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Reliable determination of oxygen and hydrogen isotope ratios in atmospheric water vapour adsorbed on 3A molecular sieve.

The isotope ratio of atmospheric water vapour is determined by wide-ranging feedback effects from the isotope ratio of water in biological water pools, soil surface horizons, open water bodies and precipitation. Accurate determination of atmospheric water vapour isotope ratios is important for a broad range of research areas from leaf-scale to global-scale isotope studies. In spite of the importance of stable isotopic measurements of atmospheric water vapour, there is a paucity of published data available, largely because of the requirement for liquid nitrogen or dry ice for quantitative trapping of water vapour. We report results from a non-cryogenic method for quantitatively trapping atmospheric water vapour using 3A molecular sieve, although water is removed from the column using standard cryogenic methods. The molecular sieve column was conditioned with water of a known isotope ratio to 'set' the background signature of the molecular sieve. Two separate prototypes were developed, one for large collection volumes (3 mL) and one for small collection volumes (90 microL). Atmospheric water vapour was adsorbed to the column by pulling air through the column for several days to reach the desired final volume. Water was recovered from the column by baking at 250 degrees C in a dry helium or nitrogen air stream and cryogenically trapped. For the large-volume apparatus, the recovered water differed from water that was simultaneously trapped by liquid nitrogen (the experimental control) by 2.6 per thousand with a standard deviation (SD) of 1.5 per thousand for delta(2)H and by 0.3 per thousand with a SD of 0.2 per thousand for delta(18)O. Water-vapour recovery was not satisfactory for the small volume apparatus.

Adsorption↗

Monoterpene biosynthesis: isotope effects associated with bicyclic olefin formation catalyzed by pinene synthases from sage (Salvia officinalis).

The three pinene synthases (cyclases) from common sage (Salvia officinalis) catalyze the conversion of geranyl pyrophosphate to the bicyclic olefins (+)-alpha-pinene and (+)-camphene (cyclase I), (-)-alpha-pinene, (-)-beta-pinene, and (-)-camphene (cyclase II), and (+)-alpha-pinene and (+)-beta-pinene (cyclase III), in addition to smaller amounts of monocyclic and acyclic monoterpene olefins. [1-3H,4-2H2]- and [10-2H2]-geranyl pyrophosphates were prepared and used in conjunction with 1-3H- and 1-3H,10-2H3-labeled geranyl precursors to examine the isotope effects attending the C4- and C10-deprotonation steps in the enzymatic synthesis of the pinenes. The observation of isotopically sensitive branching within each set of stereochemically related bicyclic olefins confirmed that each product set was synthesized by the respective pinene synthase by partitioning of common carbocationic intermediates along different reaction channels at the active site. The changes in product distribution resulting from deuterium substitution at C4 and C10 of the substrate were used to determine kinetic isotope effects (KIEs) for the terminating deprotonations; these observed KIEs represent the lower limits of the intrinsic isotope effects. The intramolecular isotope effects for the methyl-methylene elimination in beta-pinene formation by cyclases II and III were also evaluated with [10-2H2]geranyl pyrophosphate as substrate and by MS analysis of the olefin products. The intramolecular KIEs (kH/kD = 3.0 and 3.5) were significantly higher than the observed KIEs determined from product ratios (kH/kD = 1.7 and 2.6) since the former involves considerably less masking of the intrinsic isotope effects.

Alkenes↗

Determination of the mechanism of human malic enzyme with natural and alternate dinucleotides by isotope effects.

Human malic enzyme was studied by steady state kinetics, deuterium isotope effects, and 13C isotope effects with both the physiological dinucleotide cofactor and several alternate cofactors. The log V vs pH profile with NAD revealed two pK(a) values too close to be separately determined, but with an average value of 7.33. The log V/K vs pH profile with NAD revealed two pK(a) values at 7.4 and 5.6. Deuterium and 13C isotope effects indicate that the mechanism of human malic enzyme is stepwise with both NAD and epsilonNAD, but that hyperconjugation in the transition state for hydride transfer is detectable only with the former. With thioNAD and APAD, the isotope effects do not clearly indicate whether the mechanism is stepwise or concerted. The intrinsic 13C isotope effect for decarboxylation was calculated to be 1.0485 by measurement of the partition ratio of oxaloacetate in the presence of NADH and human malic enzyme (decarboxylation to pyruvate/reduction to malate = 2.33). The isotope effect and partitioning data suggest that the energy barrier for decarboxylation of oxaloacetate is not as high relative to the barrier for reduction of oxaloacetate as with the chicken liver enzyme.

