A lead isotopic study of the human bioaccessibility of lead in urban soils from Glasgow, Scotland.

The human bioaccessibility of lead (Pb) in Pb-contaminated soils from the Glasgow area was determined by the Unified Bioaccessibility Research Group of Europe (BARGE) Method (UBM), an in vitro physiologically based extraction scheme that mimics the chemical environment of the human gastrointestinal system and contains both stomach and intestine compartments. For 27 soils ranging in total Pb concentration from 126 to 2160 mg kg(-1) (median 539 mg kg(-1)), bioaccessibility as determined by the 'stomach' simulation (pH ~1.5) was 46-1580 mg kg(-1), equivalent to 23-77% (mean 52%) of soil total Pb concentration. The corresponding bioaccessibility data for the 'stomach+intestine' simulation (pH ~6.3) were 6-623 mg kg(-1) and 2-42% (mean 22%) of soil Pb concentration. The soil (206)Pb/(207)Pb ratios ranged from 1.057 to 1.175. Three-isotope plots of (208)Pb/(206)Pb against (206)Pb/(207)Pb demonstrated that (206)Pb/(207)Pb ratios were intermediate between values for source end-member extremes of imported Australian Pb ore (1.04)--used in the manufacture of alkyl Pb compounds (1.06-1.10) formerly added to petrol--and indigenous Pb ores/coal (1.17-1.19). The (206)Pb/(207)Pb ratios of the UBM 'stomach' extracts were similar (<0.01 difference) to those of the soil for 26 of the 27 samples (r=0.993, p<0.001) and lower in 24 of them. A slight preference for lower (206)Pb/(207)Pb ratio was discernible in the UBM. However, the source of Pb appeared to be less important in determining the extent of UBM-bioaccessible Pb than the overall soil total Pb concentration and the soil phases with which the Pb was associated. The significant phases identified in a subset of samples were carbonates, manganese oxides, iron-aluminium oxyhydroxides and clays.

Determination of the bioaccessibility of chromium in Glasgow soil and the implications for human health risk assessment.

The Unified Bioaccessibility Method (UBM), which simulates the fluids of the human gastrointestinal tract, was used to assess the oral bioaccessibility of Cr in 27 Glasgow soils. These included several contaminated with Cr(VI), the most toxic form of Cr, from the past disposal of chromite ore processing residue (COPR). The extraction was employed in conjunction with the subsequent determination of the bioaccessible Cr by ICP-OES and Cr(VI) by the diphenylcarbazide complexation colorimetric procedure. In addition, Cr(III)-containing species were determined by (i) HPLC-ICP-MS and (ii) ICP-OES analysis of gel electrophoretically separated components of colloidal and dissolved fractions from centrifugal ultrafiltration of extracts. Similar analytical procedures were applied to the determination of Cr and its species in extracts of the <10 µm fraction of soils subjected to a simulated lung fluid test to assess the inhalation bioaccessibility of Cr. The oral bioaccessibility of Cr was typically greater by a factor of 1.5 in the 'stomach' (pH ~1.2) compared with the 'stomach+intestine' (pH ~6.3) simulation. On average, excluding two COPR-contaminated soil samples, the oral bioaccessibility ('stomach') was 5% of total soil Cr and, overall, similar to the soil Cr(VI) concentration. Chromium(VI) was not detected in the extracts, a consequence of pH- and soil organic matter-mediated reduction in the 'stomach' to Cr(III)-containing species, identified as predominantly Cr(III)-humic complexes. Insertion of oral bioaccessible fraction data into the SNIFFER human health risk assessment model identified site-specific assessment criteria (for residential land without plant uptake) that were exceeded by the soil total Cr (3680 mg kg(-1)) and Cr(VI) (1485 mg kg(-1)) concentration at only the most COPR-Cr(VI)-contaminated location. However, the presence of measurable Cr(VI) in the <10 µm fraction of the two most highly Cr(VI)-contaminated soils demonstrated that inhalation of Cr(VI)-containing dust remains the most potentially harmful exposure route.

Symposium on 'Geographical and geological influences on nutrition': Factors controlling the distribution of selenium in the environment and their impact on health and nutrition.

Se is essential to human and animal health but can be toxic in excess. An interest in its geochemistry has developed alongside a greater understanding of its function in a number of health conditions. Geology exerts a strong control on the Se status of the surface environment; low-Se rock-types (0.05-0.09 mg Se/kg) make up the majority of rocks occurring at the Earth's surface, which in turn account for the generally low levels of Se in most soils. However, there are exceptions such as associations with sulfide mineralisation and in some types of sedimentary rocks (e.g. black shales) in which contents of Se can be much higher. Baseline geochemical data now enable a comparison to be made between environmental and human Se status, although a direct link is only likely to be seen if the population is dependent on the local environment for sustenance. This situation is demonstrated with an example from the work of the British Geological Survey in the Se-deficiency belt of China. The recent fall in the daily dietary Se intake in the UK is discussed in the context of human Se status and declining use of North American wheat in bread making. Generally, US wheat has ten times more Se than UK wheat, attributed to the fact that soils from the wheat-growing belt of America are more enriched in Se to a similar order of magnitude. In agriculture effective biofortification of crops with Se-rich fertilisers must be demonstrably safe to the environment and monitored appropriately and baseline geochemical data will enable this process to be done with confidence.