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PubMed2005

Stable isotopes in studies of intestinal absorption, exchangeable pools and mineral status: the example of magnesium.

Magnesium (Mg) is a biologically essential mineral and Mg deficiency is known to lead to severe biochemical and symptomatic disorders. Radioactive isotopes and, more recently, stable isotopes have been used as research tools to determine intestinal Mg absorption in humans and animals under different nutritional and physiological conditions. Mg isotopes are given orally or orally plus intravenously and analysed in faeces and/or in plasma and urine in order to calculate intestinal Mg absorption and possibly endogenous Mg excretion. Mg isotopes have been used to assess exchangeable pools of Mg under nutritional and physiopathological conditions. Mg isotopes are given intravenously and are analysed in plasma and urine to calculate the size and half-life of the various Mg exchangeable pools. More recently, in vitro isotopic tests have been developed to study the need of cells for Mg in different nutritional and genetic conditions. Whole blood is incubated with Mg isotopes and isotopic blood cell enrichment is measured, which reflects the avidity of cells for Mg and thus its initial status. This paper is a report on the use of stable Mg isotopes and their advantages in these different fields of Mg absorption and metabolism. The studies available have clearly demonstrated that stable isotopes provide a useful research tool for determining intestinal Mg absorption, and represent a precious research tool for the study of Mg metabolism and the assessment of Mg status.

Animals↗
PubMed1997

Kinetic isotope effect characterization of the transition state for oxidized nicotinamide adenine dinucleotide hydrolysis by pertussis toxin.

Pertussis toxin from Bordatella pertussis catalyzes the ADP ribosylation of several G-proteins, using NAD+ as a substrate. In the absence of an acceptor protein, the toxin acts as a NAD+ glycohydrolase. Pertussis toxin is one of the virulent factors for whooping cough and therefore a target for site-specific inhibitors based on the transition state structure. A family of kinetic isotope effects was determined for the hydrolysis reaction, using NAD+ labeled with 3H, 14C, and 15N as substrates. Primary isotope effects were 1.021 +/- 0.001 for [1'N-14C]NAD+ and 1.021 +/- 0.004 for [1N-15N]NAD+, and the double-primary effect of [1'N-14C,1N-15N]NAD+ was 1.049 +/- 0.004. Secondary kinetic isotope effects were 1.207 +/- 0.010 for the [1'N-3H]-, 1.144 +/- 0.005 for the [2'N-3H]-, 0.989 +/- 0.001 for the [4'N-3H]-, and 1.019 +/- 0.004 for the [5'N-3H]NAD+, respectively. Commitment to catalysis was excluded by isotope trapping experiments, and the experimental kinetic isotope effects were independent of pH. The measured isotope effects are therefore intrinsic. The isotope effects are remarkable because they indicate an oxocarbenium-like ribose ring at the transition state but a stiffer than expected vibrational environment for C1' at the reaction center. On the basis of these isotope effects, a bond order vibrational analysis was performed to locate a transition state structure consistent with the isotope effects. The kinetic isotope effects predict a residual bond order to the nicotinamide leaving group of 0.11, corresponding to a distance of 2.14 A. Participation of the water nucleophile is weak, consistent either with an S(N)1-like transition state with no water interaction or with the water oxygen no closer than 3.5 A from the reaction center. The positive charge of the ribose oxocarbenium is stabilized by delocalization between the C1'-O4' and C1'-C2' bonds. The enzyme contacts restrict the vibrational environment of the reaction coordinate requiring increased bonding force constants for the enzyme-stabilized transition state. NAD+ analogues with the nicotinamide ribose replaced by an iminoribitol ring, mimicking the flattened ribose ring of the transition state, are expected to be transition state inhibitors.

Carbon Radioisotopes↗
PubMed2004

Using chromium stable isotope ratios to quantify Cr(VI) reduction: lack of sorption effects.

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr(VI) and Cr(VI) adsorbed onto gamma-Al2O3 and goethite is less than 0.04 per thousand (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO4(2-) was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in delta53Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Absorption↗
PubMed2005

A new concept linking observable stable isotope fractionation to transformation pathways of organic pollutants.

