A robust interpolation-based method for forensic soil provenancing: A Bayesian likelihood ratio approach.

Soil is a complex and spatially variable material that has a demonstrated potential as a useful evidence class in forensic casework and intelligence operations. Here, the capability to spatially constrain police search areas and prioritise resources by triaging areas as low and high interest is advantageous. Conducted between 2017 and 2021, a forensically relevant topsoil survey (0-5 cm depth; 1 sample per 1 km2) was carried out over Canberra, Australia, aiming to document the distribution of chemical elements in an urban/suburban environment, and of acting as a testbed for investigating various aspects of forensic soil provenancing. Geochemical data from X-Ray Fluorescence (XRF; for total major oxides) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS; for trace elements) following a total digestion (HF + HNO3) of the fused XRF beads were obtained from the survey's 685 topsoil samples (plus 138 additional quality control samples and six "Blind" simulated evidentiary samples). Using those "Blind" samples, we document a likelihood ratio approach where for each grid cell the analytical similarity between the grid cell and evidentiary sample is attributed from a measure of overlap between the two Cauchy distributions, including appropriate uncertainties. Unlike existing methods that base inclusion/exclusion on an arbitrary threshold (e.g., ± three standard deviations), our approach is free from strict binary or Boolean thresholds, providing an unconstrained gradual transition dictated by the analytical similarity. Using this provenancing model, we present and evaluate a new method for upscaling from a fine (25 m x 25 m) interpolated grid to a more appropriate coarser (500 m x 500 m) grid. In addition, an objective method using Random Match Probabilities for ranking individual variables to be used for provenancing prior to receiving evidentiary material was demonstrated. Our results show this collective procedure generates more consistent and robust provenance maps when applied to two different interpolation algorithms (e.g., inverse distance weighting, and natural neighbour), with different grid placements (e.g., grid shifts to the north or east) and by different theoretical users (e.g., different computer systems, or forensic geoscientists).

A fresh scientific look at transfer and persistence: From a materials science and tribology perspective.

Knowledge of the mechanisms governing transfer, persistence, and recovery of trace evidence, together with background prevalence in the population of interest, and other task relevant information, is key for the forensic interpretation and reconstruction of what happened at the activity level. Up to now, this informational "toolkit" has largely been developed through empirical forensic studies on specific trace materials such as glass, textile fibers, and soil. Combined with the identified systemic siloing between disciplines, while valuable, such research tends to be very material-dependent, introducing specific parameters and interpretations that may have actually impeded the recognition of underlying foundational factors applicable to most material types. In Australia, there has been a renewed interest in developing a discipline-independent framework for the interpretation and/or reconstruction of trace evidence to interpret specific circumstances in casework. In this paper, we present a discipline agnostic "way of thinking" that has been anchored in foundational science underpinning the trace evidence discipline. Physical and mechanical material properties such as material geometry and surface topography, strength, stiffness, and hardness collectively influence contact interactions through underlying friction, wear, and lubrication cause and effect mechanisms. We discuss how these fundamental factors and parameters stemming from materials science and tribology may be adopted and adapted by forensic practitioners and researchers to contribute to a better understanding of transfer, persistence, and recovery mechanisms irrespective of evidence discipline and material type. Examples are provided to demonstrate the practical significance to real-life casework and academic research.

Bioavailable 87Sr/86Sr in European soils: A baseline for provenancing studies.

We present 87Sr/86Sr isotope ratios for ~1200 selected soil samples, collected by the GEMAS consortium from grazing (Gr) and agricultural (Ap) soils in Europe with the aim to better understand the strontium isotope distribution in the bioavailable fraction of the top-soil and its potential for provenancing applications. Spatial analysis shows that there is a clear distinction between coastal (<100 km) and non-coastal (>100 km) samples in their variance and that this variance is mirrored in the sodium concentration, suggesting an important but highly variable contribution from seaspray. We present two 87Sr/86Sr maps at 25 km × 25 km scale: one based solely on the measured data using a classical kriging approach and one based on a Random Forest model using complementary GEMAS data to predict the strontium isotope composition at the remaining 3000+ GEMAS sampling locations, including appropriate uncertainty assessment. Using a forensic Bayesian likelihood ratio approach, a tool was developed in R to create provenancing likelihood ratio maps. The maps delineate areas of high and low likelihood and allow investigators to direct their resources to areas of interest. For actual forensic case work either the measured or the modelled data can be used as reference data for the overall distribution of 87Sr/86Sr values in Europe.

Sodium and bone health: impact of moderately high and low salt intakes on calcium metabolism in postmenopausal women.

