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1.
A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C1/C2+ > 100), high C2/C3 and i-C4/n-C4 ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ13CCH4 from −79.5‰ to −45.0‰, δ13CC2H6 from −53.7‰ to −32.2‰, δ13CC3H8 from −36.5‰ to −20.1‰, δ13CnC4H10 from −32.7‰ to −24.5‰, and δ13CCO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with 13C enriched methane and 13C depleted CO2, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, 13C enriched methane and variable δ13C of CO2, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with 13C depleted methane and 13C enriched CO2, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain 13C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.  相似文献   

2.
We evaluate the impact of exceptionally sparse plant cover (0-20%) and rainfall (2-114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ13C and δ18O values of carbonates from the Atacama are the highest of any desert in the world. δ13C (VPDB) values from soil carbonate range from −8.2‰ at the wettest sites to +7.9‰ at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229-240], in which we assumed an exponential form of the soil CO2 production function, and relatively shallow (20-30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ13C value of soil carbonate in the Atacama, whereas the fraction C3 to C4 biomass at individual sites has a subordinate influence. The high average δ13C value (+4.1‰) of carbonate from the driest study sites indicates it formed—perhaps abiotically—in the presence of pure atmospheric CO218O (VPDB) values from soil carbonate range from −5.9‰ at the wettest sites to +7.3‰ at the driest and show much less regular variation with elevation change than δ13C values. δ18O values for soil carbonate predicted from local temperature and δ18O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ18O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.  相似文献   

3.
We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ13C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ13C values of odd carbon numbered C23-C33n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ13C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C25-C31n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.  相似文献   

4.
The effect of standard processing techniques on the δ13C value of plant tissue was tested using species representing the three photosynthetic pathways, including angiosperms and gymnosperms within the C3 taxonomic division. The species include Cowania mexicana (C3 angiosperm), Juniperus osteosperma (C3 gymnosperm), Opuntia spp. (crassulacean acid metabolism [CAM] angiosperm), and Atriplex canescens (C4 angiosperm). Each species is represented by 5 plants collected at two different sites, for a total of 10 samples. The samples were processed to whole plant tissue, holocellulose, α-cellulose, and nitrocellulose. An additional process was added with the discovery of residual Ca-oxalate crystals in holocellulose samples. Both C3 species show δ13C values becoming 13C enriched with increased processing. The CAM representative shows the opposite trend, with 13C depletion during the progression of treatments. The greatest range of values and most inconsistent trends occur in the C4 representative. Removal of the Ca-oxalate fraction resulted in different mean weight percentages and δ13C values among the species. Calculated δ13C values of the Ca-oxalate crystals show depletion from the tissue values in the two C3 species and enrichment in the C4 and CAM representatives. The C. mexicana samples show the greatest change between the tissue and Ca-oxalates (7.3‰) but the least mean weight percentage (11%), whereas A. canescens shows the greatest overall change, with a −2.8‰ isotopic shift and over 48% mean weight percentage. Variability within the samples undergoing each treatment remained relatively unchanged even with increased cellulose purity. This paper provides estimates of isotopic offsets necessary to correct from one treatment to another. Significant differences in δ13C among different treatments confirm the need to state the tissue fraction analyzed when reporting δ13C results.  相似文献   

5.
The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that Corg/Ntot ratios and isotopic signatures of bulk organic matter (δ13Corg) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased Corg/Ntot and δ13Corg (up to −17‰) were driven by generally nitrogen-poor but 13C-enriched terrigenous plant debris and SOM from C4/C3 vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C3/C4 vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower Corg/Ntot and δ13Corg (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and 12C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of Corg/Ntot and δ13Corg for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO2.  相似文献   

6.
Soils of the Chinese Loess Plateau(CLP)contain substantial amounts of soil inorganic carbon(SIC),as well as recent and ancient soil organic carbon(SOC).With the advent of the Anthropocene,human perturbation,including excavation,has increased soil CO2 emission from the huge loess carbon pool.This study aims to determine the potential of loess CO2 emission induced by excavation.Soil CO2 were continuously monitored for seven years on a newly-excavated profile in the central CLP and the stable C isotope compositions of soil CO2 and SOC were used to identify their sources.The results showed that the soil CO2 concentrations ranged from 830μL·L-1 to 11190μL·L-1 with an annually reducing trend after excavation,indicating that the human excavation can induce CO2 production in loess profile.Theδ13 C of CO2 ranged from–21.27‰to–19.22‰(mean:–20.11‰),with positive deviation from top to bottom.The range of δ13CSOC was–24.0‰to–21.1‰with an average of–23.1‰.Theδ13 C-CO2 in this study has a positive relationship with the reversed CO2 concentration,and it is calculated that 80.22%of the soil CO2 in this profile is from the microbial decomposition of SOC and 19.78%from the degasification during carbonate precipitation.We conclude that the human excavation can significantly enhance the decomposition of the ancient OC in loess during the first two years after perturbation,producing and releasing soil CO2 to atmosphere.  相似文献   