Measuring stable isotope fractionation of carbon, hydrogen, and other elements by Compound Specific Isotope Analysis (CSIA) is a new, innovative approach to assess organic pollutant degradation in the environment. Central to this concept is the Rayleigh equation which relates degradation-induced decreases in concentrations directly to concomitant changes in bulk (= average over the whole compound) isotope ratios. The extent of in situ transformation may therefore be inferred from measured isotope ratios in field samples, provided that an appropriate enrichment factor (epsilonbulk) is known. This epsilonbulk value, however, is usually only valid for a specific compound and for specific degradation conditions. Therefore, a direct comparison of epsilonbulk values for different compounds and for different types of reactions has in general not been feasible. In addition, it is often uncertain how robust and reproducible epsilonbulk values are and how confidently they can be used to quantify contaminant degradation in the field. To improve this situation and to achieve a more in-depth understanding, this critical review aims to relate fundamental insight about kinetic isotope effects (KIE) found in the physico(bio)chemical literature to apparent kinetic isotope effects (AKIE) derived from epsilonbulk values reported in environmentally oriented studies. Starting from basic rate laws, a quite general derivation of the Rayleigh equation is given, resulting in a novel set of simple equations that take into account the effects of (1) nonreacting positions and (2) intramolecular competition and that lead to position-specific AKIE values rather than bulk enrichment factors. Reevaluation of existing epsilonbulk literature values result in consistent ranges of AKIE values that generally are in good agreement with previously published data in the (bio)-chemical literature and are typical of certain degradation reactions (subscripts C and H indicate values for carbon and hydrogen): AKIEc = 1.01-1.03 and AKIEH = 2-23 for oxidation of C-H bonds; AKIEc = 1.03-1.07 for SN2-reactions; AKIEc = 1.02-1.03 for reductive cleavage of C-Cl bonds; AKIEc = 1.00-1.01 for C=C bond epoxidation; AKIEc = 1.02-1.03 for C=C bond oxidation by permanganate. Hence, the evaluation scheme presented bridges a gap between basic and environmental (bio)chemistry and provides insight into factors that control the magnitude of bulk isotope fractionation factors. It also serves as a basis to identify degradation pathways using isotope data. It is shown how such an analysis may be even possible in complex field situations and/or in cases where AKIE values are smaller than intrinsic KIE values, provided that isotope fractionation is measured for two elements simultaneously ("two-dimensional isotope analysis"). Finally, the procedure is used (1) to point outthe possibility of estimating approximate epsilonbulk values for new compounds and (2) to discuss the moderate, but non-negligible variability that may quite generally be associated with epsilonbulk values. Future research is suggested to better understand and take into account the various factors that may cause such variability.

Biochemical Phenomena↗
PubMed1989

Isotopic determination of selenium in biological materials with inductively coupled plasma mass spectrometry.

A method for the isotopic determination of selenium in biological matrices is described. The method is based on hydride generation inductively coupled plasma mass spectrometry (ICP-MS). The development is specifically related to the requirements of stable isotope tracer studies in human subjects. The method is based on isotope dilution using 82Se as the in vitro spike and can quantify the 74Se and 77Se contents of samples. It involves wet oxidation (HNO3 - H2O2 or HNO3 - HClO4) of the 82Se-spiked matrix, reduction to selenite by boiling with HCl followed by measurement of the isotope ratios (82Se/77Se and 74Se/77Se) in the gas stream (H2Se) generated from on-line reduction of the sample selenite with NaBH4. Compared with the isotopic signal resulting from a selenite solution containing 5 ng ml-1 of Se, the total sample blank contributions at m/z = 74, 77 and 82 were less than 5% of the respective isotope signal. Worst-case absolute detection limits were 0.2-0.9 ng of Se, depending on the isotope used. Ion beam intensity ratios were measured with an over-all precision [relative standard deviation (RSD)] of 1% for both isotope pairs. Measured ratios (MRa/b) were stable during a given day's operation within the expected precision of the measurements but varied for different days. The magnitude of MRa/b was generally independent of the nature of the matrix. Highly linear relationships were found between ion beam intensity ratios (MRa/b) and the corresponding true isotope ratios for calibration solutions whose isotope ratios had been altered by as much as one order of magnitude.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗
PubMed2003

Source partitioning using stable isotopes: coping with too many sources.

