Source Isotope Ratio Research Articles

Diffusive fractionation complicates isotopic partitioning of autotrophic and heterotrophic sources of soil respiration

Carbon isotope ratios (δ¹³C) of heterotrophic and rhizospheric sources of soil respiration under deciduous trees were evaluated over two growing seasons. Fluxes and δ¹³C of soil respiratory CO₂ on trenched and untrenched plots were calculated from closed chambers, profiles of soil CO₂ mole fraction and δ¹³C and continuous open chambers. δ¹³C of respired CO₂ and bulk carbon were measured from excised leaves and roots and sieved soil cores. Large diel variations (>5‰) in δ¹³C of soil respiration were observed when diel flux variability was large relative to average daily fluxes, independent of trenching. Soil gas transport modelling supported the conclusion that diel surface flux δ¹³C variation was driven by non-steady state gas transport effects. Active roots were associated with high summertime soil respiration rates and around 1‰ enrichment in the daily average δ¹³C of the soil surface CO₂ flux. Seasonal δ¹³C variability of about 4‰ (most enriched in summer) was observed on all plots and attributed to the heterotrophic CO₂ source.

Resolving the Germanium Atomic Weight Disparity Using Multicollector ICPMS

Two most recent mass spectrometric measurements of natural isotopic composition germanium gave discordant Ge atomic weight values of 72.6276(64)(k=2) and 72.6390(69)(k=2), respectively, a decade ago. Each measurement was performed with a different mass spectrometry platform, gas source isotope ratio mass spectrometry and thermal ionization mass spectrometry, respectively. Herein we report results obtained by multicollector inductively coupled plasma mass spectrometry yielding an atomic weight of germanium 72.6296(19)(k=2) which is in support of the upcoming 2009 Standard Atomic Weight adjustment by IUPAC. Germanium isotope ratios were calibrated using a regression mass bias correction model and NIST SRM 994 gallium isotopic reference material. In this model, no assumptions are made regarding the mass bias differences between gallium and germanium or between the isotopes of germanium. Isotope ratios of 0.5620(21), 0.7515(16), 0.2125(7), and 0.2121(12) were obtained for n((70)Ge)/n((74)Ge), n((72)Ge)/n((74)Ge), n((73)Ge)/n((74)Ge), and n((76)Ge)/n((74)Ge), respectively, with expanded uncertainties (k = 2) estimated in accordance with the ISO/BIPM Guide to the Expression of Uncertainty in Measurements.

Aquatic food webs in mangrove and seagrass habitats of Centla Wetland, a Biosphere Reserve in Southeastern Mexico

Mangrove and seagrass habitats are important components of tropical coastal zones worldwide, and are conspicuous habitats of Centla Wetland Biosphere Reserve (CWBR) in Tabasco, Mexico. In this study, we examine food webs in mangrove- and seagrass-dominated habitats of CWBR using stable isotope ratios of carbon and nitrogen. Our objective was to identify the importance of carbon derived from mangroves and seagrasses to secondary production of aquatic consumers in this poorly studied conservation area. Carbon and nitrogen isotope ratios of basal sources and aquatic consumers indicated that the species-rich food webs of both habitats are dependent on riparian production sources. The abundant Red mangrove Rhizophora mangle appears to be a primary source of carbon for the mangrove creek food web. Even though dense seagrass beds were ubiquitous, most consumers in the lagoon food web appeared to rely on carbon derived from riparian vegetation (e.g. Phragmites australis). The introduced Amazon sailfin catfish Pterygoplichthys pardalis had isotope signatures overlapping with native species (including high-value fisheries species), suggesting potential competition for resources. Future research should examine the role played by terrestrial insects in linking riparian and aquatic food webs, and impacts of the expanding P. pardalis population on ecosystem function and fisheries in CWBR. Our findings can be used as a baseline to reinforce the conservation and management of this important reserve in the face of diverse external and internal human impacts.

