Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.     

Effects of sugar cane monocultures on origin and characteristics of dissolved organic matter in the Manguaba lagoon in northeast Brazil

Brazil has extensive sugar cane monocultures, which significantly alter hydrogeochemical material fluxes. We studied dissolved organic matter (OM) fluxes in the Manguaba lagoon-estuary system, which drains a sugar cane monoculture-dominated hinterland and discharges into the Atlantic coastal ocean. The OM fluxes into the lagoon originate from baseflow, field runoff and sugar cane factory effluents. In the study, dissolved organic carbon (DOC) concentration, δ¹³C DOC and UV absorbance were analysed along a freshwater-seawater salinity gradient that encompasses river (DOC 9-11 mg l⁻¹, δ¹³C −22.2‰ to −25.5‰); lagoon (4-11 mg l⁻¹, −20.5‰ to −24.8‰); estuary (3-9 mg l⁻¹, −22.6‰ to −25.3‰) and coastal waters (1.64 mg l⁻¹, −21‰) with different intra-seasonal runoff conditions. We used the carbon isotope data to quantify the sugar cane derived DOC. Where river water meets brackish lagoon water, substantial loss of DOC occurs during rainy conditions, when suspended sediment from eroded fields in the river is very high. During dry weather, at much lower suspension levels, DOC increases, however, presumably from addition of photolysed resuspended sedimentary OM. In the estuary, mixing of DOC is strictly conservative. Ca. 1/3 of riverine DOM discharged into the lagoon has a sugar cane source. Within the lagoon on avg. 20% of the bulk DOM is comprised of sugar cane DOM, whereas during heavy rainfall the amount increases to 31%, due to intensified drainage flow and soil erosion. In the estuary, 14-26% is of sugar cane origin. The sugar cane-derived component follows the mixing patterns of bulk DOM.     

The stable carbon isotope biogeochemistry of acetate and other dissolved carbon species in deep subseafloor sediments at the northern Cascadia Margin

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ¹³C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ¹³C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in ¹³C. Broadly, ¹³C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while ¹³C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO₂-reduction can coexist with methanogenic CO₂-reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.     

Chemical and isotopic tracers of the contribution of microbial gas in Devonian organic-rich shales and reservoir sandstones,northern Appalachian Basin

In this study, the geochemistry and origin of natural gas and formation waters in Devonian age organic-rich shales and reservoir sandstones across the northern Appalachian Basin margin (western New York, eastern Ohio, northwestern Pennsylvania, and eastern Kentucky) were investigated. Additional samples were collected from Mississippian Berea Sandstone, Silurian Medina Sandstone and Ordovician Trenton/Black River Group oil and gas wells for comparison. Dissolved gases in shallow groundwaters in Devonian organic-rich shales along Lake Erie contain detectable CH₄ (0.01–50.55 mol%) with low δ¹³C–CH₄ values (−74.68 to −57.86‰) and no higher chain hydrocarbons, characteristics typical of microbial gas. Nevertheless, these groundwaters have only moderate alkalinity (1.14–8.72 meq/kg) and relatively low δ¹³C values of dissolved inorganic C (DIC) (−24.8 to −0.6‰), suggesting that microbial methanogenesis is limited. The majority of natural gases in Devonian organic-rich shales and sandstones at depth (>168 m) in the northern Appalachian Basin have a low CH₄ to ethane and propane ratios (3–35 mol%; C₁/C₂ + C₃) and high δ¹³C and δD values of CH₄ (−53.35 to −40.24‰, and −315.0 to −174.6‰, respectively), which increase in depth, reservoir age and thermal maturity; the molecular and isotopic signature of these gases show that CH₄ was generated via thermogenic processes. Despite this, the geochemistry of co-produced brines shows evidence for microbial activity. High δ¹³C values of DIC (>+10‰), slightly elevated alkalinity (up to 12.01 meq/kg) and low SO₄ values (<1 mmole/L) in select Devonian organic-rich shale and sandstone formation water samples suggest the presence of methanogenesis, while low δ¹³C–DIC values (<−22‰) and relatively high SO₄ concentrations (up to 12.31 mmole/L) in many brine samples point to SO₄ reduction, which likely limits microbial CH₄ generation in the Appalachian Basin. Together the formation water and gas results suggest that the vast majority of CH₄ in the Devonian organic-rich shales and sandstones across the northern Appalachian Basin margin is thermogenic in origin. Small accumulations of microbial CH₄ are present at shallow depths along Lake Erie and in western NY.     

