Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China

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 (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 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.     

Soils at the hyperarid margin: The isotopic composition of soil carbonate from the Atacama Desert, Northern Chile

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 CO₂.δ¹⁸O (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.     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

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.     

The effect of chemical processing on the δC value of plant tissue

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.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

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 C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) 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 C_org/N_tot and δ¹³C_org (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 C_org/N_tot and δ¹³C_org (< −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 C_org/N_tot and δ¹³C_org 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.     

Variation characteristics of CO2 in a newly-excavated soil profile,Chinese Loess Plateau: Excavation-induced ancient soil organic carbon decomposition

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.     

Stable carbon isotopic evidence for differences in the dietary origin of bone cholesterol, collagen and apatite: implications for their use in palaeodietary reconstruction

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 (Δ¹³C_prot-engy = δ¹³C_protein - δ¹³C_energy) and whole diet-to-bone component fractionations (Δ¹³C_bcomp-wdiet = δ¹³C_{bone component} - δ¹³C_{whole 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 (Δ¹³C_apat-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.     

Diet and habitat of toxodont megaherbivores (Mammalia, Notoungulata) from the late Quaternary of South and Central America

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.     

Controls on dissolved inorganic carbon and δC in cave waters from DeSoto Caverns: Implications for speleothem δC assessments

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 δ¹³C_DIC 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 δ¹³C_DIC values of cave waters range from 0.2 to 6.0 mM and 2.7 to −12.9 (‰ VPDB), respectively. [DIC] and δ¹³C_DIC of “seasonal drips” show seasonal, albeit noisy, variability and are inversely related (δ¹³C_DIC = −2.49[DIC] + 0.64, r² = 0.84). A shallow pool fed by multiple drips shows a bimodal δ¹³C_DIC 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 δ¹³C_DIC variability. Measured values of high [DIC] and low δ¹³C_DIC from cave waters collected during the summer/early fall closely approximate isotopic equilibrium conditions. Conversely, low [DIC] and high δ¹³C_DIC 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.     

Sources of carbon isotope variation in kangaroo bone collagen and tooth enamel

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.     

Spatial patterns of soil δC reveal grassland-to-woodland successional processes

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.     

Sources of dissolved organic carbon in forest soils: evidences from the differences of organic carbon concentration and isotope composition studies

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 ¹³C_DOC) are closer to δ ¹³C of litter than δ ¹³C values of SOC (δ ¹³C_SOC). In the litter-lacking surface soil samples, the range of δ ¹³C_DOC is between δ ¹³C_SOC 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 ¹³C_SOC and δ ¹³C_DOC become more positive, and the absolute values of Δ (δ ¹³C_DOC − δ ¹³C_SOC) 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.     

Contribution of maize root derived C to soil organic carbon throughout an agricultural soil profile assessed by compound specific C analysis

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.     

Carbon-isotopic analysis of individual pollen grains from C3 and C4 grasses using a spooling-wire microcombustion interface

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.     

Evidence for multiple, episodic, mid-Holocene Hypsithermal recorded in two soil profiles along an alluvial floodplain catena, southeastern Tennessee, USA

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.     

Environmental significance of C/C and O/O ratios of modern land-snail shells from the southern great plains of North America

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.     

Non-biological fractionation of stable Ca isotopes in soils of the Atacama Desert, Chile

We measured Ca stable isotope ratios (δ^44/40Ca) 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, δ^44/40Ca_E 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-δ^44/40Ca in the top six horizons resembles that of sulfate-δ^44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ^44/40Ca values observed on Earth. Linear correlation among δ^44/40Ca, 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 δ^44/40Ca_E values (R² = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ^44/40Ca 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.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

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 δ¹⁸O_VSMOW and δ²H_VSMOW, 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 δ¹⁸O_VSMOW 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 δ¹⁸O_VSMOW 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‰ δ¹³C_VPDB 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‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), 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.     

Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

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.     

Limitations on the climatic and ecological signals provided by the δC values of phytoliths from a C4 North American prairie grass

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 δ¹³C_tissue = −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.