Isotopic composition of tropospheric and soil N2O from successive depths of agricultural plots with contrasting crops and nitrogen amendments

Agricultural soils are the dominant contributor to increases in atmospheric nitrous oxide (N2O). Few studies have investigated the natural N and O isotopic composition of soil N2O. We collected soil gas samples using horizontal sampling tubes installed at successive depths under five contrasting agricultural crops (e.g., unamended alfalfa, fertilized cereal), and tropospheric air samples. Mean d 15N and d 18O values of soil N2O ranged from -28.0 to +8.9‰, and from +29.0 to +53.6‰. The mean d 15N and d 18O values of tropospheric N2O were +4.6 ± 0.7‰ and +48.3 ± 0.2‰, respectively. In general, d values were lowest at depth, they were negatively correlated to soil [N2O], and d 15N was positively correlated to d 18O for every treatment on all sampling dates. N2O from the different agricultural treatments had distinct d 15N and d 18O values that varied among sampling dates. Fertilized treatments had soil N2O with low d values, but the unamended alfalfa yielded N2O with the lowest d values. Diffusion was not the predominant process controlling N2O concentration profiles. Based on isotopic and concentration data, it appears that soil N2O was consumed, as it moved from deeper to shallower soil layers. To better assess the main process(es) controlling N2O within a soil profile, we propose a conceptual model that integrates data on net N2O production or consumption and isotopic data. The direct local impact of agricultural N2O on the isotopic composition of tropospheric N2O was recorded by a shift toward lower d values of locally measured tropospheric N2O on a day with very high soil N2O emissions.

Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and groundwater of Luxembourg

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, d34Ssulfate values between -3.0 and -20.0‰, and d18Osulfate values between +1.5 and +5.0‰; nitrate was characterized by concentrations varying between

A modified commercial DRIFTS cell for kinetically relevant operando studies of heterogeneous catalytic reactions

This paper discusses a number of checks that should be carried out to ensure that the kinetic and spectroscopic measurements made using a DRIFTS cell are meaningful. The observations reported here demonstrate how an appropriately modified commercial DRIFTS cell can provide pertinent kinetic information about both gaseous products and the related surface intermediates. The oxidation of CO with 02 was used as a test to assess the catalyst bed bypass by the reaction mixture. Full CO conversion was obtained after the light-off temperature in the case of the modified cell, contrary to the case of the original cell, for which 80% of the reaction mixture bypassed the catalyst bed. The water-gas shift reaction over a Pt/CeO2 catalyst was used as a model reaction to further characterize the behavior of the cell under reaction conditions. The catalyst bed was shown not to be a dead-zone and was purged in essentially the same time as that needed to purge the cell. The reaction chamber globally operated in a quasi plug-flow mode and the gas composition in the thin catalyst bed appears to be homogeneous when operated under differential conditions. The production of the gas-phase reaction product CO2 could be simultaneously followed both by mass spectrometry and DRIFTS, both techniques leading to identical results. Various IR bands integration methods were discussed to allow a precise and accurate determination of the surface concentration of adsorbates during isotopic exchange. (c) 2008 Elsevier B.V. All rights reserved.

Two-colour pulsed Raman studies of the lowest excited singlet state of tetraphenylporphyrin: band assignments and electronic structure

The resonance Raman spectra of the lowest lying singlet (S-1) state of free-base tetraphenylporphyrin and seven of its isotopomers were recorded under pump-and-probe conditions with a time delay of -2 ns between pump and probe laser pulses, In the S-1 spectra of the isotopomers, as in the ground state, there are dramatic splittings of what appear to be single bands in the natural isotopic abundance spectrum. The most structurally significant bands of the S-1 state were assigned on the basis of the isotope data, In some cases it was necessary to curve fit unresolved bands in the excited-state spectra in order to account for observed intensity ratios and to rationalize isotope shifts, The changes in band positions on excitation to the S-1 state were compared with those from earlier studies on the T-1 state. The changes in band positions were found to be similar For both excited states. Most notable was the similar shift in nu(2), the most widely used marker band for orbital character. The data are interpreted as implying that the lowest lying singlet state is a configuration interaction admixture of b(1u)b(2g) + a(u)b(3g) configurations with the coefficients weighted heavily in favour of b(1n)b(2g), which Is the configuration of the T-1 state. Copyright (C) 2000 John Wiley & Sons, Ltd.

