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PubMedDate not supplied

[Lipid metabolism and lipogenesis: application of stable isotopes].

Fat metabolism is regulated by several neuroendocrine and nutritional factors, which affect equilibrium between lipogenesis and lipolysis. Lipid utilization and fate in the organism can be assessed by in vivo and in vitro methods by measuring the rate of the different metabolic pathways (dynamic aspects), but also the net balance which may lead to fat accumulation or loss (static aspects). The quantitation of synthesis and breakdown reactions can be performed by using different tracers such as radioactive and stable isotopes. Fatty acid synthesis can be independently measured by the intravenous infusion of 13C acetate and application of the MIDA technique. In brief, this method uses probability analysis to measure the synthesis of biological polymers. It is based on the mathematical principle that the labeling pattern of a polymer synthesized from a stable-isotopically labeled precursor will conform to a predicted binomial or multinomial expansion. Thus, the isotopic enrichment of the precursor pool is calculated from measurements on the product alone. In the case of fatty acid synthesis, the proportions of excess (above natural background abundance) of single-labeled and double labeled (EM1 and EM2 species respectively) are a function of the probability (p) that the precursor subunits were isotopically labeled. Using this value of P for the isotopic enrichment of the acetylCoA pool, the theoretical 13C enrichment in the fatty acid if 100% were newly formed from this acetate pool is calculated. The actual isotopic enrichment is measured by gas chromatography-mass spectrometry (GCMS). This value divided by the theoretical maximum value equals the fraction of the fatty acid that is newly formed (f). The value for f represents dilution of de novo synthesized fatty acid by non-de novo sources. This method requires that newly synthesized (labeled) and preformed (unlabeled) mix in the liver and communicate with plasma VLDL over the period of the isotope infusion. It also assumes that the major de novo fatty acid is only a single fatty acid, with minor elongation and/or desaturation processes. Finally, the infused isotopic acetate should have no physiologically important effect. This methodology can be applied to assess lipogenesis in very different nutritional and physiopathological conditions such as diabetes, AIDS, obesity, etc.

Acetates↗
PubMedDate not supplied

[The mechanism of carbon isotope fractionation in the metabolic process].

The mechanism of carbon isotope fractionation in metabolic paths of autotrophic organisms is considered. The principal features of the mechanism proposed are: 1) the emergence of a one-stage kinetic isotope effect of pyruvate decarboxylation during respiration resulting in the formation of two flows of the carbon substrate with different isotope compositions; 2) the multiplication of the one-stage isotope effect by means of the repeated circulation of a light isotope fraction (C2-fragments) in lipid-carbohydrate metabolism and by the simultaneous removal of a heavy isotope carbon dioxide in the Krebs cycle. On the basis of the above mechanism carbon isotope effects are explained of CO2 assimilation and respiration as well as sequential decrease of 13C content in the series of lipids, carbohydrates and proteins. The cuase of the enrichment of the whole organisms in the light isotope in respect to the carbon dioxide of the environment is discussed.

Carbon Isotopes↗
PubMed1995

The validity of extrinsic stable isotopic labeling for mineral absorption studies in rats.

The use of extrinsic stable and radioisotopic labels (Fe, Zn, Cu and Se) was compared with the use of intrinsic labels by measuring label retention in rats. Saccharomyces cerevisiae (Hansen strain CBS 1171) was prepared intrinsically enriched with a stable isotope of iron, zinc, copper or selenium, and unenriched freeze-dried yeast was extrinsically labeled with the appropriate stable and/or radioisotope. Male Wistar rats, weighing 80-100 g and fed a purified diet, were given a test meal of one of the above labeled yeasts. Isotopic retention was determined by fecal monitoring. Retention of the stable isotopes was determined by thermal ionization quadruple mass spectrometry (TIQMS) and retention of the radioisotopes by counting feces in a whole-body counter. The results indicated that the behavior of the labels differed among the minerals, with copper as the only one in which the intrinsic and extrinsic stable isotopes were comparably retained. With zinc, retention of the extrinsic radiolabel and intrinsic label was similar, but retention of the extrinsic stable isotope label was higher. With iron, the intrinsic label had a significantly lower retention than the two extrinsic labels; with selenium, retention of all three labels was different, but these differences were not of a sufficient magnitude to conclude that extrinsic stable isotopic labelling is not valid. These results demonstrate that an extrinsic stable isotope label can be used for copper, selenium and inorganic iron, but that such a label is not valid for studies on zinc.