7.
Rats were raised on a variety of isotopically controlled diets comprising 20% C3, C4 or marine protein and C3 and/or C4 non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope (δ13C) analysis was performed on the cholesterol isolated from the diet (n=7 ) and bone (n=15 ) of these animals and the values compared with bulk δ13C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ13C values of bone cholesterol were shown to reflect whole diet δ13C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ13Cprot-engy = δ13Cprotein - δ13Cenergy) and whole diet-to-bone component fractionations (Δ13Cbcomp-wdiet = δ13Cbone component - δ13Cwhole diet) indicates that for hypothetical diets where protein δ13C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ13Capat-bchol) suggests that cholesterol δ13C values can potentially also be used as an independent test for the isotopic integrity of apatite δ13C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ13C analysis of bone is employed.  相似文献   

8.
The toxodont megaherbivores Toxodon and Mixotoxodon were endemic to South and Central America during the late Quaternary. Isotopic signatures of 47 toxodont teeth were analyzed to reconstruct diet and ancient habitat. Tooth enamel carbon isotope data from six regions of South and Central America indicate significant differences in toxodont diet and local vegetation during the late Quaternary. Toxodonts ranged ecologically from C3 forest browsers in the Amazon (mean δ13C = −13.4‰), to mixed C3 grazers and/or browsers living either in C3 grasslands, or mixed C3 forested and grassland habitats in Honduras (mean δ13C = −9.3‰), Buenos Aires province, Argentina (δ13C = −8.7‰), and Bahia, Brazil (mean δ13C = −8.6‰), to predominantly C4 grazers in northern Argentina (δ13C = −4.4‰), to specialized C4 grazers in the Chaco of Bolivia (δ13C = −0.1‰). Although these toxodonts had very high-crowned teeth classically interpreted for grazing, the isotopic data indicate that these megaherbivores had the evolutionary capacity to feed on a variety of dominant local vegetation. In the ancient Amazon region, carbon isotope data for the toxodonts indicate a C3-based tropical rainforest habitat with no evidence for grasslands as would be predicted from the Neotropical forest refugia hypothesis.  相似文献   

9.
Unraveling the factors controlling the carbon chemistry and transport of carbon within extant karst systems has important implications concerning the assessment of time-series δ13C records of speleothems. Here we report the results of a 3-year study of total dissolved inorganic carbon [DIC] and δ13CDIC from cave waters at DeSoto Caverns (Southeastern USA) that offer valuable insight on carbon transport and the accompanied isotope fractionations from end-member sources to speleothems.[DIC] and δ13CDIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ13CDIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ13CDIC = −2.49[DIC] + 0.64, r2 = 0.84). A shallow pool fed by multiple drips shows a bimodal δ13CDIC distribution with an isotopically heavier mode during winter (−4‰ to −5‰ VPDB) relative to summer months (−9‰ to −10‰ VPDB). A multi-year trend of decreasing water availability during the study period is not reflected in a response of cave water carbon chemistry suggesting that rainfall amount may not be a significant controlling factor of the carbon chemistry. Coupled cave air winter ventilation/summer stagnation and varying CO2 fluxes through the soil horizon and epikarst exert the strongest influence on seasonal [DIC] and δ13CDIC variability. Measured values of high [DIC] and low δ13CDIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ13CDIC values during winter/early months indicate kinetically enhanced isotopic fractionations within the cave waters. The kinetically enhanced isotopic fractionation of partitioned between degassed CO2 and precipitated CaCO3(1000lnα[(CO2-HCO3)+(CaCO3(AR)-HCO3)]/2) is greater by about a factor of two (−6.7 ± 0.3‰) relative to the same isotopic fractionation under equilibrium conditions (−3.1‰).On the basis of 14C mass balance and paired 14C-U/Th measurements we estimate that on average about ∼23% of C delivered annually by the drips to the aragonite stalagmites is derived from 14C-dead dolomite cap while the remainder of ∼77% is derived from 14C-live biomass. δ13C measurements of aragonite (n = 12) sampled from the tips of active speleothems during the summer months are consistent with theoretical aragonite δ13C values calculated using the shallow pool summer/early fall data thus confirming the δ13C seasonality in both drips and coeval aragonite. δ13C values of an active stalagmite section spanning the last 200 years show a normal distribution with a mean of −7.1 ± 1.2‰ (n = 81) and a mode of −7‰ to −8‰ that are statistically indistinguishable from the annual mean and mode of all dripwaters. Thus secular time-series δ13C records of stalagmites at DeSoto Caverns with resolving power >10−1 year will likely carry the imprints of drip annual means that record climate-driven δ13C seasonal biases.  相似文献   