Energetic costs of male reproduction in a scramble competition mating system

1. The assumption that the primary limitations on reproductive success differ between the sexes is inherent in traditional sexual selection theory. Although the energy that can be allocated to reproduction is assumed to be the main limitation to females, the ability to attract and defend oestrous females is assumed to be the primary limitation to males. 2. Estimates of the energetic costs of reproduction in male mammals are, however, limited and have largely been obtained from sexually dimorphic species exhibiting female defence mating systems. These studies often reveal that the energetic cost of male reproduction is similar to or even exceeds that of females, and therefore challenge long-held assumptions of inter-sexual reproductive limitations, but their generality is little known. 3. We coupled measurements of energy expenditure with detailed behavioural observations of reproductive male North American red squirrels (Tamiasciurus hudsonicus). This species displays minimal sexual dimorphism and exhibits a scramble competition mating system, under which sexual selection favours enhanced mate searching effort by males. 4. We conducted the study over 2 years characterized by a substantial variation in upcoming natural food availability and across two study populations that experienced either natural food abundance or an ad libitum food-supplementation to investigate the influence of resource availability on male reproductive energy expenditure. 5. Under natural conditions, mean energy expenditure of males across the 2 years was high, approximating that of females during lactation. Furthermore, in the anticipation of high upcoming natural food availability and resultant offspring survival, expenditure approximately doubled (from 290 +/- 7 to 579 +/- 73 kJ day(-1)). When current food availability (and consequently the density of receptive females) was experimentally elevated, males displayed the highest levels of energy expenditure we recorded (873 +/- 98 kJ day(-1)). 6. Our results provide compelling evidence that the energy available for reproductive allocation places a strong limitation on reproduction in male North American red squirrels and contribute to previous work suggesting that high and limiting energetic costs of male reproduction may be a general feature of mammalian reproduction.

Carbon isotope fractionation in phospholipid fatty acid biomarkers of bacteria and fungi native to an acid mine drainage lake

This study identifies isotope signatures associated with autotrophic and heterotrophic microbial communities that may provide a means to determine carbon cycling relationships in situ for acid mine drainage (AMD) sites. Stable carbon isotope ratios (δ13C) of carbon sources, bulk cells, and membrane phospholipids (PLFA) were measured for autotrophic and heterotrophic microbial enrichment cultures from a mine tailings impoundment in northern Ontario, Canada, and for pure strains of the sulfur oxidizing bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. The autotrophic enrichments had indistinguishable PLFA distributions from the pure cultures, and the PLFA cyc-C19:0 was determined to be a unique biomarker in this system for these sulfur oxidizing bacteria. The PLFA distributions produced by the heterotrophic enrichments were distinct from the autotrophic distributions and the C18:2 PLFA was identified as a biomarker for these heterotrophic enrichments. Genetic analysis (16S, 18S rRNA) of the heterotrophic cultures indicated that these communities were primarily composed of Acremonium fungi.Stable carbon isotope analysis revealed that bulk cellular material in all autotrophic cultures was depleted in δ13C by 5.6–10.9‰ relative to their atmospheric CO2 derived carbon source, suggesting that inorganic carbon fixation in these cultures is carbon limited. Individual PLFA from these autotrophs were further depleted by 8.2–14.6‰ compared to the bulk cell δ13C, which are among the largest biosynthetic isotope fractionation factors between bulk cell and PLFA reported in the literature. In contrast, the heterotrophic bulk cells were not significantly fractionated in δ13C relative to their carbon source and heterotrophic PLFA ranged from 3‰ enriched to 4‰ depleted relative to the isotopic composition of their total biomass. These distinct PLFA biomarkers and isotopic fractionations associated with autotrophic and heterotrophic activity in this laboratory study provide potential biomarkers for delineating autotrophic and heterotrophic carbon cycling in AMD environments.

