Stable Carbon Isotope Fractionation Research Articles

The soil-air interfacial migration process of volatile PFAS at the contaminated sites: Evidence from stable carbon isotopes with CSIA

Volatile per- and polyfluoroalkyl substances (PFAS) are prone to transport among various environmental media, with the soil-air interfacial migration process being an important pathway that significantly influences their environmental fate. To assess the migration and transformations of target volatile PFAS at contaminated site using compound-specific stable isotope analysis (CSIA), it is necessary to understand the isotopic fractionation that occurs during their transfer from soil to air. We have established methods for pre-treatment and GC/CSIA analysis methods of target volatile PFAS in soil and air samples and ensured the accuracy of carbon isotope analysis. GC/IRMS δ13C measurements showed optimal precision at instrumental response above 1.35–2.75 Vs, with recommended minimum on-column C levels of 1.67–5.00 nmol for target volatile PFAS. Stable carbon isotope fractionation factors related to the soil-air interfacial migration process for target volatile PFAS were determined by performing laboratory simulations. The observed εsoil-air values are all negative, suggesting that the soil-air interfacial migration process for target volatile PFAS is kinetic fractionation, the removal of molecules containing lighter isotopes. By comparing the simulated and experimentally observed δ13C (‰) values of target volatile PFAS, we found consistent trends in the soil and inverse trends in the air. These δ13C (‰) values and the related isotope fractionation model provide valuable insights into the isotopic behavior of target volatile PFAS during soil-air interfacial migration process, aiding in the assessment of their environmental fate.

Tracking atrazine degradation in soil combining 14C-mineralisation assays and compound-specific isotope analysis

The quantification of pesticide dissipation in agricultural soil is challenging. In this study, we investigated atrazine biodegradation in both liquid and soil experiments bioaugmented with distinct atrazine-degrading bacterial isolates. This was achieved by combining 14C-mineralisation assays and compound-specific isotope analysis of atrazine. In liquid experiments, the three bacterial isolates mineralised over 40% of atrazine, demonstrating their potential for extensive degradation. However, the kinetics of mineralisation and degradation varied among the isolates. Carbon stable isotope fractionation was similar for Pseudomonas isolates ADPT34 and ADP2T0, but slightly higher for Chelatobacter SR27. In soil experiments, atrazine primarily degraded into atrazine-desethyl, while atrazine-hydroxy was mainly observed in experiments with SR27. Atrazine mineralisation in soil by ADPT34 and SR27 exceeded 40%, whereas ADP2T0 exhibited a mineralisation rate of 10%. In experiments with ADPT34 and SR27, atrazine 14C-residues were predominantly found in the non-extractable fraction, whereas they accumulated in the extractable fraction in the experiment with ADP2T0. Compound-specific isotope analysis (CSIA) relies on changes of stable isotope ratios and holds potential to evaluate herbicide transformation in soil. CSIA of atrazine indicated atrazine biodegradation in water and solvent extractable soil fractions and varied between 29% and 52%, depending on the bacterial isolate. Despite atrazine degradation in both soil fractions, a significant portion of atrazine residues persisted, depending on the bacterial degrader, initial cell concentration, and mineralisation and degradation rates. Overall, our approach can aid in quantifying atrazine persistence and degradation in soil, and in optimizing bioaugmentation strategies for remediating soils contaminated with persistent herbicides.

Dual C–Cl isotope fractionation offers potential to assess biodegradation of 1,2-dichloropropane and 1,2,3-trichloropropane by Dehalogenimonas cultures

