Extending the Limit of Measurement for Dual H and O Isotope Ratios Using Thermolysis.

Hydrogen and oxygen isotope ratios are of use to determine the origin of matter. Thermolysis is used to convert matter to H2 and CO gases, which are the respective substrates for measurement of these two isotope ratios, using isotope ratio mass spectrometry (IRMS). This work was done in response to the need for analysis of small invasive insects, requiring a decrease in the limit of measurement for isotope ratiometry of hydrogen and oxygen, while determining both isotope ratios on the same sample. Miniaturization of a thermolysis reactor using commercially available components is presented that results in improvement in the limit of measurement for both hydrogen and oxygen isotope ratios. δ2H was determined on 0.4 µg of H and δ18O determined on 5 µg of O with precisions of 3 mUr and 0.7 mUr, respectively. To extend the usable sample size range or increase the resolution of sampling gives obvious advantages in forensic and environmental sciences. The technique has been applied to determining the natural origin of Tephritidae fruit flies for which only the wing is suitable for analysis and provides just 60 µg of material for analysis.

Precipitation isoscapes for New Zealand: enhanced temporal detail using precipitation-weighted daily climatology.

Predictive understanding of precipitation δ(2)H and δ(18)O in New Zealand faces unique challenges, including high spatial variability in precipitation amounts, alternation between subtropical and sub-Antarctic precipitation sources, and a compressed latitudinal range of 34 to 47 °S. To map the precipitation isotope ratios across New Zealand, three years of integrated monthly precipitation samples were acquired from >50 stations. Conventional mean-annual precipitation δ(2)H and δ(18)O maps were produced by regressions using geographic and annual climate variables. Incomplete data and short-term variation in climate and precipitation sources limited the utility of this approach. We overcome these difficulties by calculating precipitation-weighted monthly climate parameters using national 5-km-gridded daily climate data. This data plus geographic variables were regressed to predict δ(2)H, δ(18)O, and d-excess at all sites. The procedure yields statistically-valid predictions of the isotope composition of precipitation (long-term average root mean square error (RMSE) for δ(18)O = 0.6 ‰; δ(2)H = 5.5 ‰); and monthly RMSE δ(18)O = 1.9 ‰, δ(2)H = 16 ‰. This approach has substantial benefits for studies that require the isotope composition of precipitation during specific time intervals, and may be further improved by comparison to daily and event-based precipitation samples as well as the use of back-trajectory calculations.

Compound-specific isotope analysis of diesel fuels in a forensic investigation.

Compound-specific isotope analysis (CSIA) offers great potential as a tool to provide chemical evidence in a forensic investigation. Many attempts to trace environmental oil spills were successful where isotopic values were particularly distinct. However, difficulties arise when a large data set is analyzed and the isotopic differences between samples are subtle. In the present study, discrimination of diesel oils involved in a diesel theft case was carried out to infer the relatedness of the samples to potential source samples. This discriminatory analysis used a suite of hydrocarbon diagnostic indices, alkanes, to generate carbon and hydrogen isotopic data of the compositions of the compounds which were then processed using multivariate statistical analyses to infer the relatedness of the data set. The results from this analysis were put into context by comparing the data with the δ(13)C and δ(2)H of alkanes in commercial diesel samples obtained from various locations in the South Island of New Zealand. Based on the isotopic character of the alkanes, it is suggested that diesel fuels involved in the diesel theft case were distinguishable. This manuscript shows that CSIA when used in tandem with multivariate statistical analysis provide a defensible means to differentiate and source-apportion qualitatively similar oils at the molecular level. This approach was able to overcome confounding challenges posed by the near single-point source of origin, i.e., the very subtle differences in isotopic values between the samples.

Assessing carbon and hydrogen isotopic fractionation of diesel fuel n-alkanes during progressive evaporation.