10.
The stable carbon isotopic composition (expressed as δ13C) of herbivore remains is commonly used to reconstruct past changes in the relative abundance of C4 versus C3 grass biomass (C4 relative abundance). However, the strength of the relationship between herbivore δ13C and C4 relative abundance in extant ecosystems has not been thoroughly examined. We determined sources of variation in δ13C of bone collagen and tooth enamel of kangaroos (Macropus spp.) collected throughout Australia by measuring δ13C of bone collagen (779 individuals) and tooth enamel (694 individuals). An index of seasonal water availability, i.e. the distribution of rainfall in the C4 versus C3 growing seasons, was used as a proxy for C4 relative abundance, and this variable explained a large proportion of the variation in both collagen δ13C (68%) and enamel δ13C (68%). These figures increased to 78% and 77%, respectively, when differences between kangaroo species were accounted for. Vegetation characteristics, such as woodiness and the presence of an open forest canopy, had no effect on collagen or enamel δ13C. While there was no relationship between collagen δ13C and kangaroo age at death, tooth enamel produced later in life, following weaning, was enriched in 13C by 3.5‰ relative to enamel produced prior to weaning. From the observed relationships between seasonal water availability and collagen and enamel δ13C, enrichment factors (ε) for collagen-diet and enamel-diet (post-weaning) were estimated to be 5.2‰ ± 0.5 (95% CI) and 11.7‰ ± 0.6 (95% CI), respectively. The findings of this study confirm that at a continental scale, collagen and enamel δ13C of a group of large herbivores closely reflect C4 relative abundance. This validates a fundamental assumption underpinning the use of isotopic analysis of herbivore remains to reconstruct changes in C4 relative abundance.  相似文献   

11.
Cutin and suberin structural units might be stabilized in subsoils and contribute to the aliphatic structures observed in stabilized soil organic matter (SOM). We studied their dynamics in subsoils by measuring the concentrations and 13C contents of cutin and suberin markers in soil profiles under wheat (C3) and after 9 years of maize cropping (C4 plant). Alkandioic acids were considered as markers for roots, mid-chain hydroxy acids were only present in shoots and ω-hydroxy acids were identified in both roots and shoots. The diacid concentrations greatly increased below the ploughed layer after 9 years of maize cropping, possibly due to a higher root density of maize compared to wheat or to a faster turnover of fine roots and increased exudation of maize compared to wheat. From 0-75 cm, 9 years of maize cropping did not affect the distribution of shoot biomarkers but increased their concentrations. By contrast, below 75 cm, the shoot marker concentrations drastically decreased from the wheat control to the 9 year maize soil. The difference of δ13C observed for shoot markers was always lower than that observed for ω-hydroxy acids, and below 15 cm, it was close to that observed for SOC. The difference in δ13C of diacids was much more variable along the profile. Since the concentrations of the different markers were not at equilibrium, it was not possible to estimate their turnover. This study suggests several caveats for the use of molecular markers of roots and shoots to study the dynamics of SOM in deep soils: the higher heterogeneity compared to the ploughed layer, the presence of long history record of past vegetation that may hinder the short time scale changes tracked with the 13C isotope technique, and the difficulty in evaluating root inputs in the soil systems.  相似文献   

