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.     

Coupling between Pbex and organic matter in sediments of a nutrient-enriched lake: An example from Lake Chenghai, China

Sediment cores were collected from deep-water areas of Lake Chenghai, China in June 1997. The vertical profile of ¹³⁷Cs activity gives reliable geochronological results. The results also indicate that sediment accumulation rates in deep-water areas of Lake Chenghai were relatively constant in recent decades, averaging 0.43 g cm^− 2 y^− 1, despite a variable organic carbon influx. ²¹⁰Pb_eq (= ²²⁶Ra) activity was relatively constant also, with an average value of 54.3 ± 3.2 Bq kg^− 1. Vertical profiles of ²¹⁰Pb_ex (= ²¹⁰Pb_total − ²²⁶Ra) decreased exponentially, resulting in somewhat lower sediment accumulation rates (0.3 g cm^− 2 y^− 1). These lower rates are likely less reliable, as the relatively large fluctuations in ²¹⁰Pb_ex activities correlate closely to the organic carbon (C_org) content of the sediments. For example, the vertical profile of ²¹⁰Pb_ex activity displays peaks at mass depths of 3.7-4.7 g cm^− 2 (10-12 cm) and 10-11 g cm^− 2(25-28 cm), similar to the maxima in the vertical profile of C_org. This phenomenon must be related to the delivery of particulate organic matter (POM) from the water to the sediments, or to watershed soil erosion. Since the mean atomic ratios of H_org / C_org and C_org / N_org in Lake Chenghai sediments are 5.5 and 7.0, respectively, indicating that POM was predominantly derived from the remains of authigenic algae, this eliminates watershed erosion rates as a primary control on lake sedimentation rates as resolved by ²¹⁰Pb_ex. Sedimentation fluxes (F(C_org)) of particulate organic carbon since 1970 varied between 60 to 160 g m^− 2 y^− 1, and appeared to closely influence variations in ²¹⁰Pb_ex concentrations. For example, sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) showed maxima in the years 1972-1974 and 1986-1989, likely reflecting historical variations of lake biological productivity or carbon preservation.     

The isotopic composition of particulate organic carbon in mountain rivers of Taiwan

Small rivers draining mountain islands are important in the transfer of terrestrial particulate organic carbon (POC) to the oceans. This input has implications for the geochemical stratigraphic record. We have investigated the stable isotopic composition of POC (δ¹³C_org) in rivers draining the mountains of Taiwan. In 15 rivers, the suspended load has a mean δ¹³C_org that ranges from −28.1±0.8‰ to −22.0±0.2‰ (on average 37 samples per river) over the interval of our study. To investigate this variability we have supplemented suspended load data with measurements of POC in bedrock and river bed materials, and constraints on the composition of the terrestrial biomass. Fossil POC in bedrock has a range in δ¹³C_org from −25.4±1.5‰ to −19.7±2.3‰ between the major geological formations. Using coupled δ¹³C_org and N/C we have found evidence in the suspended load for mixing of fossil POC with non-fossil POC from the biosphere. In two rivers outside the Taiwan Central Range anthropogenic land use appears to influence δ¹³C_org, resulting in more variable and lower values than elsewhere. In all other catchments, we have found that 5‰ variability in δ¹³C_org is not controlled by the variable composition of the biomass, but instead by heterogeneous fossil POC.In order to quantify the fraction of suspended load POC derived from non-fossil sources (F_nf) as well as the isotopic composition of fossil POC (δ¹³C_fossil) carried by rivers, we adapt an end-member mixing model. River suspended sediments and bed sediments indicate that mixing of fossil POC results in a negative trend between N/C and δ¹³C_org that is distinct from the addition of non-fossil POC, collapsing multiple fossil POC end-members onto a single mixing trend. As an independent test of the model, F_nf reproduces the fraction modern (F_mod) in our samples, determined from ¹⁴C measurements, to within 0.09 at the 95% confidence level. Over the sampling period, the mean F_nf of suspended load POC was low (0.29 ± 0.02, n = 459), in agreement with observations from other mountain rivers where physical erosion rates are high and fossil POC enters river channels. The mean δ¹³C_fossil in suspended POC varied between −25.2±0.5‰ and −20.2±0.6‰ from catchment to catchment. This variability is primarily controlled by the distribution of the major geological formations. It also covers entirely the range of δ¹³C_org found in marine sediments which is commonly thought to derive from mixing between marine and terrigenous POC. If land-sourced POC is preserved in marine sediments, then changes in the bulk δ¹³C_org observed offshore Taiwan could instead be explained by changes in the onshore provenance of sediment. The range in δ¹³C_org of fossil organic matter in sedimentary rocks exposed at the surface is large and given the importance of these rocks as a source of clastic sediment to the oceans, care should be taken in accounting for fossil POC in marine deposits supplied by active mountain belts.     

