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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. [ABSTRACT FROM AUTHOR]

Abstract: 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 2160mgkg−1 (median 539mgkg−1), bioaccessibility as determined by the ‘stomach’ simulation (pH ~1.5) was 46–1580mgkg−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 6–623mgkg−1 and 2–42% (mean 22%) of soil Pb concentration. The soil 206Pb/207Pb ratios ranged from 1.057 to 1.175. Three-isotope plots of 208Pb/206Pb against 206Pb/207Pb demonstrated that 206Pb/207Pb 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 206Pb/207Pb 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 206Pb/207Pb 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. [Copyright &y& Elsevier]

Abstract: 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 (430–450m) of the catchment was not significantly different (Student''s 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. [Copyright &y& Elsevier]

Abstract: The historical accumulation rates of mercury resulting from atmospheric deposition to four Scottish ombrotrophic peat bogs, Turclossie Moss (northeast Scotland), Flanders Moss (west-central), Red Moss of Balerno (east-central) and Carsegowan Moss (southwest), were determined via analysis of 210Pb- and 14C-dated cores up to 2000years old. Average pre-industrial rates of mercury accumulation of 4.5 and 3.7μg m−2 y−1 were obtained for Flanders Moss (A.D. 1–1800) and Red Moss of Balerno (A.D. 800–1800), respectively. Thereafter, mercury accumulation rates increased to typical maximum values of 51, 61, 77 and 85μg m−2 y−1, recorded at different times possibly reflecting local/regional influences during the first 70years of the 20th century, at the four sites (TM, FM, RM, CM), before declining to a mean value of 27±15μg m−2 y−1 during the late 1990s/early 2000s. Comparison of such trends for mercury with those for lead and arsenic in the cores and also with direct data for the declining UK emissions of these three elements since 1970 suggested that a substantial proportion of the mercury deposited at these sites over the past few decades originated from outwith the UK, with contributions to wet and dry deposition arising from long-range transport of mercury released by sources such as combustion of coal. Confidence in the chronological reliability of these core-derived trends in absolute and relative accumulation of mercury, at least since the 19th century, was provided by the excellent agreement between the corresponding detailed and characteristic temporal trends in the 206Pb/207Pb isotopic ratio of lead in the 210Pb-dated Turclossie Moss core and those in archival Scottish Sphagnum moss samples of known date of collection. The possibility of some longer-term loss of volatile mercury released from diagenetically altered older peat cannot, however, be excluded by the findings of this study. [Copyright &y& Elsevier]

Analyzes Sphagnum moss samples collected in Scotland from 1838 to 2000. Presence of lead in the mosses; Influence of Australian lead on the lead isotopic composition of the moss samples; Prevalence of lead deposition prior to the introduction of leaded petrol in the bottom sediments from southern Loch Lomond.

Presents a profile on stable lead isotopes record of lead pollution in Loch Lomond sediments in Scotland since 1630 A.D. Information on t

Presents a foreword about the 18th European Conference of SEGH, organised by Harry Duncan, held in Glasgow and South Lanarkshire, Scotland, from September 11-12, 2000.

Elevated concentrations of antimony (Sb), arsenic (As) and lead (Pb) in upland organic-rich soils have resulted from past Sb mining activities at Glendinning, southern Scotland. Transfer of these elements into soil porewaters was linked to the production and leaching of dissolved organic matter and to leaching of spoil material. Sb was predominantly present in truly dissolved (< 3 kDa) forms whilst As and Pb were more commonly associated with large Fe-rich/organic colloids. The distinctive porewater behaviour of Sb accounts for its loss from deeper sections of certain cores and its transport over greater distances down steeper sections of the catchment. Although Sb and As concentrations decreased with increasing distance down a steep gully from the main spoil heap, elevated concentrations (~ 6-8 and 13-20 μg L − 1 , respectively) were detected in receiving streamwaters. Thus, only partial attenuation occurs in steeply sloping sections of mining-impacted upland organic-rich soils and so spoil-derived contamination of surface waters may continue over time periods of decades to centuries. Capsule abstract Production and leaching of dissolved organic matter led to the concomitant transfer of truly dissolved Sb to soil porewaters. Leaching of spoil-derived Sb impacted on the quality of receiving stream waters. [ABSTRACT FROM AUTHOR]

Loch Bradan, a drinking water reservoir in SW Scotland, frequently exhibits unacceptably high dissolved Mn concentrations. Both the surrounding catchment and the loch sediments are potential sources of Mn to the loch water. This study focused on the catchment soils, which are peaty, and found that redox cycling was an important process with respect to retention of Mn in the top sections (0–15 cm). Under more reducing conditions, reduction to Mn(II) and subsequent complexation by humic substances was observed at greater depth in some soil profiles. Complexation by humic substances is important because lateral water flow can remove soluble complexes and indeed this study observed that about 50% of Mn was humic-complexed in the stream waters feeding into the loch. It was particularly evident that the soil profile with the lowest Mn inventory exhibited the greatest extent of humification and that the remaining Mn was predominantly in a non-easily reducible form. [Copyright &y& Elsevier]