12.
Pollen grains from grasses using the C3 and C4 photosynthetic pathways have distinct ranges of δ13C values that may be used to estimate their relative abundance in paleorecords. We evaluated a spooling-wire microcombustion device interfaced with an isotope-ratio mass spectrometer (SWiM-IRMS) for δ13C analysis of individual grass-pollen grains. Pollen from four C3 and four C4 grass species was isolated through micromanipulation and analyzed as single grains suspended in water. A carbon yield greater than the 2σ range of the carbon content of blanks containing only water was used to distinguish samples containing pollen (“pollen present”) from those not containing pollen. This criterion resulted in the exclusion of ∼45% of the 946 samples applied to the wire. The average δ13C values (±1σ) of the remaining samples were −26.9‰ (±6.3‰) and −11.5‰ (±9.6‰) for C3 grasses and C4 grasses, respectively, after blank-correcting the δ13C data. These results suggest that the SWiM-IRMS system can be used to distinguish C3 from C4 grass pollen. The high variability in measured δ13C values is likely caused by a combination of factors. These include natural isotopic variability among individual pollen grains; the relatively poor precision that can be obtained when determining δ13C values of such small samples; and the uncertainty in the magnitude, isotopic composition, and stability of the analytical blank. Nonetheless, high percentages of individual pollen grains were correctly classified as being of either C3 or C4 origin. On average, 90% (range = 78-100%) of pollen grains from C3 grasses had δ13C values more negative than the cutoff threshold of −19.2‰; while 84% (range = 77-90%) of pollen grains from C4 grasses had δ13C values more positive than −19.2‰. Compared with analysis using an elemental analyzer interfaced with an IRMS (EA-IRMS), the number of pollen grains required for δ13C-based evaluation of C3/C4 grass composition is many times lower with the SWiM-IRMS. Additionally, δ13C data from the SWiM-IRMS does not need to be incorporated into a mixing model to derive estimates of the abundance of C3 and C4 grass pollen. Carbon-isotopic analysis of individual grass-pollen grains using the SWiM-IRMS system may help improve our understanding of the evolutionary and ecological significance of grass taxa in the paleorecord.  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.
Many grasslands and savannas around the world have experienced woody plant encroachment in recent history. In the Rio Grande Plains of southern Texas, subtropical woodlands dominated by C3 trees and shrubs have become significant components of landscapes once dominated almost exclusively by C4 grasslands. In this study, spatial variation of soil δ13C to was used to investigate patterns of transformation. Previous research has shown that grassland-to-shrubland transitions are initiated when discrete, multi-species shrub clusters organized around a honey mesquite (Prosopis glandulosa) tree nucleus established in grassland. It is inferred from space-for-time substitution and modeling studies that as new shrub clusters are initiated and existing clusters enlarge, coalescence will occur, leading to the formation of groves; and that groves will eventually merge to form woodlands. The hypothesis that present-day mesquite groves represent areas where individual discrete shrub clusters have proliferated and coalesced was evaluated by comparing patterns of soil δ13C within isolated shrub clusters (n = 6) to those in nearby groves (n = 3). Mean soil δ13C within discrete clusters was lowest in the center (−23.3‰), increased exponentially toward the dripline (−20.1‰), and stabilized at a relatively high value approximately 15 cm beyond the dripline (−18.9‰). The spatial structure of soil δ13C in groves was consistent with that which would be expected to occur if present-day grove communities were a collection of what once were individual discrete clusters that had fused. As such, it provides direct evidence in support of conceptual and mathematical models derived from indirect assessments. However, spatial patterns of soil δ13C suggest that groves are not simply a collection of clusters with respect to primary production and SOC turnover. This study illustrates how soil δ13C values can be used to reconstruct successional processes accompanying vegetation compositional change, and its consequences for ecosystem function.  相似文献   

15.
Floodplain soil-paleosol successions are valuable archives for reconstructing Pleistocene-Holocene climate changes but have been relatively unstudied in the southern Appalachian region. Two soil profiles on a small floodplain in southeastern Tennessee, USA were described and sampled in detail using both pedological and geological approaches, including stable carbon isotope analysis of soil organic matter (SOM). Correlation between the 2 profiles was constrained by uncalibrated AMS 14C ages of bulk humates, and using SOM δ13C values, both mobile and immobile elements. Four distinct 2.5-4‰ shifts towards less negative δ13C values for SOM suggest ∼ 300-yr cyclicity and transient warmer and drier climate events, with either water-stressed C3 vegetation or as much as 35% C4 plants present during the mid-Holocene. These postulated multi-episodic drier climate conditions have never before been documented in the southern Appalachian region and are tentatively correlated with mid-Holocene warming and drying in the eastern US, the nearly time-equivalent mid-Holocene events documented in Texas, the US High Plains and in the Gulf of Mexico. High rates of floodplain sediment accumulation (0.5-3 mm/yr), high clay content and maintenance of poorly drained soil conditions favor preservation of high-resolution climate archives in floodplain deposits by inhibiting oxidation and translocation of organic C.  相似文献   