Sources of organic matter and methylmercury in littoral macroinvertebrates: a stable isotope approach

The main objective of this study was to assess organic matter (OM) and methylmercury (MeHg) sources for freshwater littoral macroinvertebrate primary consumers. The carbon and nitrogen stable isotope ratios (δ13C, δ15N) of sources (epiphytes, macrophytes, suspended particulate matter _SPM) and of macroinvertebrate consumers were measured in a fluvial lake with extensive macrophyte beds (emergent and submerged). To determine the relative contribution of each OM source to macroinvertebrate diets we used the IsoSource model that examines all possible combinations of solutions for each source. Total and MeHg concentrations of consumers were also measured. Results show that epiphytes and macrophytes are dominant in the diet of macroinvertebrates, especially in early summer (July). In mid-summer (August), SPM constitutes a non-negligible OM source to the primary consumers. Hg concentrations were higher in epiphytes than in the other OM sources. The proportion of epiphytes in macroinvertebrate diet was positively correlated with the percentage of MeHg in their tissues. There was no relationship between SPM assimilation and Hg concentration in macroinvertebrate consumers. These results suggest that epiphytes and macrophytes constitute the main pathway of Hg bioaccumulation in littoral food webs.

Revised δ34S reference values for IAEA sulfur isotope reference materials S‐2 and S‐3

Revised delta(34)S reference values with associated expanded uncertainties (95% confidence interval (C.I.)) are presented for the sulfur isotope reference materials IAEA-S-2 (22.62 +/- 0.16 per thousand) and IAEA-S-3 (-32.49 +/- 0.16 per thousand). These revised values are determined using two relative-difference measurement techniques, gas source isotope ratio mass spectrometry (GIRMS) and double-spike multi-collector thermal ionization mass spectrometry (MC-TIMS). Gas analyses have traditionally been considered the most robust for relative isotopic difference measurements of sulfur. The double-spike MC-TIMS technique provides an independent method for value-assignment validation and produces revised values that are both unbiased and more precise than previous value assignments. Unbiased delta(34)S values are required to anchor the positive and negative end members of the sulfur delta (delta) scale because they are the basis for reporting both delta(34)S values and the derived mass-independent Delta(33)S and Delta(36)S values.

Measurement of longitudinal sulfur isotopic variations by laser ablation MC-ICP-MS in single human hair strands

A new method for the measurement of longitudinal variations of sulfur isotope amount ratios in single hair strands using a laser ablation system coupled to a multicollector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) is reported here for the first time. Ablation parameters have been optimized for the measurement of sulfur isotope ratios in scalp human hair strands of 80-120-microm thickness and different washing procedures have been evaluated. The repeatability of the method has been tested and the ability to measure sulfur isotopic variations in 1,000-microm-long hair segments has been evaluated. A horse hair sample previously characterized for carbon and nitrogen isotope ratios in an interlaboratory study has been characterized by LA-MC-ICP-MS to be used as an in-house standard for the bracketing of human hair strands. (34)S/(32)S isotope amount ratios have been measured and corrected for instrumental mass bias adopting the external standardization approach using National Institute of Standards and Technology (NIST) RM8553 and full uncertainty budgets have been calculated using the Kragten approach. Results are reported as both (34)S/(32)S isotope amount ratios and deltaS(V-CDT) values (sulfur isotopic differences relative to a reference sample expressed in the Vienna Canyon Diablo Troilite (V-CDT) scale) calculated using NIST RM8553, NIST RM8554, and NIST RM8556 to anchor results to the V-CDT scale. The main advantage of the new method versus conventional gas source isotope ratio mass spectrometry measurements is that longitudinal variations in sulfur isotope amount ratios can be resolved. Proof of concept is shown with human scalp hair strands from three individuals, two UK residents and one traveler (long periods of time abroad). The method enables monitoring of longitudinal isotope ratio variations in single hair strands. Absolute ratios are reported and delta(34)S(V-CDT) values are plotted for comparison. Slight variations of <1.2 per thousand were detected in the hair strands from UK residents whereas the traveler presented a variation of >5 per thousand. Thus, the measurement of sulfur isotopic variations in hair samples has potential to be an indicator of geographical origin and recent movements and could be used in combination with isotope ratio measurements in water/foodstuffs from different geographical locations to provide important information in nutritional and geographical studies.

