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1.
The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ13C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ34S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ34S and δ13C data which deviate from a negative correlation line toward higher δ13C values suggest methanogenic CO2 production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH4 and CO2. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U6+ to U4+. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH4 and HCO3 − existed and reduced sulfur species (H2S, HS−) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO4 2− among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U4+ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997  相似文献   

2.
Authigenic carbonates in the caldera of an Arctic (72°N) submarine mud volcano with active CH4bearing fluid discharge are formed at the bottom surface during anaerobic microbial methane oxidation. The microbial community consists of specific methane-producing bacteria, which act as methanetrophic ones in conditions of excess methane, and sulfate reducers developing on hydrogen, which is an intermediate product of microbial CH4 oxidation. Isotopically light carbon (δ13Cav =−28.9%0) of carbon dioxide produced during CH4 oxidation is the main carbonate carbon source. Heavy oxygen isotope ratio (δ18Oav = 5%0) in carbonates is inherited from seawater sulfate. A rapid sulfate reduction (up to 12 mg S dm−3 day−1) results in total exhausting of sulfate ion in the upper sediment layer (10 cm). Because of this, carbonates can only be formed in surface sediments near the water-bottom interface. Authigenic carbonates occurring within sediments occur do notin situ. Salinity, as well as CO 3 2− /Ca and Mg/Ca ratios, correspond to the field of nonmagnesian calcium carbonate precipitation. Calcite is the dominant carbonate mineral in the methane seep caldera, where it occurs in the paragenetic association with barite. The radiocarbon age of carbonates is about 10000 yr.  相似文献   

3.
The Kara Sea is an area uniquely suitable for studying processes in the river-sea system. This is a shallow sea into which two great Siberian rivers, Yenisei and Ob, flow. From 1995 to 2003, the sea was studied by six international expeditions aboard the R/V Akademik Boris Petrov. This publication summarizes the results obtained, within the framework of this project, at the Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences. Various hydrogeochemical parameters, concentrations and isotopic composition of organic and carbonate carbon of the sediments, plankton, particulate organic matter, hydrocarbons, and dissolved CO2 were examined throughout the whole sea area at more than 200 sites. The δ13C varies from −22 and −24‰ where Atlantic waters enter the Kara Sea and in the North-eastern part of the water area to −27‰ in the Yenisei and Ob estuaries. The value of δ13C of the plankton is only weakly correlated with the δ13C of the organic matter from the sediments and is lower by as much as 3–4‰. The paper presents the results obtained from a number of meridional river-sea profiles. It was determined from the relations between the isotopic compositions of plankton and particulate matter that the riverwaters carry material consisting of 70% detrital-humus matter and 30% planktonogenic material in the river part, and the material contained in the off-shore waters consists of 30% terrigenous components, with the contribution of bioproducers amounting to 70%. The carbon isotopic composition of the plankton ranges from −29 to −35‰ in the riverine part, from −28 to −27‰ in the estuaries, and from −27.0 to −25% in the marine part. The relative lightness of the carbon isotopic composition of plankton in Arctic waters is explained by the temperature effect, elevated CO2 concentrations, and long-distance CO2 supply to the sea with riverwaters. The data obtained on the isotopic composition of CO2 in the surface waters of the Kara Sea were used to map the distribution of δ13CCO 2. The complex of hydrocarbon gases extracted from the waters included methane, C2–C5, and unsaturated C2=–C4= hydrocarbons, for which variations in the concentrations in the waters were studied along river-estuary-sea profiles. The geochemistry of hydrocarbon gases in surface fresh waters is characterized by comparable concentrations of methane (0.3–5 μl/l) and heavier hydrocarbons, including unsaturated ones. Microbiological methane with δ13C from −105 to −90‰ first occurs in the sediments at depths of 40–200 cm. The sediments practically everywhere display traces of methane oxidation in the form of a shift of the δ13C of methane toward higher values and the occurrence of autogenic carbonate material, including ikaite, enriched in the light isotope. Ikaite (δ13C from −25 to −60‰) was found and examined in several profiles. The redox conditions in the sediments varied from normal in the southern part of the sea to highly oxidized along the Novaya Zemlya Trough. Vertical sections through the sediments of the latter exemplify the complete suppression of the biochemical activity of microorganisms. Our data provide insight into the biogeochemistry of the Kara Sea and make it possible to specify the background values needed for ecological control during the future exploration operations and extraction of hydrocarbons in the Kara Sea. Original Russian Text ? E.M. Galimov, L.A. Kodina, O.V. Stepanets, G.S. Korobeinik, 2006, published in Geokhimiya, 2006, No. 11, pp. 1139–1191.  相似文献   