16.
13C/12C and 18O/16O ratios of aragonite shells of modern land snails from the southern Great Plains of North America were measured for samples from twelve localities in a narrow east-west corridor that extended from the Flint Hills in North Central Oklahoma to the foothills of the Sangre de Cristo Mountains in Northern New Mexico, USA. Across the study area, shell δ18O values (PDB scale) ranged from −4.1‰ to 1.2‰, while δ13C values ranged from −13.2‰ to 0.0‰. δ18O values of the shell aragonite were predicted with a published, steady state, evaporative flux balance model. The predicted values differed (with one exception) by less than 1‰ from locality averages of measured δ18O values. This similarity suggests that relative humidity at the time of snail activity is an important control on the δ18O values of the aragonite and emphasizes the seasonal nature of the climatic information preserved in the shells. Correlated δ13C values of coexisting Vallonia and Gastrocopta suggest similar feeding habits and imply that these genera can provide information on variations in southern Great Plains plant ecology. Although there is considerable scatter, multispecies, transect average δ13C values of the modern aragonite shells are related to variations in the type of photosynthesis (i.e., C3, C4) in the local plant communities. The results of this study emphasize the desirability of obtaining isotope ratios representing averages of many shells in a locale to reduce possible biases associated with local variations among individuals, species, etc., and thus better represent the “neighborhood” scale temporal and/or spatial environmental variations of interest in studies of modern and ancient systems.  相似文献   

17.
Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ18OVSMOW and δ2HVSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ18OVSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ18OVSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ13CVPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO2 and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ13CVPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ13CVPDB), indicating carbon isotopic fractionation from methanogenesis via CO2 reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH4-degassing during sampling.  相似文献   

18.
We measured Ca stable isotope ratios (δ44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m−2) is present as sulfates (2.5 kmol m−2), and to a lesser extent carbonates (0.4 kmol m−2). In aqueous extracts of variably hydrated calcium sulfate minerals, δ44/40CaE values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ44/40Ca in the top six horizons resembles that of sulfate-δ44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ44/40Ca values observed on Earth. Linear correlation among δ44/40Ca, δ34S and δ18O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ34S values are positively correlated with sulfate-δ18O values (R2 = 0.78) and negatively correlated with sulfate δ44/40CaE values (R2 = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ44/40Ca fractionation factor of −0.4‰ in CaSO4. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO4 is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.  相似文献   

19.
Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ13C, δ15N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ13C = −22.8 ± 1.0‰; δ15N = 5.5 ± 0.6‰). δ13C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ15N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL1, HL2, HL4, and HL5), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ13C (down to −28‰) and δ15N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL1, HL2, and with lesser extent for HL4. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL5, only the δ13C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL5 to HL1 (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ13C, increasing OC/TN and decreasing δ15N values.  相似文献   

20.
Silica phytoliths, which are deposits of opal-A that precipitate in the intra- and intercellular spaces of plant tissues during transpiration, commonly contain small amounts of occluded organic matter. In this paper, we investigate whether the δ13C values of phytoliths from a C4 grass, Calamovilfa longifolia, vary in response to climatic variables that can affect the carbon-isotope composition of plant tissues. There is no significant correlation (r2 < 0.3) between climate variables and the δ13C values of C. longifolia tissues (average δ13Ctissue = −13.1 ± 0.6 ‰; n = 70) across the North American prairies. However, plant tissue δ13C values are lower for grasses collected in populated areas where the δ13C value of atmospheric CO2 is expected to be lower because of fossil fuel burning. Phytolith δ13C values are more variable (δ13C = −27.3 to −23.0‰; average = −25.1 ± 1.3‰; n = 34) and more sensitive to changes in aridity than whole tissue δ13C values. The strongest correlations are obtained between the δ13C values of stem or sheath phytoliths and humidity (r2 = 0.3), latitude (r2 = 0.4) and amount of precipitation (r2 = 0.5). However, use of these relationships is limited by the wide spread in δ13C values of phytoliths from different plant tissues at the same location. We have been unable to infer any relationship between δ13C values of phytoliths and expected variations in the δ13C values of atmospheric CO2. The C. longifolia phytoliths are depleted of 13C relative to tissue carbon by 10-14‰. This means that the phytoliths examined in this study have carbon isotopic compositions within the range reported previously for phytoliths from C3 plants. This observation may further limit the usefulness of soil-phytolith assemblage δ13C values for identifying shifts in grassland C3:C4 ratios.  相似文献   

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