The isotopic composition of respired carbon dioxide in scleractinian corals: Implications for cycling of organic carbon in corals

The origin of δ¹³C variations within the skeletons of zooxanthellate scleractinian corals is still a matter of considerable debate. In particular, the role respired CO₂ plays in controlling the eventual δ¹³C of the skeleton remains unclear. In this study, the temporal variability of the δ¹³C of respired CO₂ produced by Montastraea faveolata has been measured at approximately monthly intervals over a 1-year period. In these experiments, three corals maintained on a platform at 8 m depth near Molasses Reef in the Florida Keys were incubated in closed chambers for 24-h periods and samples of the incubation water analyzed for the δ¹³C of the dissolved inorganic carbon (ΣCO₂) at ∼3-h intervals. Throughout the incubation, the concentration of O₂ was measured continuously within the chamber. Our results show that during daylight, the δ¹³C of the ΣCO₂ in the incubation water becomes enriched in ¹³C as a result of fractionation during the fixation of C by photosynthesis, whereas at night the δ¹³C of the ΣCO₂ becomes more negative. The δ¹³C of the respiratory CO₂ ranges from −9‰ in the late spring to values as low as −17‰ in the autumn. The lighter values are significantly more negative than those reported by previous workers for coral tissue and zooxanthellae. An explanation for this discrepancy may be that the corals respire a significant proportion of isotopically negative substances, such as lipids, which are known to have values up to 10‰ lighter compared to the bulk δ¹³C of the tissue. The clear seasonal cycle in the δ¹³C of the respiratory CO₂ suggests that there is also seasonal variability in either the δ¹³C of the coral tissue or the type and/or amount of organic material being respired. A similar temporal pattern and magnitude of change was observed in the δ¹³C of the coral tissue samples collected from a nearby reef at monthly intervals between 1995 and 1997. These patterns are similar in timing to the δ¹³C measured in the coral skeletons. We have also calculated an annual mean value for the fractionation factor between dissolved CO₂⁻ in the external environment and photosynthate fixed by the zooxanthellae of 1.0121 (±0.003). This value is inversely correlated with the ratio of photosynthesis to respiration (P/R) of the entire organism and shows the highest values during the summer months.     

Genesis of fumarolic emissions as inferred by isotope mass balances: CO2 and water at Vulcano Island, Italy

We have developed a quantitative model of CO₂ and H₂O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H₂O and CO₂ and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H₂O and CO₂ content and the δD, δ¹⁸O, and δ¹³C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ¹³C_CO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO₂ concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ¹³C_CO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ¹³C of the entire hydrothermal system, including mixed H₂O-CO₂ vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO₂. On these grounds, we think that Mediterranean marine water (δD_H2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO₂ and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.     

Tracing the decomposition of dissolved organic carbon in artificial groundwater recharge using carbon isotope ratios

Reducing the concentration of dissolved organic C (DOC) in water is one of the main challenges in the process of artificial groundwater recharge. At the Tuusula waterworks in southern Finland, surface water is artificially recharged into an esker by pond infiltration and an equal amount of groundwater is daily pumped from the aquifer. This groundwater study was conducted to consider the role of redox processes in the decomposition of DOC. The isotopic composition of dissolved inorganic C (δ¹³C_DIC) in the recharged water was used as a tracer for redox reactions. The isotopic composition of O and H in water was determined in order to calculate mixing ratios between the local groundwater and the infiltrated surface water. Three distinct processes in the reduction of the DOC content were traced using isotopic methods and concentration analyses of DIC and DOC: (1) the decomposition of DOC, (2) adsorption of DOC on mineral matter, and (3) the dilution of artificially recharged water by mixing with local groundwater. The largest decrease (44%) in the DOC content occurred during the early stage of subsurface flow, within 350 m of the infiltration ponds. The reduction of DOC was accompanied by an equal increase in DIC and a significant drop in δ¹³C_DIC. This change is attributed to the oxidative decomposition of DOC. A further 23% decrease in DOC is attributed to adsorption and a final drop of 14% to dilution with local groundwater.     