Precise and Traceable 13C/12C Isotope Amount Ratios by Multicollector ICPMS

A new method for the measurement of SI traceable carbon isotope amount ratios using a multicollector inductively coupled mass spectrometer (MC-ICPMS) is reported for the first time. Carbon (13)C/(12)C isotope amount ratios have been measured for four reference materials with carbon isotope amount ratios ranging from 0.010659 (delta(13)C(VPDB) = -46.6 per thousand) to 0.011601 (delta(13)C(VPDB) = +37 per thousand). Internal normalization by measuring boron (11)B/(10)B isotope amount ratios has been used to correct for the effects of instrumental mass bias. Absolute (13)C/(12)C ratios have been measured and corrected for instrumental mass bias and full uncertainty budgets have been calculated using the Kragten approach. Corrected (13)C/(12)C ratios for NIST RM8545 (Lithium Carbonate LSVEC), NIST RM8573 (L-Glutamic Acid USGS40), NIST RM8542 (IAEA-CH6 Sucrose) and NIST RM8574 (L-Glutamic Acid USGS41) differed from reference values by 0.06-0.20%. Excellent linear correlation (R = 0.9997) was obtained between corrected carbon isotope amount ratios and expected carbon isotope amount ratios of the four chosen NIST RMs. The method has proved to be linear within this range (from (13)C/(12)C = 0.010659 to (13)C/(12)C =0.011601), and therefore, it is suitable for the measurement of carbon isotope amount ratios within the natural range of variation of organic carbon compounds, carbonates, elemental carbon, carbon monoxide, and carbon dioxide. In addition, a CO2 gas sample previously characterized in-house by conventional dual inlet isotope ratio mass spectrometry has been analyzed and excellent agreement has been found between the carbon isotope amount ratio value measured by MC-ICPMS and the IRMS measurements. Absolute values for carbon isotope amount ratios traceable to the SI are given for each NIST RM, and the combined uncertainty budget (including instrumental error and each parameter contributing to Russell expression for mass bias correction) has been found to be < 0.1% for the four materials. The advantage of the method versus conventional gas source isotope ratio mass spectrometry measurements is that carbon isotope amount ratios are measured as C(+) instead of CO2(+), and therefore, an oxygen (17)O correction due to the presence of (12)C(17)O(16)O(+) is not required. Organic compounds in solution can be measured without previous derivatization, combustion steps, or both, thus making the process simple. The novel methodology opens new avenues for the measurement of absolute carbon isotope amount ratios in a wide range of samples.

Potential glacial‐interglacial changes in stable carbon isotope ratios of methane sources and sink fractionation

Past atmospheric methane emissions can be constrained by δ13CH4 records from ice cores only if changes to source δ13CH4 signatures and sink isotope effects with varying environmental and climatic conditions are accurately known. We present reconstructions of such changes based on paleodata and recent systems observations. The results are specific for budget scenarios and are reported here for two alternative types of budgets, one including aerobic methane emissions (AMP) from plants and the other type without AMP. Shifting atmospheric δ13CO2 potentially led to 13CH4 enrichment by 0.8‰ in the preindustrial Holocene (PIH) (∼150–11,000 years (a) B.P.) and ∼0.3–0.6‰ at the Last Glacial Maximum (LGM) (∼18,000 a B.P.) relative to today. Differing distribution of C3 and C4 plant precursor material may account for 13CH4 enrichment of ∼0.4‰ (PIH) and ∼0.6–1.1‰ (LGM). Temperature‐dependent fractionation and varying methanogenic pathways in wetlands may lead to atmospheric 13CH4 depletion by ∼0.1–1.2‰. Sink fractionation today (7.4‰) is higher than during the PIH (∼7.0‰) and the LGM (∼5.7‰). The cumulative effect of all processes is ∼0.8‰ 13CH4 enrichment in the PIH and ∼1–1.2‰ 13CH4 depletion at the LGM. Budget reconstructions will be inaccurate if these changes are not included.