Stable isotopes are increasingly being used as tracers in environmental studies. One application is to use isotopic ratios to quantitatively determine the proportional contribution of several sources to a mixture, such as the proportion of various pollution sources in a waste stream. In general, the proportional contributions of n+1 different sources can be uniquely determined by the use of n different isotope system tracers (e.g., delta13C, delta15N, delta18O) with linear mixing models based on mass balance equations. Often, however, the number of potential sources exceeds n+1, which prevents finding a unique solution of source proportions. What can be done in these situations? While no definitive solution exists, we propose a method that is informative in determining bounds for the contributions of each source. In this method, all possible combinations of each source contribution (0-100%) are examined in small increments (e.g., 1%). Combinations that sum to the observed mixture isotopic signatures within a small tolerance (e.g., +/-0.1 per thousand ) are considered to be feasible solutions, from which the frequency and range of potential source contributions can be determined. To avoid misrepresenting the results, users of this procedure should report the distribution of feasible solutions rather than focusing on a single value such as the mean. We applied this method to a variety of environmental studies in which stable isotope tracers were used to quantify the relative magnitude of multiple sources, including (1) plant water use, (2) geochemistry, (3) air pollution, and (4) dietary analysis. This method gives the range of isotopically determined source contributions; additional non-isotopic constraints specific to each study may be used to further restrict this range. The breadth of the isotopically determined ranges depends on the geometry of the mixing space and the similarity of source and mixture isotopic signatures. A sensitivity analysis indicated that the estimated ranges vary only modestly with different choices of source increment and mass balance tolerance parameter values. A computer program (IsoSource) to perform these calculations for user-specified data is available at http://www.epa.gov/wed/pages/models.htm.

Carbon Isotopes↗
PubMed2003

Isotope variations in white-tailed kites from various habitats in California: possible limitations in assessing prey utilization and population dynamics.

White-tailed kite (Elanus leucurus) populations in the 1930s were close to extirpation in the United States. But by the 1940s, an upward trend towards recovery was apparent and continued to their current stable population levels. These dramatic fluctuations in kite numbers may have been related to changes in rodent prey populations due to the conversion of native habitats to agriculture. To address this question, we evaluated the use of stable isotope analysis in determining if a shift in diet could be isotopically differentiated in current and historic kite populations. We first compared delta13C, delta15N, and delta34S values from present-day kite flight feathers and prey fur samples from four locations in California. The total ranges of isotope values for kite and their rodent prey were similar within each site. Carbon isotope values ranged from -27.1 to -22.2 per thousand in Arcata, -26.1 to -16.9 per thousand in Davis, -27.0 to -15.0 per thousand in Cosumnes, and -28.2 to -11.6 per thousand in Santa Barbara. Nitrogen isotope values ranged from 3.2 to 15.7 per thousand in Arcata, 2.8 to 12.7 per thousand in Davis, 4.0 to 15.7 per thousand in Cosumnes, and 1.7 to 20.0 per thousand in Santa Barbara. Sulfur isotope values ranged from -7.8 to 12.4 per thousand in Arcata, -1.1 to 9.2 per thousand in Davis, 0.7 to 10.9 per thousand in Cosumnes, and -8.6 to 15.6 per thousand in Santa Barbara. Carbon, nitrogen, and sulfur isotope values at each site reflect typical trophic enrichments due to physiological processes. At each site, delta13C and delta15N values reflected the influence of a predominantly C3 or a mixed C3/C4 plant community. Sulfur isotope values reflect the influence of predominant marine or terrestrial sulfur sources at each site. However, variability in isotope values may limit the usefulness of such analyses for addressing prey utilization and population dynamics.

