a conservative isotopic composition is the dominant form of residual nitrogen at higher metamorphic grade.  相似文献   

15.
Major element, Sr isotope and trace element data for 16 elements are reported for various weathered zones in three submarine basalt pillows. During the initial stages of alteration, it appears that SiO2, Al2O3, CaO, S, and Ga are lost from the basalt, whereas Fe2O3, total Fe, MnO, K2O, H2O, Cl, B, Rb, and Cs increase. Sr87/Sr86 ratios also increase during weathering. MgO, Na2O, P2O5, Ba, Ni and Cu show significant (10–50%) but less consistent changes. TiO2, Zr, Sr and V show only minor changes (<7%). Zn, Cr, Co, Y and Nb show no changes outside experimental error.  相似文献   

16.
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17.
滇池地区下寒武统磷块岩以碳酸盐类磷块岩为主。原生矿多属中低品位矿，风化后富集。磷块岩经历风化强弱可用风化成熟度来表示，风化磷块岩是风化成熟期的产物，表明矿石风化进入了风化门限之内。根据磷块岩的特点及风化磷块岩形成机制初步建立的本区风化磷块岩的成矿模式将磷块岩的风化分三个阶段，不同的风化阶段，磷块岩的风化成熟度存在明显的差异，风化磷块岩是前两个风化阶段的产物。  相似文献   

18.
Basalt weathering in Central Siberia under permafrost conditions   总被引：2，自引：0，他引：2  
Chemical weathering of basalts in the Putorana Plateau, Central Siberia, has been studied by combining chemical and mineralogical analysis of solids (rocks, soils, river sediments, and suspended matter) and fluid solution chemistry. Altogether, 70 large and small rivers, 30 soil pore waters and groundwaters and over 30 solids were sampled during July to August 2001. Analysis of multiannual data on discharge and chemical composition of several rivers of the region available from the Russian Hydrological Survey allowed rigorous estimation of mean annual major element concentrations, and dissolved and suspended fluxes associated with basalt weathering. For the rivers Tembenchi and Taimura that drain monolithologic basic volcanic rocks, the mean multiannual flux of total dissolved cations (TDS_c = Ca + Mg + Na + K) corrected for atmospheric input is 5.7 ± 0.5 t/km2/yr. For the largest river Nizhniya Tunguska—draining essentially basic rocks—the TDS_c is 6.1 ± 1.5 t/km2/yr. The overall CO2 consumption flux associated with basalt weathering in the studied region (∼700,000 km2) achieves 0.08 × 1012 mol/yr, which represents only 2.6% of the total CO2 consumption associated with basalt weathering at the Earth’s surface. The fluxes of suspended matter were estimated as 3.1 ± 0.5, 9.0 ± 0.8, and 6.5 ± 2.0 t/km2/yr for rivers Taimura, Eratchimo, and Nizhniya Tunguska, respectively. Based on chemical analyses of river solutes and suspended matter, the relative dissolved versus particulate annual transport of major components is Cinorg ≥ Corg > Na + K > Ca > Mg > Si > Fe ≥ Mn ≥ Ti ≥ Al which reflects the usual order of element mobility during weathering.According to chemical and mineralogical soil and sediment analyses, alteration of basalt consists of (1) replacement of the original basaltic glass by Si-Al-Fe rich amorphous material, (2) mechanical desegregation and grinding of parent rocks, leading to accumulation of “primary” hydrothermal trioctahedral smectite, and (3) transformation of these trioctahedral (oxy)smectites and mixed-layer chlorite-smectite, into secondary dioctahedral smectite accompanied by removal of Ca, Mg, and Fe, and enrichment in Al. No vertical chemical differentiation of fluid and solid phases within the soil profile was identified. All sampled soil pore waters and groundwaters were found to be close to equilibrium with respect to chalcedony, gibbsite, halloysite, and allophanes, but strongly supersaturated with respect to goethite, nontronite, and montmorillonite.Over the annual cycle, the contribution of atmospheric precipitation, permafrost melting, underground reservoirs, litter degradation, and rock and soil mineral weathering for the overall TDS_c transport in the largest river of the region (Nizhniya Tunguska) is 9.3 ± 3, 10 ± 5, 10.5 ± 5, 25 ± 20, and 45 ± 30%, respectively. In the summertime, direct contribution of rocks and soil mineral weathering via solid/fluid interaction does not exceed 20%. The main unknown factors of element mobilization from basalt to the river is litter degradation in the upper soil horizon and parameters of element turnover in the vegetation.  相似文献   

