Stable oxygen isotopes in water of concentrated liquid foodstuffs: Are the commonly determined values accurate?

RATIONALE: Oxygen isotope analysis of water molecules of liquid foodstuffs is commonly performed under isotopic equilibrium between water in the solution and the vapour water, assuming that the liquid water activity is equal to unity and that liquid water is an ideal mixture of H2 O isotopologues. A priori this behaviour is not realistic for all foodstuffs, which frequently are very concentrated solutions. In this paper we mainly consider "balsamic vinegar" with the aim of defining an appropriate procedure of oxygen isotope ratio analysis of water molecules in these concentrated solutions. METHODS: Isotope ratio mass spectrometry (IRMS) measurements of the oxygen isotope ratios (δ18 O values) were carried out on CO2 equilibrated with water molecules at 22 ± 0.1°C. Three independently calibrated, very low salinity waters were used as standards. RESULTS: For grape must and wine vinegar (density < 1.15 g/cm3 ) the δ18 O values for water determined directly on these solutions are "true" values. On the contrary, for balsamic vinegar with density higher than 1.15-1.20 g/cm3 , the δ18 O values obtained directly on the solutions are systematically different from those obtained on water produced by distillation of the same samples at 70°C under vacuum. CONCLUSIONS: In the case of balsamic vinegar with density higher than 1.15-1.20 g/cm3 , to avoid severe systematic errors, the isotopic analyses must be carried out on water obtained by distillation under stirring.

Oxygen isotopic composition of fulgurites from the Egyptian Sahara and other locations.

RATIONALE: Fulgurites are glassy crusts or hollow glassy tubes formed by the impact of a lightning strike on a target material on the Earth's surface. The oxygen isotopic composition of fulgurites has never been measured and, consequently, it is unknown whether or not isotopic fractionations take place between the target material and the fulgurite glass during the lightning event which is an excellent natural example of extremely fast melting process. METHODS: Following well-established procedures (high-temperature reaction of the fulgurite material with BrF(5), conversion into CO(2) of the evolved O(2) and measurement of the(18)O/(16)O ratio on a Finnigan Delta S mass spectrometer) we measured for the first time the oxygen isotopic composition of sets of fulgurites coming from various locations on the Earth's surface. RESULTS: The range of isotopic values is quite large, probably reflecting the oxygen isotopic values of the target materials. In the case of fulgurites from the Sahara Desert the isotopic values obtained from the bulk material, quartz crystals sticking to the fulgurite body, tiny samples of loose sand coming from fulgurite bubbles, and sand samples collected near the fulgurites, are very close to one another. CONCLUSIONS: Although we do not have indisputable evidence, we conclude that, at least in the case of oxygen, the fusion process of the material struck by lightning, as well as all the extremely fast high-temperature fusion processes, probably take place without any isotopic fractionation effect.

CO2 concentrations and delta13C (CO2) values in monthly sets of air samples from downtown Parma and the Parma and Taro river valleys, Emilia-Romagna, Italy.

Monthly sets of discrete air samples were collected from September 2004 to June 2005 in the town of Parma, along North-South and East-West runs (8 plus 8 samples), using four-litre Pyrex flasks. The CO2 concentrations and delta13C values were determined on these samples with the aim of evaluating quantitatively the contribution of domestic heating to the winter atmospheric CO2 pollution in downtown Parma by comparing autumn and spring atmospheric values with winter values. After separation of CO2 from the other air gases in the laboratory, the CO2 concentrations were calculated from the intensity of the 12C16O2+ ion beam in the mass spectrometer, after calibration with artificial air samples whose CO2 concentration was very carefully determined by the Monte Cimone Observatory (Sestola, Modena, Italy). The reproducibility of these measurements was of approximately +/-0.4 % and, consequently, the most probable error is not higher than+/-2-3 ppmv and does not affect the magnitude of the gradients between different samples. The standard deviation of delta13C measurements ranges from+/-0.02 to +/-0.04 per thousand (1sigma). The results suggest that the contribution of domestic heating to atmospheric CO2 pollution is almost negligible in the case of ground level atmosphere, where the main CO2 pollution is essentially related to the heavy car traffic. This is probably because of the fact that the gases from the domestic heating systems are discharged tens of metres above ground level at a relatively high temperature so that they rise quickly to the upper atmospheric layers and are then displaced by air masses dynamics. Monthly sets of discrete air samples were also collected from October 2004 to June 2005 along North-South runs from the town of Parma to the Apennine ridge following the Parma and the Taro river valleys (8 samples and 7 samples per set, respectively) and measured using the same technique. The aim of this study was the comparison between the town samples, the plain country samples and the samples collected on the northern slope of the Apennines. The results reveal huge variations of both CO2 concentration and delta13C through space and time, some of which can be reasonably explained whereas others are rather difficult to understand. The sets of values are discussed and various hypotheses are suggested.