scholarly journals Isotope Fractionation of Toluene: A Perspective to Characterise MicrobialIn SituDegradation

2002 ◽  
Vol 2 ◽  
pp. 1227-1234 ◽  
Author(s):  
H.H. Richnow ◽  
A. Vieth ◽  
M. Kastner ◽  
M. Gehre ◽  
R.U. Meckenstock

A concept to assessin situbiodegradation of organic contaminants in aquifers is presented. The alteration of the carbon isotope composition of contaminants along the groundwater flow path indicates microbial degradation processes and can be used as an indicator forin situbiodegradation. The Rayleigh equation was applied to calculate the percentage of thein situbiodegradation (B[%]) using the change in the isotopic composition of contaminants (Rt/R0) along the ground water flow path and a kinetic carbon isotope fractionation factor (αC) derived from defined biodegradation experiments in the laboratory. When the groundwater hydrology is known and a representative source concentration (C0) for a groundwater flow path can be determined, the extent ofin situbiodegradation can be quantified.

2004 ◽  
Vol 70 (5) ◽  
pp. 2935-2940 ◽  
Author(s):  
Barbara Morasch ◽  
Hans H. Richnow ◽  
Andrea Vieth ◽  
Bernhard Schink ◽  
Rainer U. Meckenstock

ABSTRACT Stable isotope fractionation was studied during the degradation of m-xylene, o-xylene, m-cresol, and p-cresol with two pure cultures of sulfate-reducing bacteria. Degradation of all four compounds is initiated by a fumarate addition reaction by a glycyl radical enzyme, analogous to the well-studied benzylsuccinate synthase reaction in toluene degradation. The extent of stable carbon isotope fractionation caused by these radical-type reactions was between enrichment factors (ε) of −1.5 and −3.9, which is in the same order of magnitude as data provided before for anaerobic toluene degradation. Based on our results, an analysis of isotope fractionation should be applicable for the evaluation of in situ bioremediation of all contaminants degraded by glycyl radical enzyme mechanisms that are smaller than 14 carbon atoms. In order to compare carbon isotope fractionations upon the degradation of various substrates whose numbers of carbon atoms differ, intrinsic ε (εintrinsic) were calculated. A comparison of εintrinsic at the single carbon atoms of the molecule where the benzylsuccinate synthase reaction took place with compound-specific ε elucidated that both varied on average to the same extent. Despite variations during the degradation of different substrates, the range of ε found for glycyl radical reactions was reasonably narrow to propose that rough estimates of biodegradation in situ might be given by using an average ε if no fractionation factor is available for single compounds.


Minerals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 208
Author(s):  
Takuma Hasegawa ◽  
Kotaro Nakata ◽  
Rhys Gwynne

For radioactive waste disposal, it is important that local groundwater flow is slow as groundwater flow is the main transport medium for radioactive nuclides in geological formations. When the groundwater flow is very slow, diffusion is the dominant transport mechanism (diffusion-dominant domain). Key pieces of evidence indicating a diffusion-dominant domain are the separation of components and the fractionation of isotopes by diffusion. To prove this, it is necessary to investigate the different diffusion coefficients for each component and the related stable isotope fractionation factors. Thus, in this study, through-diffusion and effective-porosity experiments were conducted on selected artificial materials and natural rocks. We also undertook measurements relating to the isotope fractionation factors of Cl and Br isotopes for natural samples. For natural rock samples, the diffusion coefficients of water isotopes (HDO and H218O) were three to four times higher than those of monovalent anions (Cl−, Br- and NO3−), and the isotope fractionation factor of 37Cl (1.0017–1.0021) was slightly higher than that of free water. It was experimentally confirmed that the isotope fractionation factor of 81Br was approximately 1.0007–1.0010, which is equivalent to that of free water. The enrichment factor of 81Br was almost half that of 37Cl. The effective porosity ratios of HDO and Cl were slightly different, but the difference was not significant compared to the ratio of their diffusion coefficients. As a result, component separation was dominated by diffusion. For artificial samples, the diffusion coefficients and effective porosities of HDO and Cl were almost the same; it was thus difficult to assess the component separation by diffusion. However, isotope fractionation of Cl and Br was confirmed using a through-diffusion experiment. The results show that HDO and Cl separation and isotope fractionation of Cl and Br can be expected in diffusion-dominant domains in geological formations.