Animals↗
PubMedDate not supplied

High-precision continuous-flow isotope ratio mass spectrometry.

Although high-precision isotope determinations are routine in many areas of natural science, the instrument principles for their measurements have remained remarkably unchanged for four decades. The introduction of continuous-flow techniques to isotope ratio mass spectrometry (IRMS) instrumentation has precipitated a rapid expansion in capabilities for high-precision measurement of C, N, O, S, and H isotopes in the 1990s. Elemental analyzers, based on the flash combustion of solid organic samples, are interfaced to IRMS to facilitate routine C and N isotopic analysis of unprocessed samples. Gas/liquid equilibrators have automated O and H isotopic analysis of water in untreated aqueous fluids as complex as urine. Automated cryogenic concentrators permit analysis at part-per-million concentrations in environmental samples. Capillary gas chromatography interfaced to IRMS via on-line microchemistry facilitates compound-specific isotope analysis (CSIA) for purified organic analytes of 1 nmol of C, N, or O. GC-based CSIA for hydrogen and liquid chromatography-based interfaces to IRMS have both been demonstrated, and continuing progress promises to bring these advances to routine use. Automated position-specific isotope analysis (PSIA) using noncatalytic pyrolysis has been shown to produce fragments without appreciable carbon scrambling or major isotopic fractionation, and shows great promise for intramolecular isotope ratio analysis. Finally, IRMS notation and useful elementary isotopic relationships derived from the fundamental mass balance equation are presented.

Animals↗
PubMed1997

Clinical value of triple-energy window scatter correction in simultaneous dual-isotope single-photon emission tomography with 123I-BMIPP and 201Tl.

To improve the image quality in simultaneous dual-isotope single-photon emission tomography (SPET) with iodine-123 labelled 15-(p-iodophenyl)-3-methylpentadecanoic acid (BMIPP) and thallium-201, we applied the triple-energy window method (TEW) for correction of the cross-talk and scatter artifact. Seventy-one patients with coronary artery disease were included. 201Tl cross-talk into the 123I acquisition window (group 1, n = 30) and 123I cross-talk into the 201Tl window (group 2, n = 41) were studied. In group 1, 123I images were first obtained (single-isotope images), followed by 201Tl injection and SPET acquisition using dual-isotope windows (dual-isotope images). In group 2, the order was reversed. The dual-isotope SPET images with and without TEW were compared with the single-isotope images. Qualitative evaluation was performed by scoring the segmental defect pattern. Detectability of the mismatched fatty acid metabolism on dual-isotope SPET was evaluated by receiver operating characteristic (ROC) curve analysis. Segmental defect pattern agreement between dual and corrected single images was significantly improved by TEW correction (P<0.01). The agreement was particularly improved in segments with absence of uptake. There was no significant difference between TEW-corrected dual-isotope SPET and corresponding single-isotope SPET with regard to either % defect count or background activity. Mismatched fatty acid metabolism depicted by dual-isotope SPET predicted abnormal wall motion more accurately with TEW than without TEW. With TEW, a practical method for scatter and cross-talk correction in clinical settings, simultaneous dual 123I-BMIPP/201Tl SPET is feasible for the assessment of myocardial perfusion/metabolism mismatch.

Case-Control Studies↗
PubMed2004

Chromatographic separation and multicollection-ICPMS analysis of iron. Investigating mass-dependent and -independent isotope effects.