Modeling CO2 chemistry, δC, and oxidation of organic carbon and methane in sediment porewater: Implications for paleo-proxies in benthic foraminifera

I present a numerical diffusion-advection-reaction model to simulate CO₂ chemistry, δ¹³C, and oxidation of organic carbon and methane in sediment porewater. The model takes into account detailed reaction kinetics of dissolved CO₂ compounds, H₂O, H⁺, OH⁻, boron and sulfide compounds. These reactions are usually assumed to be in local equilibrium, which is shown to be a good approximation in most cases. The model also includes a diffusive boundary layer across which chemical species are transported between bottom water and the sediment-water interface. While chemical concentrations and δ¹³C_TCO2 at these locations are frequently assumed equal, I demonstrate that they can be quite different. In this case, shells of benthic foraminifera do not reflect the desired properties of bottom water, even for species living at the sediment-water interface (z = 0 cm). Environmental conditions recorded in their shells are strongly influenced by processes occurring within the sediment. The model is then applied to settings in the Santa Barbara Basin and at Hydrate Ridge (Cascadia Margin), locations of strong organic carbon and methane oxidation. In contrast to earlier studies, I show that a limited contribution of methane-derived carbon to porewater TCO₂ in the Santa Barbara Basin cannot be ruled out. Simulation of methane venting shows that at oxidation rates greater than , the δ¹³C of porewater TCO₂ at z > 1 cm is depleted by more than 15‰ relative to bottom water. Depletions of this magnitude have not been observed in living benthic foraminifera, even at methane vents with much higher oxidation rates. This suggests that foraminifera at these sites either calcify at very shallow sediment depth or during times when oxidation rates are much lower than ∼50 μmol cm⁻² y⁻¹.     

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.     

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland II: Isotopic and chemical compositions and comparison with Paleoproterozoic banded iron formations

