From stable isotope ecology to forensic isotope ecology - Isotopes' tales.

Stable isotope ecology and forensic isotope ecology are not only linked by name. More often than not, knowledge and insights gained through the former serve as a springboard for application focused work of the latter. This review aims to offer a glimpse into the fascinating world of both though with more emphasis on forensic isotope ecology.

Spatial variability of H and O composition of meteoric freshwater lakes in Scotland.

Coastal regions, and in particular islands where precipitation from clouds formed out at sea occurs for the first time, are prime candidates for regions where H and O composition of precipitation will deviate significantly from the global mean geographic and physiographic trends of vapour-transport patterns. The results reported here are the outcome of a study that aimed to test this hypothesis by 'isotopographically' mapping the characteristic δH and δO signatures of Scottish freshwaters. The resulting isotope abundance landscapes or 'isoscapes' will underpin studies aiming to authenticate origin of Scottish produce but may also offer a baseline against which environmental changes could be assessed.

A guide for proper utilisation of stable isotope reference materials.

Many scientific publications about stable isotope ratios suffer from flawed practices regarding calibration and normalisation of raw δ values in conjunction with prescribed δ values of reference materials. Violations of the identical treatment principle with regards to samples and standards (i.e.

Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements: Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils.

An international project developed, quality-tested, and determined isotope-δ values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-600 (caffeine). These new RMs enable users to normalize measurements of samples to isotope-δ scales. The RMs span a range of δ(2)H(VSMOW-SLAP) values from -210.

Discrimination of unprocessed cotton on the basis of geographic origin using multi-element stable isotope signatures.

Rationale: Cotton is the most commonly used natural plant product for the manufacture of yarns and textiles. Consumer perception regarding differences in textile quality in relation to geographic provenance of cotton as well as stringent product labelling requirements demand for the supply chain to furnish proof of geographic provenance beyond merely paper-based audit trails.

Methods: We have applied isotope ratio mass spectrometry to generate multivariate data sets of raw cotton.

Critique: measuring hydrogen stable isotope abundance of proteins to infer origins of wildlife, food and people.

Measurement of the relative abundance of (2)H (expressed in δ(2)H values) in tissues of plants, wildlife and people has evolved into a powerful forensic tool. The approach is based on the strong linkage between spatial patterns of δ(2)H values in precipitation at local and continental scales, and the tissues of plants and animals produced on these 'isoscapes'. Unfortunately, despite this exciting potential, difficulties inherent in the measurement of δ(2)H values in complex organic materials such as proteins, as well as the accuracy of such measurements, and a reluctance to adopt strict quality assurance/QC approaches to address challenges associated with these measurements, has clearly limited this potential.

Influence of precursor solvent extraction on stable isotope signatures of methylamphetamine prepared from over-the-counter medicines using the Moscow and Hypophosphorous routes.

A number of methods of clandestine manufacture of methylamphetamine involve the extraction and subsequent reaction of pseudoephedrine hydrochloride with other essential chemicals. The precursor can be easily extracted from over-the-counter medication widely available in the UK and elsewhere. Essential chemicals such as iodine and red phosphorous are also readily available and can be extracted from iodine tinctures and matchboxes, respectively.

Using isotopic fractionation to link precursor to product in the synthesis of (±)-mephedrone: a new tool for combating "legal high" drugs.

Several recent deaths in the U.K. have been attributed to "legal high" drugs and in particular to (±)-4-methylmethcathinone ((±)-mephedrone).

Dietary differentiation and the evolution of population genetic structure in a highly mobile carnivore.

Recent studies on highly mobile carnivores revealed cryptic population genetic structures correlated to transitions in habitat types and prey species composition. This led to the hypothesis that natal-habitat-biased dispersal may be responsible for generating population genetic structure. However, direct evidence for the concordant ecological and genetic differentiation between populations of highly mobile mammals is rare.

An inter-laboratory comparative study into sample preparation for both reproducible and repeatable forensic 2H isotope analysis of human hair by continuous flow isotope ratio mass spectrometry.

Stable isotope analysis of organic materials for their hydrogen ((2)H), carbon ((13)C), nitrogen ((15)N) or oxygen ((18)O) isotopic composition using continuous flow isotope ratio mass spectrometry (CF-IRMS) is an increasingly used tool in forensic chemical analysis. (2)H isotopic analysis can present a huge challenge, especially when dealing with exhibits comprising exchangeable hydrogen such as human scalp hair. However, to yield forensic data that are fit for purpose, analysis of the (2)H isotopic composition of the same homogeneous human hair sample by any laboratory worldwide must yield the same isotopic composition within analytical uncertainty.

Investigating the provenance of un-dyed spun cotton fibre using multi-isotope profiles and chemometric analysis.

The analysis of un-dyed spun cotton fibres can be challenging within a forensic science context where discrimination of one fibre from another is of importance. Conventional microscopic and chemical analysis of these fibres is generally unsuccessful because of their similar morphology. In this work we have explored the potential of isotope ratio mass spectrometry (IRMS) as a tool for spun cotton fibre analysis in an attempt to reveal any discriminatory information available.

Simplifying and improving the extraction of nitrate from freshwater for stable isotope analyses.

Determining the isotopic composition of nitrate (NO(3)(-)) in water can prove useful to identify NO(3)(-) sources and to understand its dynamics in aquatic systems. Among the procedures available, the 'ion-exchange resin method' involves extracting NO(3)(-) from freshwater and converting it into solid silver nitrate (AgNO(3)), which is then analysed for (15)N/(14)N and (18)O/(16)O ratios. This study describes a simplified methodology where water was not pre-treated to remove dissolved organic carbon (DOC) or barium cations (added to precipitate O-bearing contaminants), which suited samples with high NO(3)(-) (≥ 00 μM or 25 mg L(-1) NO(3)(-)) and low DOC (typically < 17 μM of C or 5 mg L(-1) C) levels.

