Stable Carbon Isotope Fractionation Research Articles

Study on stable carbon isotope fractionation of rape honey from rape flowers (Brassica napus L.) to its unifloral ripe honey

A new idea and strategy for honey traceability and identification was provided by studying the carbon isotope fractionation of rape honey and its components in the different ripening process, as well as the fractionation from rape flowers, stamens, nectar to rape honey. The results showed the moisture content of rape honey continued to decrease, and the glucose and fructose content continued to increase during the ripening process. The δ13C of rape honey and its protein were less affected by honey ripeness, while the δ13C of sugars in rape honey were greatly affected by this. At the same time, the fractionation of carbon isotope from rape flowers to honey was significant. The δ13C of rape honey and its protein, disaccharide, fructose, and glucose had a strong correlation, and the δ13C of rape honey and its components were mainly related to rape flowers and its stamens.

Semi-closed artificial thermal maturation of type I source rock with the presence of natural formation water: hydrocarbon generation and individual n-alkane stable carbon isotope partitioning pattern

Hydrous pyrolysis is a significant laboratory method to investigate oil generation with the presence of water. Generally, distilled water is utilized in hydrous pyrolysis but not natural formation water, which is ubiquitous in oilfields and has elevated salinities. To understand the influence of formation water on hydrocarbon generation and stable carbon isotopic ratios of expelled oils, two series of semi-closed hydrous pyrolysis experiments were conducted in a wide temperature range (250–550 °C) for the type I Green River Shale source rocks using distilled water and formation water with a salinity of 76 g/L. Oil generation peak occurred at a lower temperature (325 °C) in experiments using formation water compared to experiments using distilled water (375 °C), suggesting that the presence of formation water has facilitated the oil generation. The presence of formation water also promoted the hydrocarbon expulsion at lower temperatures in hydrous pyrolysis (325–350 °C). Stable carbon isotopic fractionation between unpyrolyzed kerogen and n-alkanes (n-C17 to n-C28) generated during the primary stage of oil generation (325–375 °C) is minor (<2.6‰) in the presence of formation water, but smaller relative to those in experiments using distilled water at individual temperature points. Positive correlations between pyrolysis temperatures and δ13C ratios of n-C17, n-C18 and n-C19 during oil generation were observed in the experiments using formation water, which is consistent with the knowledge that 12C–12C bonds are more readily to be cleaved than 13C–12C bonds. Outcomes of this study not only support that stable carbon isotopic analysis of n-alkanes is a powerful tool for fingerprinting oil source in sedimentary basins, but also highlight the significance of using formation water as a medium in hydrous pyrolysis to improve the understanding of chemical/isotopic variations during hydrocarbon generation.

Carbon and Hydrogen Stable Isotope Fractionation of Sulfamethoxazole During Anaerobic Transformation Catalyzed by Desulfovibrio Vulgaris Hildenborough

Carbon and Hydrogen Stable Isotope Fractionation of Sulfamethoxazole During Anaerobic Transformation Catalyzed by Desulfovibrio Vulgaris Hildenborough

Fractionation of stable carbon isotopes during acetate consumption by methanogenic and sulfidogenic microbial communities in rice paddy soils and lake sediments