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.     

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.     

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.     

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.     

The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO¹³C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins. The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However, this view is not consistent with the bulk of our data from a survey of DOC and DO¹³C distributions in estuaries on the East and Gulf coasts of the USA. While it is accurate that the DOC in estuaries includes material derived from land and from the ocean, the distributions of DOC and DO¹³C in several estuaries reflect additional DOC inputs from estuarine phytoplankton and tidal marshes. Even when DOC concentrations were distributed conservatively, the isotopic composition of the DOC revealed the existence of a dynamic cycle of DOC input and removal in some systems.     

Stable isotope geochemical characteristics of dissolved inorganic carbon in the Jiulong River Estuary,Fujian Province,China

The isotopic composition of dissolved inorganic carbon （DIC） in estuarine environments has been studied for its significant role in determining the isotopic composition of inorganic/organic matter and its applications to the study of various natural processes. In this paper, based on the stable isotope geochemical characteristics of dis- solved inorganic carbon in the Jiulong River Estuary, the following conclusions are drawn： （1） δ13CDIC values are mainly controlled by the mixing ratio of fresh water and sea water; （2）δ13Cphytoplankton values are linearly related to the δ13CDIC values; （3） δ13CpoM values for the Jiulong River Estuary are affected by anthropogenic pollution signifi- cantly; and （4） the comprehensive analysis of δ13Cphytoplankton, δ13CpoM and δ13CDIc shows that along with increasing salinity, the proportion of POM derived from the degradation of phytoplanktons gradually increases.     

Temporal variability in sources of dissolved organic carbon in the lower Mississippi river

Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and ¹³C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 × 10⁻³ Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 ±163 and 115 ± 47 μM, respectively. ¹³C-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly ¹³C-depleted with respect to bulk HMW DOM indicating that C₄ grass inputs to the HMW DOM were not significant. It is speculated that C₄ organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C₃ organic matter is, because of the association of C₄ organic matter with finer sediments. The predominantly aliphatic ¹³C NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC.     

Silicon isotope compositions of dissolved silicon and suspended matter in the Yangtze River, China

Silicon isotope compositions of main channel samples of the Yangtze River were systematically investigated along with their chemical compositions. The concentration of suspended matter in the Yangtze River tends to decrease from the upper reaches to the lower reaches, corresponding to settling of the sediments in the lakes and reservoirs due to reduction of the velocity of water flow. The silica contents of suspended matter vary from 52.1% to 56.9% and their δ³⁰Si values vary from 0 to −0.7‰, both similar to those of shales. From the upper to lower reaches, the silica contents of suspended matter tend to increase, whilst their δ³⁰Si values tend to decrease. Both trends reflect the increase of clay minerals and decrease of carbonates in suspended matter.The concentrations of dissolved silicon vary from 97 to 121 μmol/L and their δ³⁰Si values vary over a wide range from 0.7 to 3.4‰. From the upper to lower reaches, dissolved silica concentrations tend to decrease and their δ³⁰Si values tend to increase. These trends mainly reflect the change of chemical and isotopic characteristics of the tributaries from the upper to lower reaches. The major factors responsible for these changes may be the high meteoric precipitation and significant silicon absorption by grass (in wetlands) and rice (in paddy fields) in drainage areas of the middle and lower reaches.There is no correlation between δ³⁰Si of dissolved silicon and that of suspended matter. The Δ³⁰Si_Diss-SPM values vary over a wide range of 1.0-3.7‰, indicating that (1) they are out of isotopic equilibrium, (2) dissolved silicon and the associated suspended matter do not belong to one physico-chemical system, and (3) isotopic exchange rate between them is very slow.The δ³⁰Si value of dissolved silicon output from the Yangtze River to the East Sea is estimated to be 3.0‰, much higher than the values reported for the Amazon and Congo rivers. This increases the δ³⁰Si range of dissolved silicon in the world’s rivers from 0.4-1.2%; to 0.4-3.4%.     