4.
The stable carbon isotope composition in surface soil organic matter (δ13Csoil) contains integrative information on the carbon isotope composition of the standing terrestrial plants (δ13Cleaf). In order to obtain valuable vegetation information from the δ13C of terrestrial sediment, it is necessary to understand the relationship between the δ13C value in modern surface soil and the standing vegetation. In this paper, we studied the δ13C value in modern surface soil organic matter and standing vegetation in arid areas in China, Australia and the United States. The isotopic discrepancy between δ13Csoil and δ13Cleaf of the standing dominant vegetation was examined in those different arid regions. The results show that the δ13Csoil values were consistently enriched compared to the δ13Cleaf. The δ13Cleaf values were positively correlated with δ13Csoil, which suggests that the interference of microorganisms and hydrophytes on the isotopic composition of surface soil organic matter during soil organic matter formation could be ignored in arid regions. The averaged discrepancy between δ13Csoil and δ13Cleaf is about 1.71%in Tamarix L. in the Tarim Basin in China, 1.50% in Eucalytus near Orange in Australia and 1.22% in Artemisia in Saratoga in the United States, which are different from the results of other studies. The results indicate that the discrepancies in the δ13C value between surface soil organic matter and standing vegetation were highly influenced by the differences in geophysical location and the dominant species of the studied ecosystems. We suggest that caution should be taken when organic matter δ13C in terrestrial sediment is used to extract paleovegetation information (C3/C4 vegetation composition), as the δ13C in soil organic matter is not only determined by the ratio of C3/C4 species, but also profoundly affected by climate change induced variation in the δ13C in dominant species.  相似文献   

5.
Natural gases of shallow reservoirs with the carbon isotopic compositions of methane ranging from -50‰ to -60‰ (PDB) were considered as mixed gases of biogenic and thermogenic origins previously and some of them were considered as low-mature (or low temperature thermogenic) gases lately. In this paper natural gases with the carbon isotopic compositions of methane in the above range were identified using the molecular and stable carbon isotopic compositions of methane, ethane and propane. The mixed gases of biogenic and mature thermogenic origins display the characteristics of δ 13 C1 ranging from -50‰to -60‰,δ13C2 ＞ -35‰,Δvalues (δ13C3 -δ13C2) ＜ 5‰ and C1/∑C2 ratios ＜ 40. Immature to low-mature gases display the characteristics of δ 13 C1 ranging from - 50‰ to - 60‰, δ13 C2 ＜- 40‰,Δ values (δ13C3 -δ13C2) ＞7‰, and C1/∑C 2 ratios ＞60.  相似文献   

6.
The effect of Co2 and CH4 degassing from the mantle on the carbon isotopic composition of diamond has been quantitatively modeled in terms of the principles of Rayleigh distillation.Assuming the δ^13 C value of -5‰ for the mantle,the outgassing of CO2 can result in the large negative δ^13 C values of diamond,whereas the outgassing of CH4 can drive the δ^13C values of diamond in the positive direction.The theoretical expectations can be used to explain the full range of δ^13 C values from-34.4‰5 to 5‰ observed for natural diamonds.It is possible that diamond formation was triggered by the degassing of Co2 and/or CH4 from the mantle and the associated fractional crystallization of carbonate-bearing melt.  相似文献   