1,2-dichloropropane (1,2-DCP) and 1,2,3-trichloropropane (1,2,3-TCP) are hazardous chemicals frequently detected in groundwater near agricultural zones due to their historical use in chlorinated fumigant formulations. In this study, we show that the organohalide-respiring bacterium Dehalogenimonas alkenigignens strain BRE15 M can grow during the dihaloelimination of 1,2-DCP and 1,2,3-TCP to propene and allyl chloride, respectively. Our work also provides the first application of dual isotope approach to investigate the anaerobic reductive dechlorination of 1,2-DCP and 1,2,3-TCP. Stable carbon and chlorine isotope fractionation values for 1,2-DCP (ƐC = −13.6 ± 1.4 ‰ and ƐCl = −27.4 ± 5.2 ‰) and 1,2,3-TCP (ƐC = −3.8 ± 0.6 ‰ and ƐCl = −0.8 ± 0.5 ‰) were obtained resulting in distinct dual isotope slopes (Λ12DCP = 0.5 ± 0.1, Λ123TCP = 4 ± 2). However direct comparison of ΛC-Cl among different substrates is not possible and investigation of the C and Cl apparent kinetic isotope effects lead to the hypothesis that concerted dichloroelimination mechanism is more likely for both compounds. In fact, whole cell activity assays using cells suspensions of the Dehalogenimonas-containing culture grown with 1,2-DCP and methyl viologen as electron donor suggest that the same set of reductive dehalogenases was involved in the transformation of 1,2-DCP and 1,2,3-TCP. This study opens the door to the application of isotope techniques for evaluating biodegradation of 1,2-DCP and 1,2,3-TCP, which often co-occur in groundwaters near agricultural fields.

Fractionation of stable carbon isotopes during formate consumption in anoxic rice paddy soils and lake sediments

Abstract. Formate is energetically equivalent to hydrogen and thus is an important intermediate during the breakdown of organic matter in anoxic rice paddy soils and lake sediments. Formate is a common substrate for methanogenesis, homoacetogenesis and sulfate reduction. However, how much these processes contribute to formate degradation and fractionate carbon stable isotopes is largely unknown. Therefore, we measured the conversion of formate to acetate, CH4 and CO2 and the δ13C of these compounds in samples of paddy soils from Vercelli, Italy, and the International Rice Research Institute (IRRI) in the Philippines and of sediments from the NE and SW basins of Lake Fuchskuhle, Germany. The samples were suspended in a phosphate buffer (pH 7.0) in both the absence and presence of sulfate (gypsum) and of methyl fluoride (CH3F), an inhibitor of aceticlastic methanogenesis. In the paddy soils, formate was mainly converted to acetate under both methanogenic and sulfidogenic conditions. Methane was only a minor product and was mainly formed from the acetate. In the lake sediments, the product spectrum was similar but only under methanogenic conditions. In the presence of sulfate, however, acetate and CH4 were only minor products. The isotopic enrichment factors (εform) of formate consumption, determined by Mariotti plots, were in the low range of −8 ‰ to −2.5 ‰ when sulfate was absent, and formate was mainly converted to acetate and CH4. However, no enrichment factor was detectable when formate was degraded with sulfate to mainly CO2. The δ13C of acetate was by about 25 ‰–50 ‰ more negative than that of formate, indicating acetate production by chemolithotrophic homoacetogenesis. Hence, formate seems to be an excellent substrate for homoacetogenesis in anoxic soils and sediments, so that this process is competing well with methanogenesis and sulfate reduction.

Differences in Methanogenic Pathways and Communities in Paddy Soils Under Three Typical Cropping Modes