We present detailed petrographic surveys of apatite grains in association with carbonaceous material (CM) in two banded iron formations (BIFs) from the Paleoproterozoic of Uruguay and Michigan for comparison with similar mineral associations in the highly debated Akilia Quartz-pyroxene (Qp) rock. Petrographic and Raman spectroscopic surveys of these Paleoproterozoic BIFs show that apatite grains typically occur in bands parallel to bedding and are more often associated with CM when concentrations of organic matter are high. Carbonaceous material in the Vichadero BIF from Uruguay is generally well-crystallized graphite and occurs in concentrations around 0.01 wt% with an average δ¹³C_gra value of −28.6 ± 4.4‰ (1σ). In this BIF, only about 5% of apatite grains are associated with graphite. In comparison, CM in the Bijiki BIF from Michigan is also graphitic, but occurs in concentrations around 2.4 wt% with δ¹³C_gra values around −24.0 ± 0.3‰ (1σ). In the Bijiki BIF, more than 78% of apatite grains are associated with CM. Given the geologic context and high levels of CM in the Bijiki BIF, the significantly higher proportion of apatite grains associated with CM in this rock is interpreted to represent diagenetically altered biomass and shows that such diagenetic mineral associations can survive metamorphism up to the amphibolite facies.Isotope compositions of CM in muffled acidified whole-rock powders from the Akilia Qp rock have average δ¹³C_gra values of −17.5 ± 2.5‰ (1σ), while δ¹³C_carb values in whole-rock powders average −4.0 ± 1.0‰ (1σ). Carbon isotope compositions of graphite associated with apatite and other minerals in the Akilia Qp rock were also measured with the NanoSIMS to have similar ranges of δ¹³C_gra values averaging −13.8 ± 5.6‰ (1σ). The NanoSIMS was also used to semi-quantitatively map the distributions of H, N, O, P, and S in graphite from the Akilia Qp rock, and relative abundances were found to be similar for graphite associated with apatite or with hornblende, calcite, and sulfides. These analyses revealed generally lower abundances of trace elements in the Akilia graphite compared to graphite associated with apatite from Paleoproterozoic BIFs.Graphite associated with hornblende, calcite, and sulfides in the Akilia Qp rock was fluid-deposited at high-temperature from carbon-bearing fluids, and since this graphite has similar ranges of δ¹³C_gra values and of trace elements compared to graphite associated with apatite, we conclude that the Akilia graphite in different mineral associations formed from the same source(s) of CM. Collectively our results do not exclude a biogenic origin of the carbon in the Akilia graphite, but because some observations can not exclude graphitization of abiogenic carbon from CO₂- and CH₄-bearing mantle fluids, there remain ambiguities with respect to the exact origin of carbon in this ancient metasedimentary rock. Accordingly, there may have been several generations of graphite formation along with possibly varying mixtures of CO₂- and CH₄-bearing fluids that may have resulted in large ranges of δ¹³C_gra values. The possibility of fluid-deposited graphite associated with apatite should be a focus of future investigations as this may prove to be an alternative pathway of graphitization from phosphate-bearing fluids. Correlated micro-analytical approaches tested on terrestrial rocks in this work provide insights into the origin of carbon in ancient graphite and will pave the way for the search for life on other ancient planetary surfaces.     

The origins and behaviour of carbon in a major semi-arid river,the Murray River,Australia, as constrained by carbon isotopes and hydrochemistry

δ¹³C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ¹⁸O and δ²H values of water, δ³⁴S values of dissolved SO₄, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ¹³C_DIC values in the Murray River vary between −9.5 and −4.7‰ with a range of <3‰ within any sampling round. δ¹³C_DIC values of the tributaries are −11.0‰ to −5.1‰. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45–55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6–0.7 in the headwaters to ∼0.2–0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO₂; this interpretation is consistent with pCO₂ values that are in the range 550–11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ¹³C_DIC values are similar to those that would be produced by the weathering of marine limestone (δ¹³C ∼ 0‰). However, the lack of marine limestones cropping out in the Murray–Darling Basin and the relatively uniform δ¹³C_DIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO₂ values and δ¹³C_DIC values are best explained by a combination of mineralisation of low δ¹³C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ¹³C values.     

Late Quaternary environmental change of Yellow River Basin: An organic geochemical record in Bohai Sea (North China)

Bulk geochemical characterization (total organic carbon, grain size distribution, carbon isotope composition) and molecular biomarkers (lignin phenols, straight chain aliphatic hydrocarbons, glycerol dialkyl glycerol tetraethers) were analyzed for a 21 m core from the Bohai Sea (North China), spanning ca 21 ka BP. These paleo-proxies presented remarkable differences between the late glacial period and the Holocene, reflecting continental and coastal environments, respectively. Two peat layers were deposited during the period of ca 9000-8460 yr BP. Thereafter the core site has been consistently covered by seawater until recent reclamation of land from the sea. The occurrence of a total organic carbon maximum from ca 6000-3800 yr BP was attributed to delivery of organic carbon enriched sediments via the Yellow River, consistent with increased vegetation density and higher development of soil under warm and humid mid-Holocene climate conditions. The distributions of lignin phenol compositions and C₃₁/C₂₉n-alkane ratio suggested the largest expansion of woody plants between ca 5300 and 4000 yr BP, corresponding to the extremely favorable climatic conditions. Since ca 3800 yr BP, an abrupt increase in the C₃₁/C₂₉n-alkane ratio suggested higher abundance of grasses, consistent with a drying climate trend after the mid-Holocene. Since our coastal sediments close to the Yellow River outflow contain catchment-integrated environmental signals of the river basin, molecular proxies demonstrate that the variability of vegetation distributions in the Holocene is a widespread phenomenon in those areas adjacent to Yellow River Basin.     