High salt intake is a well-recognized risk factor for osteoporosis because it induces calciuria, but the effects of salt on calcium metabolism and the potential impact on bone health in postmenopausal women have not been fully characterized. This study investigated adaptive mechanisms in response to changes in salt and calcium intake in postmenopausal women. Eleven women completed a randomized cross-over trial consisting of four successive 5-wk periods of controlled dietary intervention, each separated by a minimum 4-wk washout. Moderately low and high calcium (518 versus 1284 mg) and salt (3.9 versus 11.2 g) diets, reflecting lower and upper intakes in postmenopausal women consuming a Western-style diet, were provided. Stable isotope labeling techniques were used to measure calcium absorption and excretion, compartmental modeling was undertaken to estimate bone calcium balance, and biomarkers of bone formation and resorption were measured in blood and urine. Moderately high salt intake (11.2 g/d) elicited a significant increase in urinary calcium excretion (p = 0.0008) and significantly affected bone calcium balance with the high calcium diet (p = 0.024). Efficiency of calcium absorption was higher after a period of moderately low calcium intake (p < 0.05) but was unaffected by salt intake. Salt was responsible for a significant change in bone calcium balance, from positive to negative, when consumed as part of a high calcium diet, but with a low calcium intake, the bone calcium balance was negative on both high and low salt diets.

Effect of high-dose iron supplements on fractional zinc absorption and status in pregnant women.

BACKGROUND: Women have an increased risk of iron deficiency during pregnancy because of the demands of the developing fetus. Iron supplements are commonly advocated as a prophylactic treatment and are generally taken with meals to reduce side effects, but iron can interfere with the absorption of zinc. OBJECTIVE: The aim was to determine the effect of consuming an iron supplement (100 mg Fe/d as ferrous gluconate) with meals from 16 wk gestation to term on zinc status and absorption. DESIGN: Stable-isotope techniques were used to measure zinc status (exchangeable zinc pool, EZP) and fractional zinc absorption (FZA) in early and late pregnancy from a meal consumed at a different time from that of iron supplement or placebo consumption in 6 women given iron supplements and 7 given a placebo. RESULTS: FZA increased during pregnancy, independent of iron supplementation. FZA was significantly higher (P < 0.001) at week 34 than at weeks 16 and 24, and urinary zinc excretion was higher at week 34 than at week 16 (P = 0.02). The size of the EZP remained unchanged throughout pregnancy and was unaffected by iron supplementation. The iron status of iron-supplemented women was higher than that of the placebo group. CONCLUSIONS: In iron-replete pregnant women who consumed a Western diet, no detectable adverse effects on zinc metabolism were observed after ingestion of 100 mg Fe/d. An increase in the efficiency of zinc absorption was observed during late pregnancy.

Development and evaluation of a standard method for the quantitative determination of elements in float glass samples by LA-ICP-MS.

Forensic analysis of glass samples was performed in different laboratories within the NITE-CRIME (Natural Isotopes and Trace Elements in Criminalistics and Environmental Forensics) European Network, using a variety of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) systems. The main objective of the interlaboratory tests was to cross-validate the different combinations of laser ablation systems with different ICP-MS instruments. A first study using widely available samples, such as the NIST SRM 610 and NIST SRM 612 reference glasses, led to deviations in the determined concentrations for trace elements amongst the laboratories up to 60%. Extensive discussion among the laboratories and the production of new glass reference standards (FGS 1 and FGS 2) established an improved analytical protocol, which was tested on a well-characterized float glass sample (FG 10-1 from the BKA Wiesbaden collection). Subsequently, interlaboratory tests produced improved results for nearly all elements with a deviation of < 10%, demonstrating that LA-ICP-MS can deliver absolute quantitative measurements on major, minor and trace elements in float glass samples for forensic and other purposes.

Use of mathematical modeling to study copper metabolism in humans.

BACKGROUND: An improved understanding of copper metabolism is needed to derive more precise estimates of dietary requirements. OBJECTIVES: The objectives were to validate a method for estimating endogenous losses of copper, test whether a simple model can predict true absorption from the plasma appearance of labeled copper, and develop a compartmental model for copper metabolism by using stable isotopes. DESIGN: A stable isotope of copper was intravenously administered to 6 men, and fecal samples were collected for 14 d. Four weeks later the study was repeated, but with an oral dose, and blood samples were collected for 7 d and fecal samples for 14 d. RESULTS: There was no significant difference (P = 0.48) in the estimated endogenous loss of copper calculated by using either the excreted intravenous dose (x +/- SD: 32 +/- 5%) or the absorbed and excreted oral dose (35 +/- 2%). A simple mathematical model fitted to plasma isotope appearance data estimated true absorption to be 8 +/- 2% compared with 48-49% measured by fecal monitoring. A more complicated compartmental model predicted that, when newly absorbed copper first enters the blood, 74% is removed by the liver and 99% is bound to ceruloplasmin in the plasma. The exchangeable pool of copper was estimated to be 43 +/- 30 mg. Daily endogenous losses were predicted to be 2.4 mg. CONCLUSIONS: The results showed that fecal monitoring is the only method that can reliably measure labeled copper absorption, and it is not necessary to administer an intravenous dose of copper to estimate endogenous losses. The compartmental model provides new insights into human copper metabolism.

Iron absorption in male C282Y heterozygotes.