Absorption↗
PubMed2003

Molecular and carbon isotopic composition of leaf wax in vegetation and aerosols in a northern prairie ecosystem.

We measured the molecular and carbon isotopic composition of major leaf wax compound classes in northern mixed mesic prairie species (Agropyron smithii, Stipa viridula, Bouteloua gracilis, Tragopogon dubius) and in selected crops (Triticum aestivum, Brassica napus, Hordeum vulgare, Medicago sativa) of southern Alberta and also in aerosols collected 4 m above the prairie canopy. Our aims were to better constrain the wax biosynthetic carbon isotopic fractionation relative to the plant's carbon isotopic discrimination and to quantitatively assess the correspondence between wax composition in vegetation and in boundary layer aerosols. Wax molecular composition of the C(3)prairie species and bulked vegetation was characterized by high abundance of C(28) n-alkanol and C(31) n-alkane compounds whereas the C(4) species B. gracilis had several co-dominant n-alkanol and n-alkane compounds. Wax molecular composition of crop species differed significantly from that of prairie vegetation and was often dominated by a single compound. Results indicate that leaf wax isotopic composition is quantitatively related to the plant's carbon isotopic discrimination. Although species variations were evident, n-alcohol, n-acid and n-alkane wax compounds were on average depleted in (13)C by approximately 6.0+/-1 per thousand relative to total plant carbon. The magnitude of the depletion in wax delta(13)C was unaffected by environmental factors which altered photosynthetic carbon isotopic discrimination. No consistent difference in the magnitude of wax biosynthetic fractionation was observed between C(3) and C(4) species, indicating that photosynthetic pathway has little influence on the isotopic fractionation of wax during biosynthesis. The isotopic composition of ablated waxes in aerosols collected above the canopy was similar to that of the grassland vegetation but the molecular composition differed significantly and indicated that the source "footprint" of the ablated leaf wax particles we sampled in boundary layer air masses was of a regional or larger spatial scale.

Aerosols↗
PubMed2001

Stable isotope approaches, applications, and issues related to polyunsaturated fatty acid metabolism studies.

The use of stable isotope tracers for investigating fatty acid metabolism in human subjects has increased substantially over the last decade. Advances in analytical instrumentation, commercial availability of labeled substrates, and safety considerations are major reasons for this increased use of stable isotope tracers. Several experimental design options are available for using either deuterium or carbon-13 as tracers for fatty acid and lipid studies. Options include feeding a pulse dose of labeled fat or a mixture containing two or more labeled fats. Multiple doses of the labeled fat can be fed at timed intervals to increase enrichments. Administration by injection or continuous intravenous infusion is an alternative. Another option is to use diets containing foods from plants that have slightly higher natural carbon-13 enrichment. Each basic experimental design has its specific strengths, and the best choice of experimental design depends on the study objectives. Stable isotope studies have been used to address a variety of questions related to unsaturated fatty acid metabolism in humans. Examples are provided that illustrate the use of stable isotopes to investigate oxidation of docosahexaenoic acid, desaturation of linoleic and linolenic acids in infants and adults, incorporation of long-chain n-6 and n-3 fatty acids, bioequivalency of linolenic acid in primates, 13C nuclear magnetic resonance spectra of arachidonic acid in living rat brain, and effect of triacylglycerol structure on absorption. Radioisotope and stable isotope tracer studies in animals and humans are responsible for much of our understanding of fatty acid and lipid metabolism. However, tracer studies have limitations, and there are some unresolved issues associated with isotope studies. Examples of unresolved issues are quantification of isotope data, validity of in vivo fatty acid metabolite results, kinetic modeling, subject variability, and use of blood lipid data as a reflection of tissue lipid metabolism. Resolving these issues, developing novel methodology, and applying stable isotope tracer methods to questions related to PUFA metabolism are broad areas of interesting and challenging research opportunities.

Adult↗
PubMed1982

Lithium toxicology: effect of isotopic composition on lethality and behavior.