Carbon Isotopes↗

Lead concentrations and isotopic signatures in vintages of French wine between 1950 and 1991.

Vintages of French wine from 1950 to 1991 were analyzed for lead isotopes and concentrations to investigate whether they might be used to archive the isotopic composition of the anthropogenic lead in aerosols to which the vineyard was exposed. Early vintages (1950-1980) contained 78-227 ng/g of lead with 206Pb/207Pb ratios between 1.152 and 1.173, while the later vintages displayed significantly lower concentrations and a smaller range of isotopic ratios. The concentration of trimethyl lead, which is associated with automobile emissions, was found to be poorly correlated with total lead in the wines, suggesting that automobile aerosols were not a significant source of the lead. This result was supported by lead isotope data which showed a poor correlation with the available petrol and aerosol data. To identify its origin lead isotopes were measured in vineyard aerosols, soil particles, bottle caps, corks, and brass components used to dispense the wine. Although a dominant source could not be identified there was some evidence to suggest that brass which had a high lead concentration was a significant contributor. Because the lead contribution from the processing of wine was probably relatively high in the past it is unlikely that old vintages of wine will be a suitable archive for lead isotopes in aerosols.

Aerosols↗

The isotopic composition of anthropogenic boron and its potential impact on the environment.

The present study investigates the isotopic composition of anthropogenic boron (B) and its potential affects on the environment. The isotopic ratios of B in synthetic products from the main ores in the world have been measured by negative thermal ionization mass spectrometry. The data show that the isotopic compositions of Na-borate products and washing powders overlap with those of natural Na-borate minerals. In contrast, the 11B/10B ratios of synthetic Ca-borate and Na/Ca borate products are significantly lower (by 15 permil) and overlap with those of the natural Ca-borate minerals. Consequently, the original isotopic signature of natural borate minerals is not modified during the manufacturing process of synthetic products. The B isotopic composition of domestic wastewater from Israel and Riverside, California suggests that B in sewage is derived from Na-borate components used in detergents. Since B, like other inorganic ions, is not removed during conventional sewage treatment, it accumulates in domestic wastewater. Although the B concentration in pristine groundwaters is generally low (<0.05 mg/L), contaminant sources (e.g., wastewater) are relatively enriched in B (0.5-1 mg/L). The isotopically distinguished signature of borate compounds is used to trace groundwater contamination.

Biological Evolution↗

Species-specific isotope-ratio measurements of volatile tin and antimony compounds using capillary GC-ICP-time-of-flight MS.

The analytical performance of an axial inductively-coupled-plasma time-of-flight mass spectrometer (ICP-TOFMS) as a detector for fast transient chromatographic signals resulting from the coupling to capillary gas chromatography (CGC) was investigated. A cryotrapping GC-ICP-TOFMS method for the determination of volatile metal(loid) compounds (VOMs) in gases was used and the suitability of the TOF mass analyzer for multielemental speciation analysis and multi-isotope ratio determinations was studied in terms of accuracy and precision. Isotope ratios 118Sn/120Sn and 121Sb/123Sb have been determined in in-house gas standard atmospheres in Tedlar bags at two different levels (100 pg and 1 ng) for different elemental species (SnH4, MeSnH3, Me2SnH2, Me3SnH, BuSnH3, SbH3, and MeSbH2). A limitation arising from counting statistics in both detection modes could be shown. A solution containing rhodium (10 ng mL(-1)) and cadmium (40 ng mL(-1)) was introduced simultaneously to the GC outlet. Rhodium acts as a continuous internal standard and Cd is used for mass-bias correction (by measuring the 111Cd/113Cd ratio). The detection system in both pulse counting and analog mode was examined. The best attainable precision was established for Me2SnH2 (analog mode, 12 replicates, 1 ng, RSD 0.34%, accuracy 0.31%) whereas most other species ranged between 0.4 and 0.5% RSD if higher concentrations were used. The limitations of the pulse counting system are clearly seen, with peak heights of more than 2000 counts reaching saturation (for an integration time of 100 ms), which reduces the accuracy of isotope ratio determinations. A dozen VOM could be detected in an aged landfill gas sample; several unidentified Sn compounds were present. Although their isotope ratios are within the confidence value of the standards, it is not yet clear if the acquired precision is good enough to identify isotopic fractionation of metal(loid)s through biovolatilization processes. With the precision achieved, the combination of cryotrapping GC and ICP-TOFMS is a powerful tool for monitoring volatile multi-element species in multi-tracer experiments and isotope dilution methodology.