Insights into C and H storage in the altered oceanic crust: Results from ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with δD values from −64‰ to −25‰. All samples are enriched in water relative to fresh basalts. The δD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO₂, extracted by step-heating technique, ranges between 564 and 2823 ppm with δ¹³C values from −14.9‰ to −26.6‰. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with δ¹³C = −4.5‰ and (2) an organic compound with δ¹³C = −26.6‰. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO₂ yield after H₃PO₄ attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO₂ degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO₂ is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when “fresh” oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO₂, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ∼ −4.7‰, similar to the δ¹³C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 × 10¹² molC/yr.     

Geochemical characteristics and organic carbon sources within the upper reaches of the Xi River,southwest China during high flow

Carbon (POC, DOC) and carbon isotopes (δ¹³C) within two headwater tributaries to the Xi River Basin, southwest China were analyzed to document the geochemical characteristics and sources of organic carbon (C) within basins characterized by a monsoonal climate and karst landforms. δ¹³ C _POC value and C/N ratio data indicate that suspended soil organic carbon (SOC) was an important source of POC in both the Nanpan and Beipan rivers (i.e., the studied tributaries). However, differences in C sources exist between the Nanpan and Beipan River Basins. Higher terrestrial plants supplied a portion of the POC within the Beipan River. In contrast, the Nanpan River was characterized by an inverse correlation between POC and DOC, and a positive relationship between the δ¹³C values. These trends indicate that DOC within the Nanpan River was partly derived from the degradation of soil C within the water column. In addition, the interception of C by hydrological projects (e.g., dams) positioned along the Nanpan River led to higher DOC/POC ratios. In contrast, within the Beipan River δ¹³C _DOC values range from ?20 to ?25.2 ‰ and are consistent with ratios associated with soil C, suggesting that leaching of C from catchment soil was the dominant source of DOC. Organic C in tributaries to the Beipan River may also have been derived from intense upland soil erosion, a process that resulted in the lowest DOC/POC ratios. The collected data indicate that land-use changes have potentially influenced regional- to local-scale organic C budgets within subtropical basins subjected to karstification.     

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.     

Carbon geochemistry of serpentinites in the Lost City Hydrothermal System (30°N, MAR)

The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and δ¹³C_TC values ranging from −28.7‰ to +2.3‰. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (δ¹³C_TOC: −28.9‰ to −21.5‰) and variations in δ¹³C_TC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C₁₅ to C₃₀. Longer-chain hydrocarbons (up to C₄₀) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C₁₆ to n-C₂₀ alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central dome implies fracture-controlled seawater circulation deep into the gabbroic core of the massif. Thus, our study indicates that hydrocarbons account for an important proportion of the total carbon stored in the Atlantis Massif basement and suggests that serpentinites may represent an important—as yet unidentified—reservoir for dissolved organic carbon (DOC) from seawater.     