BACKGROUND: The suggestion that carriers of the HFE C282Y mutation absorb nonheme iron more efficiently than do carriers of the wild type has public health implications for countries where the C282Y mutation is common and foods are fortified with iron. OBJECTIVE: We investigated the effect of C282Y heterozygosity on nonheme-iron absorption from a diet high in bioavailable iron and from iron-fortified cereals. DESIGN: The subjects were recruited from a parallel study investigating the relation between HFE mutations, habitual diet, and iron status. Iron absorption was measured in 15 wild-type carriers and 15 C282Y heterozygotes aged >/=40 y. Each subject consumed 3 meals of high iron bioavailability (labeled with Fe-57) for 2 d and 2 meals with fortified cereal products (labeled with Fe-54) for the next 3 d. Iron absorption was measured from isotope incorporation into red blood cells 14 d after the last labeled meal and was corrected for utilization of absorbed iron by means of an intravenous infusion of Fe-58. RESULTS: Absorption of Fe-57 with the high-iron-bioavailability diet was 6.8 +/- 6.8% (0.6 +/- 0.6 mg/d) in the wild-type carriers and 7.6 +/- 3.2% (0.7 +/- 0.3 mg/d) in the C282Y heterozygotes. Absorption of Fe-54 with cereal products was 4.9 +/- 2.0% (0.7 +/- 0.3 mg/d) in the wild-type carriers and 5.3 +/- 1.3% (0.8 +/- 0.2 mg/d) in the C282Y heterozygotes. CONCLUSIONS: There was no overall significant difference between C282Y heterozygotes and wild-type men in iron absorption from either dietary nonheme iron or fortified cereal products.

Iron supplements inhibit zinc but not copper absorption in vivo in ileostomy subjects.

BACKGROUND: Iron supplements may inhibit intestinal zinc and copper uptake because these elements may compete for binding to a transporter molecule (divalent metal transporter 1) that is located on the apical side of the small intestinal epithelium. OBJECTIVE: We quantified the interaction between different amounts of administered iron and the absorption of zinc and copper in humans. DESIGN: Eleven subjects with an ileostomy [mean (+/- SD) age: 55 +/- 9 y] ingested a stable-isotope-labeled zinc and copper solution containing 12 mg Zn ((66)Zn and (67)Zn) and 3 mg Cu ((65)Cu) in the presence of 0, 100, or 400 mg Fe as ferrous gluconate on 3 respective test days. Subsequently, 1 mg (70)Zn was injected intravenously. Subjects collected ileostomy effluent and urine for 24 h and 7 d, respectively. Zinc status and true zinc absorption were calculated from the urinary excretion of the zinc isotopes. Apparent copper absorption was calculated from ileostomy effluent excretion of the orally administered copper isotopes. RESULTS: Zinc status did not differ significantly between the 3 iron doses. Mean (+/- SEM) zinc absorption was significantly higher in the absence of iron than with the concomitant ingestion of 100 or 400 mg Fe (44 +/- 22% compared with 26 +/- 14% and 23 +/- 6%, respectively; P < 0.05), whereas zinc absorption did not differ significantly between the 100- and 400-mg Fe doses. Apparent copper absorption was 48 +/- 14%, 54 +/- 26%, and 53 +/- 7% in the presence of 0, 100, and 400 mg Fe, respectively, and did not differ significantly between the 3 iron doses. CONCLUSION: Oral iron therapy may impair zinc absorption and thus zinc status in a dose-independent fashion but does not affect copper absorption.

A chemical and mineralogical reconstruction of Zn-smelter emissions in the Kempen region (Belgium), based on organic pool sediment cores.

The atmospheric pollution history of a former Belgian Zn-smelter complex is preserved in organic sediments of a nearby peat bog pool. The stratigraphy of trace metals, Pb-isotope ratios and mineralogy indicate extreme heavy metal pollution in recent sediments. In the pollutant trend, extremes coincide with maxima in 20th century metal production, minima during major war conflicts and the final shutdown of the smelter. Peak pollution concentrations measure up to 4.7 wt.% Zn, 1.1 wt.% Pb and 0.1 wt.% Cd, which correspond to calculated atmospheric deposition rates of 9.0, 1.6 and 0.16 g m(-2) yr(-1), respectively. 206Pb/207Pb isotope ratios show higher values in the polluted interval (1.135-1.162) relative to local geogenic values deeper down-core (1.194-1.215). Within the polluted interval, three significantly different 208Pb/206Pb plateaus are recognized and suggested to indicate changes in the origins of processed ores. Microprobe analyses on sediment thin sections show extensive in situ FeS2 and ZnS precipitation, which suggests that anoxic processes are responsible for the immobilization of the atmospheric metal inputs. The occurrence of oxidized smelter dusts in an independent surface soil sample indicates a rapid diagenetic transformation of metal oxides into sulfides. Morphology and chemical characteristics allow the distinction between smelter related and diagenetic mineral deposits, and give evidence for dust from open-air ore repositories, as well as smelter operation without dust filters.