Vanessa Pashley

The oxygen isotope relationship between the phosphate and structural carbonate fractions of human bioapatite

RATIONALE Oxygen isotope analysis of archaeological human dental enamel is widely used as a proxy for the drinking water composition (δ(18)O(DW)) of the individual and thus can be used as an indicator of their childhood place of origin. In this paper we demonstrate the robustness of structural carbonate oxygen isotope values (δ(18)O(C)) in bioapatite to preserve the life signal of human tooth enamel by comparing it with phosphate oxygen isotope values (δ(18)O(P)) derived from the same archaeological human tooth enamel samples. METHODS δ(18)O(C) analysis was undertaken on 51 archaeological tooth enamel samples previously analysed for δ(18)O(P) values and strontium isotopes. δ(18)O(C) values were determined on a GV IsoPrime dual inlet mass spectrometer, following a series of methodological tests to assess: (1) The reaction time needed to ensure complete release of CO(2) from structural carbonate in the enamel; (2) The effect of an early pre-treatment with dilute acetic acid to remove diagenetic carbonate; (3) Analytical error; (4) Intra-tooth variation; and (5) Diagenetic alteration. RESULTS This study establishes a direct relationship between δ(18)O(C) and δ(18)O(P) values from human tooth enamel (δ(18)O(P) =  1.0322 × δ(18)O(C) - 9.6849). We have combined this equation with the drinking water equation of Daux et al. (J. Hum. Evol. 2008, 55, 1138) to allow direct calculation of δ(18)O(DW) values from human bioapatite δ(18)O(C) (δ(18)O(DW)  =  1.590 × δ(18)O(C) - 48.634). CONCLUSIONS This is the first comprehensive study of the relationship between the ionic forms of oxygen (phosphate oxygen and structural carbonate) in archaeological human dental enamel. The new equation will allow direct comparison of data produced by the different methods and allow drinking water values to be calculated from structural carbonate data with confidence.

Zircon age constraints on the provenance of Llandovery to Wenlock sandstones from the Midland Valley terrane of the Scottish Caledonides

Synopsis Detrital zircon populations within the Llandovery to Wenlock sandstones of the southern Midland Valley of Scotland indicate that the recycled orogenic provenance for these sedimentary rocks was essentially bimodal, comprising a younger Lower Palaeozoic component and an older predominantly Mesoproterozoic component. The Lower Palaeozoic contribution is dominated by Arenig/Llanvirn (c. 475 Ma) zircons interpreted as having been derived from a volcanic-plutonic source located within the Midland Valley terrane. The dominant Mesoproterozoic component within the sandstones is c. 1000 Ma and is thought to represent detritus shed from a Grenvillian (c. 1000–1800Ma) basement to the Midland Valley terrane. The scarcity of Archaean zircons precludes the Grampian metamorphic terrane Dalradian Supergroup as a supplier of sediment to the Ordovician–Silurian basins located along the southern margin of the Midland Valley. The age profiles of detrital zircon populations do not fit with a simple model of unroofing of a volcanic-arc complex. Rather they point to the periodic uplift of fault-bound, dismembered blocks of volcanic and plutonic rocks during a prolonged (Llandovery through to at least early Devonian) period of sinistral strike-slip deformation, and it was this which controlled basin development, sedimentary facies distribution and deformation along the southern side of the Midland Valley terrane. Appendices 1 & 2 can be found at http://www.geolsoc.org.uk/SUP18370

Evolving Pb isotope signatures of London airborne particulate matter (PM10)—constraints from on-filter and solution-mode MC-ICP-MS

Pb isotope compositions of biologically significant PM(10) atmospheric particulates from a busy roadside location in London UK were measured using solution- and laser ablation-mode MC-ICP-MS. The solution-mode data for PM(10) sampled between 1998-2001 document a dramatic shift to increasingly radiogenic compositions as leaded petrol was phased out. LA-MC-ICP-MS isotope analysis, piloted on a subset of the available samples, is shown to be a potential reconnaissance analytical technique. PM(10) particles trapped on quartz filters were liberated from the filter surface, without ablating the filter substrate, using a 266 nm UV laser and a dynamic, large diameter, low-fluence ablation protocol. The Pb isotope evolution noted in the London data set obtained by both analytical protocols is similar to that observed elsewhere in Western Europe following leaded petrol elimination. The data therefore provide important baseline isotope composition information useful for continued UK atmospheric monitoring through the early 21(st) century.

