The diet-body offset in human nitrogen isotopic values: a controlled dietary study

The ‘trophic level enrichment’ between diet and body results in an overall increase in nitrogen isotopic values as the food chain is ascended. Quantifying the diet–body Δ15N spacing has proved difficult, particularly for humans. The value is usually assumed to be +3-5‰ in the archaeological literature. We report here the first (to our knowledge) data from humans on isotopically known diets, comparing dietary intake and a body tissue sample, that of red blood cells. Samples were taken from 11 subjects on controlled diets for a 30-d period, where the controlled diets were designed to match each individual’s habitual diet, thus reducing problems with short-term changes in diet causing isotopic changes in the body pool. The Δ15Ndiet-RBC was measured as +3.5‰. Using measured offsets from other studies, we estimate the human Δ15Ndiet-keratin as +5.0-5.3‰, which is in good agreement with values derived from the two other studies using individual diet records. We also estimate a value for Δ15Ndiet-collagen of ≈6‰, again in combination with measured offsets from other studies. This value is larger than usually assumed in palaeodietary studies, which suggests that the proportion of animal protein in prehistoric human diet may have often been overestimated in isotopic studies of palaeodiet.

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.