7.
Anaerobic oxidation of methane (AOM) and sulfate reduction (SR) were investigated in sediments of the Chilean upwelling region at three stations between 800 and 3000 m water depth. Major goals of this study were to quantify and evaluate rates of AOM and SR in a coastal marine upwelling system with high organic input, to analyze the impact of AOM on the methane budget, and to determine the contribution of AOM to SR within the sulfate-methane transition zone (SMT). Furthermore, we investigated the formation of authigenic carbonates correlated with AOM. We determined the vertical distribution of AOM and SR activity, methane, sulfate, sulfide, pH, total chlorins, and a variety of other geochemical parameters. Depth-integrated rates of AOM within the SMT were between 7 and 1124 mmol m−2 a−1, effectively removing methane below the sediment-water interface. Single measurements revealed AOM peaks of 2 to 51 nmol cm−3 d−1, with highest rates at the shallowest station (800 m). The methane turnover was higher than in other diffusive systems of similar ocean depth. This higher turnover was most likely due to elevated organic matter input in this upwelling region offering significant amounts of substrates for methanogenesis. SR within the SMT was mostly fuelled by methane. AOM led to the formation of isotopically light DIC (δ13C: −24.6‰ VPDB) and of distinct layers of authigenic carbonates (δ13C: −14.6‰ VPDB).  相似文献   

8.
A series of samples, including vegetation, soil organic matter, soil waters, spring, bedrock, pool water, drip waters (upper-drip waters and ground-drip waters) and their corresponding speleothems were collected at Liangfeng Cave (LFC) system of Guizhou Province, southwest of China, respectively, from 2003 to 2004 year, then their stable carbon isotopes were measured and analyzed. Results reveal that vegetation is C3 type in LFC system; cave overlying δ 13C signals, including values and variations, could be transmitted to drip water (speleothem); speleothem δ 13C mainly shows a biogenic δ 13C value character (soil CO2 from plant respiration and decay); and there are remarkable seasonal variations of δ 13C values for drip water TDIC (speleothem), which are lighter at least 2.0‰ in the rainy seasons than in the dry ones. So, it could be feasible to reconstruct high-resolution changes of paleoecology and paleoclimate by using speleothem δ 13C values.  相似文献   

9.
Gravity driven mass-flow deposits proven by sedimentary and digital echosounder data are indicative for prevailing dynamic sedimentary conditions along the continental margin of the western Argentine Basin. In this study we present geochemical data from a total of 23 gravity cores. Pore-water SO4 is generally depleted within a few meters below the sediment surface by anaerobic oxidation of methane (AOM). The different shapes of SO4 profiles (concave, kink- and s-type) can be consistently explained by sedimentary slides possibly in combination with changes in the CH4 flux from below, thus, mostly representing transient pore-water conditions. Since slides may keep their original sedimentary signature, a combined analysis and numerical modeling of geochemical, physical properties, and hydro acoustic data could be applied in order to reconstruct the sedimentary history. We present first order estimates of the dating of sedimentary events for an area where conventional stratigraphic methods failed to this day. The results of the investigated sites suggest that present day conditions are the result of events that occurred decades to thousands of years ago and promote a persisting mass transport from the shelf into the deep-sea, depositing high amounts of reactive compounds. The high abundance of reactive iron phases in this region maintains low hydrogen sulfide levels in the sediments by a nearly quantitative precipitation of all reduced sulfate by AOM. For the total region we estimate a SO4 (or CH4) flux of 6.6 × 1010 moles per year into the zone of AOM. Projected to the global continental slope and rise area, this may sum up to about 2.6 × 1012 moles per year. Provided that the sulfur is completely fixed in the sediments it is about twice the global value of the recent global sulfur burial in marine sediments of 1.2 × 1012 moles per year as previously estimated. Thus, AOM obviously contributes very significantly to the regulation of global sulfur reservoirs, which is hitherto not sufficiently recognized. This finding may have implications for global geochemical models, as sulfur burial is an important control factor in the development of atmospheric oxygen levels over time.  相似文献   