AbstractThe methane (CH4) production process in paddy fields varies depending on different cropping modes. However, there is limited knowledge on the changes in anaerobically produced CH4 isotopic ratios (δ13CH4), the methanogenic pathways, and the dominant communities of methanogens in paddy soils under different modes. To address this, we conducted experiments using anaerobic incubation methods, stable carbon isotope fractionation through inhibition studies with fluoromethane, and high‐throughput sequencing. These methods allowed us to measure the CH4 production potential (MPP), the relative contribution of acetoclastic methanogenesis to CH4 production (fac), and the composition of the methanogen community in paddy soils under three typical cropping modes: Rice‐Wheat (RW), Rice‐Fallow (RF), and Double‐Rice (DR) in China. The results showed that MPP was 30.7 μg CH4 g−1 d−1 in DR soil, around 57% and 66% higher than that in RW and RF soils, respectively, possibly due to the lower pH, clay content, and higher abundance of the mcrA gene. Moreover, RF soil had the highest value of produced δ13CH4 (−43.9‰) but the lowest value of produced δ13CO2 (−26.3‰). Based on the carbon isotope fractionation associated with methanogenesis via H2/CO2 reduction (1.049–1.062), the values of fac estimated in the RF soil (80%–98%) were much higher than that in the RW (39%–60%) and DR soils (52%–75%). This could be supported by the finding showing that Methanosarcina, the acetoclastic methanogens, were dominant in RF soil, while Methanosarcina and Methanobacterium (the hydrogenotrophic methanogens) dominated in RW and DR soils. Redundancy analysis revealed that the community structure of methanogens was significantly affected by soil pH. The findings suggest that differences in the abundance and composition of methanogens, possibly driven by soil pH, play a key role in regulating methanogenesis in the paddy soils, and further provide valuable insights into the process of CH4 production in different cropping modes.

Novel Insights into Uptake, Translocation, and Transformation Mechanisms of 2,2',4,4'-Tetra Brominated Diphenyl Ether (BDE-47) in Wheat (Triticum aestivum L.): Implication by Compound-Specific Stable Isotope and Transcriptome Analysis.

The uptake, translocation, and transformation of 2,2',4,4'-tetra brominated diphenyl ether (BDE-47) in wheat (Triticum aestivum L.) were comprehensively investigated by hydroponic experiments using compound-specific stable isotope analysis (CSIA) and transcriptome analysis. The results indicated that BDE-47 was quickly adsorbed on epidermis of wheat roots and then absorbed in roots via water and anion channels as well as an active process dependent on energy. A small fraction of BDE-47 in roots was subjected to translocation acropetally, and an increase of δ13C values in shoots than roots implied that BDE-47 in roots had to cross at least one lipid bilayer to enter the vascular bundle via transporters. In addition, accompanied by the decreasing concentrations, δ13C values of BDE-47 showed the increasing trend with time in shoots, indicating occurrence of BDE-47 transformation. OH-PBDEs were detected as transformation products, and the hydroxyl group preferentially substituted at the ortho-positions of BDE-47. Based on transcriptome analysis, genes encoding polybrominated diphenyl ether (PBDE)-metabolizing enzymes, including cytochrome P450 enzymes, nitrate reductases, and glutathione S-transferases, were significantly upregulated after exposure to BDE-47 in shoots, further evidencing BDE-47 transformation. This study first reported the stable carbon isotope fractionation of PBDEs during translocation and transformation in plants, and application of CSIA and transcriptome analysis allowed systematically characterize the environmental behaviors of pollutants in plants.

Carbon and hydrogen stable isotope fractionation due to monooxygenation of short-chain alkanes by butane monooxygenase of Thauera butanivorans Bu-B1211.

Multi element compound-specific stable isotope analysis (ME-CSIA) is a tool to assess (bio)chemical reactions of molecules in the environment based on their isotopic fingerprints. To that effect, ME-CSIA concepts are initially developed with laboratory model experiments to determine the isotope fractionation factors specific for distinct (bio)chemical reactions. Here, we determined for the first time the carbon and hydrogen isotope fractionation factors for the monooxygenation of the short-chain alkanes ethane, propane, and butane. As model organism we used Thauera butanivorans strain Bu-B1211 which employs a non-haem iron monooxygenase (butane monooxygenase) to activate alkanes. Monooxygenation of alkanes was associated with strong carbon and hydrogen isotope effects: εbulkC = -2.95 ± 0.5 ‰ for ethane, -2.68 ± 0.1 ‰ for propane, -1.19 ± 0.18 ‰ for butane; εbulkH = -56.3 ± 15 ‰ for ethane, -40.5 ± 2.3 ‰ for propane, -14.6 ± 3.6 ‰ for butane. This resulted in lambda (Λ ≈ εHbulk/εCbulk) values of 16.2 ± 3.7 for ethane, 13.2 ± 0.7 for propane, and 11.4 ± 2.8 for butane. The results show that ME-CSIA can be used to track the occurrence and impact of monooxygenase-dependent aerobic processes converting short-chain alkanes in natural settings like marine and terrestrial seeps, gas reservoirs, and other geological formations impacted by natural gas.