A procedure was developed that allows precise determination of Fe isotopic composition. Purification of Fe was achieved by ion chromatography on AG1-X8 strongly basic anion-exchange resin. No isotopic fractionation is associated with column chemistry within 0.02 per thousand /amu at 2sigma. The isotopic composition was measured with a Micromass IsoProbe multicollection inductively coupled plasma hexapole mass spectrometer. The Fe isotopic composition of the Orgueil CI1 carbonaceous chondrite, which best approximates the solar composition, is indistinguishable from that of IRMM-014 (-0.005 +/- 0.017 per thousand /amu). The IRMM-014 reference material is therefore used for normalization of the isotopic ratios. The protocol for analyzing mass-dependent variations is validated by measuring geostandards (IF-G, DTS-2, BCR-2, AGV-2) and heavily fractionated Fe left after vacuum evaporation of molten wüstite (FeO) and solar (MgO-Al(2)O(3)-SiO(2)-CaO-FeO in chondritic proportions) compositions. It is shown that the isotopic composition of Fe during evaporation of FeO follows a Rayleigh distillation with a fractionation factor alpha equal to (m(1)/m(2)()1/2), where m(1) and m(2) are the masses of the considered isotopes. This agrees with earlier measurements and theoretical expectations. The isotopic composition of Fe left after vacuum evaporation of solar composition also follows a Rayleigh distillation but with a fractionation factor (1.013 22 +/- 0.000 67 for the (56)Fe/(54)Fe ratio) that is lower than the square root of the masses (1.018 35). The protocol for analyzing mass-independent variations is validated by measuring terrestrial rocks that are not expected to show departure from mass-dependent fractionation. After internal normalization of the (57)Fe/(54)Fe ratio, the isotopic composition of Fe can be measured accurately with precisions of 0.2epsilon and 0.5epsilon at 2sigma for (56)Fe/(54)Fe and (58)Fe/(54)Fe ratios, respectively (epsilon refers to relative variations in parts per 10 000). For (58)Fe, this precision is an order of magnitude better than what had been achieved before. The method is applied to rocks that could potentially exhibit mass-independent effects, meteorites and Archaean terrestrial samples. The isotopic composition of a 3.8-Ga-old banded iron formation from Isua (IF-G, Greenland), and quartz-pyroxene rocks from Akilia and Innersuartuut (GR91-26 and SM/GR/171770, Greenland) are normal within uncertainties. Similarly, the Orgueil (CI1), Allende (CV3.2), Eagle Station (ESPAL), Brenham (MGPAL), and Old Woman (IIAB) meteorites do not show any mass-independent effect.

Journal Article↗
PubMed2000

Anomaly of 155Gd and 157Gd isotope effects in ligand exchange reactions observed by ion exchange chromatography

The isotope effects of gadolinium in Gd-EDTA ligand exchange system were studied by means of ion exchange chromatography. The separation coefficients of gadolinium isotopes, epsilon, and the local enrichment factors, beta, were calculated from the observed isotopic ratios at the front and rear boundaries of the gadolinium adsorption band. Clear mass independent anomalies were observed in the isotope effects of 155Gd and 157Gd. The relation between the isotope effects of gadolinium isotopes, studied by the three-isotope plot and the separation coefficient methods, and the mass of gadolinium isotopes was found to be related to the change in the mean square radius of the nuclear charge distribution parameter, (r2), of these isotopes, which suggests that the nucleus shape and size highly affect the gadolinium isotope effects in chemical exchange reactions.

Journal Article↗
PubMed1998

Deuterium kinetic isotope effects and the mechanism of the bacterial luciferase reaction.

A combined experimental and theoretical investigation of the deuterium isotope effects on the bacterial luciferase reaction is described. The experimental studies focus on determining if the unusual aldehydic deuterium isotope effect of approximately 1.5 observed in these reactions is an intrinsic isotope effect resulting from a single rate-limiting step or is a composite of multiple rate-limiting steps. The isotope effect observed is not significantly affected by variation in the aldehyde chain length, changes in the pH over a range of 6-9, use of alphaC106A and alphaC106S site-directed mutants, or chloride substitution at the 8-position of the reduced flavin, though the isotope effect is decreased when the 8-methoxy-substituted flavin is used as a substrate. From these observations it is concluded that the aldehydic isotope effect arises from the change in rate of a single kinetic step. A stopped-flow kinetic analysis of the microscopic rate constants for the reactions of 1-[1H]decanal and 1-[2H]decanal in the bacterial luciferase reaction was carried out, and aldehyde hydration isotope effects were determined. From the results it is estimated that the aldehydic deuterium isotope effect is approximately 1.9 after formation of an intermediate flavin C4a-hydroperoxy hemiacetal. Ab initio calculations were used to examine the transformation of the aldehyde into a carboxylic acid and to predict isotope effects for possible mechanisms. These calculations indicate that the mechanism involving rate-limiting electron transfer from the flavin C4a-hydroxide to an intermediate dioxirane is consistent with the enigmatic aldehydic isotope effect and that the intermediacy of a dioxirane is energetically plausible.

