13C/12C- and 18O/16O-signatures of Calcite Precipitations in Drainage Systems Measurements of drainage waters show two distinct processes of calcite precipitation: 1. reprecipitation of calcium carbonate previously dissolved in groundwaters and 2. absorption of atmospheric CO2 by alkaline solutions. Both processes may be distinguished by the stable isotopes of oxygen and carbon. Calcite precipitated from carbonate groundwater yields δ13C ≈ ?13%0 (PDB) and δ18O ≈ 24%0 (SMOW), whereas calcite produced by CO2-absorption shows δ13C ≈ ?25%0 (PDB) and δ18O ≈ 10%0 (SMOW). 相似文献
The Nyangqu River, the largest right bank tributary of the Yarlung Zangbo River in the Qinghai–Tibet Plateau, was representative of an alpine riverine carbon cycle experiencing climate change. In this study, dissolved inorganic carbon (DIC) spatial and seasonal variations, as well as their carbon isotopic compositions (δ13CDIC) in river water and groundwater were systematically investigated to provide constraints on DIC sources, recharge and cycling. Significant changes in the δ13CDIC values (from −2.9‰ to −23.4‰) of the water samples were considered to be the result of different contributions of two dominant DIC origins: soil CO2 dissolution and carbonate weathering. Three types of rock weathering (dissolution of carbonate minerals by H2CO3 and H2SO4, and silicate dissolution by H2CO3) were found to control the DIC input into the riverine system. In DIC cycling, groundwater played a significant role in delivering DIC to the surface water, and DIC supply from tributaries to the main stream increased from the dry season to the wet season. Notably, the depleted δ13CDIC ‘peak’ around the 88.9° longitude, especially in the September groundwater samples, indicated the presence of ‘special’ DIC, which was attributed to the oxidation of methane from the Jiangsa wetland located nearby. This wetland could provide large amounts of soil organic matter available for bacterial degradation, producing 13C-depleted methane. Our study provided insights regarding the role of wetlands in riverine carbon cycles and highlighted the contribution of groundwater to alpine riverine DIC cycles. 相似文献
13C and ΣCO2 data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ13C of the ΣCO2 in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO2 per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO2, while the remainder is attributed to dissolution of calcium carbonate.The δ13C of the dissolved CO2 in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO2 at a mean temperature of 16°C. The δ13C and ΣCO2 values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water. 相似文献
Lake Albano (Alban Hills volcanic complex, Central Italy) is located in a densely populated area near Rome. The deep lake
waters have significant dissolved CO2 concentrations, probably related to sub-lacustrine fluid discharges fed by a pressurized CO2-rich reservoir. The analytical results of geochemical surveys carried out in 1989–2010 highlight the episodes of CO2 removal from the lake. The total mass of dissolved CO2 decreased from ∼5.8 × 107 kg in 1989 to ∼0.5 × 107 kg in 2010, following an exponential decreasing trend. Calculated values of both dissolved inorganic carbon and CO2 concentrations along the vertical profile of the lake indicate that this decrease is caused by CO2 release from the epilimnion, at depth <9 m, combined with (1) water circulation at depth <95 m and (2) CO2 diffusion from the deeper lake layers. According to this model, Lake Albano was affected by a large CO2 input that coincided with the last important seismic swarm at Alban Hills in 1989, suggesting an intimate relationship between
the addition of deep-originated CO2 to the lake and seismic activity. In the case of a CO2 degassing event of an order of magnitude larger than the one that occurred in 1989, the deepest part of Lake Albano would
become CO2-saturated, resulting in conditions compatible with the occurrence of a gas outburst. These results reinforce the idea that
a sudden CO2 input into the lake may cause the release of a dense gas cloud, presently representing the major volcanic threat for this
densely populated area. 相似文献
This paper focuses on the chemical and isotopic features of dissolved gases (CH4 and CO2) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH4 and CO2. The δ13C-CH4 and δD-CH4 values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH4 is mainly produced by microbial activity. The δ13C-CO2 values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO2 contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO2 source feeding the regional thermal and cold CO2-rich fluid emissions. In contrast, the relatively low δ13C-CO2 values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO2. Chemical and isotopic compositions of dissolved CO2 and CH4 at different depths are mainly depending on (1) CO2 inputs from external sources (hydrothermal and/or anthropogenic); (2) CO2–CH4 isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO2 and CH4 concentrations. In the hypolimnion, where the δ13C-CO2 values progressively increase with depth and the δ13C-CH4 values show an opposite trend, biogenic CO2 production from CH4 using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ13C-CO2 values, and measured δ13CTDIC values are not consistent, indicating that CO2 and the main carbon-bearing ion species (HCO3?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO2 and CH4. This study demonstrates that the vertical patterns of the CO2/CH4 ratio and of δ13C-CO2 and δ13C-CH4 are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO2 input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes. 相似文献
The chemical composition and D/H,
and
