Lorna J. Eades

Stable lead isotopic characterisation of the historical record of environmental lead contamination in dated freshwater lake sediment cores from northern and central Scotland.

Sediment cores from three Scottish freshwater lakes, Loch Ness in the remote north and Loch Lomond and the Lake of Menteith, much closer to the heavily populated and industrialised central belt were analysed for 210Pb, 137Cs, Pb and stable Pb isotopic composition (206Pb/207Pb). The radionuclide data were used to establish chronologies for the Loch Ness and Loch Lomond cores, but a chronology could not be developed for the Lake of Menteith core, in which the surface sediment had been subject to intense mixing. Although Pb concentrations generally started increasing during the mid-17th Century, a small peak occurred for Loch Ness in the early 16th Century, perhaps attributable to the influence of medieval mining and smelting in mainland Europe. Temporal trends in the pattern of Pb accumulation were similar for Loch Ness and both sites in Loch Lomond, with 40-50% of the anthropogenic Pb deposited prior to the 20th Century. Fluxes of anthropogenic Pb to the lake sediments peaked during the 1950s at all locations where chronologies could be established. The 5-fold increase in anthropogenic Pb inventory for the southern basin of Loch Lomond relative to Loch Ness reflected geographical proximity to the main polluting sources. The 206Pb/207Pb data for anthropogenic Pb in the sediments from Loch Ness and Loch Lomond exhibited largely similar trends related to five different time periods. Pre-1820, the 206Pb/207Pb ratio was close to that for coal (1.181). From 1820 to 1900, a fairly constant 206Pb/207Pb ratio of approximately 1.17 probably resulted from a combination of emissions from the smelting of indigenous Pb ore (1.170) and coal burning (1.181) in Scotland, and industrial activity to the south in England, where Australian Pb of characteristically low 206Pb/207Pb ratio (1.04) was already in use. From 1901 to 1930, the 206Pb/207Pb ratio declined by <0.01, due to the increasing influence of Australian Pb. From 1931 to 1975/1985, the 206Pb/207Pb ratio of anthropogenic Pb declined by a further 0.03 to 0.04, to minimum values from approximately 1975 to 1985, primarily a consequence of car-exhaust emissions of Pb arising from the introduction of alkyl Pb petrol additives (206Pb/207Pb approximately 1.06-1.09). From 1975/1985 to the mid-1990s, the 206Pb/207Pb ratio of anthropogenic Pb increased by up to 0.015, a consequence of a reduction in car-exhaust emissions of Pb, resulting from reductions in the maximum permitted concentration of Pb in petrol, and the introduction and increasing uptake of unleaded petrol. Source apportionment calculations, on the basis of 206Pb/207Pb values in surface sediment, suggested that the contribution of Pb emissions from the use of leaded petrol was 27-40% of the atmospheric burden by the mid-1990s, in line with estimates from rainwater 206Pb/207Pb data.

The lead content and isotopic composition of british coals and their implications for past and present releases of lead to the UK environment

More than 60 coal samples, predominantly from the principal coalfields of England and Wales (25) and Scotland (30), were analysed for lead by AAS and for stable lead isotopes by ICP‐MS. While the average lead content of Scottish coal, 23.9 mg kg−1, was more than double that of coal from England and Wales, 11.0 mg kg−1, the corresponding mean 206Pb/207Pb ratios (± 1 s.d.) were nearly identical, at 1.181±0.011 and 1.184±0.006, respectively. In the light of the lead isotopic signatures of British coals and of both indigenous (206Pb/207Pb ∼ 1.17) and imported Australian (206Pb/207Pb ∼ 1.04) lead ores, an approach based on estimated lead emissions from these sources and the deconvolution of the historical lead and 206Pb/207Pb records preserved in lake sediments, peat bogs and archival herbage material indicates that coal combustion became an increasingly significant contributor to atmospheric lead deposition in the UK during the period 1830–1930, especially after the onset of England’s decline as a major location of lead mining and smelting in the late‐19th Century. Since 1930 and the introduction of leaded petrol, the atmospheric 206Pb/207Pb ratio in the UK has been strongly influenced by car‐exhaust emissions of comparatively 206Pb‐depleted lead of predominantly Australian origin, counter‐balanced to some extent by coal‐combustion emissions of lead, although these have fallen dramatically since the mid‐1950s. Nevertheless, with the introduction and substantial uptake of unleaded petrol in the UK during the last decade, even the declining releases from coal, along with contributions from other sources, are continuing to affect the atmospheric lead content and 206Pb/207Pb ratio.