Abstract. Acetate is an important intermediate during the degradation of organic matter in anoxic flooded soils and sediments. Acetate is disproportionated to CH4 and CO2 by methanogenic or is oxidized to CO2 by sulfate-reducing microorganisms. These reactions result in carbon isotope fractionation, depending on the microbial species and their particular carbon metabolism. To learn more about the magnitude of the isotopic enrichment factors (ε) involved, acetate conversion to CH4 and CO2 was measured in anoxic paddy soils from Vercelli (Italy) and the International Rice Research Institute (IRRI, the Philippines) and in anoxic lake sediments from the northeastern and the southwestern basins of Lake Fuchskuhle (Germany). Acetate consumption was measured using samples of paddy soil or lake sediment suspended in water or in phosphate buffer (pH 7.0), both in the absence and presence of sulfate (gypsum), and of methyl fluoride (CH3F), an inhibitor of aceticlastic methanogenesis. Under methanogenic conditions, values of εac for acetate consumption were always in a range of −21 ‰ to −17 ‰ but higher in the lake sediment from the southwestern basin (−11 ‰). Under sulfidogenic conditions εac values tended to be slightly lower (−26 ‰ to −19 ‰), especially when aceticlastic methanogenesis was inhibited. Again, εac in the lake sediment of the southwestern basin was higher (−18 ‰ to −14 ‰). Determination of εCH4 from the accumulation of 13C in CH4 resulted in much lower values (−37 ‰ to −27 ‰) than from the depletion of 13C in acetate (−21 ‰ to −17 ‰ ), especially when acetate degradation was measured in buffer suspensions. The microbial communities were characterized by sequencing the bacterial 16S rRNA (ribosomal ribonucleic acid) genes as well as the methanogenic mcrA and sulfidogenic dsrB genes. The microbial communities were quite different between lake sediments and paddy soils but were similar in the sediments of the two lake basins and in the soils from Vercelli and the IRRI, and they were similar after preincubation without and with addition of sulfate (gypsum). The different microbial compositions could hardly serve for the prediction of the magnitude of enrichment factors.

Methane in Lakes: Variability in Stable Carbon Isotopic Composition and the Potential Importance of Groundwater Input

Methane (CH4) is an important component of the carbon (C) cycling in lakes. CH4 production enables carbon in sediments to be either reintroduced to the food web via CH4 oxidation or emitted as a greenhouse gas making lakes one of the largest natural sources of atmospheric CH4. Large stable carbon isotopic fractionation during CH4 oxidation makes changes in 13C:12C ratio (δ13C) a powerful and widely used tool to determine the extent to which lake CH4 is oxidized, rather than emitted. This relies on correct δ13C values of original CH4 sources, the variability of which has rarely been investigated systematically in lakes. In this study, we measured δ13C in CH4 bubbles in littoral sediments and in CH4 dissolved in the anoxic hypolimnion of six boreal lakes with different characteristics. The results indicate that δ13C of CH4 sources is consistently higher (less 13C depletion) in littoral sediments than in deep waters across boreal and subarctic lakes. Variability in organic matter substrates across depths is a potential explanation. In one of the studied lakes available data from nearby soils showed correspondence between δ13C-CH4 in groundwater and deep lake water, and input from the catchment of CH4via groundwater exceeded atmospheric CH4 emissions tenfold over a period of 1 month. It indicates that lateral hydrological transport of CH4 can explain the observed δ13C-CH4 patterns and be important for lake CH4 cycling. Our results have important consequences for modelling and process assessments relative to lake CH4 using δ13C, including for CH4 oxidation, which is a key regulator of lake CH4 emissions.

Isotope fractionation (δ13C, δ15N) and microbial community response in degradation of petroleum hydrocarbons by biostimulation in contaminated soil.

This study investigated the isotope effects of δ13C and δ15N and microbial response during biodegradation of hydrocarbons by biostimulation with nitrate or compost in the petroleum-contaminated soil. Compost and KNO3 amendments promoted the total petroleum hydrocarbon (TPH) removal accompanied by a significant increase of Actinobacteria and Firmicutes phyla. Soil alpha diversity decreased after 90 days of biostimulation. An inverse significant carbon isotope effect (εc = 16.6 ± 0.8‰) and strong significant nitrogen isotope effect (εN = -24.20 ± 9.54‰) were shown by the KNO3 supplementation. For compost amendment, significant carbon and nitrogen isotope effect were εc = 38.8 ± 1.1‰ and εN = -79.49 ± 16.41‰, respectively. A clear difference of the carbon and nitrogen stable isotope fractionation was evident by KNO3 or compost amendment, which indicated that the mechanisms of petroleum degradation by adding compost or KNO3 may be different.