10.
This paper investigates kerogen carbon isotopes, the difference between carbonate and kerogen carbon isotopes (Δ13Ccarb-kero = δ 13Ccarb − δ 13Ckero) and the difference between carbonate and n-C19 alkane compound-specific carbon isotopes (Δ13Ccarb-n-C19 = δ 13Ccarb − δ 13C n-C19) during the Permian–Triassic transition at Meishan, South China. The results show that kerogen carbon isotopes underwent both gradual and sharp shifts in beds 23–25 and 26–29, respectively. The differences between carbonate and organic carbon isotopes, both the Δ13Ccarb-kero and Δ13Ccarb-n-C19, which are mainly affected by CO2-fixing enzyme and pCO2, oscillated frequently during the Permian–Triassic transition. Both the variations of Δ13Ccarb-n-C19 and Δ13Ccarb-kero coupled with the alternation between cyanobacteria and green sulfur bacteria indicated by biomarkers. The episodic low values of Δ13Ccarb-n-C19 corresponded to episodic blooms of green sulfur bacteria, while the episodic high values of Δ13Ccarb-n-C19 corresponded to episodic blooms of cyanobacteria. The relationships between the variation of carbon isotopes and biota show that the microbes which flourished after the extinction of macroorganism affected the carbon isotope fractionation greatly. Combining the carbon isotope compositions and the pattern of size variation of the conodont Neogondolella, this paper supposes that anoxia of the photic zone at bed 24 was episodic and it would be caused by the degradation of terrigenous organic matters by sulfate reducing bacteria in the upper water column. Considered together with results from previous research, the high resolution variation of the biogeochemistry presents the sequence of the important geo-events during the Permian–Triassic crisis.  相似文献   

11.
A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C2–C9 range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% Ro), a systematic depletion in 12C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ13C-values of organic carbon due to the preferential release of 12C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999  相似文献   

12.
The stable isotope compositions of sedimentary organic carbon and content of organic carbon for sediment cores recovered at two sites (sites 724C and 725C) during Ocean Drilling Program (ODP) Leg. 117 on the Oman continental margin are used to document variability of the monsoon winds for the past 350 ka. Although both sites have a mean δ13C value of -20.1‰, three zones depleted in13C are observable at site 724C during isotope stages 3, 8 and 10, while only one zone is recognizable at site 725C. Increased coastal upwelling during isotope stage 3 owing to intense SW monsoon winds resulted in higher concentration of CO2 in the water column causing the formation of organic matter that was depleted in13C. The other two zones deposited during oxygen isotope stages 8 and 10, which are also characterized by low values of organic carbon, nitrogen and C/N ratios, could be attributed to the dilution by terrestrial material derived from paleosol by transported by northwester lies. Because of utilization of13C enriched dissolved CO2 during the last glacial maximum Holocene sedimentary organic materials are depleted in13C relative to the the fomer. The content of residues organic carbon (ROC) is higher at site 724C (with an average of 2.3 ± 1.2%) relative to site 725C, which averages to 0.9 ± 0.4% probably because of differences in the degree of preservation. Organic material deposited at site 725C has undergone more degradation relative to site 724C as reflected by a systematic downcore decrease in13C resulting from a loss of13C enriched organic compounds. Owing to lack of good chronology at site 725C, a zone that is characterized by low δ13C values it could not be correlated with the other three zones observed at Site 724C.  相似文献   

13.
There is considerable discussion and uncertainty in the literature regarding the importance of fresh litter versus older soil organic matter as sources of soil dissolved organic carbon (DOC) in forest floor. In this study, the differences of organic carbon concentration and stable isotope composition were analyzed under different background conditions to identify the origins of DOC in forest soil. The data show that there is no significant difference in SOC content between these collected soil samples (P > 0.05), but the litter-rich surface soils have relatively higher DOC concentration than the litter-lacking (P < 0.01) ones, and the δ 13C values of DOC (δ 13CDOC) are closer to δ 13C of litter than δ 13C values of SOC (δ 13CSOC). In the litter-lacking surface soil samples, the range of δ 13CDOC is between δ 13CSOC and δ 13C of dominant plant leaves. These results suggest that DOC mainly derive from litter in the litter-rich surface soil with, and the main path of DOC sources may change with surrounding conditions. In addition, δ 13CSOC and δ 13CDOC become more positive, and the absolute values of Δ (δ 13CDOC − δ 13CSOC) decrease with depth in the soil profiles, which indicate that the percentage of DOC below 5 cm, derived from degradation of humus, may increase with soil depth.  相似文献   