Naturally occurring lithium consists largely of the stable lithium-7 isotope but it contains 7.6% of a second stable isotope, lithium-6. Biological effects of these two isotopes were not identical. When administered in isotopically pure form, the chloride of lithium-6 was more toxic after acute intake than the chloride of pure lithium-7:its LD in Swiss-Webster mice was 13.2 mEq/kg as opposed to 15.9 mEq/kg for the salt of the heavier isotope and 14.9 mEq/kg for that of the natural mixture of the two isotopes. A single injection of one or the other pure isotope in a constant dose, 14.5 mEq/kg led to a 90% mortality in mice given lithium-6 but only 10% in mice given lithium-7. Side effects such as hypoactivity, ataxia, intense perspiration and diarrhea appeared within 10 min after administration of toxic doses of lithium-6 but more gradually after lithium-7. The differences between the isotopes in toxicity and rate of appearance of effects on spontaneous motor activity were significant at the p less than 1% level.

Animals↗
PubMed2006

Carbon isotopes and iodine concentrations in a Mississippi River delta core recording land use, sediment transport, and dam building in the river's drainage basin.

Sedimentary material from coastal and nearshore areas in the Mississippi Delta region are comprised of different organic carbon sources with diverse ages that require isotopic and elemental records for resolving the various sources of plant residues. Carbon isotopic ((13)C, (14)C) values were used to differentiate contributions from plants using the C3, C4, and/or CAM (crassulacean acid metabolism) carbon fixation pathways., and iodine concentrations indicated that wetland plant residues are a significant source of organic carbon in a sediment core from the Mississippi River delta region collected at a 60 m water depth. This sediment core had been extensively described in Oktay et al. [Oktay, S.D., Santschi, P.H., Moran, J.E., Sharma, P., 2000. The (129)Iodine Bomb Pulse Recorded in Mississippi River delta Sediments: Results from Isotopes of I, Pu, Cs, Pb, and C. Geochim. Cosmochim. Acta 64 (6), 989-996.] and significantly, includes unique features that had not previously been seen in the marine environment. These special features include a plutonium isotopic close-in fallout record that indicates a purely terrestrial source for these sediment particles and the elements associated with it, and a distinct iodine isotopic peak (as well as peaks for plutonium and cesium isotopes) that indicate little bioturbation in this core. Our carbon isotopic and iodine data can thus be compared to published records of changes in drainage basin land use, river hydrology, and hydrodynamic sorting of suspended particles to elucidate if these changes are reflected in nearshore sediments. This comparison suggests a significant contribution for organic carbon (OC) from C4 plants to these sediments during the 1950's to early 1960's. Relative older carbon isotopes, and episodically high iodine concentrations (up to 34 ppm) were observed during this time period that (1) indicate sediment deposition that is coincident with the times of major hydrological changes induced from dam and levee building in both the upper and lower reaches of the Mississippi River drainage basin, and (2) suggest episodic organic carbon deposition from wetland plant residues.

Carbon Isotopes↗
PubMed2005

Influence of temporal variations in water chemistry on the Pb isotopic composition of rainbow trout (Oncorhynchus mykiss).

Field and laboratory investigations were undertaken to determine (1) the relations between discharge, Pb concentration, and the Pb isotopic composition of the dissolved load in Richland Creek, western North Carolina, and (2) the potential influence of varying Pb water chemistry on the Pb isotopic abundances in liver and bone tissues of rainbow trout (Oncorhynchus mykiss). Stream waters were characterized by relatively low Pb concentrations during periods of base flow exceeding 10 days in length. Moreover, greater than 65% of the Pb was derived from orchard soils located upstream of the monitoring site which are contaminated by lead arsenate. During small to moderate floods, the dissolved load exhibited Pb concentrations more than twice as high as those measured during base flow, but the contribution of Pb from lead arsenate was relatively low and varied directly with discharge. In contrast to smaller events, Pb from lead arsenate in an 8- to 10-year (overbank) event in May 2003 was minimal during peak flow conditions, suggesting that discharge-source relations are dependent on flood magnitude. The hydrologic and geochemical data demonstrate that aquatic biota in Richland Creek are subjected to short-term variations in Pb concentrations and Pb isotopic abundances within the dissolved load ranging from a few hours to few a weeks. Laboratory studies demonstrated that when rainbow trout were exposed to elevated Pb concentrations with a distinct isotopic fingerprint, the bone and liver rapidly acquire isotopic ratios similar to that of the water. Following exposure, bone retains Pb from the contaminant source for a period of months, while the liver excreted approximately 50% of the accumulated Pb within a few days and nearly all of the Pb within a few weeks. Differences in the rates of excretion resulted in contrasting isotopic ratios between the tissues. It seems plausible, then, that previously observed differences between the isotopic composition of bone and liver in rainbow trout from Richland Creek are related to their short-term exposure to Pb from soils contaminated with Pb arsenate that result from fluctuating hydrologic conditions. If these trends prove to be common in other contaminated aquatic environments, it may be possible to use the Pb isotopic composition of bone as an indicator of the long-term exposure to Pb and the liver as a biomarker for short-term Pb exposures.