2003 ◽  
Vol 81 (5) ◽  
pp. 871-876 ◽  
Author(s):  
Matt Sponheimer ◽  
Todd Robinson ◽  
Linda Ayliffe ◽  
Ben Passey ◽  
Beverly Roeder ◽  
...  

The carbon-isotope composition of hair and feces offers a glimpse into the diets of mammalian herbivores. It is particularly useful for determining the relative consumption of browse and graze in tropical environments, as these foods have strongly divergent carbon-isotope compositions. Fecal δ13C values reflect the last few days consumption, whereas hair provides longer term dietary information. Previous studies have shown, however, that some fractionation occurs between dietary δ13C values and those of hair and feces. Accurate dietary reconstruction requires an understanding of these fractionations, but few controlled-feeding studies have been undertaken to investigate these fractionations in any mammalian taxa, fewer still in large mammalian herbivores. Here, we present data from the first study of carbon-isotope fractionation between diet, hair, and feces in multiple herbivore taxa. All taxa were fed pure alfalfa (Medicago sativa) diets for a minimum period of 6 months, at which point recently grown hair was shaved and analyzed for carbon isotopes. The mean observed diet–hair fractionation was +3.2‰, with a range of +2.7 to +3.5‰. We also examined diet–feces fractionation for herbivores on alfalfa and bermudagrass (Cynodon dactylon) feeds. The mean diet–feces fractionation for both diets was –0.8‰, with less fractionation for alfalfa (–0.6‰) than bermudagrass (–1.0‰). Fecal carbon turnover also varies greatly between taxa. When diets were switched, horse (Equus caballus) feces reflected the new diet within 60 h, but alpaca (Lama pacos) feces did not equilibrate with the new diet for nearly 200 h. Thus, fecal carbon isotopes provide far greater dietary resolution for hindgut-fermenting horses than foregut-fermenting alpacas.


2019 ◽  
Vol 15 (2) ◽  
pp. 635-646 ◽  
Author(s):  
Holly L. Taylor ◽  
Isaac J. Kell Duivestein ◽  
Juraj Farkas ◽  
Martin Dietzel ◽  
Anthony Dosseto

Abstract. Lithium (Li) isotopes in marine carbonates have considerable potential as a proxy to constrain past changes in silicate weathering fluxes and improve our understanding of Earth's climate. To date the majority of Li isotope studies on marine carbonates have focussed on calcium carbonates. The determination of the Li isotope fractionation between dolomite and a dolomitizing fluid would allow us to extend investigations to deep times (i.e. Precambrian) when dolostones were the most abundant marine carbonate archives. Dolostones often contain a significant proportion of detrital silicate material, which dominates the Li budget; thus, pretreatment needs to be designed so that only the isotope composition of the carbonate-associated Li is measured. This study aims to serve two main goals: (1) to determine the Li isotope fractionation between Ca–Mg carbonates and solution, and (2) to develop a method for leaching the carbonate-associated Li out of dolostone while not affecting the Li contained within the detrital portion of the rock. We synthesized Ca–Mg carbonates at high temperatures (150 to 220 ∘C) and measured the Li isotope composition (δ7Li) of the precipitated solids and their respective reactive solutions. The relationship of the Li isotope fractionation factor with temperature was obtained: 103ln⁡αprec-sol=-(2.56±0.27)106(1)/T2+(5.8±1.3) Competitive nucleation and growth between dolomite and magnesite were observed during the experiments; however, there was no notable effect of their relative proportion on the apparent Li isotope fractionation. We found that Li isotope fractionation between the precipitated solid and solution is higher for Ca–Mg carbonates than for Ca carbonates. If the temperature of a precipitating solution is known or can be estimated independently, the above equation could be used in conjunction with the Li isotope composition of dolostones to derive the composition of the solution and hence make inferences about the past Li cycle. In addition, we also conducted leaching experiments on a Neoproterozoic dolostone and a Holocene coral. Results show that leaching with 0.05 M hydrochloric acid (HCl) or 0.5 % acetic acid (HAc) at room temperature for 60 min releases Li from the carbonate fraction without a significant contribution of Li from the siliciclastic detrital component. These experimental and analytical developments provide a basis for the use of Li isotopes in dolostones as a palaeo-environmental proxy, which will contribute to further advance our understanding of the evolution of Earth's surface environments.