ratios have been determined for the acid hot waters and volcanic gases discharging from Zaō volcano in Japan. The thermal springs in Zaō volcano issue acid sulfate-chloride type waters (Zaō) and acid sulfate type waters (Kamoshika). Gases emitted at Kamoshika fumaroles are rich in CO2, SO2 and N2, exclusive of H2O. Chloride concentrations and oxygen isotope data indicate that the Zaō thermal waters issue a fluid mixture from an acid thermal reservoir and meteoric waters from shallow aquifers. The waters in the Zaō volcanic system have slight isotopic shifts from the respective local meteoric values. The isotopic evidence indicates that most of the water in the system is meteoric in origin. Sulfates in Zaō acid sulfate-chloride waters with δ34S values of around +15‰, are enriched in 34S compared to Zaō H2S, while the acid sulfate waters at Kamoshika contain supergene light sulfate (δ34S = + 4‰) derived from volcanic sulfur dioxide from the volcanic exhalations. The sulfur species in Zaō acid waters are lighter in δ34S than those of other volcanic areas, reflecting the difference in total pressure. 相似文献
Nearly 200 analyses of meltwaters, ice and snow from three alpine glacial sites in carbonate terrain are summarized and discussed in terms of sources of solutes and kinetic controls on the progress of weathering reactions. Most data derive from the Swiss Glacier de Tsanfleuron which is based on Cretaceous and Tertiary pure and impure limestones. Two other sites (Marmolada, Italian Dolomites and the Saskatchewan Glacier, Alberta) are based on a mixed calcitic-dolomitic substrate. Most solutes originate from carbonate dissolution; moreover, where pyrite is present its oxidation supplies significant sulphate and forces more dissolution of carbonate. The ratios Sr2+/Ca2+ and Mg2+/Ca2+ are much higher in Tsanfleuron melt-waters than local bedrock, a phenomenon that can be reproduced in the laboratory at small percentages of dissolution. These anomalous ratios are attributed to incongruent dissolution of traces of the metastable carbonates Mg-calcite and aragonite. These phases also provide Na+ to solution. K+ is argued to originate mainly by ion-exchange on clays with solute Ca2+. Quartz and very minor feldspar dissolution are also inferred. Locally enhanced input from atmospheric sources is recognized by high Cl? and associated Na+. The progress of weathering reactions has been evaluated by the trends in the data, computer modelling and some simple laboratory experiments. The most dilute samples show a trend towards removal of CO2 to low partial pressures (c. 10?5.5 atmospheres), reflecting initially rapid carbonate dissolution and relatively slow dissolution of gaseous CO2. Later addition of atmospheric CO2 or acid from pyrite oxidation allows further carbonate dissolution, but solutions show a wide range of saturations, and CO2 pressures as high as 10?2.2 where pyrite oxidation is important. In a carbonate terrain, measurement of electroconductivity (corrected to 25°C) and alkalinity in the field allows the following preliminary deductions (where meq stands for milliequivalents): where S is the minimum meq(Ca2+ + Mg2+) produced by simple dissolution of carbonate unconnected with pyrite oxidation. As with any proxy method, these deductions do not remove the need for chemical analysis of waters in a given study area. 相似文献
A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO2 degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,13C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The13C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO3 is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The18O composition of dissolved carbonate and H2O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO3 deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO2 degassing, calcite saturation and isotopic fractionation. Measurements of PCO2, SC and13C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO2 degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates. 相似文献
We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic
composition of CO2 in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct
sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are
in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at
volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method
to Mount Etna where we derived a δ13C of volcanic CO2 between −0.9 ± 0.27‰ and −1.41 ± 0.27‰ (Bocca Nuova and Voragine craters). The comparison of our measurements to data reported
in previous work highlights a temporal trend of systematic increase of δ13C values of Etna CO2 from ~ −4‰, in the 1970’s and the 1980’s, to ~ −1‰ at the present time (2009). This shift toward more positive δ13C values matches a concurrent change in magma composition and an increase in the eruption frequency and energy. We discuss
such variations in terms of two possible processes: magma carbonate assimilation and carbon isotopic fractionation due to
magma degassing along the Etna plumbing system. Finally, our results highlight potential of systematic measurements of the
carbon isotopic composition of the CO2 emitted by volcanic plumes for a better understanding of volcanic processes and for improved surveillance of volcanic activity. 相似文献
Dissolved major ions, Sr concentrations and 87Sr/86Sr ratios of 10 coastal lakes from the Larsemann Hills, East Antarctica have been studied to constrain their solute sources, transport and glacial weathering patterns in their catchments. In absence of perennial river/streams, lakes serve as only reliable archive to study land surface processes in these low-temperature regions. The lake water chemistry is mostly Na-Cl type and it does not show any significant depth variations. Sr isotope compositions of these lakes vary from 0.7110 to 0.7211 with an average value of 0.7145, which is higher than modern seawater value. In addition to oceanic sources, major ions and Sr isotopic data show appreciable amount of solute supply from chemical weathering of silicate rocks in lake catchments and dissolution of Ca-Mg rich salts produced during the freezing of seawaters. The role of sulphide oxidation and carbonate weathering are found to be minimal on lake hydro-chemistry in this part of Antarctica. Inverse model calculations using this chemical dataset provide first-order estimates of dissolved cations and Sr; they are