Compound-specific isotope analysis offers potential for fingerprinting of diesel fuels, however, possible confounding effects of isotopic fractionation due to evaporation need to be assessed. This study measured the fractionation of the stable carbon and hydrogen isotopes in n-alkane compounds in neat diesel fuel during evaporation. Isotope ratios were measured using a continuous flow gas chromatograph/isotope ratio mass spectrometer. Diesel samples were progressively evaporated at 24 ± 2°C for 21 days. Increasing depletion of deuterium in nC12-nC17 alkanes in the remaining liquid with increasing carbon chain length was observed. Negligible carbon isotope fractionation was observed. Preferential vaporization was measured for the shorter chain n-alkanes and the trend decreased with increasing chain length. The decrease in δ(2) H values indicates the preferential vaporization of the isotopically heavier species consistent with available quantitative data for hydrocarbons. These results are most important in the application of stable isotope technology to forensic analysis of diesel.

Correlation of geographical location with stable isotope values of hydrogen and carbon of fatty acids from New Zealand milk and bulk milk powder.

The aim of this study was to investigate the correlation of δ²H and δ¹³C of bulk milk powder and milk powder fatty acids to their production region. A total of 46 milk powder samples from across New Zealand were collected and analyzed. Principal component analysis (PCA) showed that the δ²H and δ¹³C of four fatty acids (C4:0, C14:0, C16:0, C18:1) and bulk milk powder were found to be correlated with regional production area. Linear discriminant analysis (LDA) models were prepared using different combinations of bulk and fatty acid δ²H and δ¹³C. All models were effective in discriminating samples from the North and South Islands. The LDA model using just fatty acid δ²H and δ¹³C provided the best separation. Therefore, the isotopic composition of the aforementioned fatty acids can be utilized as a good biomarker in milk powder that conveys reliable isotopic information to track milk powders to their regional origin.

Isotope fractionation during precipitation of methamphetamine HCl and discrimination of seized forensic samples.

Methamphetamine is a widely abused illicit drug. Increasingly, studies have focused on stable isotope analysis by isotope ratio mass spectrometry (IRMS) to link samples of methamphetamine synthesized together or from the same source of precursor. For this reason, it is important to understand potential sources of isotope fractionation that could cause variability in forensic data sets. In this study, methamphetamine free base samples were synthesized from (-)-ephedrine HCl using the HI/red phosphorus synthetic route and then precipitated as HCl salts by bubbling with HCl gas. The entire sample did not precipitate when first bubbled with gas, and multiple precipitation steps were required. Fractions of precipitate were individually analyzed for delta(13)C, delta(15)N and delta(2)H by IRMS. Both delta(15)N and delta(2)H were found to become more negative, with the heavy isotopes depleted, in successive fractions of precipitate. Homogenizing the precipitate fractions together could eliminate this fractionation. However, in a clandestine situation this fractionation could lead to greater than expected delta(15)N and delta(2)H variability between illicit samples of methamphetamine HCl that have been synthesized from the same sample of ephedrine. This needs to be taken into account when interpreting forensic IRMS data. We also present an analysis of four separate seized case lots of methamphetamine HCl, taking into account the possible sources of fractionation and available intelligence information.

The use of carbon and nitrogen isotope ratios to identify landfill leachate contamination: Green Island Landfill, Dunedin, New Zealand.

A study was undertaken to determine whether the isotopic ratios of C and N could be used to uniquely identify municipal solid waste landfill leachate as a source of contamination in the Kaikorai Estuary, Dunedin, New Zealand. Leachate samples were taken from the adjacent Green Island Landfill (GILF), and surface water samples were collected over an 8-month period from the stream and estuary, upstream and downstream of the landfill. Samples were analysed for delta(13)C-dissolved inorganic carbon (DIC), delta(15)N-NO(3)(-), delta(15)N-NH(4)(+), and particulate organic matter (POM) delta(13)C and delta(15)N. Plant material collected along the Kaikorai Stream was analysed for POM delta(13)C and delta(15)N. Leachate was found to have a distinct isotopic signature characterised by a highly enriched delta(13)C-DIC (as much as 16.11+/-0.23 per thousand ) and highly enriched delta(15)N-NH(4)(+) (as much as 27.42+/-0.90 per thousand ). Evidence of leachate contamination was found in the isotopic signatures of downstream delta(13)C-DIC, delta(15)N-NH(4)(+), and delta(13)C and delta(15)N of plant material POM. Other potential sources of enriched delta(13)C-DIC and delta(15)N-NH(4)(+) present in the study area, such as estuarine waters and livestock effluent, were eliminated on the basis of their isotopic characteristics.