Antimony↗

Uptake and elimination of lead, zinc, and copper by caddisfly larvae (Trichoptera: Hydropsychidae) using stable isotope tracers.

Stable isotopes of Pb, Zn, and Cu were used in laboratory experiments to determine the uptake and elimination of these metals by stream-dwelling caddisfly (Trichoptera: Hydropsychidae) larvae. For Pb and Cu, larvae were exposed to environmentally realistic levels (2.5 and 4.5 microg x L(-1), respectively) of one isotope for 9 days followed by a 9-day exposure to either the same isotope, to a second stable isotope of the same metal, or to RW containing no added isotope (two phases in total). For zinc, the exposure concentration was 15 microg x L(-1), and the experiment lasted for a total of 27 (i.e., three phases) rather than 18 days to see if uptake and elimination changed during the extended time period. The uptake clearances (k(u)) determined for the various metals averaged 7.8, 1.4, and 0.6 L x g dw(-1) x d(-1) for Pb, Zn, and Cu, respectively, if the total metal concentration in the water was used in the calculations. The clearance rate constants (k(e)) were less variable, averaging 0.15 d(-1) for Pb, 0.22 d(-1) for Zn, and approximately 0.1 d(-1) for Cu and were similar in both the presence (i.e., elimination) and absence (i.e., depuration) of metal in the water. These values are also comparable with those reported in the literature for other aquatic invertebrates. The use of stable isotopes thus allowed simultaneous measurement of uptake and clearance (elimination and depuration) of these metals at environmentally realistic concentrations and could be of great benefit for determining partitioning, assimilation efficiency, and pathways of these and other metals in the environment.

Animals↗

Patterns of intramolecular carbon isotopic heterogeneity within amino acids of autotrophs and heterotrophs.

A survey of the intramolecular C isotopic composition of a variety of organisms was conducted to investigate the potential of intramolecular isotopic measurements as a tracer of biological or geochemical processes. Based on a consideration of inorganic C sources and enzymatic fractionations, contrasting predictions were made for the relative (13)C enrichments of the alpha-carboxyl carbons fixed by the anapleurotic (beta)-carboxylation pathway during amino acid synthesis by photoautotrophs and heterotrophs. To test the model predictions, the stable C isotopic compositions of the acid hydrolyzable C fraction, the total amino acid alpha-carboxyl C fraction and the alpha-carboxyl C of glutamate from a variety of autotrophic and heterotrophic organisms were compared. The relative (13)C enrichments of carboxyl carbons in the bulk amino acid fraction and in glutamate conformed qualitatively to model predictions. Macroalgal taxa possessed a significantly less enriched carboxyl C fraction than did either C3 or C4 vascular plants, indicating the presence of a different beta-carboxylation pathway operating in these organisms. In most multicellular heterotrophs, the isotopic composition of the amino acid carboxyl carbons closely resembled that of their food sources. Amino acids are apparently assimilated into tissue proteins directly from their diets without significant metabolic modification. However, shifts in the isotopic composition of the carboxyl C fractions in some organisms were detected that were consistent with the occurrence of significant resynthesis of amino acids from non-amino acid precursors. Comparison of plant leaves and roots provided evidence of environmentally controlled assimilate partitioning. Intramolecular isotopic measurements of biological molecules provide unique insights into the origins and transformations of bio-molecules.

Amino Acids↗

Resolving temporal variation in vertebrate diets using naturally occurring stable isotopes.