14.
Stable and radiogenic isotope composition of stratiform Cu–Co–Zn mineralization and associated sedimentary rocks within the Boléo district of the Miocene Santa Rosalía basin, Baja California Sur, constrains the evolution of seawater and hydrothermal fluids and the mechanisms responsible for sulfide and oxide deposition. Stable isotope geochemistry of limestone and evaporite units indicates a strong paleogeographic influence on the chemistry of the water column. Near-shore limestone at the base of the Boléo Formation is characterized by modified marine carbon (δ 13CPDB=−6.0 to +4.4‰) and oxygen (δ 18OSMOW=+19.5 to +26.2‰) isotope composition due to the influx of 13C- and 18O-depleted fluvial water. Sulfate sulfur isotope composition (δ 34SCDT=+17.21 to +22.3‰ and δ 18OSMOW=+10.7 to +13.1‰) for basal evaporite and claystone facies are similar to Miocene seawater. Strontium isotopes are less radiogenic than expected for Miocene seawater due to interaction with volcanic rocks. Low S/C ratios, high Mn contents and sedimentological evidence indicate the basin water column was oxidizing. The oxygenated basin restricted sulfide precipitation to within the sedimentary pile by replacement of early diagenetic framboidal pyrite and pore-space filling by Cu–Co–Zn sulfides to produce disseminated sulfides. Quartz–Mn oxide oxygen isotope geothermometry constrains mineralization temperature between 18 and 118°C. Sulfur isotopes indicate the following sources of sulfide: (1) bacterial sulfate reduction within the sedimentary pile produced negative δ 34S values (<−20‰) in framboidal pyrite; and (2) bacterial sulfate reduction at high temperature (80–118°C) within the sedimentary pile during the infiltration of the metal-bearing brines produced Cu–Co–Zn sulfides with negative, but close to 0‰, δ 34S values. Isotope modeling of fluid-rock reaction and fluid mixing indicates: (1) sedimentary and marine carbonates (δ 13C=−11.6 to −3.2‰ and δ 18O=+19.0 to +21.8‰) precipitated from basin seawater/pore water that variably mixed with isotopically depleted meteoric waters; and (2) hydrothermal calcite (δ 13C=−7.9 to +4.3‰ and δ 18O=+22.1 to +25.8‰) formed by dissolution and replacement of authigenic marine calcite by downward-infiltrating metalliferous brine and brine-sediment exchange, that prior to reaction with calcite, had mixed with isotopically depleted pore water. The downward infiltration of metalliferous brine is inferred from lateral and stratigraphic metal distributions and from the concentration of Cu sulfides along the upper contact of pyrite-bearing laminae. The co-existence and textural relationships among framboidal pyrite, base metal sulfides, carbonate and Mn–Fe oxides (including magnetite) within mineralized units are consistent with carbonate replacement and high-temperature bacterial reduction within the sedimentary pile occurring simultaneously below a seawater column under predominantly oxygenated conditions.  相似文献   