Seasonal changes in stable carbon isotopic composition in the bulk aerosol and gas phases at a suburban site in Prague

Isotope fractionation between the gas and aerosol phases is an important phenomenon for studying atmospheric processes. Here, for the first time, seasonally resolved stable carbon isotope ratio (δ13C) values are systematically used to study phase interactions in bulk aerosol and gaseous carbonaceous samples. Seasonal variations in the δ13C of total carbon (TC; δ13CTC) and water-soluble organic carbon (WSOC; δ13CWSOC) in fine aerosol particles (PM2.5) as well as in the total carbon of part of the gas phase (TCgas; δ13CTCgas) were studied at a suburban site in Prague, Czech Republic, Central Europe. Year-round samples were collected for the main and backup filters from 14 April 2016 to 1 May 2017 every 6 days with a 48 h sampling period (n = 66). During all seasons, the highest 13C enrichment was found in WSOC, followed by particulate TC, whereas the highest 13C depletion was found in gaseous TC. We observed a clear seasonal pattern for all δ13C, with the highest values in winter (avg. δ13CTC = −25.5 ± 0.8‰, δ13CWSOC = −25.0 ± 0.7‰, δ13CTCgas = −27.7 ± 0.5‰) and the lowest values in summer (avg. δ13CTC = −27.2 ± 0.5‰, δ13CWSOC = −26.4 ± 0.3‰, δ13CTCgas = −28.9 ± 0.3‰). This study supports the existence of different aerosol sources at the site during the year. Despite the different seasonal compositions of carbonaceous aerosols, the isotope difference (Δδ13C) between δ13CTC (aerosol) and δ13CTCgas (gas phase) was similar during the seasons (year avg. 1.97 ± 0.50‰). Moreover, Δδ13C between WSOC and TC in PM2.5 showed a difference between spring and winter, but in general, these values were also similar year-round (year avg. 0.71 ± 0.37‰). During the entire period, TCgas and WSOC were the most 13C-depleted and most 13C-enriched fractions, respectively, and although the resulting difference Δ(δ13CWSOC − δ13CTCgas) was significant, it was almost invariant throughout the year (2.67 ± 0.44‰). The present study suggests that the stable carbon isotopic fractionation between the bulk aerosol and gas phases is probably not entirely dependent on the chemical composition of individual carbonaceous compounds from different sources.

Carbon, hydrogen and nitrogen stable isotope fractionation allow characterizing the reaction mechanisms of 1H-benzotriazole aqueous phototransformation

1H-benzotriazole is part of a larger family of benzotriazoles, which are widely used as lubricants, polymer stabilizers, corrosion inhibitors, and anti-icing fluid components. It is frequently detected in urban runoff, wastewater, and receiving aquatic environments. 1H-benzotriazole is typically resistant to biodegradation and hydrolysis, but can be transformed via direct photolysis and photoinduced mechanisms. In this study, the phototransformation mechanisms of 1H-benzotriazole were characterized using multi-element compound-specific isotope analysis (CSIA). The kinetics, transformation products, and isotope fractionation results altogether revealed that 1H-benzotriazole direct photolysis and indirect photolysis induced by OH radicals involved two alternative pathways. In indirect photolysis, aromatic hydroxylation dominated and was associated with small carbon (εC = -0.65 ± 0.03‰), moderate hydrogen (εH = -21.6‰), and negligible nitrogen isotope enrichment factors and led to hydroxylated forms of benzotriazole. In direct photolysis of 1H-benzotriazole, significant nitrogen (εN = -8.4 ± 0.4 to -4.2 ± 0.3‰) and carbon (εC = -4.3 ± 0.2 to -1.64 ± 0.04‰) isotope enrichment factors indicated an initial N-N bond cleavage followed by nitrogen elimination with a C-N bond cleavage. The results of this study highlight the potential for multi-element CSIA application to track 1H-benzotriazole degradation in aquatic environments.