Assessments of temporal variation in diets are important for our understanding of the ecology of many vertebrates. Ratios of naturally occurring stable isotopes in animal tissues are a combination of the source elements and tissue specific fractionation processes, and can thus reveal dietary information. We review three different approaches that have been used to resolve temporal diet variation through analysis of stable isotopes. The most straightforward approach is to compare samples from the same type of tissue that has been sampled over time. This approach is suited to address either long or short-term dietary variation, depending on sample regime and which tissue that is sampled. Second, one can compare tissues with different metabolic rates. Since the elements in a given tissue have been assimilating during time spans specific to its metabolic rate, tissues with different metabolic rates will reflect dietary records over different periods. Third, comparisons of sections from tissues with progressive growth, such as hair, feathers, claws and teeth, will reveal temporal variation since these tissues will retain isotopic values in a chronological order. These latter two approaches are mainly suited to address questions regarding intermediate and short-term dietary variation. Knowledge of tissue specific metabolic rates, which determine the molecular turnover for a specific tissue, is of central importance for all these comparisons. Estimates of isotopic fractionation between source and measured target are important if specific hypotheses regarding the source elements are addressed. Estimates of isotopic fractionation, or at least of differences in fractionation between tissues, are necessary if different tissues are compared. We urge for more laboratory experiments aimed at improving our understanding of differential assimilation of dietary components, isotopic fractionation and metabolic routing. We further encourage more studies on reptiles and amphibians, and generally more studies utilizing multiple tissues with different turnover rates.

Animals↗

Determining biological tissue turnover using stable isotopes: the reaction progress variable.

The reaction progress variable is applied to stable isotope turnover of biological tissues. This approach has the advantage of readily determining whether more than one isotope turnover pool is present; in addition, the normalization process inherent to the model means that multiple experiments can be considered together although the initial and final isotope compositions are different. Consideration of multiple isotope turnover pools allows calculation of diet histories of animals using a time sequence of isotope measurements along with isotope turnover pools. The delayed release of blood cells from bone marrow during a diet turnover experiment can be quantified using this approach. Turnover pools can also be corrected for increasing mass during an experiment, such as when the animals are actively growing. Previous growth models have been for exponential growth; the approach here can be used for several different growth models.

Animals↗

Effect of increased metabolic rate on oxygen isotopic fractionation.

16O16O is preferentially used over 18O16O (a stable isotope of oxygen comprising about 0.2% of atmospheric O2) as oxygen is consumed during respiration in humans (Epstein and Zeiri, 1988, Proc. Natl. Acad. Sci. USA 85: 1727-1731). To test the hypothesis that oxygen isotopic fractionation is related to the metabolic rate, 8 healthy adults performed 5 min of constant work rate cycle ergometer exercise below and above their anaerobic threshold. Moreover, 3 subjects performed an incremental exercise to the limit of tolerance. Oxygen uptake (VO2) was measured breath by breath. Samples of the exhaled breath for oxygen isotope measurement were obtained at rest and at various times during exercise and recovery. Oxygen isotopic fractionation was determined by isotope ratio mass spectrometry and calculated as the ratio of the degree of fractionation to the oxygen consumed in the breath sample (Z value). For the constant work rate protocol, both low and high intensity exercise resulted in a significant decrease in Z compared to the rest values (P less than 0.01). However, for the high intensity exercise the reduction in fractionation was greater compared to the low intensity protocol (P less than 0.05). For the incremental test, there was a significant negative correlation between oxygen isotopic fractionation and VO2 expressed as percent of the maximal oxygen uptake (r = -0.91, P less than 0.0001). These data suggest that during exercise low-fractionating processes become more important as limiting steps for O2 transport.

Adult↗

Stable isotope methodology in the pharmacokinetic studies of androgenic steroids in humans.

The use of stable isotopically labeled steroids combined with gas chromatography/mass spectrometry (GC/MS) has found a broad application in pharmacologic studies. Initially, stable isotopically labeled steroids served as the ideal analytic internal standard for GC/MS analysis; however, their in vivo use has expanded and has proven to be a powerful pharmacokinetic tool. We have successfully used stable isotope methodology to study the pharmacokinetic/bioavailability of androgens. The primary advantage of the technique is that endogenous and exogenous steroids with the same basic structure can be differentiated by using stable isotopically labeled analogs. The method was used to examine the pharmacokinetics of testosterone and testosterone propionate, and to clarify the influence of endogenous testosterone. Another advantage of the isotope methods is that steroidal drugs can be administered concomitantly in two formulations (e.g., solution and solid dosage). A single set of blood samples serves to describe the time course of the formulations being compared. This stable isotope coadministration technique was used to estimate the relative bioavailability of 17 alpha-methyltestosterone.