Responses of radial growth and stable carbon isotopes to climate in the northern Tianshan Mountains

Climate change has profound effects on forest ecosystems. Schrenk spruce (P. schrenkiana) is a natural conifer species endemic to the arid inland areas of Asia. In this study, the relationship between tree-ring parameters of P. schrenkiana and major meteorological factors were analyzed, and the main limiting factors for tree radial growth and stable carbon isotope fractionation were explored. Our results indicate that moisture stress before and during the growing season have an important influence on radial growth of P. schrenkiana, especially, the correlation coefficient between tree-ring width and vapor pressure deficit (VPD) from previous August to current July is as high as −0.622 (n = 51, p < 0.01). Collinearity analysis further supports the conclusion that the limiting factor for the radial growth of P. schrenkiana is moisture. Although the correlation analysis results show that the tree-ring δ13Ccorr is significantly positively correlated with sunshine duration (SD), additional analysis based on first order difference variables suggests that the climate factor may not be the only limiting factor for the stable carbon isotope fractionation of tree rings in the Sayram Lake Basin. This lays the foundation for the assessment of forest management practices and carbon sink capacity in light of future climate change.

Differences in the Responses of Tree-Ring Stable Carbon Isotopes of L. sibirica and P. schrenkiana to Climate in the Eastern Tianshan Mountains

The eastern Tianshan Mountains are located in the arid interior of Asia, where tree growth is especially sensitive to climate. The ratio of stable carbon isotopes (δ13C) in the tree rings can provide information on changes in atmospheric CO2 concentrations, water availability, and physiological processes within the tree. In particular, the use of tree-ring δ13C values as a proxy for past atmospheric CO2 concentrations has gained widespread acceptance. In this study, detrended stable carbon isotope chronologies (13Ccorr) of Larix sibirica Ledeb. and Picea schrenkiana Fisch. et Mey was established using tree-ring samples from high elevations in the eastern Tianshan Mountains of Xinjiang, China. The relationships between the tree-ring 13Ccorr and different climatic factors were explored using the correlation function and collinearity analysis. Our results demonstrate that the tree-ring δ13Ccorr of L. sibirica is significantly and negatively correlated with precipitation and relative humidity during the growing season. The main climate factor affecting the stable carbon isotope fractionation of L. sibirica during the growing season is relative humidity during the growing season. The tree-ring δ13Ccorr of P. schrenkiana is significantly and negatively correlated with the mean temperature, mean minimum temperature, precipitation, and vapor pressure deficit from the end of the previous growing season and throughout the current growing season, especially in summer. However, it is significantly and positively correlated with relative humidity, indicating that the relationship between the climate factors and the tree-ring stable carbon isotope fractionation of P. schrenkiana is more complex. Further analysis showed that summer temperature and summer precipitation jointly controlled the tree-ring stable carbon isotope fractionation of P. schrenkiana at a high elevation. This research has important implications for our understanding of past and future climate change, as well as for the development of effective strategies to mitigate and adapt to these changes. This study also contributed to the development of a more in-depth understanding of the effects of climate change on tree growth in extremely arid environments and provided evidence to support effective forest management in arid regions.