Not all jellyfish are equal: isotopic evidence for inter- and intraspecific variation in jellyfish trophic ecology

Jellyfish are highly topical within studies of pelagic food-webs and there is a growing realisation that their role is more complex than once thought. Efforts being made to include jellyfish within fisheries and ecosystem models are an important step forward, but our present understanding of their underlying trophic ecology can lead to their oversimplification in these models. Gelatinous zooplankton represent a polyphyletic assemblage spanning >2,000 species that inhabit coastal seas to the deep-ocean and employ a wide variety of foraging strategies. Despite this diversity, many contemporary modelling approaches include jellyfish as a single functional group feeding at one or two trophic levels at most. Recent reviews have drawn attention to this issue and highlighted the need for improved communication between biologists and theoreticians if this problem is to be overcome. We used stable isotopes to investigate the trophic ecology of three co-occurring scyphozoan jellyfish species (Aurelia aurita, Cyanea lamarckii and C. capillata) within a temperate, coastal food-web in the NE Atlantic. Using information on individual size, time of year and ;delta C-13 and delta N-15 stable isotope values, we examined: (1) whether all jellyfish could be considered as a single functional group, or showed distinct inter-specific differences in trophic ecology; (2) Were size-based shifts in trophic position, found previously in A. aurita, a common trait across species?; (3) When considered collectively, did the trophic position of three sympatric species remain constant over time? Differences in delta N-15 (trophic position) were evident between all three species, with size-based and temporal shifts in delta N-15 apparent in A. aurita and C. capillata. The isotopic niche width for all species combined increased throughout the season, reflecting temporal shifts in trophic position and seasonal succession in these gelatinous species. Taken together, these findings support previous assertions that jellyfish require more robust inclusion in marine fisheries or ecosystem models.

Studies in molecular mechanics using spectroscopic data exact force field and bond in homogeneity

This thesis deals with some studies in molecular mechanic using spectroscopic data. It includes an improvement in the parameter technique for the evaluation of exact force fields, the introduction of a new and simple algebraic method for the force field calculation and a study of asymmetric variation of bonding forces along a bond.

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 (delta(37)Cl). 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 (2sigma) of the delta(37)Cl of this collection is +/-0.08 parts per thousand, which is in fact as large as our precision of measurement ( +/- 0.10 parts per thousand). 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 delta(37)Cl has been completed. For this purpose, geological fluid samples of various chemical compositions and a manufactured CH3Cl gas sample, with delta(37)Cl from about -6 parts per thousand to +6 parts per thousand 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 parts per thousand to +1.4 parts per thousand 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: delta(37)Cl(Reading)= (1.007 +/- 0.009)delta(37)Cl(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 parts per thousand to +6.0 parts per thousand. On six samples, the agreement between these two laboratories, using different techniques is good: delta(37)Cl(Leeds)=(1.052 +/- 0.038)delta(37)Cl(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 delta(37)Cl values from -4.4 parts per thousand to +6.0 parts per thousand and show a good agreement: delta(37)Cl(TIMS)=(1.039 +/- 0.023)delta(37)Cl(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 parts per thousand, their measurements either by IRMS or TIMS will give comparable results within less than +/- 0.10 parts per thousand, while for delta(37)Cl values as far as 10 parts per thousand (either positive or negative) from SMOC, both techniques will agree within less than +/- 0.30 parts per thousand. (C) 2004 Elsevier B.V. All rights reserved.

The gas-phase reaction between silylene and 2-butyne: kinetics, isotope studies, pressure dependence studies and quantum chemical calculations