Androgens↗

Use of stable isotopes to determine compliance.

The natural variation in the abundance of stable isotopes of light elements (C, H, O, N) in humans is less than 0.5%. Much larger variations can be induced through administration of drugs labeled with enriched isotopes of these elements. Such labels thus can be used as tracers of compliance. Variations of several percent can be generated without adverse physiological effect. An example is presented of the use of deuterium oxide as a tracer, and a scheme of sampling moisture in expired air is proposed, in which the subject can easily collect a sample and present it for rapid analysis. Tracer levels can be used to estimate the degree of compliance. The labeled compound can be selected to match the drug being tested with respect to residence time in the body. Except for deuterium, the cost of such stable isotope tracers is at present prohibitive. The main problem with the use of stable isotopes in compliance studies is the cost of the tracer, a biologically acceptable substance labeled with a rare-stable isotope. Our original experiments were carried out using 13C-glucose, which costs at present about $600/g. To carry out a tracer experiment on an individual, approximately 10 mg of uniformly labeled tracer would be administered, which would result in a 5% shift of the 13C/12C ratio, which is easily detectable. To minimize the cost of such a study, we proposed utilizing the cheapest enriched light isotope that is available, namely, deuterium. Using a ratio-detecting mass spectrometer in which a sample is compared with a standard, it is possible to detect enrichment or depletion of deuterium with respect to 1H at the level of 0.1%.(ABSTRACT TRUNCATED AT 250 WORDS)

Clinical Trials as Topic↗

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters.

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO2 evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1-5 micromoles of carbon and has an associated blank of 0.1-0.2 micromole of carbon. Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO2 as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3%. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The delta 13C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC. The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average delta 13C = -12.4%). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and delta 13C of pore-water DOC was nearly 8% lighter at 1.5-2.0-cm depth than in the mat surface layer (0-0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and delta 13C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.

Carbon↗

Assessing microbial degradation of o-xylene at field-scale from the reduction in mass flow rate combined with compound-specific isotope analyses.

In recent years, natural attenuation (NA) has evolved into a possible remediation alternative, especially in the case of BTEX spills. In order to be approved by the regulators, biodegradation needs to be demonstrated which requires efficient site investigation and monitoring tools. Three methods--the Integral Groundwater Investigation method, the compound-specific isotope analysis (CSIA) and a newly developed combination of both--were used in this work to quantify at field scale the biodegradation of o-xylene at a former gasworks site which is heavily contaminated with BTEX and PAHs. First, the Integral Groundwater Investigation method [Schwarz, R., Ptak, T., Holder, T., Teutsch, G., 1998. Groundwater risk assessment at contaminated sites: a new investigation approach. In: Herbert, M. and Kovar, K. (Editors), GQ'98 Groundwater Quality: Remediation and Protection. IAHS Publication 250, pp. 68-71; COH 4 (2000) 170] was applied, which allows the determination of mass flow rates of o-xylene by integral pumping tests. Concentration time series obtained during pumping at two wells were used to calculate inversely contaminant mass flow rates at the two control planes that are defined by the diameter of the maximum isochrone. A reactive transport model was used within a Monte Carlo approach to identify biodegradation as the dominant process for reduction in the contaminant mass flow rate between the two consecutive control planes. Secondly, compound-specific carbon isotope analyses of o-xylene were performed on the basis of point-scale samples from the same two wells. The Rayleigh equation was used to quantify the degree of biodegradation that occurred between the wells. Thirdly, a combination of the Integral Groundwater Investigation method and the compound-specific isotope analysis was developed and applied. It comprises isotope measurements during the integral pumping tests and the evaluation of delta13C time series by an inversion algorithm to obtain spatially integrated mean isotope values at the control planes. It was shown that the Rayleigh equation is applicable to spatially integrated mean isotope values in order to obtain the mean biodegradation between the consecutive control planes. All three approaches yielded consistently a 98-99% degradation of o-xylene.