Aldehydes↗
PubMed2004

Isotopic analysis of Fe in human red blood cells by multiple collector-ICP-mass spectrometry.

Precise 56Fe/54Fe and 57Fe/54Fe isotopic ratios on human red blood cell (RBC) samples have been measured using multiple collector-ICP-mass spectrometry (MC-ICPMS). The mass spectrometric interferences on Fe isotopes (e.g., 56ArO+ and 57ArOH+) were successfully minimized by a dry plasma condition achieved by a desolvating nebulizer sample-introduction technique. In order to eliminate possible variations in the measured isotopic ratios due to non-mass spectrometric interferences, Fe was separated from remaining organic compounds and major co-existing elements using an ion chromatographic technique. The resulting precisions of the 56Fe/54Fe and 57Fe/54Fe ratio measurements were 0.12 per thousand and 0.20 per thousand, respectively, which were high enough to detect the isotopic variation of Fe in nature. For an interlaboratory comparison, all of the Fe isotopic ratio data were normalized by the ratios for the IRMM-014 international isotopic standard. A series of 12 RBC samples were collected from one person through monthly-based sampling over a period of one year. These were analyzed to test possible seasonal changes in the 56Fe/54Fe and 57Fe/54Fe ratios. Moreover, in order to test possible variations in the 56Fe/54Fe and 57Fe/54Fe ratios among different people, RBC samples were collected from five volunteers (four males and one female). The 56Fe/54Fe and 57Fe/54Fe ratios for a series of 12 RBC samples collected over a one-year period show 3.06 per thousand and 4.51 per thousand lower than the values of IRMM-014, and no significant seasonal change could be found in the ratios. The lack in seasonal changes in the Fe isotopic ratios could be explained by a small contribution of the daily net-intake of Fe (1 - 2 mg/day) onto the total amount of Fe in the human body (2 - 4 g). The 56Fe/54Fe and 57Fe/54Fe ratios for RBC samples collected from four male samples did not vary measurably, whereas the Fe isotopic ratios for a female RBC were 0.3 per thousand/amu heavier than the mean value of four male samples. This difference in Fe isotopes among the individuals can be the result of a difference in uptake efficiency of the Fe through a dietary process from the digestive tract. The data obtained here demonstrate that the isotopic ratios of trace metals can provide new information about metabolic efficiencies of the metallic elements.

Cell Separation↗
PubMed2006

Geographical patterns of human diet derived from stable-isotope analysis of fingernails.

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail delta13C values (mean +/- standard deviation) were -15.4 +/- 1.0 and -18.8 +/- 0.8 per thousand and delta15N values were 10.4 +/- 0.7 and 9.4 +/- 0.6 per thousand for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region.

Brazil↗
PubMed2006

Assessing trophic interactions in a guild of primary parasitoids and facultative hyperparasitoids: stable isotope analysis.