Animals↗
PubMed2002

Isotopic fractionation during reductive dechlorination of trichloroethene by zero-valent iron: influence of surface treatment.

During reductive dechlorination of trichloroethene (TCE) by zero-valent iron, stable carbon isotopic values of residual TCE fractionate significantly and can be described by a Rayleigh model. This study investigated the effect of observed reaction rate, surface oxidation and iron type on isotopic fractionation of TCE during reductive dechlorination. Variation of observed reaction rate did not produce significant differences in isotopic fractionation in degradation experiments. However, a small influence on isotopic fractionation was observed for experiments using acid-cleaned electrolytic iron versus experiments using autoclaved electrolytic iron, acid-cleaned Peerless cast iron or autoclaved Peerless cast iron. A consistent isotopic enrichment factor of epsilon = -16.7/1000 was determined for all experiments using cast iron, and for the experiments with autoclaved electrolytic iron. Column experiments using 100% cast iron and a 28% cast iron/72% aquifer matrix mixture also resulted in an enrichment factor of -16.9/1000. The consistency in enrichment factors between batch and column systems suggests that isotopic trends observed in batch systems may be extrapolated to flowing systems such as field sites. The fact that significant isotopic fractionation was observed in all experiments implies that isotopic analysis can provide a direct qualitative indication of whether or not reductive dechlorination of TCE by Fe0 is occurring. This evidence may be useful in answering questions which arise at field sites, such as determining whether TCE observed down-gradient of an iron wall remediation scheme is the result of incomplete degradation within the wall, or of the dissolved TCE plume by passing the wall.

Carbon Isotopes↗
PubMed1998

Determination of selenium stable isotopes by gas chromatography-mass spectrometry with negative chemical ionisation.

A gas chromatography mass spectrometric method using negative chemical ionisation was developed for the determination of stable isotopes of selenium for evaluation of selenium absorption and retention from foods in humans. The method involves an acid digestion to convert all selenium into selenite, which subsequently reacts with 4-nitro-o-phenylene-diamine to form a volatile piazselenole. The piazselenole, after extraction into an organic solvent, was analysed for its isotopic selenium composition by gas chromatography mass spectrometry. Negative chemical ionisation is reported for the first time for the determination of selenium stable isotopes and its analytical characteristics were compared to those of electron impact mass spectrometric ionisation, classically used for the determination of selenium. The negative chemical ionisation technique allowed accurate determination of total selenium by isotope dilution and of selenium isotope ratios in biological samples. The repeatability for total selenium and for stable isotope ratios was good (R.S.D.< or =10%) within the range of 50 to 250 ng selenium. The detection limit for the investigated selenium isotopes was approximately 1 pg (signal to noise ratio at 3). The applicability of the developed stable isotope methodology was demonstrated by the determination of the selenium absorption and retention from foods in a pilot study using one human adult.

Adult↗
PubMed2002

Infrared laser spectrometer with balanced absorption for measurement of isotopic ratios of carbon gases.