Biodegradation, Environmental↗

Quantifying chlorinated ethene degradation during reductive dechlorination at Kelly AFB using stable carbon isotopes.

Stable isotope analysis of chlorinated ethene contaminants was carried out during a bioaugmentation pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. In this pilot test, cis-1,2-dichloroethene (cDCE) was the primary volatile organic compound. A mixed microbial enrichment culture, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene, was added to the pilot test area. Following bioaugmentation with KB-1, perchloroethene (PCE), trichloroethene (TCE) and cDCE concentrations declined, while vinyl chloride (VC) concentrations increased and subsequently decreased as ethene became the dominant transformation product. Shifts in carbon isotopic values up to 2.7 per thousand, 6.4 per thousand, 10.9 per thousand and 10.6 per thousand were observed for PCE, TCE, cDCE and VC, respectively, after bioaugmentation, consistent with the effects of biodegradation. While a rising trend of VC concentrations and the first appearance of ethene were indicative of biodegradation by 72 days post-bioaugmentation, the most compelling evidence of biodegradation was the substantial carbon isotope enrichment (2.0 per thousand to 5.0 per thousand) in ä13C(cDCE). Fractionation factors obtained in previous laboratory studies were used with isotope field measurements to estimate first-order cDCE degradation rate constants of 0.12 h(-1) and 0.17 h(-1) at 115 days post-bioaugmentation. These isotope-derived rate constants were clearly lower than, but within a factor of 2-4 of the previously published rate constant calculated in a parallel study at Kelly AFB using chlorinated ethene concentrations. Stable carbon isotopes can provide not only a sensitive means for early identification of the effects of biodegradation, but an additional means to quantify the rates of biodegradation in the field.

Biodegradation, Environmental↗

REE characteristics and Pb, Sr and Nd isotopic compositions of steel plant emissions.

A comprehensive Pb-Sr-Nd isotope and REE tracer study of atmospheric trace metal pollution by a steel plant situated to the north of the urban communities of Strasbourg (France) and Kehl (Germany) has been performed using tree barks as biomonitors. The 206Pb/207Pb and 208Pb/207Pb isotopic ratios of the steel plant's filter dust are similar to values found in dust of waste incinerators. The 87Sr/86Sr ratio is similar to present-day ratios of Phanerozoic or Precambrian granitic rocks. The 143Nd/144Nd isotopic composition is very low and corresponds to an (Nd) value of -17.5. Such a low value is characteristic of old Precambrian granitic rocks and banded iron formations. Thus, this low (Nd) value might point to the origin of the iron necessary for the steel production. The fact, that this isotopic composition does not occur in crustal rocks of Western Central Europe makes the Nd isotope ratio a powerful tool to trace steel plants atmospheric emissions. The rare earth element (REE) distribution pattern of the steel plant's filter dust shows very specific fractionations like La and Nd enrichments which are traceable in tree barks over a distance of 4 km. The Pb, Sr and Nd isotope ratios not only enable the steel plant's emissions to be traced in a north-easterly direction, along the principal wind pathway but also enables the interference of this emission at 4 km NE from the steel plant with another atmospheric component originating from the Strasbourg Rhine harbour to be identified.

Air Pollutants↗

Separation of vanadium isotopes by ion-exchange chromatography.

Cation-exchange displacement chromatography of VO2+ was carried out for studying vanadium isotope effects in carboxylate ligand-exchange systems. The heavier isotope 51V was enriched in the carboxylate complex solution. The isotope separation coefficients epsilon(= alpha-1) for 50V/51V were 2.2 x 10(-4) and 2.4 x 10(-4) for citrate and lactate systems at 298 K, respectively. These values are much larger than those obtained in a previous study on the malate system. The existence of binuclear complexes of VO2+ may create the conditions for larger isotope fractionation. From the viewpoint of the process development of isotope separation, the heights equivalent to a theoretical plate of these processes were analyzed and found to be very small in each system due to the homogeneous, small and highly porous resin used. Citrate may be better than the other tested systems for the vanadium isotope separation.

Cation Exchange Resins↗