A laboratory experiment of carbon stable isotope fractionation by several fungal species

A laboratory experiment of carbon stable isotope fractionation by several fungal species

Rice grain-weight dependency on carbon and nitrogen isotope fractionation

Multi-stable isotope analysis is effective for exposing the mislabeling of food production areas. However, in the case of rice, grain dry weight can influence the fractionation of stable carbon (δ13C) and nitrogen (δ15N) isotopes of grains within a production area. The relationship between these isotope fractionations and grain weight remains unclear; thus, the reason for the fractionation has not yet been elucidated.We collected Koshihikari rice grains from four production areas in Japan (Niigata, Aichi, Kagawa and Miyazaki prefecture) and analysed the effect of grain weight on the fractionation of δ13C and δ15N. δ13C was positively fractionated, depending on grain weight by translocation (grain-weight dependency) in all areas, whereas δ15N was not. The statistical analysis of δ13C adjusted by grain weight was able to distinguish between Aichi and Miyazaki, which was not the case for unadjusted δ13C. Our findings suggest that the applicability of δ13C for discrimination can be expanded by considering its grain-weight dependency.

Quantification of biological nitrogen fixation by Mo-independent complementary nitrogenases in environmental samples with low nitrogen fixation activity

Biological nitrogen fixation (BNF) by canonical molybdenum and complementary vanadium and iron-only nitrogenase isoforms is the primary natural source of newly fixed nitrogen. Understanding controls on global nitrogen cycling requires knowledge of the isoform responsible for environmental BNF. The isotopic acetylene reduction assay (ISARA), which measures carbon stable isotope (13C/12C) fractionation between ethylene and acetylene in acetylene reduction assays, is one of the few methods that can quantify isoform-specific BNF fluxes. Application of classical ISARA has been challenging because environmental BNF activity is often too low to generate sufficient ethylene for isotopic analyses. Here we describe a high sensitivity method to measure ethylene δ13C by in-line coupling of ethylene preconcentration to gas chromatography-combustion-isotope ratio mass spectrometry (EPCon-GC-C-IRMS). Ethylene requirements in samples with 10% v/v acetylene are reduced from > 500 to ~ 20 ppmv (~ 2 ppmv with prior offline acetylene removal). To increase robustness by reducing calibration error, single nitrogenase-isoform Azotobacter vinelandii mutants and environmental sample assays rely on a common acetylene source for ethylene production. Application of the Low BNF activity ISARA (LISARA) method to low nitrogen-fixing activity soils, leaf litter, decayed wood, cryptogams, and termites indicates complementary BNF in most sample types, calling for additional studies of isoform-specific BNF.

Carbon and hydrogen stable isotope fractionation of sulfamethoxazole during anaerobic transformation catalyzed by Desulfovibrio vulgaris Hildenborough

The fate of antibiotics in aquatic environments is of high concern and approaches are needed to assess the transformation of antibiotics in wastewater treatment plants. Here we used the model organism Desulfovibrio vulgaris Hildenborough to analyze compound specific isotope fractionation associated with anaerobic transformation of the antibiotic sulfamethoxazole (SMX). The results show that the rearrangement of the isoxazole ring in SMX is leading to significant carbon and hydrogen isotopic fractionation (εC = −5.8 ± 0.7‰, εH = −34 ± 9‰) during anaerobic transformation. The observed carbon isotopic fractionation is significantly higher than the values reported for aerobic degradation (εC = −0.6 ± 0.1‰) or abiotic reactions (εC = −0.8 to −4.8‰ for photolysis, εC = −0.8 to −2.2‰ for advanced oxidation). This indicates that carbon isotope fractionation can be used as a parameter to differentiate reaction mechanisms of SMX transformation. The corresponding apparent kinetic isotope effect (AKIEC) for anaerobic transformation of SMX was 1.029 ± 0.003, suggesting that the mechanism for anaerobic transformation is distinct from the mechanism reported for microbial aerobic degradation (AKIEC = 1.006 ± 0.001). In addition, dual-element (C–H) isotope analysis of SMX was performed in the present study, which was achieved by utilizing gas chromatography (GC) as the separation method instead of routine liquid chromatography. This dual-element isotope analysis resulted in a Λ value of 4.5 ± 2.2. Overall, compound specific isotope analysis can be a feasible tool to monitor the mitigation of SMX in wastewater treatment plants.