Reply to the comment on “Non-uniqueness and interpretation of the seawater 87Sr/ 86Sr curve” by John M. McArthur and Paul B. Wignall

Waltham and Grocke (2006) introduced a new methodology for analysis of the seawater strontium-isotope curve, which showed that changes to a source-flux (e.g., the continental weathering flux) or a source-isotope ratio (e.g., the hydrothermal flux isotope ratio) could be estimated simply by scaling and shifting the time-derivative of the isotopic curve. We used this methodology to analyse the Lower Jurassic and in particular the Toarcian oceanic anoxic event (T-OAE). The power of this approach is nicely illustrated by the fact that, as a consequence, the scale of the T-OAE strontium-isotope excursion is shown to be controlled almost entirely by the time-duration of this event. However, the comment by McArthur and Wignall (M&W) argues that the change in the Toarcian portion of the curve is solely controlled by sedimentation rate and that the weathering event as produced by Waltham and Grocke (2006) is an artefact of this factor. No criticisms in the comment were associated with our mathematical model itself, and thus this shows our approach’s usefulness for understanding the strontium-isotope cycle on geological time scales. There is unequivocal evidence for an environmental perturbation during the T-OAE that resulted in global warming, an intensified hydrological cycle and increased weathering (see [Hesselbo et al., 2000], [Hesselbo et al., 2007], [Cohen et al., 2004], Kemp et al., 2005 D.B. Kemp, A.L. Coe, A.S. Cohen and L. Schwark, Astronomical pacing of methane release in the Early Jurassic period, Nature 437 (2005), pp. 396–399. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (60)[Kemp et al., 2005] and [McElwain et al., 2005]). Many independent lines of evidence support the Toarcian weathering event and suggest that the degree of condensation proposed by M&W is extreme with limited sedimentological evidence and constraint, especially considering the uncertainties of chronostratigraphic constraint for the Jurassic. The exact magnitudes of all the above require additional, concentrated research efforts. We eagerly await the outcome of such research endeavours and the information they will provide to us for understanding the global perturbation during the Early Jurassic, T-OAE.

A practical guide to clumped isotope geochemistry

Clumped isotope geochemistry examines the spatial organization of rare isotopes within molecules and structural units of minerals. It principally focuses on the ordering, or ‘clumping’ of rare isotopes into bonds with or near each other rather than with isotopically normal atoms. Measurements of isotopic clumping encounter unique problems and limitations. Here, I discuss and illustrate the practical sides of this field, by way of a set of pithy aphorisms that should be followed when making such measurements by gas source isotope ratio mass spectrometry.

Automated Determination of Silicon Isotope Natural Abundance by the Acid Decomposition of Cesium Hexafluosilicate

A procedure for the automated determination of isotopic abundances of silicon from biogenic and lithogenic particulate matter and from dissolved silicon in fresh or saltwaters is reported. Samples are purified using proven procedures through the reaction of Si with acidified ammonium molybdate, followed by precipitation with triethylamine and combustion of the precipitate to yield silicon dioxide. The silicon dioxide is converted to cesium hexafluosilicate by dissolution in hydrogen fluoride and the addition of cesium chloride. Isotopic analysis is accomplished by decomposing the cesium hexafluosilicate with concentrated sulfuric acid to generate silicon tetrafluoride gas. Silicon tetrafluoride is purified cryogenically and analyzed on a gas source isotope ratio mass spectrometer. Yields of silicon tetrafluoride are >99.5%. The procedure can be automated by modifying commercial inlet systems designed for carbonate analysis. The procedure is free of memory effects and isotopic biases. Reproducibility is +/-0.03-0.10 per thousand for a variety of natural and synthetic materials.

Significance of instream autotrophs in trophic dynamics of the Upper Mississippi River