Stable carbon isotope fractionation of fatty acid in sea cucumber (Apostichopus japonicus): insights from an experimental study

ABSTRACT Isotope fractionation of fatty acids can reflect the metabolic pathway of fatty acids in organisms, but few studies have been conducted. In this study, stable carbon isotope fractionation of fatty acids in sea cucumber (Apostichopus japonicus) was conducted by feeding experiments of comparing the fatty acid profile and δ13C of fatty acids in body wall to diet. The results showed that the fractionation of δ13C of fatty acids in A. japonicus was −1.588–7.403‰. The fractionation of δ13C of saturated fatty acids (SFAs), monounsaturated fatty acids (MUFAs), and polyunsaturated fatty acids (PUFAs) was 1.098–7.403‰, −1.588–2.778‰, and −1.559–5.614‰, respectively. The degree of fractionation of δ13C of SFAs was greater than that of unsaturated fatty acids (UFAs). We simulated the possible metabolic process of fatty acids in A. japonicus based on fatty acid profile and δ13C of fatty acids, indicating that the combination of these two methods could be potentially used in the study of fatty acid metabolism in marine benthic animal of A. japonicus. Our finding provides a new technique for the metabolic pathways of biomolecules in organisms.

Fatty acids stable carbon isotope fractionation in the bovine organism. A compound-specific isotope analysis through gas chromatography combustion isotope ratio mass spectrometry

The contribution of dietary fatty acids to the quality of the meat and their path through the bovine organism is currently the subject of a lot of research. Stable isotope ratio analysis represents a powerful tool for this aim, one that has not been studied in depth yet. In this work, for the first time, the carbon isotopic ratios of six fatty acids (myristic 14:0, palmitic 16:0, stearic 18:0, oleic 18:1n-9, linoleic 18:2n-6 and linolenic 18:3n-3 acids) in different matrixes (diet, rumen, duodenal content, liver and loin) were analysed through gas chromatography combustion isotope ratio mass spectrometry. Moreover, the quantification of the single fatty acids was carried out, providing important information supporting the carbon isotopic ratio results. The variation in the concentration of the fatty acids in the different matrices depends on the chemical modifications they undergo in the sequential steps of the metabolic path. GC-C-IRMS turned out to be a powerful tool to investigate the fate of dietary fatty acids, providing information about the processes they undergo inside the bovine organism.

Reductive debromination by sponge-associated anaerobic bacteria coupled to carbon isotope fractionation

Marine sponges contain diverse brominated compounds as secondary metabolites and the sponge habitat appears to enrich for a population of anaerobic dehalogenating bacteria. Hence, there is interest in understanding how these natural and anthropogenic compounds are degraded in the marine environment. Compound specific isotope analysis (CSIA) is a useful tool to monitor and to quantify the degradation and fate of aquatic pollutants. The objective of this study was to evaluate whether reductive dehalogenation of brominated phenols by sponge-associated bacteria, including Desulfoluna spongiiphila, can be monitored by CSIA. Debromination of 2,6-dibromophenol to phenol by sponge-associated cultures resulted in measurable stable carbon isotope fractionation. All sponge-associated cultures showed similar isotopic enrichment factors (ε). The ε values for two independent sponge-derived dehalogenating cultures were −3.1 ± 1.5‰, and −3.0 ± 0.3‰, and that of sponge associated sediment cultures −2.0 ± 0.3‰. Thus, we demonstrate that reductive debromination of 2,6-dibromophenol resulted in measurable carbon isotope fractionation and that CSIA can be used to assess reductive debromination and to monitor and estimate in vivo dehalogenation in a sponge animal.

Algal biomarkers as a proxy for pCO2: Constraints from late quaternary sapropels in the eastern Mediterranean

Records of carbon dioxide concentrations (partial pressure expressed as pCO2) over Earth’s history provide trends that are critical to understand our changing world. To better constrain pCO2 estimations, here we test organic pCO2 proxies against the direct measurements of pCO2 recorded in ice cores. Based on the concept of stable carbon isotopic fractionation due to photosynthetic CO2 fixation (Ɛp), we use the stable carbon isotopic composition (δ13C) of the recently proposed biomarker phytol (from all photoautotrophs), as well as the conventionally used alkenone biomarkers (from specific species) for comparison, to reconstruct pCO2 over several Quaternary sapropel formation periods (S1, S3, S4, and S5) in the eastern Mediterranean Sea. The reconstructed pCO2 values are within error of the ice core values but consistently exceed the ice core values by ca. 100 µatm. This offset corresponds with atmospheric disequilibrium of present day CO2[aq] concentrations in the Mediterranean Sea from global pCO2, equivalent to ca. 100 µatm, although pCO2 estimates derived from individual horizons within each sapropel do not covary with the ice core values. This may possibly be due to greater variability in local CO2[aq] concentration changes in the Mediterranean, as compared with the global average pCO2, or possibly due to biases in the proxy, such as variable growth rate or carbon-concentrating mechanisms. Thus, the offset is likely a combination of physiological or environmental factors. Nevertheless, our results demonstrate that alkenone- and phytol-based pCO2 proxies yield statistically similar estimations (P-value = 0.02, Pearson’s r-value = 0.56), and yield reasonable absolute estimations although with relatively large uncertainties (±100 µatm).