Reactive transport of micropollutants in laboratory aquifers undergoing transient exposure periods

Groundwater quality is of increasing concern due to the ubiquitous occurrence of micropollutant mixtures. Stream-groundwater interactions near agricultural and urban areas represent an important entry pathway of micropollutants into shallow aquifers. Here, we evaluated the biotransformation of a micropollutant mixture (i.e., caffeine, metformin, atrazine, terbutryn, S-metolachlor and metalaxyl) during lateral stream water flow to adjacent groundwater. We used an integrative approach combining concentrations and transformation products (TPs) of the micropollutants, compound-specific isotope analysis (δ13C and δ15N), sequencing of 16S rRNA gene amplicons and reactive transport modeling. Duplicate laboratory aquifers (160 cm × 80 cm × 7 cm) were fed with stream water and subjected over 140 d to three successive periods of micropollutant exposures as pulse-like (6000 μg L−1) and constant (600 μg L−1) injections under steady-state conditions. Atrazine, terbutryn, S-metolachlor and metalaxyl persisted in both aquifers during all periods (<10 % attenuation). Metformin attenuation (up to 14 %) was only observed from 90 d onwards, suggesting enhanced degradation over time. In contrast, caffeine dissipated during all injection periods (>90 %), agreeing with fast degradation rates (t1/2 < 3 d) in parallel microcosm experiments and detection of TPs (theobromine and xanthine). Significant stable carbon isotope fractionation (Δδ13C ≥ 6.6 ‰) was observed for caffeine in both aquifers, whereas no enrichment in 15N occurred. A concentration dependence of caffeine biotransformation in the aquifers was further suggested by model simulations following Michaelis-Menten kinetics. Changes in bacterial community composition reflected long-term bacterial adaptation to micropollutant exposures. Altogether, the use of an integrative approach can help to understand the interplay of subsurface hydrochemistry, bacterial adaptations and micropollutants biotransformation during stream-groundwater interactions.

Variability and controls of stable carbon isotopic fractionation during aerobic methane oxidation in temperate lakes

The aerobic oxidation of methane (CH4) by methanotrophic bacteria (MOB) is the major sink of this highly potent greenhouse gas in freshwater environments. Yet, CH4 oxidation is one of the largest uncertain components in predicting the current and future CH4 emissions from these systems. While stable carbon isotopic mass balance is a powerful approach to estimate the extent of CH4 oxidation in situ, its applicability is constrained by the need of a reliable isotopic fractionation factor (αox), which depicts the slower reaction of the heavier stable isotope (13C) during CH4 oxidation. Here we explored the natural variability and the controls of αox across the water column of six temperate lakes using experimental incubation of unamended water samples at different temperatures. We found a large variability of αox (1.004–1.038) with a systematic increase from the surface to the deep layers of lake water columns. Moreover, αox was strongly positively coupled to the abundance of MOB in the γ-proteobacteria class (γ-MOB), which in turn correlated to the concentrations of oxygen and CH4, and to the rates of CH4 oxidation. To enable the applicability in future isotopic mass balance studies, we further developed a general model to predict αox using routinely measured limnological variables. By applying this model to δ13C-CH4 profiles obtained from the study lakes, we show that using a constant αox value in isotopic mass balances can largely misrepresent and undermine patterns of the extent of CH4 oxidation in lakes. Our αox model thus contributes towards more reliable estimations of stable carbon isotope-based quantification of CH4 oxidation and may help to elucidate large scale patterns and drivers of the oxidation-driven mitigation of CH4 emission from lakes.