Tracing dissolved O2 and dissolved inorganic carbon stable isotope dynamics in the Nyack aquifer: Middle Fork Flathead River, Montana, USA

The geochemistry and microbiology of shallow groundwater aquifers is greatly influenced by the concentration of dissolved oxygen gas (DO); however, the mechanisms that consume DO in groundwater (e.g., biotic or abiotic) are often ambiguous. The use of stable isotopes of molecular O₂ (δ¹⁸O-DO), in conjunction with stable isotopes of dissolved inorganic carbon (δ¹³C-DIC), has potential to discriminate between the various mechanisms causing DO depletion in subsurface waters.Here we report the results of spatial and seasonal changes in δ¹⁸O-DO and δ¹³C-DIC at the Nyack floodplain aquifer along the Middle Fork of the Flathead River near West Glacier, Montana, USA. Over a short, well constrained flow path (∼100 m) near a main recharge zone of the floodplain, the δ¹⁸O-DO consistently increased as DO concentrations decreased with distance from the recharge source. Concurrently, DIC concentrations increased and δ¹³C-DIC values decreased. These observations are explained by community respiration coupled with dissolution of calcite from cobbles in the aquifer matrix. When these results are compared to data from wells distributed over the entire floodplain (several km) a much less predictable relationship was observed between DO concentration and δ¹⁸O-DO. Many wells with low DO concentrations (e.g., <125 μmol L⁻¹ or 4 mg L⁻¹) had anomalously low δ¹⁸O-DO values (e.g., <20‰). Mass balance calculations show that approximately equal amounts of O₂ may be contributed to the aquifer by diffusion from the vadose zone and by advection from the river recharge. Calculations presented here suggest that diffusion across a narrow air-water interface can contribute isotopically light δ¹⁸O-DO to the saturated zone. Possible contributions of light δ¹⁸O-DO from other processes, such as isotopic exchange and radial oxygen loss from plant roots in or near the water table, are compared and evaluated.     

Oxygen and carbon isotopic systematics of aragonite speleothems and water in Furong Cave, Chongqing, China

To understand oxygen and carbon stable isotopic characteristics of aragonite stalagmites and evaluate their applicability to paleoclimate, the isotopic compositions of active and fossil aragonite speleothems and water samples from an in situ multi-year (October 2005-July 2010) monitoring program in Furong Cave located in Chongqing of China have been examined. The observations during October 2005-June 2007 show that the meteoric water is well mixed in the overlying 300-500-m bedrock aquifer, reflected by relatively constant δ¹⁸O, ±0.11-0.14‰ (1σ), of drip waters in the cave, which represents the annual status of rainfall water. Active cave aragonite speleothems are at oxygen isotopic equilibrium with drip water and their δ¹⁸O values capture the surface-water oxygen isotopic signal. Aragonite-to-calcite transformation since the last glaciation is not noticeable in Furong stalagmites. Our multi-year field experiment approves that aragonite stalagmite δ¹⁸O records in this cave are suitable for paleoclimate reconstruction. With high U, 0.5-7.2 ppm, and low Th, 20-1270 ppt, the Furong aragonite stalagmites provide very precise chronology (as good as ±20s yrs (2σ)) of the climatic variations since the last deglaciation. The synchroneity of Chinese stalagmite δ¹⁸O records at the transition into the Bølling-Allerød (t-BA) and the Younger Dryas from Furong, Hulu and Dongge Caves supports the fidelity of the reconstructed East Asian monsoon evolution. However, the Furong record shows that the cold Older Dryas (OD) occurred at 14.0 thousand years ago, agreeing with Greenland ice core δ¹⁸O records but ∼200 yrs younger than that in the Hulu record. The OD age discrepancy between Chinese caves can be attributable to different regionally climatic/environmental conditions or chronological uncertainty of stalagmite proxy records, which is limited by changes in growth rate and subsampling intervals in absolute dating. Seasonal dissolved inorganic carbon δ¹³C variations of 2-3‰ in the drip water and 5-7‰ in the pool and spring waters are likely attributed to variable degrees of CO₂ degassing in winter and summer. The variable δ¹³C values of active deposits from −11‰ to 0‰ could be caused by kinetically mediated CO₂ degassing processes. The complicated nature of pre-deposition kinetic isotopic fractionation processes for carbon isotopes in speleothems at Furong Cave require further study before they can be interpreted in a paleoclimatic or paleoenvironmental context.     