Carbonization of Carbonates and Fractionation of Stable Carbon Isotopes in a Dynamic Slip Zone

Data obtained on carbonates and metaterrigenous rocks of the Devonian complex of the Sultan-Uizdag Range, northwestern Uzbekistan, which are carbonized in local deformation zones, are used in a generalized interpretation of the genesis of carbonaceous matter by means of decomposition of carbonates under the effect of seismogenic movements. The release of free carbon is facilitated by synchronous Fe–Mg metasomatism and by the reducing conditions in the presence of hydrogen. Based on literature data on experimental modeling of carbonization processes at high-speed shear deformations of carbonates in a hydrogen medium, a possible scenario is considered for the generation of hydrogen on the surfaces of quartz dislocations in the presence of water in metaterrigenous rocks in association with carbonates. The variation of carbon isotope composition over the volume of the carbonate and terrigenous rocks is extremely heterogeneous, with the 13C isotope enriched in the fracture zones and 12C enriched in the near-fracture volumes of decompression-damaged rocks. It is hypothesized that deformations can affect the fractionation of stable carbon isotopes. With regard for literature data, it is demonstrated that isotope exchange can proceed between the free carbon and carbonate carbon. Various aspects are discussed of the influence of mineral-phase and structural–textural transformations of carbonate rocks at their thermomechanical decomposition under shearing on the geomechanical behavior of the fracture, manifestations of mechanical instability in it, and causes of frictional weakening.

Inorganic carbon uptake strategies in coralline algae: Plasticity across evolutionary lineages under ocean acidification and warming

Dissolved inorganic carbon (DIC) assimilation is essential to the reef-building capacity of crustose coralline algae (CCA). Little is known, however, about the DIC uptake strategies and their potential plasticity under ongoing ocean acidification (OA) and warming. The persistence of CCA lineages throughout historical oscillations of pCO2 and temperature suggests that evolutionary history may play a role in selecting for adaptive traits. We evaluated the effects of pCO2 and temperature on the plasticity of DIC uptake strategies and associated energetic consequences in reef-building CCA from different evolutionary lineages. We simulated past, present, moderate (IPCC RCP 6.0) and high pCO2 (RCP 8.5) and present and high (RCP 8.5) temperature conditions and quantified stable carbon isotope fractionation (13ε), organic carbon content, growth and photochemical efficiency. All investigated CCA species possess CO2-concentrating mechanisms (CCMs) and assimilate CO2 via diffusion to varying degrees. Under OA and warming, CCA either increased or maintained CCM capacity, which was associated with overall neutral effects on metabolic performance. More basal taxa, Sporolithales and Hapalidiales, had greater capacity for diffusive CO2 use than Corallinales. We suggest that CCMs are an adaptation that supports a robust carbon physiology and are likely responsible for the endurance of CCA in historically changing oceans.