2011 ◽  
Vol 8 (9) ◽  
pp. 2437-2459 ◽  
Author(s):  
C. Werner ◽  
A. Gessler

Abstract. Recent advances have improved our methodological approaches and theoretical understanding of post-photosynthetic carbon isotope fractionation processes. Nevertheless we still lack a clear picture of the origin of short-term variability in δ13C of respired CO2 (δ13Cres) and organic carbon fractions on a diel basis. Closing this knowledge gap is essential for the application of stable isotope approaches for partitioning ecosystem respiration, tracing carbon flow through plants and ecosystems and disentangling key physiological processes in carbon metabolism of plants. In this review we examine the short-term dynamics in δ13Cres and putative substrate pools at the plant, soil and ecosystem scales and discuss mechanisms, which might drive diel δ13Cres dynamics at each scale. Maximum reported variation in diel δ13Cres is 4.0, 5.4 and 14.8 ‰ in trunks, roots and leaves of different species and 12.5 and 8.1 ‰ at the soil and ecosystem scale in different biomes. Temporal variation in post-photosynthetic isotope fractionation related to changes in carbon allocation to different metabolic pathways is the most plausible mechanistic explanation for observed diel dynamics in δ13Cres. In addition, mixing of component fluxes with different temporal dynamics and isotopic compositions add to the δ13Cres variation on the soil and ecosystem level. Understanding short-term variations in δ13Cres is particularly important for ecosystem studies, since δ13Cres contains information on the fate of respiratory substrates, and may, therefore, provide a non-intrusive way to identify changes in carbon allocation patterns.


2007 ◽  
Vol 4 (6) ◽  
pp. 4653-4696 ◽  
Author(s):  
I. Tolosa ◽  
J.-C. Miquel ◽  
B. Gasser ◽  
P. Raimbault ◽  
L. Azouzi ◽  
...  

Abstract. The distribution of lipid biomarkers and their carbon isotope composition was investigated on suspended particles from different contrasting trophic environments at six sites in the South East Pacific. High algal biomass with diatom-related lipids was characteristic in the upwelling zone, whereas haptophyte lipids were proportionally most abundant in the nutrient-poor settings of the centre of the South Pacific Gyre and on its easter edge. Dinoflagellate–sterols were minor contributors in all of the studied area and cyanobacteria-hydrocarbons were at maximum in the high nutrient low chlorophyll regime of the subequatorial waters at near the Marquesas archipelago. The taxonomic and spatial variability of the relationships between carbon photosynthetic fractionation and environmental conditions for four specific algal taxa (diatoms, haptophytes, dinoflagellates and cyanobacteria) was also investigated. The carbon isotope fractionation factor (εp) of the diatom marker varied over a range of 16‰ along the different trophic systems. In contrast, εp of dinoflagellate, cyanobacteria and alkenone markers varied only by 7–10‰. The low fractionation factors and small variations between the different phytoplankton markers measured in the upwelling area likely reveals uniformly high specific growth rates within the four phytoplankton taxa, and/or that transport of inorganic carbon into phytoplankton cells may not only occur by diffusion but by other carbon concentrating mechanisms (CCM). In contrast, in the oligotrophic zone, i.e. gyre and eastgyre, relatively high εp values, especially for the diatom marker, indicate diffusive CO2 uptake by the eukaryotic phytoplankton. At these nutrient-poor sites, the lowest εp values for haptophytes, dinoflagellates and cyanobacteria infer higher growth rates compared to diatoms.


2008 ◽  
Vol 5 (3) ◽  
pp. 949-968 ◽  
Author(s):  
I. Tolosa ◽  
J.-C. Miquel ◽  
B. Gasser ◽  
P. Raimbault ◽  
C. Goyet ◽  
...  