Inter-laboratory calibration of new silver orthophosphate comparison materials for the stable oxygen isotope analysis of phosphates.

Stable oxygen isotope compositions (δ(18)O values) of two commercial and one synthesized silver orthophosphate reagents have been determined on the VSMOW scale. The analyses were carried out in three different laboratories: lab (1) applying off-line oxygen extraction in the form of CO(2) which was analyzed on a dual inlet and triple collector isotope ratio mass spectrometer, while labs (2) and (3) employed an isotope ratio mass spectrometer coupled to a high-temperature conversion/elemental analyzer (TC/EA) where Ag(3)PO(4) samples were analyzed as CO in continuous flow mode. The δ(18)O values for the proposed new comparison materials were linked to the generally accepted δ(18)O values for Vennemann's TU-1 and TU-2 standards as well as for Ag(3)PO(4) extracted from NBS120c.

A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable.

Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions.

What contribution do detergent fatty alcohols make to sewage discharges and the marine environment?

To investigate the potential sources of fatty alcohols arriving at a WWTP and entering the receiving waters, a study was conducted at Treborth North Wales using compound specific stable isotope mass spectrometry (¹³C and ²H). Samples were collected from soils, marine sediments, detergents used in the catchment and in the WWTP. Total fatty alcohol concentrations decreased in the liquid phases through the treatment works with the majority of the compounds accumulating in the sludge (biosolids).

The hydrological response of heavy clay grassland soils to rainfall in south-west England using delta2H.

Stable isotopes of water have been previously used in catchment studies to separate rain-event water from pre-event groundwater. However, there are a lack of studies at the smaller scale looking at the separation of event water from pre-event water. This is particularly relevant for heavy clay soil systems through which the movement of water is uncertain but is thought to be rainwater-dominated.

Stable isotope profiling of burnt wooden safety matches.

Arson is a significant problem around the world, and is a crime which results in a low number of convictions. The scene of an arson can be varied, commercial, residential or national park, and recently cases have been identified which were initiated by a lit match. Matches can be recovered from a scene, usually in a burnt condition.

N(2): a potential pitfall for bulk (2)H isotope analysis of explosives and other nitrogen-rich compounds by continuous-flow isotope-ratio mass spectrometry.

Observations made during the (13)C isotope analysis of gaseous CO(2) in the simultaneous presence of argon in the ion source of the isotope ratio mass spectrometer prompted us to investigate what influence the simultaneous presence of nitrogen would have on both accuracy and precision of bulk (2)H isotope analysis of nitrogen-rich organic compounds. Initially an international reference material, IAEA-CH7, was mixed with silver nitrate in various ratios to assess the impact that N(2) evolved from the pyrolysis of nitrogen-rich organic compounds would have on measured delta(2)H-values of IAEA-CH7. In a subsequent experiment, benzoic acid was mixed with silver nitrate to mimic the N:H ratio of organic-rich nitrogen compounds such as cellulose nitrate and RDX.

Forensic isotope analysis leads to identification of a mutilated murder victim.

The relationship between diet, geographic location and isotopic composition of human tissue has been successfully exploited in archaeological and palaeodietary studies, i.e. on ancient man, but cases in which this approach has been applied to present-day people e.

Investigation of isotopic linkage between precursor and product in the synthesis of a high explosive.

In criminal proceedings involving illegally manufactured substances, evidence demonstrating the manufacture is required for successful prosecution. In many circumstances the presence of manufacturing equipment and 'recipes' are clear indicators. However establishing chemical links between starting materials and products would be beneficial additional evidence in such circumstances.

Emerging use of isotope ratio mass spectrometry as a tool for discrimination of 3,4-methylenedioxymethamphetamine by synthetic route.

Drug profiling, or the ability to link batches of illicit drugs to a common source or synthetic route, has long been a goal of law enforcement agencies. Research in the past decade has explored drug profiling with isotope ratio mass spectrometry (IRMS). This type of research can be limited by the use of substances seized by police, of which the provenance is unknown.

Stable isotope analysis of human hair and nail samples: the effects of storage on samples.

When submitting samples for analysis, maintaining sample integrity is essential. Appropriate packaging must be used to prevent damage, contamination or loss of sample. This is particularly important for stable isotope analysis by isotope ratio mass spectrometry as this technique is capable of detecting subtle differences in isotopic composition with great precision.

Stable isotope and DNA evidence for ritual sequences in Inca child sacrifice.

Four recently discovered frozen child mummies from two of the highest peaks in the south central Andes now yield tantalizing evidence of the preparatory stages leading to Inca ritual killing as represented by the unique capacocha rite. Our interdisciplinary study examined hair from the mummies to obtain detailed genetic and diachronic isotopic information. This approach has allowed us to reconstruct aspects of individual identity and diet, make inferences concerning social background, and gain insight on the hitherto unknown processes by which victims were selected, elevated in social status, prepared for a high-altitude pilgrimage, and killed.

Stable (2)H isotope analysis of modern-day human hair and nails can aid forensic human identification.

Continuous-flow isotope ratio mass spectrometry (CF-IRMS) was used to compare (2)H isotopic composition at natural abundance level of human scalp hair and fingernail samples collected from subjects worldwide with interpolated delta(2)H precipitation values at corresponding locations. The results showed a strong correlation between delta(2)H values of meteoric water and hair (r(2) = 0.86), while the corresponding correlation for nails was not as strong (r(2) = 0.