Carbon nanotubes accelerate acetoclastic methanogenesis: From pure cultures to anaerobic soils

Direct interspecies electron transfer (DIET) between electricigens and methanogens has been shown to favour CO2 reduction to produce biomethane. Furthermore, DIET is accelerated by conductive materials. However, whether conductive materials can promote other methanogenic pathways is unclear due to a lack of detailed experimental data and the poor mechanistic studies. Here, we hypothesized that conductive carbon nanotubes (CNTs) stimulate acetoclastic methanogenesis independently of electricigens in pure cultures of Methanosarcina spp. and anaerobic wetland soil. We found a significant increase in the methane production rate during the growth phase, e.g. from 0.169 mM to 0.241 mM after addition of CNTs on the 3rd day. CNTs did not increase the abundance of electromicroorganisms or the electron transfer rate in anaerobic soils, using via microbial diversity and electrochemical analysis. 13C–CH3COOH labelling, stable carbon isotope fractionation and the CH3F inhibitor of acetoclastic methanogenesis were used to distinguish methanogenic pathways. CNTs mainly accelerated acetoclastic methanogenesis rather than CO2 reduction in both pure cultures and anaerobic soils. Furthermore, the presence of CNTs slightly alleviate the inhibition of CH3F on acetoclastic methanogenesis during the pure culture of Methanosarcina barkeri and Methanosarcina mazei with the production of more than 0.3 mM methane. CNTs closely attached to the cell surface were observed by transmission electron microscopy. Proteome analysis revealed a stimulation of protein synthesis with about twice the improvement involved in –COOH oxidation and electron transfer. Overall, our findings demonstrate that conducting CNTs favor methane production and that the mechanism involved is acetoclastic methanogenesis via acetate dismutation, at least partly, rather than classical CO2 reduction.

Testing algal-based pCO2 proxies at a modern CO2 seep (Vulcano, Italy)

Understanding long-term trends in atmospheric concentrations of carbon dioxide (pCO2) has become increasingly relevant as modern concentrations surpass recent historic trends. One method for estimating past pCO2, the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) has shown promise over the past several decades, in particular using species-specific biomarker lipids such as alkenones. Recently, the Ɛp of more general biomarker lipids, organic compounds derived from a multitude of species, have been applied to generate longer-spanning, more ubiquitous records than those of alkenones but the sensitivity of this proxy to changes in pCO2 has not been constrained in modern settings. Here, we test Ɛp using a variety of general biomarkers along a transect taken from a naturally occurring marine CO2 seep in Levante Bay of the Aeolian island of Vulcano in Italy. The studied general biomarkers, loliolide, cholesterol, and phytol, all show increasing depletion in 13C over the transect from the control site towards the seep, suggesting that CO2 exerts a strong control on isotopic fractionation in natural phytoplankton communities. The strongest shift in fractionation was seen in phytol, and pCO2 estimates derived from phytol confirm the utility of this biomarker as a proxy for pCO2 reconstruction.

Tracing the sources and microbial degradation of PCBs in field sediments by a multiple-line-of-evidence approach including compound-specific stable isotope analysis

Comprehensive monitoring is crucial for tracing micropollutants in the natural environment. To better evaluate the sources and natural attenuation of polychlorinated biphenyls (PCBs), three composite sediment cores were sampled from a closed pond near e-waste recycling plants, and a multiple-line-of-evidence approach (MLEA) including quantification, enantiomer analysis, microbial community profiling, and compound-specific isotope analysis (CSIA) was used to investigate the fate of PCBs in sediment cores. The difference in the maximum PCB concentrations and associated depths between sites 1/2 and 3 and the corresponding significant (p < 0.01) difference in δ13C values strongly indicated two different PCB inputs at sites 1/2 and 3. A significant (p < 0.01) negative correlation between the variation in chlorine per biphenyl (CPB) and Log the abundance of Dehalococcoides/total molar concentration of PCBs (Log Dhc/TPCB) along the cores suggested that different degrees of PCB degradation occurred and that Dehalococcoides likely participated in PCB degradation in these sediments. Nonracemic compositions and pronounced stable carbon isotope fractionation (Δδ13C > 1‰) of PCB congeners were observed, confirming that in situ degradation occurred in the sediment cores. The progressive enrichment in 13C with increasing core depth suggested strengthened microbial degradation of the residual congener pools. The results of this study suggested that MLEA analysis of PCBs can provide reliable information to better monitor the sources and fate of these compounds in the environment.

