Fast exchange of strontium between hair and ambient water: Implication for isotopic analysis in provenance and forensic studies.

Trace elements in hair originate from intake (e.g., diet, inhalation, skin absorption), are transported in the bloodstream, and then incorporated during hair formation. However, the trace element abundance and isotopic compositions may be altered by post-eruption environmental processes. Such alterations must be addressed to obtain a meaningful interpretation of hair analysis for biomonitoring. In this study, we used strontium (Sr) isotopic analysis together with sorption kinetics of ionic Sr to quantify the rate and extent of replacement of endogenous Sr in hair by exogenous Sr from ambient water. We found that with only 10 minutes of exposure at room temperature (22°C), more than 30% of original endogenous Sr in hair was replaced with exogenous Sr from the solution. After 16 days of exposure to the solution, more than 90% of endogenous Sr was replaced, with a warmer temperature (60°C) accelerating the exchange substantially. We also found that acid leaching of exposed hair did not remove or isolate the exogenous Sr; therefore, neither the original endogenous nor the exogenous 87Sr/86Sr signal could be separated. Nonetheless, these findings illustrated that the quantitative correlation between the fraction of exogenous Sr and the soaking time, if established, could be used to estimate the length of water contact time for hair in forensic studies. Even if such time since initial contact cannot be established, the combination of acid leaching and 87Sr/86Sr analysis of hair samples may still be valuable in provenance studies to identify recent changes in the exogenous Sr pool, including movements or changes in water source.

Trace element concentrations in horn: Endogenous levels in keratin and susceptibility to exogenous contamination.

As a recorder containing both physiological and environmental information, keratinized tissues, such as hair and feather, can be used to reveal geographical information, to monitor the exposure to pollutants, and to reconstruct dietary history. However, trace element analysis of keratinized tissues is complicated by the lack of reference endogenous ranges of trace element and the lack of understanding of the susceptibility of each element to exogenous contamination. The interior of animal horn is the cleanest of all keratinized tissues with minimum exogenous contamination because of its large size. Thus, the trace element concentrations in horn interior samples can provide reliable endogenous concentration ranges. Here we measured the concentrations of trace elements in horn interior samples of cattle and wild animals, which we propose to be used as the reference ranges for endogenous levels of trace elements in keratin. We calculated the enrichment factors of 30 trace elements in horn interior samples relative to the continental crust, which we considered the average exogenous contamination. We compared the ranges of elemental concentrations measured in horn interior samples, in the order of decreasing enrichment factor, to their reference ranges in hair, fingernails, and toenails, as well as their concentrations in caprine horns. Such comparison validates the use of the enrichment factor as an indicator of the susceptibility of an element to contamination: an element with a high enrichment factor is generally less likely to be affected by contamination and vice versa.

Strontium isotope ratios of human hair from the United States: Patterns and aberrations.

RATIONALE: Strontium isotope ratios (87 Sr/86 Sr) of hair may be a valuable tool to estimate human provenance. However, the systematics and mechanisms controlling spatial variation in 87 Sr/86 Sr of modern human hair remain unclear. Here, we measure 87 Sr/86 Sr of hair specimens from across the USA to assess the presence of geospatial relationships. METHODS: Ninety-eight human hair specimens were collected from salon/barbershop floors in 48 municipalities throughout the conterminous USA. [Sr] and 87 Sr/86 Sr ratios were measured from hair using quadrupole and multi-collector inductively coupled plasma mass spectrometers, respectively. The [Sr] and 87 Sr/86 Sr ratios of hair were compared with the measured [Sr] and 87 Sr/86 Sr ratios of tap waters from the collection locations. In addition, the 87 Sr/86 Sr ratio of hair was compared with the modeled ratios of bedrock and surface waters. RESULTS: Hair color was independent of the 87 Sr/86 Sr ratio, but related to [Sr]. The 87 Sr/86 Sr ratios of hair and leachate were not statistically different and were positively correlated; however, in several hair-leachate pairs, the ratios were conspicuously different. The 87 Sr/86 Sr ratios of both hair and leachate were linearly correlated with tap water. The 87 Sr/86 Sr ratio of hair was also significantly correlated with the modeled ratio of bedrock and surface waters, although the 87 Sr/86 Sr ratio of hair was most strongly correlated with the measured ratio of tap water. CONCLUSIONS: The 87 Sr/86 Sr ratio of hair is related to the ratio of tap water, which varied geographically. The ratio of hair provided geographic information about an individual's recent residence. Differences in the 87 Sr/86 Sr ratios of hair and hair leachate may be concomitant with travel and could potentially be used as a screening tool to identify recent movements.