Facultative hyperparasitism is likely to be the most common form of intraguild predation among parasitoids. However, difficulties associated with studying facultative hyperparasitoids in the field have hampered a thorough understanding of their trophic ecology. In this study, we used a combination of stable isotope analysis and published natural history information to infer trophic interactions in a guild of field-collected primary parasitoids and facultative hyperparasitoids that attack a gall-making midge on Baccharis pilularis. Our three a priori hypotheses were: (1) stable isotope values should increase incrementally from the host plant to higher trophic levels; (2) the two species of ectoparasitoids should exhibit higher stable isotope signatures than the two endoparasitoids, and; (3) the two facultative hyperparasitoids should exhibit stable isotope signatures that fall between zero and one trophic level steps above that observed for the primary parasitoids. Food webs inferred from stable isotope data generally agreed with previously published accounts of community structure. As expected, both delta(13)C and delta(15)N were progressively enriched in the heavy isotope from the host plant to the herbivorous midge to the parasitic wasps. Multivariate analysis of stable isotope data revealed that the two primary ectoparasitoids occupied a similar trophic niche, but were significantly different from the primary endoparasitoids. We attribute this result to "coincidental intraguild predation" by ectoparasitoids that develop on already-parasitized midge larvae. One of the facultative hyperparasitoids, Zatropis capitis, exhibited a stable isotope signature approximately one trophic step above the primary parasitoids. Unexpectedly, the second facultative hyperparasitoid, Mesopolobus sp., appeared to be developing as a primary parasitoid at all sites. Coupled with independent assessments of community structure, stable isotope analysis validated trophic links constructed by previous researchers and identified potential taxon-specific differences in trophic interactions for two facultative hyperparasitoids in the B. pilularis gall community.

Animals↗
PubMed1991

Correlated Si isotope anomalies and large 13C enrichments in a family of exotic SiC grains.

A suite of morphologically distinctive silicon carbide (SiC) grains from the Orgueil and Murchison carbonaceous chondrite meteorites contains Si and C of highly anomalous isotopic composition. All of the SiC grains in this suite are characterized by a distinctive platy morphology and roughly developed hexagonal crystal forms that allow them to be distinguished from other types of SiC found in the host meteorites. The delta 29Si and delta 30Si values of individual SiC crystals deviate from those of normal solar material by more than 100%, while the delta 13C values range from 150 to 5200%. Isotopically normal C and Si are not found in any of these SiC crystals. The SiC grains belonging to this morphological suite are isotopically distinct from fine-grained SiC aggregates and other morphological types of SiC in unequilibrated meteorites. The 29Si/28Si and 30Si/28Si ratios of these platy grains are well correlated and define a linear array that does not pass through the composition of normal, solar Si. This behavior contrasts sharply with the diverse and poorly correlated Si isotopic compositions shown by the total SiC population. We suggest that the distinctive morphological characteristics and comparatively simple Si isotope systematics identify the platy SiC crystals as a genetically related family, formed around a single, isotopically heterogeneous presolar star or an association of related stars. The enrichments in 13C and the Si isotope systematics of the platy SiC are broadly consistent with theoretical models of nucleosynthesis in low-mass, carbon stars on the asymptotic giant branch. The Si isotope array most plausibly reflects mixing between 28Si-rich material, inherited from a previous generation of stars, and material enriched in 29Si and 30Si, produced in intershell regions by neutron capture during He-burning. 13C is also produced in intershell regions by proton reactions on 12C seed nuclei and is carried with s-process nuclei to the stellar envelope by convection which penetrates down to the He shell. The absence of a correlation between the Si and C isotopic compositions of the SiC suggests either episodic condensation of SiC, extending over several thermal pulses, in the atmosphere of a single star, or derivation of the SiC from several stars characterized by different rates of 13C production. In the multiple star scenario, the linear correlation of the 29Si/28Si and 30Si/28Si ratios among the platy SiC indicates that these stars evolved from a common Si seed composition under similar conditions of neutron-capture nucleosynthesis. The 29Si/30Si ratio of the SiC, inferred by us to be produced by neutron capture in the stellar interior, is distinct from values calculated from models of nucleosynthesis in AGB stars.

Astronomical Phenomena↗
PubMed1991

Strontium isotopic variations of Neoproterozoic seawater: implications for crustal evolution.