Regional lead isotope study of a polluted river catchment: River Wear, Northern England, UK

High precision, lead isotope analyses of archived stream sediments from the River Wear catchment, northeast England (1986-88), provide evidence for three main sources of anthropogenic lead pollution; lead mining, industrial lead emissions and leaded petrol. In the upper catchment, pollution is totally controlled and dominated by large lead discharges from historic mining centres in the North Pennine Orefield ((208)Pb/(206)Pb, (207)Pb/(206)Pb ratios range from 2.0744-2.0954 and 0.8413-0.8554 respectively). In the lower catchment, co-extensive with the Durham Coalfield and areas of high population density, pollution levels are lower and regionally more uniform. Isotope ratios are systematically higher than in the upper catchment ((208)Pb/(206)Pb, (207)Pb/(206)Pb ratios range from 2.0856-2.1397 and 0.8554-0.8896 respectively) and far exceed values determined for the geogenic regional background. Here, the pollution is characterised by the atmospheric deposition of industrial lead and petrol lead. Lead derived from the combustion of coal, although present, is masked by the other two sources. Recent sediments from the main channel of the River Wear are isotopically indistinguishable from older, low order stream sediments of the North Pennine Orefield, indicating that contamination of the river by lead mining waste (up to several 1000 mg/kg Pb at some locations) continues to pose an environmental problem; a pattern that can be traced all the way to the tidal reach. Using within-catchment isotope variation and sediment lead concentrations, estimates can be made of the discharges from discrete mines or groups of mines to the overall level of lead pollution in the River Wear. As well as providing information pertinent to source apportionment and on-going catchment remediation measures, the database is a valuable resource for epidemiologists concerned with the health risks posed by environmental lead.

Constraining modern‐day silicon cycling in Lake Baikal

Constraining the continental silicon cycle is a key requirement in attempts to understand both nutrient fluxes to the ocean and linkages between silicon and carbon cycling over different time scales. Silicon isotope data of dissolved silica (δ30SiDSi) are presented here from Lake Baikal and its catchment in central Siberia. As well as being the worlds oldest and voluminous lake, Lake Baikal lies within the seventh largest drainage basin in the world and exports significant amounts of freshwater into the Arctic Ocean. Data from river waters accounting for ~92% of annual river inflow to the lake suggest no seasonal alteration or anthropogenic impact on river δ30SiDSi composition. The absence of a change in δ30SiDSi within the Selenga Delta, through which 62% of riverine flow passes, suggests a net balance between biogenic uptake and dissolution in this system. A key feature of this study is the use of δ30SiDSi to examine seasonal and spatial variations in DSi utilization and export across the lake. Using an open system model against deepwater δ30SiDSi values from the lake, we estimate that 20–24% of DSi entering Lake Baikal is exported into the sediment record. While highlighting the impact that lakes may have upon the sequestration of continental DSi, mixed layer δ30SiDSi values from 2003 and 2013 show significant spatial variability in the magnitude of spring bloom nutrient utilization with lower rates in the north relative to south basin.

Geogenic lead isotope signatures from meat products in Great Britain: potential for use in food authentication and supply chain traceability

This paper presents lead (Pb) isotope data from samples of farm livestock raised in three areas of Britain that have elevated natural Pb levels: Central Wales, the Mendips and the Derbyshire Peak District. This study highlights three important observations; that the Pb found in modern British meat from these three areas is geogenic and shows no clear evidence of modern tetraethyl anthropogenic Pb contribution; that the generally excellent match between the biological samples and the ore field data, particularly for the Mendip and Welsh data, suggests that this technique might be used to provenance biological products to specific ore sites, under favourable conditions; and that modern systems reflect the same process of biosphere averaging that is analogous to cultural focusing in human archaeological studies that is the process of biological averaging leading to an homogenised isotope signature with increasing Pb concentration.

Tracking natural and anthropogenic Pb exposure to its geological source.

Human Pb exposure comes from two sources: (i) natural uptake through ingestion of soils and typified by populations that predate mining activity and (ii) anthropogenic exposure caused by the exposure to Pb derived from ore deposits. Currently, the measured concentration of Pb within a sample is used to discriminate between these two exposure routes, with the upper limit for natural exposure in skeletal studies given as 0.5 or 0.7 mg/kg in enamel and 0.5/0.7 μg/dL in blood. This threshold approach to categorising Pb exposure does not distinguish between the geological origins of the exposure types. However, Pb isotopes potentially provide a more definitive means of discriminating between sources. Whereas Pb from soil displays a crustal average 238U/204Pb (μ) value of c 9.7, Pb from ore displays a much wider range of evolution pathways. These characteristics are transferred into tooth enamel, making it possible to characterize human Pb exposure in terms of the primary source of ingested Pb and to relate mining activity to geotectonic domains. We surmise that this ability to discriminate between silicate and sulphide Pb exposure will lead to a better understanding of the evolution of early human mining activity and development of exposure models through the Anthropocene.