Trophic dynamics of large river-floodplain ecosystems are still not well understood despite development of several conceptual models over the last 25 years. To help resolve questions about the relative contribution of algal and detrital organic matter to food webs in the Upper Mississippi River, we (1) separated living and detrital components of ultrafine and fine transported organic matter (UTOM and FTOM, respectively) by colloidal silica centrifugation; (2) identified stable isotope signatures (delta(13)C and delta(15)N) for these two portions of transported organic matter and other potential organic matter sources; and (3) employed a multiple source, dual-isotope mixing model to determine the relative contribution of major energy sources to primary consumers and the potential contribution of basal sources to the biomass of secondary consumers. The delta(13)C and delta(15)N of living and detrital fractions of UTOM and FTOM were distinct, indicating clear differences in isotopic composition of the algal and detrital fractions of transported organic matter. Living and detrital transported organic matter also differed from other potential organic matter sources by either delta(13)C or delta(15)N. A six-source mixing model using both delta(13)C and delta(15)N indicated that algal transported organic matter was the major resource assimilated by primary consumers. The contribution of detrital transported organic matter was small in most cases, but there were a small number of taxa for which it could potentially contribute to more than half the assimilated diet. Colloidal dissolved organic matter, which includes heterotrophic bacteria, accounted for only a small fraction of the organic matter assimilated by most primary consumers, indicating that coupling between microbial processes and metazoan production is minimal. Terrestrial C(3) litter from the floodplain forest floor and aquatic macrophytes were also relatively unimportant to the assimilated diet of primary consumers. Application of the mixing model to compare basal source isotopic ratios to secondary consumers revealed that most organic matter moving from primary to secondary consumers originated from algal TOM. Our findings indicate that autochthonous organic matter is the major energy source supporting metazoan production in the main channel of this large river, at least during the summer. This study joins a number of other investigations performed globally that indicate organic matter originating from instream production of sestonic and benthic microalgae is a major driver in the trophic dynamics of large river ecosystems.

A cross-calibration of chlorine isotopic measurements and suitability of seawater as the international reference material

A collection of 24 seawaters from various worldwide locations and differing depth was culled to measure their chlorine isotopic composition ( δ 37Cl). These samples cover all the oceans and large seas: Atlantic, Pacific, Indian and Antarctic oceans, Mediterranean and Red seas. This collection includes nine seawaters from three depth profiles down to 4560 mbsl. The standard deviation (2 σ) of the δ 37Cl of this collection is ±0.08‰, which is in fact as large as our precision of measurement (±0.10‰). Thus, within error, oceanic waters seem to be an homogeneous reservoir. According to our results, any seawater could be representative of Standard Mean Ocean Chloride (SMOC) and could be used as a reference standard. An extended international cross-calibration over a large range of δ 37Cl has been completed. For this purpose, 13 geological fluid samples of various chemical compositions and a manufactured CH 3Cl gas sample, with δ 37Cl from about −6‰ to +6‰ have been compared. Data were collected by gas source isotope ratio mass spectrometry (IRMS) at the Paris, Reading and Utrecht laboratories and by thermal ionization mass spectrometry (TIMS) at the Leeds laboratory. Comparison of IRMS values over the range −5.3‰ to +1.4‰ plots on the Y= X line, showing a very good agreement between the three laboratories. On 11 samples, the trend line between Paris and Reading Universities is: δ 37Cl Reading=(1.007±0.009) δ 37Cl Paris−(0.040±0.025), with a correlation coefficient: R 2=0.999. TIMS values from Leeds University have been compared to IRMS values from Paris University over the range −3.0‰ to+6.0‰. On six samples, the agreement between these two laboratories, using different techniques is good: δ 37Cl Leeds=(1.052±0.038) δ 37Cl Paris+(0.058±0.099), with a correlation coefficient: R 2=0.995. The present study completes a previous cross-calibration between the Leeds and Reading laboratories to compare TIMS and IRMS results (Anal. Chem. 72 (2000) 2261). Both studies allow a comparison of IRMS and TIMS techniques between δ 37Cl values from −4.4‰ to +6.0‰ and show a good agreement: δ 37Cl TIMS=(1.039±0.023) δ 37Cl IRMS+(0.059±0.056), with a correlation coefficient: R 2=0.996. Our study shows that, for fluid samples, if chlorine isotopic compositions are near 0‰, their measurements either by IRMS or TIMS will give comparable results within less than ±0.10‰, while for δ 37Cl values as far as 10‰ (either positive or negative) from SMOC, both techniques will agree within less than ±0.30‰.