The changing nature of the 206Pb/207Pb isotopic ratio of lead in rainwater, atmospheric particulates, pine needles and leaded petrol in Scotland, 1982–1998

The inductively coupled plasma-mass spectrometry (ICP-MS)-determined 206Pb/207Pb ratio of 145 samples of rainwater collected at 25 locations around Scotland during December 1997 and January 1998 and at three longterm monitoring stations in the northeast, central belt and southeast of the country from November 1997 to December 1998 averaged 1.144+/-0.017 (1 s). This represents a significant increase from the mean value of 1.120+/-0.016 recorded for the long-term sites in 1989 1991, only partly attributable to a concomitant increase in the 206Pb/207Pb ratio of leaded petrol from 1.075+/-0.013 to 1.088+/-0.007. The rainwater 206Pb/207Pb data for the late 1990s also contrast markedly with the lower 206Pb/207Pb ratios found for pine needle and atmospheric particulate samples from Scotland (e.g. Glasgow: 1.085+/-0.012 in 1985-1986, 1.099+/-0.007 in 1991-1992), England and Western Europe in this study for the period 1982-1992 when emissions of lead to the atmosphere from petrol-engined vehicles in the UK were approximately 2-9 times higher. The observed change in the lead isotopic signature of rainwater predominantly reflects the impact of measures, such as the introduction and growing uptake of unleaded petrol, to reduce car exhaust emissions of lead to the atmosphere in the UK. Based on the rainwater data, source apportionment calculations suggest a general decline in the contribution of leaded petrol to atmospheric lead in Scotland from 53-61% in 1989-1991 to 32-45% in 1997-1998, with a corresponding decline in the urban environment from 84-86% to 48-58%.

Analytical and sampling constraints in 210Pb dating

²¹⁰Pb dating provides a valuable, widely used means of establishing recent chronologies for sediments and other accumulating natural deposits. The Constant Rate of Supply (CRS) model is the most versatile and widely used method for establishing ²¹⁰Pb chronologies but, when using this model, care must be taken to account for limitations imposed by sampling and analytical factors. In particular, incompatibility of finite values for empirical data, which are constrained by detection limit and core length, with terms in the age calculation, which represent integrations to infinity, can generate erroneously old ages for deeper sections of cores. The bias in calculated ages increases with poorer limit of detection and the magnitude of the disparity increases with age. The origin and magnitude of this effect are considered below, firstly for an idealized, theoretical ²¹⁰Pb profile and secondly for a freshwater lake sediment core. A brief consideration is presented of the implications of this potential artefact for sampling and analysis.

Influences on the extent and record of heavy metal pollution in sediment cores from Loch Tay in a mineralised area of Scotland

The distribution and Inventories of Pb in the sediments of Loch Tay have been strongly influenced by inputs from past Pb mining activity, as demonstrated by correlation with the characteristic 206Pb/207Ph signature of the Tyndrum ore deposit. A major depositional event, perhaps associated with the cessation of Pb mining in the area, has been dated at 1906–1928 by the 210Pb method. Zinc and Cu have been influenced to a lesser extent by mining, as shown by comparison with inventories in Loch Lomond. Profiles of As, Mn and Fe have been affected by post-depositional diagenetic remobilisation processes. The results serve as a benchmark, with Au mining set to commence at Cononish, near Tyndrum, in 1996.

A comparison of the isotopic composition of lead in rainwater, surface vegetation and tree bark at the long-term monitoring site, Glensaugh, Scotland, in 2007.