Tracking photodegradation products and bond-cleavage reaction pathways of triclosan using ultra-high resolution mass spectrometry and stable carbon isotope analysis

Triclosan (TCS) is an antimicrobial compound ubiquitously found in surface waters throughout the world. Although several studies have focused on the photochemical degradation of TCS, there is still limited knowledge about its environmental fate. In this study, we got molecular-level insights into the photochemical degradation of TCS. Significant stable carbon isotope fractionation was observed during photodegradation; different bond-cleavage reaction pathways under different photolytic conditions were characterized, using compound specific isotope analysis (CSIA). Photochemical modeling of TCS photodegradation showed that direct photolysis would be the main transformation pathway if pH > 7, even in presence of dissolved organic matter. Moreover, by use of ultrahigh resolution mass spectrometry, FT-ICR-MS, a broad and complex spectrum of organic by-products (some of which potentially toxic, as assessed by a quantitative structure-activity relationship approach) were identified. A detailed reaction mechanism was developed on the basis of the detected compounds. A possible sequence of steps leading to some of the detected product compounds in aqueous solution is suggested.

Electrolytic groundwater circulation well for trichloroethylene degradation in a simulated aquifer

An in situ groundwater remediation process, termed EGCW, was developed in this study by integrating in-well groundwater electrolysis into groundwater circulation well. Groundwater circulation carries electrolytically generated O2 and H2 into the impacted aquifer for in situ biodegradation of contaminants. In a two-dimensional tank filled with field sandy sediments, simulated trichloroethylene (TCE)-contaminated groundwater was circulated between an injection well with electrodes inside and a pumping well. Results from a 50-day EGCW experiment show that in-well electrolysis oxygenated most region near the injection well, and 10 mg/L TCE was mainly biodegraded aerobically to about 2.7 mg/L (73% removal) by the indigenous microbes. Aerobic TCE degradation was enhanced by the pulsed addition of acetate. Together with the proofs of stable carbon isotope fractionation (enrichment factor: −0.57‰–−1.53‰) and microbial community variation after EGCW treatment, aerobic cometabolism was proposed to be the most likely mechanism for TCE degradation. It is interesting to find that the intrinsic organic carbon in aquifer matrix could fuel the aerobic TCE degradation, particularly at low TCE concentrations. EGCW treatment is advantageous in terms of supplying appropriate dosages of electron acceptor (O2) and donor (H2) for in situ bioremediation because groundwater electrolysis and circulation are expedient and controllable.

Effect of water accommodated fractions of fuel oil on fixed carbon and nitrogen by microalgae: Implication by stable isotope analysis.

Effect of water accommodated fractions (WAF) of #180 fuel oil on fixed carbon and nitrogen in microalgae was studied by stable isotopes. Platymonas helgolandica, Heterosigma akashiwo and Nitzschia closterium were exposed to five WAF concentrations for 96h. The δ13C value of microalgae was significantly lower than that of the control group, indicated that carbon was limited in the WAF concentrations. The δ13C value of microalgae appeared peak valley at 48h in control group, corresponding to the enhanced capacity in carbon fixation during microalgae photosynthesis. The physiological acclimation capacity of microalgae was revealed by the occurrence time when the δ13C value was in peak valley, and thus the physiological acclimation capacity of microalgae decreased in the order of Nitzschia closterium>Heterosigma akashiwo>Platymonas helgolandica. Principal component analysis (PCA) were applied to the δ13C value in order to verify the "hormesis" phenomenon in microalgae. The δ13C value could discriminate between stimulatory effects at low doses and inhibitory effects at high doses. In addition, the present study also investigated the effect of the nitrogen on microalgae growth. Because microalgae could still absorb the NO3-N and release of NO2-N and NH4-N in present study, the nitrogen cycle in microalgae was in the equilibrium status. The δ15N value in microalgae exhibited no obvious change with the increasing of WAF concentrations at the same time. However, due to the enrichment of nitrogen, the δ15N value first increased gradually with the time and finally was stable. Overall, the fractionation of carbon and nitrogen stable isotopes illustrated that the effect of carbon on the growth of microalgae was more prominent than nitrogen. Stable isotopes was used to investigate the influence of WAF on fixed carbon and nitrogen in microalgae growth, providing a fundamental theoretical guidance for risk assessment of marine ecological environment.