Nitrogen Isotope Ratios of Synthetic and Organic Sources of Nitrate Water Contamination in Spain

This work aims to identify the sources of nitrogencontamination in nitrate vulnerable zones (NVZs) of Spain by means of the nitrogen isotope method. Three categories of nitrogen sources (synthetic fertilisers, animal wastes, and sludges and effluents from waste-water treatment plants) from three NVZs were analysed for their nitrogen isotopic composition (δ15N) in order to assess the applicability of the method to the identification of these N sources. The mean δ15N values were: +1.48‰ for synthetic fertilisers, +15.98‰ for animal wastes and +11.52‰ for sludges and effluents. The synthetic fertiliser sources were significantly different from the organic sources and so, the method can be used for their identification. The highest variability was found within the animal waste category. The range of values found for the different kinds of animal wastes (+5.86 to +36.74) was very wide and overlappedthe range found for sludges and effluents from waste-water treatmentplants (+4.57 to +20.18). Accordingly, these two nitrogen sources areisotopically indistinguishable.

A closed system digestion and purification procedure for the accurate assay of chlorine in fossil fuels

This paper describes a robust and quantitative method to separate, purify, and assay the amount of chlorine in fossil fuels using isotope dilution mass spectrometry. The digestion/extraction process uses Carius tubes containing the fossil fuel samples in the presence of HNO3, AgNO3 and a 37Cl spike. The closed system oxidation permits complete equilibration of the sample and spike Cl. The evolved chlorine is trapped as AgCl within the Carius tube, and can then be separated and cleaned. The purified AgCl is also amenable to isotopic analysis by solid or gas source isotope ratio mass spectrometry. For isotope dilution mass spectrometry, the chlorine can be readily measured in a thermal ionization mass spectrometer in a negative ion mode as 37Cl/35Cl ratios with an approximate detection limit (LOD) of 0.3 μg Cl and a precision of 0.2%, relative. This technique may also be used to produce samples suitable for high precision measurements of chlorine isotopic variations in fossil fuels and chlorinated hydrocarbons.

Tracing organic matter sources of estuarine tidal flat nematodes with stable carbon isotopes

MEPS Marine Ecology Progress Series Contact the journal Facebook Twitter RSS Mailing List Subscribe to our mailing list via Mailchimp HomeLatest VolumeAbout the JournalEditorsTheme Sections MEPS 234:127-137 (2002) - doi:10.3354/meps234127 Tracing organic matter sources of estuarine tidal flat nematodes with stable carbon isotopes Tom Moens1,*, Caroline Luyten1, Jack J. Middelburg2, Peter M. J. Herman2, Magda Vincx1 1University of Gent, Biology Department, Marine Biology Section, K.L. Ledeganckstraat 35, 9000 Gent, Belgium 2Netherlands Institute for Ecology, Centre for Estuarine and Coastal Ecology, Korringaweg 7, PO Box 140, 4400 AC Yerseke, The Netherlands *E-mail: tom.moens@rug.ac.be ABSTRACT: The present study explores the use of stable carbon isotopes to trace organic matter sources of intertidal nematodes in the Schelde estuary (SW Netherlands). Stable carbon isotope signatures of nematodes from a saltmarsh and 4 tidal flat stations were determined in spring and winter situations, and compared to isotope ratios of organic matter sources within the estuary. Nematodes collected from fine sandy tidal flat sediments in late spring and during mild and sunny late winter weather had δ13C values consistent with microphytobenthos as their prime carbon source. Nematodes from a silty station and individuals sampled under cold and dark winter conditions had δ13C values intermediate between those of microalgae and particulate organic matter. The isotopic signatures of nematodes from the saltmarsh station were intermediate between those of microalgae, Spartina anglica-litter and particulate organic matter. An in situ H13CO3- spike experiment at 2 tidal flat stations corroborated the importance of microphytobenthos as a carbon source for nematodes, yet at the same time contradicted the hypothesis that direct grazing would be the main pathway of microalgal carbon to nematode consumers. A laboratory experiment adding 13C-labeled algal detritus to sediment microcosms demonstrated the nematodes¹ ability to rapidly utilize settling organic matter too. Incorporation of carbon from phytodetritus by subsurface nematodes in both enrichment experiments was high, but, compared to carbon utilization by surface individuals, showed time-lags largely consistent with sediment mixing rates. A combination of observed natural isotope signatures and experimental results suggests that tidal flat nematodes preferentially utilize labile organic carbon derived from microphytobenthos or settling phytoplankton; organic matter from terrestrial or riverine origin does not contribute significantly to the diet of nematodes at our study sites. KEY WORDS: Food web · Nematodes · Microphytobenthos · Phytoplankton · Intertidal estuarine 13C Full text in pdf format PreviousNextExport citation RSS - Facebook - Tweet - linkedIn Cited by Published in MEPS Vol. 234. Online publication date: June 03, 2002 Print ISSN: 0171-8630; Online ISSN: 1616-1599 Copyright © 2002 Inter-Research.