We report high precision Sr isotopic data on carbonates from the Neoproterozoic Shaler Group, Victoria Island, Northwest Territories, Canada. Lithostratigraphic correlations with the relatively well-dated Mackenzie Mountains Supergroup constrain Shaler deposition to approximately 770-880 Ma, a range corroborated by 723 +/- 3 Ma lavas that disconformably overlie Shaler carbonates and by Late Riphean microfossils within the section. Samples with low 87Rb/86Sr ratios (<0.01) were selected for Sr isotopic analysis. Delta 18O, Mn, Ca, Mg, and Sr data were used to recognize altered samples. The altered samples are characterized by high Mn/Sr (> or = 2) and variable delta 18O; most are dolomites. The data indicate that between ca. 790-850 Ma the 87Sr/86Sr ratio of seawater varied between 0.70676 and 0.70561. The samples show smooth and systematic variation, with the lowest 87Sr/86Sr value of 0.70561 at ca. 830 Ma. The low 87Sr/86Sr ratio of carbonates from the lower parts of our section is similar to a value reported for one sample from the Adrar of Mauritania (approximately 900 Ma), West African Craton. Isotopic ratios from the upper part of the Shaler section are identical to values from the lower part of the Neoproterozoic Akademikerbreen Group, Spitsbergen. Although a paucity of absolute age determinations hinders attempts at the precise correlation of Neoproterozoic successions, it is possible to draw a broad outline of the Sr isotopic composition of seawater for this period. Indeed, the Sr isotope data themselves provide a stratigraphic tool of considerable potential. Data from this study and the literature are used to construct a curve of the 87Sr/86Sr ratio of Neoproterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period 790-850 Ma. The Sr isotope composition of seawater reflects primarily the balance between continental Sr input through river input and mantle input via hydrothermal circulation of seawater through mid-ocean ridges. Coupling of Nd and Sr isotopic systems allows us to model changes in seafloor spreading rates (or hydrothermal flux) and continental erosion. The Sr hydrothermal flux and the erosion rate (relative to present-day value) are modeled for the period 500-900 Ma. The results indicate that the hydrothermal flux reached a maximum value at ca. 830 Ma. In contrast, a large peak in erosion rate is indicated at ca. 570 Ma. The peaks in hydrothermal flux and erosion rate are most likely related to developments in the Pan-African and related orogenic events, whose initial development is characterized by production of juvenile crust during supercontinental break up and rifting. The time ca. 570 Ma is characterized by continent-continent collision and production of recycled crust. Sr isotope data from Proterozoic carbonates offer a valuable resource for understanding large-scale crust dynamics.

Africa, Western↗
PubMed1994

Oxygen-18 kinetic isotope effects in the dopamine beta-monooxygenase reaction: evidence for a new chemical mechanism in non-heme metallomonooxygenases.

Previous studies of dopamine beta-monooxygenase (D beta M) have implicated the formation of a substrate-derived benzylic radical via a hydrogen atom abstraction mechanism [Miller & Klinman (1985) Biochemistry 24, 2114]. We now address the nature of the oxygen species catalyzing C-H bond cleavage through the measurement of oxygen-18 isotope effects as a function of substrate structure. Using deuterium isotope effects, together with experimental O-18 isotope effects with protonated and deuterated substrates, it has been possible to calculate intrinsic O-18 isotope effects. Since the D beta M mechanism includes many steps which may involve changes in bond order at dioxygen, e.g., the reversible binding of O2 to the active-site copper and its reductive activation to a copper-hydroperoxide species, the intrinsic O-18 isotope effect is expected to be the product of two terms: (1) an overall equilibrium O-18 isotope effect on steps leading from O2 binding to the formation of the intermediate which catalyzes C-H bond cleavage and (2) a kinetic O-18 isotope effect on the C-H bond cleavage step. Thus, the magnitude of a single O-18 isotope effect measurement cannot reveal the nature of the bonding at oxygen during substrate activation. In the present study we have measured the change in O-18 isotope effect as a function of substrate structure and reactivity, finding values of 18(V/K) which decrease from 1.0281 +/- 0.001 to 1.0216 +/- 0.0003 as the rate of the C-H bond cleavage step decreases from 680 to 2 s-1.(ABSTRACT TRUNCATED AT 250 WORDS)

Binding Sites↗