Large contribution of fossil-derived components to aqueous secondary organic aerosols in China

Incomplete understanding of the sources of secondary organic aerosol (SOA) leads to large uncertainty in both air quality management and in climate change assessment. Chemical reactions occurring in the atmospheric aqueous phase represent an important source of SOA mass, yet, the effects of anthropogenic emissions on the aqueous SOA (aqSOA) are not well constrained. Here we use compound-specific dual-carbon isotopic fingerprints (δ13C and Δ14C) of dominant aqSOA molecules, such as oxalic acid, to track the precursor sources and formation mechanisms of aqSOA. Substantial stable carbon isotope fractionation of aqSOA molecules provides robust evidence for extensive aqueous-phase processing. Contrary to the paradigm that these aqSOA compounds are largely biogenic, radiocarbon-based source apportionments show that fossil precursors produced over one-half of the aqSOA molecules. Large fractions of fossil-derived aqSOA contribute substantially to the total water-soluble organic aerosol load and hence impact projections of both air quality and anthropogenic radiative forcing. Our findings reveal the importance of fossil emissions for aqSOA with effects on climate and air quality.

Stable carbon and hydrogen isotope fractionation of volatile organic compounds caused by vapor-liquid equilibrium

Several types of laboratory experiments were conducted to evaluate isotope fractionation caused by phase transfer process for a selection of common environmental contaminants. Carbon and hydrogen isotope fractionation caused by vaporization of non-aqueous phase liquid (NAPL), by volatilization from water and by dissolution into an organic solvent (tetraethylene glycol dimethylether or TGDE) under equilibrium conditions was investigated with closed system experimental setups to isolate the air-liquid partitioning process. A selection of aromatic, aliphatic and chlorinated compounds along with one fuel oxygenate (methyl tert-butyl ether or MTBE) were evaluated to determine isotope enrichment factor related to respective phase transfer process. During NAPL vaporization, the residual mass of aromatic compounds, aliphatic compounds and MTBE became progressively depleted in heavy carbon and hydrogen isotopes. In contrast, during volatilization from water, the residual mass of aromatic compounds and MTBE dissolved in the water became progressively enriched in heavy hydrogen isotopes, whereas no significant change in carbon isotope was observed, except for MTBE showing a significant depletion. For the air-TGDE partitioning process, most of the aromatic compounds tested led to no significant carbon (except ethylbenzene) or hydrogen (except toluene and o-xylene) isotope fractionation. In contrast, significant carbon isotope fractionation was observed for aliphatic and chlorinated compounds and hydrogen isotope fractionation for aliphatic compounds, and are comparable to progressive NAPL vaporization in direction and magnitude. The isotope fractionation factors determined in this study are key for interpreting the change in isotope ratios when assessing the fate of gas-phase VOCs present in the soil air or when gas-phase VOCs are sampled using TGDE as the sink matrix. The results of this study contribute to expand the list of common environmental contaminants that can be assessed by the compound-specific isotope analysis (CSIA) method deployed in the frame of gas-phase studies.

Responses of Tree Growth and Intrinsic Water Use Efficiency to Environmental Factors in Central and Northern China in the Context of Global Warming

The Loess Plateau is a fragile ecological zone that is sensitive to climate change. The response, adaptation, and feedback of tree growth in forest ecosystems to global warming and CO2 enrichment are urgent scientific issues. Intrinsic water use efficiency (iWUE) is an important indicator for understanding forest ecosystem adaptability to climate change and CO2 enrichment. In this study, tree-ring width, tree-ring stable carbon isotope ratio (δ13C), and iWUE of P. tabulaeformis Carr. were established. Climate response analysis showed that temperature was the main limiting factor affecting radial tree growth and that relative humidity significantly affected the stable carbon isotope fractionation of tree rings. During 1645–2011, the iWUE increased by 27.1%. The responses of iWUE to climate factors and atmospheric CO2 concentrations (Ca) showed that the long-term variation in iWUE was affected by Ca, which could explain 69% of iWUE variation, and temperature was the main factor causing iWUE interannual variation. The ecosystem of P. tabulaeformis showed a positive response to rising Ca, as its carbon sequestration capacity increased. In response to global warming and CO2 enrichment, rising Ca promoted increases in iWUE but ultimately failed to offset the negative impact of warming on tree growth in the study area.