Time-resolved kinetic studies of the reactions of silylene, SiH2, and dideutero-silylene, SiD2, generated by laser. ash photolysis of phenylsilane and phenylsilane-d(3), respectively, have been carried out to obtain rate coefficients for their bimolecular reactions with 2-butyne, CH3C CCH3. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 294-612 K. The second-order rate coefficients, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equations where the error limits are single standard deviations: log(k(H)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.67 +/- 0.04) + (1.71 +/- 0.33) kJ mol(-1)/RTln10 log(k(D)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.65 +/- 0.01) + (1.92 +/- 0.13) kJ mol(-1)/RTln10 Additionally, pressure-dependent rate coefficients for the reaction of SiH2 with 2-butyne in the presence of He (1-100 Torr) were obtained at 301, 429 and 613 K. Quantum chemical (ab initio) calculations of the SiC4H8 reaction system at the G3 level support the formation of 2,3-dimethylsilirene [cyclo-SiH2C(CH3)=C(CH3)-] as the sole end product. However, reversible formation of 2,3-dimethylvinylsilylene [CH3CH=C(CH3)SiH] is also an important process. The calculations also indicate the probable involvement of several other intermediates, and possible products. RRKM calculations are in reasonable agreement with the pressure dependences at an enthalpy value for 2,3-dimethylsilirene fairly close to that suggested by the ab initio calculations. The experimental isotope effects deviate significantly from those predicted by RRKM theory. The differences can be explained by an isotopic scrambling mechanism, involving H - D exchange between the hydrogens of the methyl groups and the D-atoms in the ring in 2,3-dimethylsilirene-1,1-d(2). A detailed mechanism involving several intermediate species, which is consistent with the G3 energy surface, is proposed to account for this.

Carbon and nitrogen isotopic ratios of urine and faeces as novel nutritional biomarkers of meat and fish intake

Purpose Meat and fish consumption are associated with changes in the risk of chronic diseases. Intake is mainly assessed using self-reporting, as no true quantitative nutritional biomarker is available. The measurement of plasma fatty acids, often used as an alternative, is expensive and time-consuming. As meat and fish differ in their stable isotope ratios, δ13C and δ15N have been proposed as biomarkers. However, they have never been investigated in controlled human dietary intervention studies. Objective In a short-term feeding study, we investigated the suitability of δ13C and δ15N in blood, urine and faeces as biomarkers of meat and fish intake. Methods The dietary intervention study (n = 14) followed a randomised cross-over design with three eight-day dietary periods (meat, fish and half-meat–half-fish). In addition, 4 participants completed a vegetarian control period. At the end of each period, 24-h urine, fasting venous blood and faeces were collected and their δ13C and δ15N analysed. Results There was a significant difference between diets in isotope ratios in faeces and urine samples, but not in blood samples (Kruskal–Wallis test, p < 0.0001). In pairwise comparisons, δ13C and δ15N were significantly higher in urine and faecal samples following a fish diet when compared with all other diets, and significantly lower following a vegetarian diet. There was no significant difference in isotope ratio between meat and half-meat–half-fish diets for blood, urine or faecal samples. Conclusions The results of this study show that urinary and faecal δ13C and δ15N are suitable candidate biomarkers for short-term meat and fish intake.

Nitrogen fluxes from treefrogs to tank epiphytic bromeliads: an isotopic and physiological approach

Diverse invertebrate and vertebrate species live in association with plants of the large Neotropical family Bromeliaceae. Although previous studies have assumed that debris of associated organisms improves plant nutrition, so far little evidence supports this assumption. In this study we used isotopic ((15)N) and physiological methods to investigate if the treefrog Scinax hayii, which uses the tank epiphytic bromeliad Vriesea bituminosa as a diurnal shelter, contributes to host plant nutrition. In the field, bromeliads with frogs had higher stable N isotopic composition (delta(15)N) values than those without frogs. Similar results were obtained from a controlled greenhouse experiment. Linear mixing models showed that frog feces and dead termites used to simulate insects that eventually fall inside the bromeliad tank contributed, respectively, 27.7% (+/- 0.07 SE) and 49.6% (+/- 0.50 SE) of the total N of V. bituminosa. Net photosynthetic rate was higher in plants that received feces and termites than in controls; however, this effect was only detected in the rainy, but not in the dry season. These results demonstrate for the first time that vertebrates contribute to bromeliad nutrition, and that this benefit is seasonally restricted. Since amphibian-bromeliad associations occur in diverse habitats in South and Central America, this mechanism for deriving nutrients may be important in bromeliad systems throughout the Neotropics.