Abstract. The distribution of lipid biomarkers and their stable carbon isotope composition was investigated on suspended particles from different contrasting trophic environments at six sites in the South East Pacific. High algal biomass with diatom-related lipids (24-methylcholesta-5,24(28)-dien-3β-ol, C25 HBI alkenes, C16:4 FA, C20:5 FA) was characteristic in the upwelling zone, whereas haptophyte lipids (long-chain (C37-C39) unsaturated ketones) were proportionally most abundant in the nutrient-poor settings of the centre of the South Pacific Gyre and on its easter edge. The dinoflagellate–sterol, 4α-23,24-trimethylcholest-22(E)-en-3β-ol, was a minor contributor in all of the studied area and the cyanobacteria-hydrocarbon, C17n-alkane, was at maximum in the high nutrient low chlorophyll regime of the subequatorial waters near the Marquesas archipelago. The taxonomic and spatial variability of the relationships between carbon photosynthetic fractionation and environmental conditions for four specific algal taxa (diatoms, haptophytes, dinoflagellates and cyanobacteria) was also investigated. The carbon isotope fractionation factor (εp) of the 24-methylcholesta-5,24(28)-dien-3β-ol diatom marker, varied over a range of 16% along the different trophic systems. In contrast, εp of dinoflagellate, cyanobacteria and alkenone markers varied only by 7–10‰. The low fractionation factors and small variations between the different phytoplankton markers measured in the upwelling area likely reveals uniformly high specific growth rates within the four phytoplankton taxa, and/or that transport of inorganic carbon into phytoplankton cells may not only occur by diffusion but also by other carbon concentrating mechanisms (CCM). In contrast, in the oligotrophic zone, i.e. gyre and eastgyre, relatively high εp values, especially for the diatom marker, indicate diffusive CO2 uptake by the eukaryotic phytoplankton. At these nutrient-poor sites, the lower εp values for haptophytes, dinoflagellates and cyanobacteria indicate higher growth rates or major differences on the carbon uptake mechanisms compared to diatoms.


2012 ◽  
Vol 9 (3) ◽  
pp. 1217-1224 ◽  
Author(s):  
D. R. Griffith ◽  
A. P. McNichol ◽  
L. Xu ◽  
F. A. McLaughlin ◽  
R. W. Macdonald ◽  
...  

Abstract. Arctic warming is projected to continue throughout the coming century. Yet, our currently limited understanding of the Arctic Ocean carbon cycle hinders our ability to predict how changing conditions will affect local Arctic ecosystems, regional carbon budgets, and global climate. We present here the first set of concurrent, full-depth, dual-isotope profiles for dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and suspended particulate organic carbon (POCsusp) at two sites in the Canada Basin of the Arctic Ocean. The carbon isotope composition of sinking and suspended POC in the Arctic contrasts strongly with open ocean Atlantic and Pacific sites, pointing to a combination of inputs to Arctic POCsusp at depth, including surface-derived organic carbon (OC), sorbed/advected OC, and OC derived from in situ DIC fixation. The latter process appears to be particularly important at intermediate depths, where mass balance calculations suggest that OC derived from in situ DIC fixation contributes up to 22% of POCsusp. As in other oceans, surface-derived OC is still a dominant source to Arctic POCsusp. Yet, we suggest that significantly smaller vertical POC fluxes in the Canada Basin make it possible to see evidence of DIC fixation in the POCsusp pool even at the bulk isotope level.


2000 ◽  
Vol 66 (11) ◽  
pp. 4870-4876 ◽  
Author(s):  
D. Hunkeler ◽  
R. Aravena

ABSTRACT Carbon isotope fractionation during aerobic mineralization of 1,2-dichloroethane (1,2-DCA) by Xanthobacter autotrophicusGJ10 was investigated. A strong enrichment of 13C in residual 1,2-DCA was observed, with a mean fractionation factor α ± standard deviation of 0.968 ± 0.0013 to 0.973 ± 0.0015. In addition, a large carbon isotope fractionation between biomass and inorganic carbon occurred. A mechanistic model that links the fractionation factor α to the rate constants of the first catabolic enzyme was developed. Based on the model, it was concluded that the strong enrichment of 13C in 1,2-DCA arises because the first irreversible step of the initial enzymatic transformation of 1,2-DCA consists of an SN2 nucleophilic substitution. SN2 reactions are accompanied by a large kinetic isotope effect. The substantial carbon isotope fractionation between biomass and inorganic carbon could be explained by the kinetic isotope effect associated with the initial 1,2-DCA transformation and by the metabolic pathway of 1,2-DCA degradation. Carbon isotope fractionation during 1,2-DCA mineralization leads to 1,2-DCA, inorganic carbon, and biomass with characteristic carbon isotope compositions, which may be used to trace the process in contaminated environments.


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