Physiological control on carbon isotope fractionation in marine phytoplankton

Abstract. One of the great challenges in biogeochemical research over the past half a century has been to quantify and understand the mechanisms underlying stable carbon isotope fractionation (εp) in phytoplankton in response to changing CO2 concentrations. This interest is partly grounded in the use of fossil photosynthetic organism remains as a proxy for past atmospheric CO2 levels. Phytoplankton organic carbon is depleted in 13C compared to its source because of kinetic fractionation by the enzyme RubisCO during photosynthetic carbon fixation, as well as through physiological pathways upstream of RubisCO. Moreover, other factors such as nutrient limitation, variations in light regime as well as phytoplankton culturing systems and inorganic carbon manipulation approaches may confound the influence of aquatic CO2 concentrations [CO2] on εp. Here, based on experimental data compiled from the literature, we assess which underlying physiological processes cause the observed differences in εp for various phytoplankton groups in response to C-demand/C-supply, i.e., particulate organic carbon (POC) production / [CO2]) and test potential confounding factors. Culturing approaches and methods of carbonate chemistry manipulation were found to best explain the differences in εp between studies, although day length was an important predictor for εp in haptophytes. Extrapolating results from culturing experiments to natural environments and for proxy applications therefore require caution, and it should be carefully considered whether culture methods and experimental conditions are representative of natural environments.

Carbon stable isotope constraints on CO2 degassing models of ridge, hotspot and arc magmas

Carbon dioxide emissions from volcanoes are important parameters to constrain in order to fully understand the Earth system, especially the effect of volcanic forcing on climate. The characterization of carbon concentration in magmas has been used to constrain volcanic fluxes. Because of low CO2 solubility in silicate melts, however, CO2 is significantly degassed from magmas due to decompression during transfer to the surface. The measurement of the carbon stable isotope ratio (13C/12C expressed as δ13C-values) in natural submarine glasses has been a helpful geochemical tool to study magma degassing. Carbon stable isotope fractionation at magmatic temperature between CO2 in vesicles and carbonate ions dissolved in the melt is still large enough to cause variations in δ13C-values. This variability can be used to deduce the mode of degassing (open vs. closed system, equilibrium vs. kinetic) operating in a given magmatic system.In this study, I present a review of the existing carbon isotope data for magmas of three different settings (ridge, hotspot and arc). This review allows to (1) investigate the diversity of degassing modes operating within a given setting and (2) compare the prevailing degassing mode between these three settings.Except for rare undersaturated samples and for volatile-rich, vesicular popping rocks, Mid-Ocean Ridge Basalts (MORBs) are predominantly extensively degassed and supersaturated in CO2 reflecting incomplete degassing during their last degassing step. Such a behavior is also reflected in their vesicle-dissolved carbon isotopic fractionations that are generally smaller than equilibrium values stemming from kinetic/diffusive effects. By contrast, the CO2 + H2O gas phase in hotspot and arc magmas is predominantly in chemical equilibrium with the melt because of volatile-rich initial conditions (and thus larger vesicularity) enhancing vapor-melt chemical and isotopic equilibrium. This larger initial volatile content is responsible for the extensive open-system (Rayleigh distillation) degassing generally observed in hotspot and arc magmas.This review highlights the fact that one single degassing model cannot explain the geochemical evolution of all magmas. Also, no single model can be assigned to one specific type of magma (i.e., a significant diversity of degassing mode exists within a given type of magma, notably in MORBs). It is important to take into account these observations when degassing corrections are applied on the basis of noble gas (He/Ne or He/Ar) ratios. It appears helpful to characterize the carbon concentration and stable isotope ratios in vesicles and dissolved in the glass in order to (1) identify the mode of degassing operating in a given magmatic system and (2) apply the most appropriate degassing correction to these magmas. It is only after this critical correcting step has been achieved that an assessment of initial magmatic CO2 contents can be reasonably undertaken.