Measurement of the isotopic compositions of carbon dioxide and methane is a powerful tool for quantifying their atmospheric sources and sinks, which is especially important considering the dramatic increase in these greenhouse gases during the industrial era. Laser absorption spectroscopy is a technique which has demonstrated the high sensitivity needed for isotopic measurement. A significant problem in the spectroscopic measurement of isotopic abundances is the large difference in concentrations of the major and minor isotopic constituents. The measurement of two isotopic species using lines of similar strength but very unequal concentrations leads to low precision, with either the minor constituent having too small an absorption depth, or the major constituent having too great an absorption depth. If lines with unequal strength are chosen to compensate for the absorption depth imbalance, then precision tends to suffer due to the greater temperature sensitivity of the weaker line strength. We describe the development of a compact instrument for isotopic analysis CO2 and CH4 using tunable infrared laser absorption spectroscopy which combines novel optical design and signal processing methods to address this problem. The design compensates for the large difference in concentration between major and minor isotopes by measuring them with pathlengths which differ by a factor of 72 within the same multipass cell. We have demonstrated the basic optical design and signal processing by determining delta13C (CO2) isotopic ratios with precision as small as 0.2/1000 using a lead salt diode laser based spectroscopic instrument.

Carbon Isotopes↗
PubMed1984

Use of multiple isotope effects to study the mechanism of 6-phosphogluconate dehydrogenase.

The multiple isotope effect method of Hermes et al. [Hermes, J. D., Roeske, C. A., O'Leary, M. H., & Cleland, W. W. (1982) Biochemistry 21, 5106-5114] has been used to study the mechanism of the oxidative decarboxylation catalyzed by 6-phosphogluconate dehydrogenase from yeast. 13C kinetic isotope effects of 1.0096 and 1.0081 with unlabeled or 3-deuterated 6-phosphogluconate, plus a 13C equilibrium isotope effect of 0.996 and a deuterium isotope effect on V/K of 1.54, show that the chemical reaction after the substrates have bound is stepwise, with hydride transfer preceding decarboxylation. The kinetic mechanism of substrate addition is random at pH 8, since the deuterium isotope effect is the same when either NADP or 6-phosphogluconate or 6-phosphogluconate-3-d is varied at fixed saturating levels of the other substrate. Deuterium isotope effects on V and V/K decrease toward unity at high pH at the same time that V and V/K are decreasing, suggesting that proton removal from the 3-hydroxyl may precede dehydrogenation. Comparison of the tritium effect of 2.05 with the other measured isotope effects gives limits of 3-4 on the intrinsic deuterium and of 1.01-1.05 for the intrinsic 13C isotope effect for C-C bond breakage in the forward direction and suggests that reverse hydride transfer is 1-4 times faster than decarboxylation.

Carbon Isotopes↗
PubMed2001

Monitoring biodegradation of methyl tert-butyl ether (MTBE) using compound-specific carbon isotope analysis.

Methyl tert-butyl ether (MTBE), the most common gasoline oxygenate, is frequently detected in surface water and groundwater. The aim of this study was to evaluate the potential of compound-specific isotope analysis to assess in situ biodegradation of MTBE in groundwater. For that purpose, the effect of relevant physical and biological processes on carbon isotope ratios of MTBE was evaluated in laboratory studies. Carbon isotope fractionation during organic phase/gas-phase partitioning (0.50 +/- 0.15@1000), aqueous phase/gas-phase partitioning (0.17 +/- 0.05@1000), and organic phase/aqueous-phase partitioning (0.18 +/- 0.24@1000) was small in comparison to carbon isotope fractionation measured during biodegradation of MTBE in microcosms based on aquifer sediments of the Borden site. In experiments with MTBE as the only substrate and a cometabolic experiment with 3-methypentane as primary substrate, MTBE became enriched in 13C by 5.1 to 6.9@1000 after 95 to 97% degradation. For both experiments, similar isotopic enrichment factors were obtained (-1.52 +/- 0.06 to -1.97 +/- 0.05@1000). Biodegradation of TBA, which accumulated transiently in the cometabolic microcosms, was also accompanied by carbon isotope fractionation, with an isotopic enrichment factor of -4.21 +/- 0.07@1000. This study suggests that carbon isotope analysis is a potential tool to trace in situ biodegradation of MTBE and TBA and thus to better understand the fate of these contaminants in the environment.