Supernova Grains: The Source of Cosmic-Ray Metals

We show that the Be abundances in old halo stars formed in the early Galaxy strongly suggest that the refractory cosmic-ray metals, in both the early Galaxy and the present epoch, are accelerated from fresh supernova ejecta rather than from the interstellar medium, as proposed in most current models. To resolve this problem, we suggest that the high-velocity grains formed in supernova ejecta are the injection source for these cosmic rays, including C and O. We show how this cosmic-ray injection source can refute previous arguments against cosmic-ray acceleration from fresh supernova ejecta: the enrichment of the highly refractory elements relative to the volatiles and the similarity of the refractory cosmic-ray source and solar elemental and isotopic abundance ratios. We also show that the cosmic-ray source O abundance may be the direct consequence of the condensation of O as refractory oxides and that the problematic cosmic-ray C-to-O ratio may be understood if a large fraction of the C in the ejecta is in graphite grains. We further show that if the refractory metals are accelerated from fresh ejecta, the cosmic-ray source -->54Fe/ -->56Fe should be higher than the corresponding solar value. Such a difference is apparent in some recent cosmic-ray measurements, but forthcoming Advanced Composition Explorer results are needed to confirm this finding.

The relationships between drastic changes in Sr isotope ratios of magma sources beneath the NE Japan arc and the spreading of the Japan sea back-arc basin

Based on Sr isotopic data for Tertiary and Quaternary basaltic rocks from the NE Japan arc, relationships are discussed between the temporal variation of magma source characteristics and the opening of the Japan Sea. The basaltic rocks from the trench side and from the transitional zone show initial87Sr/86Sr ratios (Sri ratios) in the range of 0.70411–0.70546 but no temporal variation in Sri ratios. The back-arc side basaltic rocks with ages of 29.8 to ≈ 15 Ma have Sri ratios similar to those of the trench side and the transitional zone, and these values also show no temporal change. In contrast, the basaltic rocks from the back-arc side, with ages younger than ≈ 15 Ma, show significantly lower Sri ratios (0.70396 to 0.70290), which are slightly higher than those of N-type MORB. These Sr isotopic features may imply that at least before ≈ 15 Ma the magma source regions (the sub-continental mantle) beneath the NE Japan arc had an enriched chemical character and that after ≈ 15 Ma, the magma sources for volcanic rocks from the back-arc side show a drastic change in Sr isotopic character, from an enriched nature to a depleted one. The depleted magmas may have been formed as a result of injection of depleted asthenosphere (or of a depleted mantle diapir) into the subcontinental mantle under the back-arc side of the NE Japan arc, during the spreading of the Japan Sea back-arc basin. The middle Miocene basaltic rocks from the back-arc side are characterized by lower contents of LIL elements such as K2O and Rb compared with those from the trench side, suggesting that during the middle Miocene (syn-opening stage of the Japan Sea) the degree of partial melting may have been higher in the back-arc side mantle than in the trench side mantle. High degree of partial melting in the back-arc side mantle can be attributed to an increasing geothermal gradient in the mantle due to the injection of hot asthenosphere. This injection might also have caused the melting of the lower crust from which the voluminous middle Miocene acidic volcanics in the back-arc side and transitional zone may have been produced.