Nitrogen fluxes from treefrogs to tank epiphytic bromeliads: an isotopic and physiological approach

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Studies on carbon-13 turnover in eggs and blood of commercial layers

This paper aimed at evaluating the influence of diets containing different isotopic values of carbon-13 turnover on the half-life of egg (yolk + albumen), yolk and albumen individually, and blood of poultry using δ‰ 13C isotopic variation. Commercial layers fed four experimental isocaloric and isonitrogenous diets (RC 4, RC 3, RMC 4 and RMC 3) containing different isotopic values, during an experimental period of 56 days. Turnover of the studied tissues was influenced by the experimental diets. Blood and albumen were more influenced by dietary treatments as compared to egg and yolk. The RMC 3 diet induced better performance (better feed intake and higher egg production) due faster rate of carbon substitution than the RC 4 diet, and lower half-life for egg (yolk + albumen), yolk, and albumen.

From doubly labelled water to half-life; validating radio-isotopic rubidium turnover to measure metabolism in small vertebrates

The doubly labelled water method (DLW) is widely used to measure field metabolic rate (FMR), but it has some limitations. Here, we validate an innovative technique for measuring FMR by comparing the turnover of isotopic rubidium (86Rb kb) with DLW depletion and the rate of CO2 production (V·co2) measured by flow-through respirometry (FTR) for two dunnart species (Marsupialia: Dasyuridae), Sminthopsis macroura (17 g) and Sminthopsis ooldea (10 g). The rate of metabolism as assessed by V·co2 (FTR) and 86Rb kb was significantly correlated for both species (S. macroura, r2 = 0·81, P = 1·19 × 10-5; S. ooldea, r2 = 0·63, P = 3·84 × 10-4), as was V·co2 from FTR and DLW for S. macroura (r2 = 0·43, P = 0·039), but not for S. ooldea (r2 = 0·29, P = 0·168). There was no relationship between V·co2 from DLW and 86Rb kb for either species (S. macroura r2 = 0·22, P = 0·169; S. ooldea r2 = 0·21, P = 0·253). We conclude that 86Rb kb provided useful estimates of metabolic rate for dunnarts. Meta-analysis provided different linear relationships between V·co2 and 86Rb kb for endotherms and ectotherms, suggesting different proportionalities between metabolic rate and 86Rb kb for different taxa. Understanding the mechanistic basis for this correlation might provide useful insights into the cause of these taxonomic differences in the proportionality. At present, it is essential that the relationship between metabolic rate and 86Rb kb be validated for each taxon of interest. The advantages of the 86Rb technique over DLW include lower equipment requirements and technical expertise, and the longer time span over which measurements can be made. The 86Rb method might be particularly useful for estimating FMR of groups for which the assumptions of the DLW technique are compromised (e.g. amphibians, diving species and fossorial species), and groups that are practically challenging for DLW studies (e.g. insects). © 2013 British Ecological Society.

Evaluation of two genera of benthic foraminifera for down-core paleotemperature studies in the western south atlantic

Neste estudo, compara-se a composição de isótopos de oxigênio de dois gêneros de foraminíferos bentônicos (Uvigerina e Cibicidoides) de amostras de topo de testemunho com a composição isotópica moderna da água do mar (d¹⁸O). Baseados em uma nova relação entre d¹⁸O e salinidade para a latitude média do Atlântico Sul ocidental, estimou-se a composição isotópica da calcita em equilíbrio (d¹⁸O_eq) a partir de duas equações diferentes: (1) O'Neil et al. (1969), modificada por McCorkle et al. (1997) e (2) Kim & O'Neil (1997). Utilizando (1), a pequena diferença entre d¹⁸O_eq e d¹⁸O de Uvigerina sugere que este gênero precipita as suas testas próximo ao equilíbrio com a água. Já os dados de d¹⁸O de Cibicidoides são 0,82 ‰ menores que a composição isotópica prevista. Ao contrário, utilizando (2) os dados de d¹⁸O de Cibicidoides mostram uma concordância excelente com a composição isotópica esperada, enquanto que os dados de d¹⁸O de Uvigerina são 0,69 ‰ maiores que os valores de equilíbrio previstos. A partir das evidências apresentadas neste trabalho e em estudos prévios sugerimos a utilização do gênero Cibicidoides e a aplicação da equação de Kim & O'Neil (1997) para pesquisas de paleotemperatura. Na ausência de suficientes espécimens de Cibicidoides sugerimos a utilização de d¹⁸O deUvigerina aplicando um fator de correção de -0,69 ‰.