Landscape variations in stream water SO4 and δSSO4 in a boreal stream network

Despite reduced anthropogenic deposition during the last decades, deposition sulphate may still play an important role in the biogeochemical cycles of S and many catchments may act as net sources of S that may remain for several decades. The aim of this study is to elucidate the temporal and spatial dynamics of both SO₄²⁻ and δ³⁴S_SO4 in stream water from catchments with varying percentage of wetland and forest coverage and to determine their relative importance for catchment losses of S. Stream water samples were collected from 15 subcatchments ranging in size from 3 to 6780 ha, in a boreal stream network, northern Sweden. In forested catchments (<2% wetland cover) S-SO₄²⁻ concentrations in stream water averaged 1.7 mg L⁻¹ whereas in wetland dominated catchments (>30% wetland cover) the concentrations averaged 0.3 mg L⁻¹. A significant negative relationship was observed between S-SO₄²⁻ and percentage wetland coverage (r² = 0.77, p < 0.001) and the annual export of stream water SO₄²⁻ and wetland coverage (r² = 0.76, p < 0.001). The percentage forest coverage was on the other hand positively related to stream water SO₄²⁻ concentrations and the annual export of stream water SO₄²⁻ (r² = 0.77 and r² = 0.79, respectively). The annual average δ³⁴S_SO4 value in wetland dominated streams was +7.6‰ and in streams of forested catchments +6.7‰. At spring flood the δ³⁴S_SO4 values decreased in all streams by 1‰ to 5‰. The δ³⁴S_SO4 values in all streams were higher than the δ³⁴S_SO4 value of +4.7‰ in precipitation (snow). The export of S ranged from 0.5 kg S ha⁻¹ yr⁻¹ (wetland headwater stream) to 3.8 kg S ha⁻¹ yr⁻¹ (forested headwater stream). With an average S deposition in open field of 1.3 kg S ha⁻¹ yr⁻¹ (2002-2006) the mass balance results in a net export of S from all catchments, except in catchments with >30% wetland. The high temporal and spatial resolution of this study demonstrates that the reducing environments of wetlands play a key role for the biogeochemistry of S in boreal landscapes and are net sinks of S. Forested areas, on the other hand were net sources of S.     

The role of sulfur in chemical weathering and atmospheric CO2 fluxes: Evidence from major ions, δCDIC, and δSSO4 in rivers of the Canadian Cordillera

Water samples from the Fraser, Skeena and Nass River basins of the Canadian Cordillera were analyzed for dissolved major element concentrations (HCO₃⁻, SO₄²⁻, Cl⁻, Ca²⁺, Mg²⁺, K⁺, Na⁺), δ¹³C of dissolved inorganic carbon (δ¹³C_DIC), and δ³⁴S of dissolved sulfate (δ³⁴S_SO4) to quantify chemical weathering rates and exchanges of CO₂ between the atmosphere, hydrosphere, and lithosphere. Weathering rates of silicates and carbonates were determined from major element mass balance. Combining the major element mass balance with δ³⁴S_SO4 (−8.9 to 14.1‰_CDT) indicates sulfide oxidation (sulfuric acid production) and subsequent weathering of carbonate and to a lesser degree silicate minerals are important processes in the study area. We determine that on average, 81% of the riverine sulfate can be attributed to sulfide oxidation in the Cordilleran rivers, and that 25% of the total weathering cation flux can be attributed to carbonate and silicate dissolution by sulfuric acid. This result is validated by δ¹³C_DIC values (−9.8 to −3.7‰ _VPDB) which represents a mixture of DIC produced by the following weathering pathways: (i) carbonate dissolution by carbonic acid (−8.25‰) > (ii) silicate dissolution by carbonic acid (−17‰) ≈ (iii) carbonate dissolution by sulfuric acid derived from the oxidation of sulfides (coupled sulfide-carbonate weathering) (+0.5‰).δ³⁴S_SO4 is negatively correlated with δ¹³C_DIC in the Cordilleran rivers, which further supports the hypothesis that sulfuric acid produced by sulfide oxidation is primarily neutralized by carbonates, and that sulfide-carbonate weathering impacts the δ¹³C_DIC of rivers. The negative correlation between δ³⁴S_SO4 and δ¹³C_DIC is not observed in the Ottawa and St. Lawrence River basins. This suggests other factors such as landscape age (governed by tectonic uplift) and bedrock geology are important controls on regional sulfide oxidation rates, and therefore also on the magnitude of sulfide-carbonate weathering—i.e., it is more significant in tectonically active areas.Calculated DIC fluxes due to Ca and Mg silicate weathering by carbonic acid (38.3 × 10³ mol C · km⁻² · yr⁻¹) are similar in magnitude to DIC fluxes due to sulfide-carbonate weathering (18.5 × 10³ mol C · km⁻² · yr⁻¹). While Ca and Mg silicate weathering facilitates a transfer of atmospheric CO₂ to carbonate rocks, sulfide-carbonate weathering can liberate CO₂ from carbonate rocks to the atmosphere when sulfide oxidation exceeds sulfide deposition. This implies that in the Canadian Cordillera, sulfide-carbonate weathering can offset up to 48% of the current CO₂ drawdown by silicate weathering in the region.     