19.
Equilibrium chlorine-isotope (37Cl/35Cl) fractionations have been determined by using published vibrational spectra and force-field modeling to calculate reduced partition function ratios for Cl-isotope exchange. Ab initio force fields calculated at the HF/6-31G(d) level are used to estimate unknown vibrational frequencies of 37Cl-bearing molecules, whereas crystalline phases are modeled by published lattice-dynamics models. Calculated fractionations are principally controlled by the oxidation state of Cl and its bond partners. Molecular mass (or the absence of C-H bonds) also appears to play a role in determining relative fractionations among simple Cl-bearing organic species. Molecules and complexes with oxidized Cl (i.e., Cl0, Cl+, etc.) will concentrate 37Cl relative to chlorides (substances with Cl−). At 298 K, ClO2 (containing Cl4+) and [ClO4]− (containing Cl7+) will concentrate 37Cl relative to chlorides by as much as 27‰ and 73‰, respectively, in rough agreement with earlier calculations. Among chlorides, 37Cl will be concentrated in substances where Cl is bonded to +2 cations (i.e., FeCl2, MnCl2, micas, and amphiboles) relative to substances where Cl is bonded to +1 cations (such as NaCl) by ∼2 to 3‰ at 298 K; organic molecules with C-Cl bonds will be even richer in 37Cl (∼5 to 9‰ at 298 K). Precipitation experiments, in combination with our results, provide an estimate for Cl-isotope partitioning in brines and suggest that silicates (to the extent that their Cl atoms are associated with nearest-neighbor +2 cations analogous with FeCl2 and MnCl2) will have higher 37Cl/35Cl ratios than coexisting brine (by ∼2 to 3‰ at room temperature). Calculated fractionations between HCl and Cl2, and between brines and such alteration minerals, are in qualitative agreement with both experimental results and systematics observed in natural samples. Our results suggest that Cl-bearing organic molecules will have markedly higher 37Cl/35Cl ratios (by 5.8‰ to 8.5‰ at 295 K) than coexisting aqueous solutions at equilibrium. Predicted fractionations are consistent with the presence of an isotopically heavy reservoir of HCl that is in exchange equilibrium with Cl−aq in large marine aerosols.  相似文献   

20.
The study area Mettur forms an important industrial town situated NW of Salem district. The geology of the area is mainly composed of Archean crystalline metamorphic complexes. To identify the major process activated for controlling the groundwater chemistry an attempt has been made by collecting a total of 46 groundwater samples for two different seasons, viz., pre-monsoon and post-monsoon. The groundwater chemistry is dominated by silicate weathering and (Na + Mg) and (Cl + SO4) accounts of about 90% of cations and anions. The contribution of (Ca + Mg) and (Na + K) to total cations and HCO3 indicates the domination of silicate weathering as major sources for cations. The plot for Na to Cl indicates higher Cl in both seasons, derived from Anthropogenic (human) sources from fertilizer, road salt, human and animal waste, and industrial applications, minor representations of Na also indicates source from weathering of silicate-bearing minerals. The plot for Na/Cl to EC indicates Na released from silicate weathering process which is also supported by higher HCO3 values in both the seasons. Ion exchange process is also activated in the study area which is indicated by shifting to right in plot for Ca + Mg to SO4 + HCO3. The plot of Na-Cl to Ca + Mg-HCO3-SO4 confirms that Ca, Mg and Na concentrations in groundwater are derived from aquifer materials. Thermodynamic plot indicates that groundwater is in equilibrium with kaolinite, muscovite and chlorite minerals. Saturation index of silicate and carbonate minerals indicate oversaturation during pre-monsoon and undersaturation during post-monsoon, conforming dissolution and dilution process. In general, water chemistry is guided by complex weathering process, ion exchange along with influence of Cl ions from anthropogenic impact.  相似文献   

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