Abstract: Recent increases in manganese (Mn) concentrations in surface waters, including drinking water supplies, have triggered renewed interest in its geochemical behaviour in freshwater systems. This study, involving analysis of bottom sediments and ultrafiltered water (stream, loch and sediment porewater) samples, identified changes in aqueous phase speciation of Mn upon entering the loch waters and during its transit from the inflow to the outflow of Loch Bradan, a drinking water reservoir in SW Scotland. Diffusion out of the bottom sediments during calm periods or mixing of porewaters with loch water during resuspension events also released Mn into the overlying waters. Although 65% Mn was in colloidal form (3kDa–0.2μm) in the main streamwater inflow at the western end, 57–66% was present in the <3kDa fraction in the proximal loch waters, at least partly as a result of the release of Mn2+ from the bottom sediments. Towards the outflow at the eastern end, however, the increase in the amount of Mn associated with large organic colloids (100kDa–0.2μm) correlated with the speciation of Mn in the bottom water and the bottom sediment porewaters. While the inflow waters do have some impact upon Mn speciation at the western end of the loch, it appears that within-loch processes have a greater impact on Mn speciation near the outflow. These findings emphasise the importance of understanding the geochemical controls on Mn behaviour in aquatic systems: it is clear that although Mn may be present as truly dissolved Mn2+ in some parts of the loch, it can also be associated to a significant extent (35–47%) with large organic colloids. These findings are important not only with respect to water treatment but also in terms of understanding the likely consequences of climatic change which may exacerbate losses of Mn from the bottom sediments. [Copyright &y& Elsevier]

Abstract: 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 <10μm 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 (3680mgkg-1) and Cr(VI) (1485mgkg-1) concentration at only the most COPR-Cr(VI)-contaminated location. However, the presence of measurable Cr(VI) in the <10μm 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. [Copyright &y& Elsevier]

Strategies for improving human health in contaminated situations have traditionally been based on restricting emissions, remedial reduction of exposure and, where appropriate and possible, medical reconnaissance of efficacy. We review these and the broader aspects of general public health approaches, including necessary understanding of epidemiology and the wider social context, before considering a specific local case study involving health issues associated with chromium-contaminated land and its remediation in an area of urban regeneration. The impact of remediation upon the common good, in its broadest environmental, health and socio-economic sense, including enhanced opportunities for members of the community to take personal responsibility for health-improving activities, should be taken into account in addition to conventional theoretical assessments and practical measurements of relief from environmental risk. Rapidly emerging toxicogenomic technologies may have a role to play in informing future risk assessment and remediation approaches in contaminated situations, although the ethical challenges of using personal genetic information could well be considerable.

Depleted uranium (DU) weapons testing programmes have been conducted at two locations within the UK. An investigation was therefore carried out to assess the extent of any environmental contamination arising from these test programmes using both alpha spectrometry and mass spectrometry techniques. Uranium isotopic signatures indicative of DU contamination were observed in soil, plant and earthworm samples collected in the immediate vicinity of test firing points and targets, but contamination was found to be localised to these areas. This paper demonstrates the superiority of the (235)U : (238)U ratio over the (234)U : (238)U ratio for identifying and quantifying DU contamination in environmental samples, and also describes the respective circumstances under which alpha spectrometry or mass spectrometry may be the more appropriate analytical tool.

Past disposal of high-lime chromite ore processing residue (COPR) from a chemical works in S.E. Glasgow, UK, has led to continuing release of toxic and carcinogenic hexavalent chromium (Cr(VI)) to groundwaters which are highly contaminated with Cr(VI)O4(2-). Traditional methods of remediating Cr(VI)-contaminated land, e.g. using ferrous sulfate and organic matter, have had limited success in converting Cr(VI) to less harmful and insoluble Cr(III). This paper describes the first application of calcium polysulfide (CaS(x)) to the remediation of contaminated groundwater and high-lime COPR in a series of laboratory experiments, which have demonstrated the effectiveness of the treatment in quantitatively and rapidly reducing Cr(VI) to Cr(III) over the pH range (8-12.5) typically found at the sites. Cr(III)-organic complexes, present in groundwater at one location, were also effectively precipitated upon treatment with CaS(x). The potential for large-scale use of CaS(x) in the remediation of Cr(VI) from COPR is also discussed.

Sequential extraction (modified BCR procedure) combined with isotope analysis has been investigated as a tool for assessing mobilisation of lead into streams at an upland catchment in NE Scotland. The maximum lead concentrations (up to 110 mg kg(-1) in air-dried soil) occurred not at the surface but at about 10 cm depth. The lowest (206)Pb/(207)Pb ratios in any profile occurred, with one exception, at 2.5-5 cm depth. In the one exception, closest to the only road in the area, significantly lower (206)Pb/(207)Pb ratios in the surface soil together with much increased chloride concentrations (in comparison to other surface waters) indicated the possible mobilisation of roadside lead and transfer to the stream. The (206)Pb/(207)Pb ratios in extractable fractions tended at depth towards the ratio measured in the residual phase but the ratios in the oxidizable fraction increased to a value higher than that of the residual phase.