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.     

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.     

Geochemical features and origin of natural gas in heavy oil area of the Western Slope,Songliao Basin,China

The Western Slope of the Songliao Basin is rich in heavy oil resources (>70 × 10⁸ bbl), around which there are shallow gas reservoirs (∼1.0 × 10¹² m³). The gas is dominated by methane with a dryness over 0.99, and the non-hydrocarbon component being overwelmingly nitrogen. Carbon isotope composition of methane and its homologs is depleted in ¹³C, with δ¹³C₁ values being in the range of −55‰ to −75‰, δ¹³C₂ being in the range of −40‰ to −53‰ and δ¹³C₃ being in the range of −30‰ to −42‰, respectively. These values differ significantly from those solution gases source in the Daqing oilfield. This study concludes that heavy oils along the Western Slope were derived from mature source rocks in the Qijia-Gulong Depression, that were biodegraded. The low reservoir temperature (30–50 °C) and low salinity of formation water with neutral to alkaline pH (NaHCO₃) appeared ideal for microbial activity and thus biodegradation. Natural gas along the Western Slope appears mainly to have originated from biodegradation and the formation of heavy oil. This origin is suggested by the heavy δ¹³C of CO₂ (−18.78‰ to 0.95‰) which suggests that the methane was produced via fermentation as the terminal decomposition stage of the oil.     

Quantifying seasonal precipitation using high-resolution carbon isotope analyses in evergreen wood

High-resolution natural abundance stable carbon isotope analyses across annual growth rings in evergreen trees reveal a cyclic increase and decrease in the measured carbon isotopic composition (δ¹³C), but the causes of this pattern are poorly understood. We compiled new and published high-resolution δ¹³C data from across annual growth rings of 33 modern evergreen trees from 10 genera and 15 globally distributed sites to quantify the parameters that affect the observed δ¹³C pattern. Across a broad range of latitude, temperature, and precipitation regimes, we found that the average, measured seasonal change in δ¹³C (Δδ¹³C_meas, ‰) within tree rings of evergreen species reflects changes in the carbon isotopic composition of atmospheric carbon dioxide (Δδ¹³C_CO2) and changes in seasonal precipitation (ΔP) according to the following equation: Δδ¹³C_meas = Δδ¹³C_CO2 - 0.82(ΔP) + 0.73; R² = 0.96. Seasonal changes in temperature, pCO₂, and light levels were not found to significantly affect Δδ¹³C_meas. We propose that this relationship can be used to quantify seasonal patterns in paleoprecipitation from intra-ring profiles of δ¹³C measured from non-permineralized, fossil wood.     

Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

This study investigates the application of sulphur isotope ratios (δ³⁴S) in combination with carbon (δ¹³C) and nitrogen (δ¹⁵N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans (n = 83), terrestrial animals (n = 11), and freshwater fish (n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ³⁴S values were found. The δ³⁴S values from the terrestrial animals were highly variable (−13.6‰ to +0.5‰), but the δ³⁴S values of the fish were clustered and ³⁴S-depleted (−20.9‰ to −17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly ³⁴S-depleted sulphur influenced the soil. The humans show the largest range of δ³⁴S values (−18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ³⁴S values were found between the males (−7.8 ± 6.0‰) and females (−5.3 ± 6.8‰), but the females had a linear correlation (R² = 0.71; p < 0.0001) between their δ¹⁵N and δ³⁴S compositions. These δ³⁴S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ³⁴S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.