Longitudinal and transverse variation of trace element concentrations in elephant and giraffe hair: implication for endogenous and exogenous contributions.

The spatial distribution of trace elements in hair is highly heterogeneous at the microscale. The relatively mild spatial variation of endogenous signal incorporated during hair growth may be amplified by orders of magnitude due to later exogenous contaminations. Here, we studied the longitudinal and transverse distributions of trace elements in elephant and giraffe hair and discussed the possible endogenous and exogenous contributions. Laser ablation ICP-MS analyses were performed on cross sections of hair to assess the surface contamination and transverse variation. We also removed the contaminated surface layer at various distances from hair root of single hair strands using physical abrasion and measured the concentrations by microwave digestion followed by ICP-MS. By comparing the concentrations of 11 trace elements between the intact and abraded hair segments as a function of distance from root and their laser ablation profiles, we rationalized the endogenous and exogenous contributions: Al and Ti concentrations are dominated by the exogenous contamination on the elephant hair surface, probably in the form of insoluble particles, but not in the giraffe hair; Mg, Ca, Sr, Ba, and Mn are enhanced on the elephant hair surface by exogenous contaminations, but a comparable amount was found in the hair interior suggesting migration of these elements from the surface towards the core; Cu, Zn, Se, and Pb did not have surface accumulation and thus were dominated by the endogenous signal. Overall, giraffe hair had minimal surficial contamination, suggesting the origin of its trace elements is predominantly endogenous, except for Mn, which might get contaminated with airborne particles. We thus demonstrate that contamination of hair may be strongly related to behavioral traits and that the interpretation of trace elemental analyses in hair as a biomonitor or for provenance studies would be highly dependent on the species considered.

Stable isotope ecology of black rhinos (Diceros bicornis) in Kenya.

Stable isotope and elemental ratios in hair are influenced by the environment, including both climate and geology. Stable carbon isotopes can be used to give estimates of the C4/CAM fraction of diets of herbivorous mammals; stable nitrogen isotopes are related to the local water deficit; strontium isotopes are determined by the local geology. We studied hair from rhinos in Kenya to determine spatial patterns in δ13C, δ15N, and 87Sr/86Sr ratios. The samples of rhino hair were collected during Kenya Wildlife Service translocation or veterinary activities. δ13C values showed diets dominated by C3 foods, but in some regions the diet, at least seasonally, contained significant quantities (i.e., > ca. 20%) of C4/CAM foods. δ15N values were related to water deficit, with higher δ15N values in regions with high water deficit. 87Sr/86Sr isotope ratios were found to be related to the local geological substrate suggesting that 87Sr/86Sr isotope ratios are provisionally useful for determining the origins of illegal wildlife materials in Kenya and elsewhere in Africa.

Reconstruction of travel history using coupled δ18 O and 87 Sr/86 Sr measurements of hair.

RATIONALE: Oxygen isotope ratios (δ18 O values) of hair largely reflect features of regional hydrology while strontium isotope ratios (87 Sr/86 Sr) are thought to reflect bedrock geology; combination of both isotope signatures may provide greater capacity for determining provenance and reconstructing travel history of an organism. To test this hypothesis, we compared the O-Sr isotope profiles of hair from domestic horses with known residency histories. METHODS: Tail hairs were collected from a pair of horses pastured together for a period of 16 months, one of which lived in a different location for the 8 months prior. Hair samples were washed with solvents to remove external contaminants prior to sequential sampling for δ18 O and 87 Sr/86 Sr analysis via TC/EA-IRMS and MC-ICP-MS, respectively. Hair digests were concentrated and analyzed employing low-flow natural aspiration to measure 87 Sr/86 Sr. RESULTS: Tail hair from the control and transported horses had mean δ18 O values of 11.25 ± 1.62 ‰ and 10.96 ± 1.53 ‰, and mean 87 Sr/86 Sr of 0.7101 ± 0.0006 and 0.7109 ± 0.0020, respectively. The δ18 O and 87 Sr/86 Sr profiles for the control and transported horses were indistinguishable when they were pastured together. The 87 Sr/86 Sr profiles were significantly different during the period that the horses were living apart, while the δ18 O values were indistinguishable during that period. CONCLUSIONS: By comparing the O-Sr isotope profiles of a control and transported horse, we investigated isotopic signal(s) potentially useful for reconstructing travel histories via high-resolution sequential sampling along single strands of tail hair. Improved analytical capabilities allowed for extremely low Sr abundance samples to be analyzed for 87 Sr/86 Sr and proved capable of resolving a horse's movement between distinct regions. Copyright © 2017 John Wiley & Sons, Ltd.