Biodegradation, Environmental↗
PubMed2001

Variability in carbon isotopic fractionation during biodegradation of chlorinated ethenes: implications for field applications.

Stable carbon isotopic analysis has the potential to assess biodegradation of chlorinated ethenes. Significant isotopic shifts, which can be described by Rayleigh enrichment factors, have been observed for the biodegradation of trichloroethlyene (TCE), cis-dichloroethylene (cDCE), and vinyl chloride (VC). However, until this time, no systematic investigation of isotopic fractionation during perchloroethylene (PCE) degradation has been undertaken. In addition, there has been no comparison of isotopic fractionation by different microbial consortia, nor has there been a comparison of isotopic fractionation by consortia generated from the same source, but growing under different conditions. This study characterized carbon isotopic fractionation during reductive dechlorination of the chlorinated ethenes, PCE in particular, for microbial consortia from two different sources growing under different environmental conditions in order to assess the extent to which different microbial consortia result in different fractionation factors. Rayleigh enrichment factors of -13.8@1000, -20.4@1000, and -22.4@1000 were observed for TCE, cDCE, and VC, respectively, for dechlorination by the KB-1 consortium. In contrast, isotopic fractionation during reductive dechlorination of perchloroethylene (PCE) could not always be approximated by a Rayleigh model. Dechlorination by one consortium followed Rayleigh behavior (epsilon = -5.2), while a systematic change in the enrichment factor was observed over the course of PCE degradation by two other consortia. Comparison of all reported enrichment factors for reductive dechlorination of the chlorinated ethenes shows significant variation between experiments. Despite this variability, these results demonstrate that carbon isotopic analysis can provide qualitative evidence of the occurrence and relative extent of microbial reductive dechlorination of the chlorinated ethenes.

Biodegradation, Environmental↗
PubMed2001

Hydrogen and carbon isotope fractionation during aerobic biodegradation of benzene.

The main aim of the study was to evaluate hydrogen and carbon isotope fractionation during biodegradation of benzene as a possible tool to trace the process in contaminated environments. Aerobic biodegradation of benzene by two bacterial isolates, Acinetobacter sp. and Burkholderia sp., was accompanied by significant hydrogen and carbon isotope fractionation with hydrogen isotope enrichment factors of -12.8 +/- 0.7 per thousand and -11.2 +/- 1.8 per thousand, respectively, and average carbon isotope enrichment factors of -1.46 +/- 0.06 per thousand and -3.53 +/- 0.26 per thousand, respectively. Inorganic carbon produced by Acinetobacter sp. was depleted in 13C by 3.6-6.2 per thousand as compared to the initial delta13C of benzene, while the produced biomass was enriched in 13C by 3.8 per thousand. The secondary aim was to determine isotope ratios of benzenes from different manufacturers with regard to the use of isotopes for source differentiation. While two of the four analyzed benzenes had similar delta13C values, each of them had a distinct delta2H-delta13C pair and delta2H values spread over a range of 66.5 per thousand. Thus, combined analyses of hydrogen and carbon isotopes may be a more promising approach to trace sources and/or biodegradation of benzene than measuring carbon isotopes only.

Acinetobacter↗
PubMed2002

Carbon and hydrogen isotopic fractionation during biodegradation of methyl tert-butyl ether.

Carbon and hydrogen isotopic fractionation during aerobic biodegradation of MTBE by a bacterial pure culture (PM1) and a mixed consortia from Vandenberg Air Force Base (VAFB) were studied in order to assess the relative merits of stable carbon versus hydrogen isotopic analysis as an indicator of biodegradation. Carbon isotopic enrichment in residual MTBE of up to 8.1/1000 was observed at 99.7% biodegradation. Carbon fractionation was reproducible in the PM1 and VAFB experiments, yielding similar enrichment factors (epsilon) of -2.0/1000 +/- 0.1/1000 to -2.4/1000 +/- 0.3/1000 for replicates in the PM1 experiment and -1.5/1000 +/- 0.1/1000 to -1.8/1000 +/- 0.1/1000 for replicates in the VAFB experiment. Hydrogen isotopic fractionation was highly reproducible for the PM1 pure cultures, with epsilon values of -33/1000 +/- 5/1000 to -37/1000 +/- 4/1000 for replicate samples. In the VAFB microcosms, there was considerably more variability in epsilon values, with values of -29/1000 +/- 4/1000 and -66/1000 +/- 3/1000 measured for duplicate sample bottles. Despite this variability, hydrogen isotopic fractionation always resulted in 2H enrichment of the residual MTBE of >80/1000 at 90% biodegradation. The reproducible carbon fractionation suggests that compound-specific carbon isotope analysis may be used to estimate the extent of biodegradation at contaminated sites. Conversely, the large hydrogen isotopic fractionation documented during biodegradation of MTBE suggests that compound-specific hydrogen isotope analysis offers the most conclusive means of identifying in-situ biodegradation at contaminated sites.