The lead concentrations and isotopic ratios (206Pb/207Pb, 208Pb/206Pb, 208Pb/207Pb) of 31 rainwater (September 2006-December 2007) and 11 surface vegetation (moss, lichen, heather) samples (October 2007) from the rural upland catchment of Glensaugh in northeast Scotland and of nine bark samples (October 2007) from trees, predominantly Scots pine, in or near Glensaugh were determined. The mean 206Pb/207Pb ratios for rainwater in 2006 and 2007 were similar to those previously determined for 2000 to 2003 at Glensaugh, yielding an average mean annual value of 1.151+/-0.005 (+/-1 SD) for the period from 2000, when an outright ban on leaded petrol came into force in the UK, to 2007. The mean 206Pb/207Pb ratio (1.146+/-0.004; n=7) for surface vegetation near the top (430-450 m) of the catchment was not significantly different (Students t test) from that of rainwater (1.148+/-0.017; n=24) collected over the 12-month period prior to vegetation sampling, but both were significantly different, at the 0.1% (i.e. p<0.001) and 1% (p<0.01) level, respectively, from the corresponding mean value (1.134+/-0.006; n=9) for the outermost layer of tree bark. When considered in conjunction with similar direct evidence for 2002 and indirect evidence (e.g. grass, atmospheric particulates, dated peat) for recent decades in the Glensaugh area, these findings confirm that the lead isotopic composition of surface vegetation, including that of suitably located moss, reflects that of the atmosphere while that of the outermost layer of Scots pine bark is affected by non-contemporaneous lead. The nature and relative extent of the different contributory sources of lead to the current UK atmosphere in the era of unleaded petrol, however, are presently not well characterised on the basis of lead isotopic measurements.

Phosphoglycerate mutase from Trypanosoma brucei is hyperactivated by cobalt in vitro, but not in vivo

Production of ATP by the glycolytic pathway in the mammalian pathogenic stage of protists from the genus Trypanosoma is required for the survival of the parasites. Cofactor-independent phosphoglycerate mutase (iPGAM) is particularly attractive as a drug target because it shows no similarity to the corresponding enzyme in humans, and has also been genetically validated as a target by RNAi experiments. It has previously been shown that trypanosomatid iPGAMs require Co(2+) to reach maximal activity, but the biologically relevant metal has remained unclear. In this paper the metal content in the cytosol of procyclic and bloodstream-form T. brucei (analysed by inductively coupled plasma-optical emission spectroscopy) shows that Mg(2+), Zn(2+) and Fe(2+) were the most abundant, whereas Co(2+) was below the limit of detection (<0.035 μM). The low concentration indicates that Co(2+) is unlikely to be the biologically relevant metal, but that instead, Mg(2+) and/or Zn(2+) may assume this role. Results from metal analysis of purified Leishmania mexicana iPGAM by inductively coupled plasma-mass spectrometry also show high concentrations of Mg(2+) and Zn(2+), and are consistent with this proposal. Our data suggest that in vivo cellular conditions lacking Co(2+) are unable to support the maximal activity of iPGAM, but instead maintain its activity at a relatively low level by using Mg(2+) and/or Zn(2+). The physiological significance of these observations is being pursued by structural, biochemical and biophysical studies.

Influences upon the Lead Isotopic Composition of Organic and Mineral Horizons in Soil Profiles from the National Soil Inventory of Scotland (2007-09)

Some 644 individual soil horizons from 169 sites in Scotland were analyzed for Pb concentration and isotopic composition. There were three scenarios: (i) 36 sites where both top and bottom (i.e. lowest sampled) soil horizons were classified as organic in nature, (ii) 67 with an organic top but mineral bottom soil horizon, and (iii) 66 where both top and bottom soil horizons were mineral. Lead concentrations were greater in the top horizon relative to the bottom horizon in all but a few cases. The top horizon (206)Pb/(207)Pb ratio was lesser (outside analytical error) than the corresponding bottom horizon (206)Pb/(207)Pb ratio at (i) 64%, (ii) 94% and (iii) 73% of sites, and greater at only (i) 8%, (ii) 3% and (iii) 8% of sites. A plot of (208)Pb/(207)Pb vs. (208)Pb/(206)Pb ratios showed that the Pb in organic top (i, ii) and bottom (i) horizons was consistent with atmospherically deposited Pb of anthropogenic origin. The (206)Pb/(207)Pb ratio of the organic top horizon in (ii) was unrelated to the (206)Pb/(207)Pb ratio of the mineral bottom horizon as demonstrated by the geographical variation in the negative shift in the ratio, a result of differences in the mineral horizon values arising from the greater influence of radiogenic Pb in the north. In (iii), the lesser values of the (206)Pb/(207)Pb ratio for the mineral top horizon relative to the mineral bottom horizon were consistent with the presence of anthropogenic Pb, in addition to indigenous Pb, in the former. Mean anthropogenic Pb inventories of 1.5 and 4.5 g m(-2) were obtained for the northern and southern halves of Scotland, respectively, consistent with long-range atmospheric transport of anthropogenic Pb (mean (206)Pb/(207)Pb ratio~1.16). For cultivated agricultural soils (Ap), this corresponded to about half of the total Pb inventory in the top 30 cm of the soil column.