The validity of the use of sycamore (Acer pseudoplatanus) tree-rings for the reconstruction of atmospheric lead pollution histories was investigated. Tree cores spanning 1892-2003 were collected from several sycamores from the eastern shore of Loch Lomond, Scotland, an area with no local point sources of lead emission. The lead concentration and 206Pb/207Pb profiles of the Loch Lomond region cores were compared with corresponding data for the 210Pb-dated loch sediment, and also with data for moss of known age from a Scottish herbarium collection. Two of the seven sycamore cores showed the same lead concentration trend as the lead flux to the loch, the rest having no similarity to either each other or the loch sediment record. Two further sycamore cores showed some similarity in their temporal 206Pb/207Pb trends to those seen in the sediment and moss records, but only in part of their profiles, whilst the 206Pb/207Pb ratios of the other sycamore cores remained relatively unchanged for the majority of the time covered, or exhibited an opposite trend. The 206Pb/207Pb ratios of the tree cores were also mostly higher than those of the previously established records for any given time period. Tree cores covering 1878-2002 were also collected along transects from Wanlockhead and Tyndrum, two areas of former lead mining and smelting associated with distinct 206Pb/207Pb ratios of 1.170 and 1.144, respectively. The Wanlockhead tree cores exhibited a generally decreasing trend in lead concentration with both time and distance from the lead mine. The characteristic 206Pb/207Pb ratio of 1.170 was observed in samples close to the mine but a decrease in the influence of the mine-derived lead was observed in more distant samples. The tree sampled at Tyndrum showed elevated lead concentrations, which decreased with time, and a fairly constant 206Pb/207Pb ratio of 1.15 reflecting input from the mine, features not observed in any other trees along the transect. Overall the data suggest that sycamore tree-ring analysis is an unsuitable method for obtaining records of historical lead deposition in areas with no large local lead input, although it can reveal some information about the temporal and spatial influence of point source emitters. The unsuitability probably arises from the number of active annual rings in a single year, the post-uptake radial translocation of elements, the relative importance of the different routes of uptake, and the soil depth(s) from which trees draw nutrients.

Processes controlling Pb release from a small organic-rich upland catchment in northeast Scotland were investigated via measurement of Pb concentrations and 206Pb/207Pb ratios in rainwater, throughflow, surface flow, and receiving streamwaters under storm and baseflow conditions. For this catchment, the output of Pb via streams was only 2.0 +/- 1.2 kg year(-1) (11.4 +/- 6.8 g ha(-1) year(-1)), much lower than the input of 7.5 +/- 2.0 kg year(-1) (42.6 +/- 11.4 g ha(-1) year(-1)), and so the catchment is still a sink for anthropogenic Pb. Most (68-87%) of the output, however, occurred under storm conditions. Size fractionation revealed that 50-60% was in large particulate form (>25 microm) with a 206Pb/ 207Pb ratio of approximately 1.16, similar to that of the surface soils. Some 30-40% of the storm Pb output was associated with dissolved organic matter in the <0.45 microm fraction and had a lower 206Pb/207Pb ratio of approximately 1.14, close to the value obtained for near-surface throughflow. Future extreme weather conditions such as prolonged dry or wet periods will increase transport of Pb to receiving waters. Although particulate forms could then rapidly be removed under low flow conditions, Pb associated with dissolved organic matter will persist longer in aquatic systems and may also be more bioavailable.

As a consequence of the accumulation of anthropogenic Pb in upland catchments, there has been much recent concern about the potential mobilisation and transport of Pb from the soils to receiving waters and also the possible harmful effects that this might have on aquatic biota. This paper presents the findings of a two-year study of Pb behaviour in an organic-rich upland catchment at Glensaugh in NE Scotland. Pb inputs to the catchment were characterised by direct measurements of Pb concentration and (206)Pb/(207)Pb ratios in rain water and interception. Pb outputs from the catchment were calculated from measurements on stream water samples taken from the two main streams, the Cairn Burn and Birnie Burn. The relative contribution of Pb from groundwater and throughflow, under different flow conditions (base flow and high flow), to stream waters was investigated via analysis of springs sourced from groundwater and of waters flowing through the various soil horizons (S (surface), A, B, C, and D), respectively. The outcome of intensive sampling and analysis over the two-year time period was that, even with marked reduction in Pb inputs over the past two decades, the catchment was still acting as a net sink for the current atmospheric deposition. Although the Pb isotopic signature for stream water is very similar to that for the contemporaneous rain water ((206)Pb/(207)Pb approximately 1.15-1.16), only a small portion of the rain water is transferred directly to stream water. Instead, the Pb input is transferred to the stream waters mainly via groundwater and it was also confirmed that the latter had a similar Pb isotopic signature. From the Pb isotopic measurements on throughflow waters, however, Pb being removed via the streams contained some previously deposited Pb, i.e. mobilisation of a small portion of soil-derived anthropogenic Pb was occurring. These findings are important not only with respect to the source/sink status of the catchment but also for calculation of the extent of retention of the current atmospheric Pb inputs, which must take account of the release of previously deposited Pb from the catchment soils, a process occurring mainly under high flow conditions.