15.
Geochemical and isotopic data for the uppermost 1.2 m of the sediments of the central Santa Monica Basin plain were examined to better understand organic matter deposition and recycling at this site. Isotopic signatures (Δ14C and δ13C) of methane (CH4) and dissolved inorganic carbon (DIC) indicate the occurrence of anaerobic oxidation of CH4 that is fueled by CH4 supplied from a relict reservoir that is decoupled from local organic carbon (Corg) degradation and methanogenesis. This finding was corroborated by a flux budget of pore-water solutes across the basal horizon of the profile. Together these results provide a plausible explanation for the anomalously low ratio between alkalinity production and sulfate consumption reported for these sediments over two decades ago. Shifts in Δ14C and δ13C signatures of Corg have previously been reported across the 20-cm depth horizon for this site and attributed to a transition from oxic to anoxic bottom water that occurred ~350 years BP. However, we show that this horizon also coincides with a boundary between the base of a hemipelagic mud section and the top of a turbidite interval, complicating the interpretation of organic geochemical data across this boundary. Radiocarbon signatures of DIC diffusing upward into surface sediments indicate that remineralization at depth is supported by relatively 14C-enriched Corg within the sedimentary matrix. While the exact nature of this Corg is unclear, possible sources are hemipelagic mud sections that were buried rapidly under thick turbidites, and 14C-rich moieties dispersed within Corg-poor turbidite sections.  相似文献   

16.
Three estuaries near Naples, Florida with variably modified watersheds have been investigated to understand the chemical consequences of altering drainage patterns. Blackwater River (near natural drainage, control site), Henderson Creek (moderately modified watershed), and Faka-Union Canal (severe channelization) were sampled for temperature, salinity, δ18O, δ13C of dissolved inorganic carbon (DIC), molality of CO2 (ΣCO2), and Mg:Ca and Sr:Ca ratios between freshwater and marine water end members over a 17-mo period. Carbon isotope composition followed similar seasonal patterns as salinity. Freshwater and seawater end members are more negative than the global average, likely reflecting equilibration with local carbon sources derived from mangrove leaf litter and groundwater. δ13C responds to differences in primary productivity between estuaries. Henderson Creek has higher primary productivity than Blackwater River (probable due to higher sewage input and agricultural runoff) and has more positive δ13C and lower ΣCO2. δ18O is affected by seasonal input of freshwater from atmospheric precipitation, evaporation, and groundwater. Late summer and fall rains lower the δ18O of estuarine water, whereas evaporative conditions in the dry season elevate δ18O to values that can be more positive upstream than those from the Gulf of Mexico (estuarine inversion). Evaporation produces water in the Gulf of Mexico that is >1‰ more positive than the global sea surface average most of the year. The very negative δ18O values in Blackwater River and Henderson Creek likely reflect atmospheric and groundwater contribution. Mg:Ca and Sr:Ca ratios of Gulf water from all three estuaries are similar to global averages at low latitudes. Freshwater end members among estuaries are different in that Blackwater River has higher ratios, suggesting a groundwater contribution. Dolomitic rocks in the subsurface likely provide a source of Mg ions.  相似文献   

17.
Complex biogeochemical studies including the determination of isotopic composition of Corg in both suspended particulate matter and surface horizon (0–1 cm) of sediments (more than 260 determinations of δ13C-Corg) were carried out for five Arctic shelf seas: White, Barents, Kara, East Siberian, and Chukchi. The aim of this study is to elucidate causes that change the isotopic composition of particulate organic carbon at the water-sediment boundary. It is shown that the isotopic composition of Corg in sediments from seas with a high river runoff (White, Kara, and East Siberian) does not inherit the isotopic composition of Corg in particles precipitating from the water column, but is enriched in heavy 13C. Seas with a low river runoff (Barents and Chukchi) show insignificant difference between the value of δ13C-Corg in both suspended load and sediment because of a low content of the isotopically light allochthonous organic matter (OM) in particulates. Complex biogeochemical studies with radioisotope tracers (14CO2, 35S, and 14CH4) revealed the existence of specific microbial filter formed from heterotrophic and autotrophic organisms at the water-sediment boundary. This filter prevents the mass influx of products of OM decomposition into water column, as well as reduces the influx of a part of OM contained in the suspended particulate matter from water into sediment.  相似文献   