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.     

Carbon mass-balance modelling and carbon isotope exchange processes in dynamic caves

Diverse interpretations have been made of carbon isotope time series in speleothems, reflecting multiple potential controls. Here we study the dynamics of ¹³C and ¹²C cycling in a particularly well-constrained site to improve our understanding of processes affecting speleothem δ¹³C values. The small, tubular Grotta di Ernesto cave (NE Italy) hosts annually-laminated speleothem archives of climatic and environmental changes. Temperature, air pressure, pCO₂, dissolved inorganic carbon (DIC) and their C isotopic compositions were monitored for up to five years in soil water and gas, cave dripwater and cave air. Mass-balance models were constructed for CO₂ concentrations and tested against the carbon isotope data. Air advection forces winter pCO₂ to drop in the cave air to ca. 500 ppm from a summer peak of ca. 1500 ppm, with a rate of air exchange between cave and free atmosphere of approximately 0.4 days. The process of cave ventilation forces degassing of CO₂ from the dripwater, prior to any calcite precipitation onto the stalagmites. This phase of degassing causes kinetic isotope fractionation, i.e. ¹³C-enrichment of dripwater whose δ¹³C_DIC values are already higher (by about 1‰) than those of soil water due to dissolution of the carbonate rock. A subsequent systematic shift to even higher δ¹³C values, from −11.5‰ in the cave drips to about −8‰ calculated for the solution film on top of stalagmites, is related to degassing on the stalagmite top and equilibration with the cave air. Mass-balance modelling of C fluxes reveals that a very small percentage of isotopically depleted cave air CO₂ evolves from the first phase of dripwater degassing, and shifts the winter cave air composition toward slightly more depleted values than those calculated for equilibrium. The systematic ¹³C-enrichment from the soil to the stalagmites at Grotta di Ernesto is independent of drip rate, and forced by the difference in pCO₂ between cave water and cave air. This implies that speleothem δ¹³C values may not be simply interpreted either in terms of hydrology or soil processes.     

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO₂ components—atmospheric CO₂ and CO₂ from in situ oxidation of organic matter. The δ¹³C values measured for the Fe(CO₃)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most ¹³C-rich Fe(CO₃)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO₂ components. δ¹³C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco₂ value of about 1 × PAL, but the scatter in the measured δ¹³C values of organic matter permits a calculated maximum Pco₂ of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO₃)OH in MCGoeth and SAP correspond to soil CO₂ concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO₂ concentrations are similar to modern soils in warm, wet environments.The average δ¹³C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ¹³C value for all profiles of −5.4‰. Thus, the value of Δ¹³C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco₂ and organic matter δ¹³C values were the same for both paleosol types. Furthermore, the atmospheric Pco₂ calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco₂ (permitted by one standard deviation of the organic matter δ¹³C value) of ∼5 × PAL.If, however, measured average δ¹³C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of ¹³C-depleted, labile organic compounds, calculated Permian atmospheric Pco₂ using these ¹³C-enriched organic values would underestimate the actual atmospheric Pco₂ using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO₂ concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO₂.The Fe(CO₃)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in ¹³C relative to Fe(CO₃)OH in goethites from soils in which there are mixtures of two isotopic CO₂ components. Field-relationships and the δ¹³C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO₂ components at the time of goethite crystallization. The three components were probably atmospheric CO₂, CO₂ from in situ oxidation of organic matter and CO₂ from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO₂ components, as recorded by Fe(CO₃)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco₂.