mostly derived from oceanic (seawater + snow) sources (cations approximately 76%) and (Sr approximately 92%) with minimal supplies from weathering of silicates (cations approximately 15%); (Sr approximately 2%) and Ca-rich minerals (cations approximately 9%); (Sr approximately 7%). The silicate weathering rate and its corresponding atmospheric CO2 consumption rate estimates for Scandrett lake catchment (3.6 ± 0.3 tons/km2/year and 0.5 × 105 moles/km2/year), are lower than that of reported values for the average global river basins (5.4 tons/km2/year and 0.9 × 105 tons/km2/year) respectively. The present study provides a comprehensive report of chemical weathering intensity and its role in atmospheric CO2 consumption in low-temperature pristine environment of Antarctica. These estimates underscore the importance of Antarctica weathering on atmospheric CO2 budget, particularly during the past warmer periods when the large area was exposed and available for intense chemical weathering. 相似文献
Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ13C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ13C values of carbonate (δ13Ccarb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ13C = δ13Ccarb ? δ13Corg). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ34S values of CAS (δ34SCAS) were inversely correlated with the δ13Ccarb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ13Ccarb. Low δ34SCAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ34SCAS–δ13Ccarb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition. 相似文献
The Sierra Gorda aquifer is one of the most extensive of southern Spain. The main groundwater discharge is produced at its northern boundary through several high‐flow springs. In this study, stable isotopes of dissolved sulfate (δ34S and δ18O) and groundwater chemistry were used to determine the origin of the sulfate and to characterize the groundwater flow. We sampled the main springs, as well as other minor outlets related to perched water tables, in order to determine the different sources of SO42? (e.g., dissolution of evaporites and atmospheric deposition). The substantial difference in the amount of dissolved SO42? between the springs located in its northwestern part (≈25 mg/L) and those elsewhere in the northern part (≈60 mg/L) suggests zones with separate groundwater flow systems. A third group of springs, far from the northeastern boundary of the permeable outcrops, shows higher SO42? content than the rest (≈125 mg/L). The isotopic range of sulfate (?0.3‰ to 14.82‰ V‐CTD) points to several sources, including dissolution of Triassic or Miocene evaporites, atmospheric deposition, and decomposition of organic material in the soil. Among these, the dissolution of Triassic gypsum—which overlies the saturated zone as a consequence of the folds and faults that deform the aquifer—is the main source of SO42? (range from 12.79‰ to 14.82‰ V‐CTD). This range is typical for Triassic gypsum. The higher karstification in the western sector, together with important differences in the saturated thickness between the western and eastern sectors, would also be due to the tectonic structure and could explain the difference in SO42? contents in the water. This singular arrangement may cause a higher residence time of groundwater in the eastern sector; thus, a higher contact time with Triassic evaporitic rocks is inferred. Accordingly, the stable isotopes of SO42? are found to be a valuable tool for identifying areas with different flow systems in the saturated zone of karstic aquifers, as well as for evaluating aspects such as the degree of karstification . 相似文献
A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (14 m) oxic epilimnion overlying a 200 m-thick anoxic hypolimnion. Dissolved CO2 concentrations reached 1000 mg/kg in the lower stratum. Loss of CO2 from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification.The Cl, SO4 and HCO3 contents of Lake Quilotoa are intermediate between those of acid–SO4–Cl Crater lakes and those of neutral-HCO3 Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid–SO4–Cl Crater lakes.The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by 4°C or providing heat to hypolimnetic waters or by seismic activity.Although Quilotoa lake contains a huge amount of dissolved CO2 (3×1011 g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO2-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended. 相似文献
Na–HCO3–CO2-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO2-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO2-rich waters. The δ2H and δ18O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO2 (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO2 inorganic origin for the gas. δ13CCO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO2. Such an assumption is supported by the 3He/4He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression). 相似文献
AbstractGroundwater of the Tertiary-Quaternary Formations in the Jeloula basin (Central Tunisia), together with rain and surface waters, were analysed to investigate the mineralization processes, the origin of the water and its recharge sources. The water samples present a large spatial variability of chemical facies which is related to their interaction with the geological formations. The main sources of the water mineralization are the dissolution of evaporitic and carbonate minerals and cation exchange reactions. Stable isotopes indicate that most groundwater samples originate from infiltration of modern precipitation. Surface water samples from small dam reservoirs show a 18O/2H enrichment, which is typical of water exposed to open-surface evaporation in a semi-arid region. Considerable data of 3H and 14C allow the qualitative identification of the present-day recharge that is probably supplied by infiltration of recent flood waters in the Wadi El Hamra valley, and by direct infiltration of meteoric water through the local carbonate outcrops.Editor D. Koutsoyiannis; Associate editor S. Faye 相似文献
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