18.
THEJINLONGSHANGOLDOREBELTINZHEN’ANCOUN TY,SOUTHERNSHAANXIPROVINCE,ISLOCATEDINTHEWEST ERNQINLINGGOLDPROVINCE(NO.16INFIG.1;CHEN YANJINGETAL.,2004).ITWASDISCOVEREDINTHEDEVO NIANSTRATAINTHELATE1980S).ITSGEOLOGICALSETTING ANDMETALLOGENICEVOLUTIONARESIMILARTOT…  相似文献   

19.
Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH4). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH4 and its hydrological implications, stable carbon isotope ratios (δ13C) and radiocarbon (14C) ages of exsolved CH4, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ13CCH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ13CCH4=38.2‰) from the Ilan plain, all CH4 samples analyzed were produced via microbially mediated CO2 reduction. Many δ13CDIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO2 reduction. (2) Almost all the 14C ages of CH4 samples from the shallow aquifer (I) (<60 m depth) are greater than the 14C ages of coexisting DIC and sediments, suggesting the presence of CH4 from underlying aquifers. (3) The 14C ages of coexisting CH4, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH4 and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH4 and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH4 sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO2 and CH4 from underlying strata.  相似文献   

20.
The early diagenetic evolution of pore-water chemistry is closely linked to mineralization reactions which consume significant portions of the metabolites released by bacterial organic matter decomposition. These reactions are most intense in high-sedimentation rate basins and include the precipitation of iron-sulfides and various carbonates leading to concretion growth. Early diagenetic pyrite is typically framboidal attesting to its recrystallization from precursor mackinawite, greigite or amorphous FeS which are the favored phases at high supersaturation levels during the initial sulfate reduction stages. The sulfur isotopic composition of early diagnetic pyrite can be used to differentiate diffusion-controlled, open-system conditions with isotopically light sulfide (δ 34S = − 35 to − 20‰) from closed system conditions, under which Raleigh distillation produces increasingly heaver sulfide (δ 34 S = − 35 to + 18‰). Alabandite (Mn-sulfide) is a rare authigenic sulfide in Mn-rich environments such as certain restricted, semi-stagnant basins (Baltic Sea). pH-buffering by hydrogen sulfide and hydrogen ion uptake by the reduction of manganese and iron oxides and hydroxides in the nitrate and sulfate reduction zones raise the pH sufficiently to cause supersaturation of the porewaters with respect to Ca-, Mg-, Fe- and Mn-carbonates and complex solid solutions of them. Fe-carbonates cannot form in the sulfate reduction zone in the presence of dissolved sulfide which competes for the dissolved iron. Likewise, dolomite formation appears to be inhibited or slowed down in the presence of substantial dissolved sulfate. The appearance of siderite and ankerite therefore signals carbonate precipitation below the sulfate reduction zone. Supporting evidence for the early diagenetic origin of many carbonate concertions is provided by their high carbonate contents (70 to 90% reflecting the porosity existing at the time of precipitation, called “minus-cement porosity”), isotopic composition, clay fabrics, and preservation of original bedding features including the shapes of fossils and fecal pellets. In these environments increasing carbon isotope ratios (δ 13 C = − 20 to + 15‰) indicate concretion growth below the sulfate reduction zone, i.e., in the methane generation zones. Continuing concretion growth at greater burial depth explains pore water profiles with constantly low Ca and downward decreasing Mg concentrations. Dissolved ammonia and phosphate profiles reguire adsorption and ion-exchange reactions as additional removal machanisms (besides apatite precipitation) in order to explain their downward decrease after they have reached maximum concentrations below the alkalinity maximum. Classification of early diagnetic environments into oxic and anoxic and further subdivision of the latter into sulfidic and non-sulfidic (with suboxic or post-oxic and methanic as further subcategories of the non-sulfidic environment) according to Berner (1981) is preferred over the previous classification in terms of pH/Eh fields. The temperature range of the early diagenetic stage extends from O to about 75°C, at which temperature thermocatalytic organic matter decomposition replaces the earlier bacterially mediated reactions and causes a whole set of new diagenetic reactions (such as feldspar dissolution, smectite to illite transformation) to start.  相似文献   

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