Bacteria↗
PubMed2004

Fertilizer characterization: isotopic data (N, S, O, C, and Sr).

A detailed isotopic characterization (delta15N(Ntotal), delta15N(NO3), delta18O(NO3), delta34S(SO4), delta18O(SO4), (delta13C(Ctotal), and 87Sr/86Sr) of 27 commercial fertilizers used in Spain is presented in this paper. Results together with a compilation of fertilizer isotopic published data are used for two purposes: (i) to identify the origin of the primary constituents and raw materials used in fertilizer manufacture and relate these data with their heavy metals and rare earth elements (REE) contents; (ii) to compare the fertilizer isotopic signatures with natural values and other anthropogenic pollutants and evaluate the usefulness of multi-isotopic analyses to trace fertilizer contaminations in future study cases. Isotope data permit us to know, in most cases, the origin of the primary constituents of fertilizers, and the 87Sr/86Sr ratio distinguishes the origin of the phosphate content--phosphorites or carbonatites--which in turn implies a qualitatively defined and potentially contaminant presence of REE and heavy metals in fertilizers. Delta15N, delta34S, and 87Sr/86Sr have already been used to trace fertilizer contaminations. Their utility can be improved by the coupled use of delta15N(NO3)-delta18O(NO3) and delta34S(SO4)-delta18O(SO4) to evaluate the fractionation processes that can affect contaminants. Moreover, multi-isotopic analyses, using heavy isotopes, allow us to see beyond the fractionation effects to the fertilizer stable isotope signatures and a better distinction from other anthropogenic contaminants.

Environmental Pollutants↗
PubMed2005

Assessment of degradation pathways in an aquifer with mixed chlorinated hydrocarbon contamination using stable isotope analysis.

The demonstration of monitored natural attenuation (MNA) of chlorinated hydrocarbons in groundwater is typically conducted through the evaluation of concentration trends and parent-daughter product relationships along prevailing groundwater flow paths. Unfortunately, at sites contaminated by mixtures of chlorinated ethenes, ethanes, and methanes, the evaluation of MNA by using solely concentration data and parent-daughter relationships can result in erroneous conclusions regarding the degradation mechanisms that are truly active at the site, since many of the daughter products can be derived from multiple parent compounds. Stable carbon isotope analysis was used, in conjunction with concentration data, to clarify and confirm the active degradation pathways at a former waste solvent disposal site where at least 14 different chlorinated hydrocarbons have been detected in the groundwater. The isotope data indicate that TCE, initially believed to be present as a disposed product and/or a PCE dechlorination intermediate, is attributable to dehydrochlorination of 1,1,2,2-PCA. The isotope data further support that vinyl chloride and ethene in the site groundwater result from dichloroelimination of 1,1,2-trichlorethane and 1,2-dichloroethane, respectively, rather than from reductive dechlorination of the chlorinated ethenes PCE, TCE, or 1,2-DCE. The isotope data confirm that the chlorinated ethanes and chlorinated methanes are undergoing significant intrinsic degradation, whereas degradation of the chlorinated ethenes may be limited. In addition to the classical trend of enriched isotope values of the parent compounds with increasing distance associated to biodegradation, shifts of isotope ratios of degradation byproduct in the opposite direction due to mixing of isotopically light byproducts of biodegradation with compounds from the source are shown to be of high diagnostic value. These data underline the value of stable isotope analysis in confirming transformation processes at sites with complex mixtures of chlorinated compounds.

Biodegradation, Environmental↗