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.

Mobility of antimony, arsenic and lead at a former antimony mine, Glendinning, Scotland.

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.

Geochemical associations and availability of cadmium (Cd) in a paddy field system, northwestern Thailand.

The Mae Tao watershed, northwest Thailand, has become contaminated with cadmium (Cd) as a result of zinc ore extraction (Padaeng deposit) in the nearby Thanon-Thongchai mountains. Consumption of contaminated rice has led to documented human health impacts. The aim of this study was to elucidate transfer pathways from creek and canal waters to the paddy field soils near Baan Mae Tao Mai village and to determine the relationship between Cd speciation in the soil and uptake by rice plants. Transfer mainly occurred in association with particulate matter during flooding and channel dredging and, in contrast with many other studies, most of the soil Cd was associated with exchangeable and carbonate-bound fractions. Moreover, there was a linear relationship between soil total Cd and rice grain Cd (R(2) = 0.715), but a stronger relationship between both the Tessier-exchangeable soil Cd and the BCR-exchangeable soil Cd and rice grain Cd (R(2) = 0.898 and 0.862, respectively).

Processes controlling manganese distributions and associations in organic-rich freshwater aquatic systems: the example of Loch Bradan, Scotland.

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 (3 kDa-0.2 µm) in the main streamwater inflow at the western end, 57-66% was present in the <3 kDa fraction in the proximal loch waters, at least partly as a result of the release of Mn(2+) from the bottom sediments. Towards the outflow at the eastern end, however, the increase in the amount of Mn associated with large organic colloids (100 kDa-0.2 µm) 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 Mn(2+) 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.

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.

The origin of lead in the organic horizon of tundra soils: atmospheric deposition, plant translocation from the mineral soil or soil mineral mixing?

Knowledge of the anthropogenic contribution to lead (Pb) concentrations in surface soils in high latitude ecosystems is central to our understanding of the extent of atmospheric Pb contamination. In this study, we reconstructed fallout of Pb at a remote sub-arctic region by using two ombrotrophic peat cores and assessed the extent to which this airborne Pb is able to explain the isotopic composition ((206)Pb/(207)Pb ratio) in the O-horizon of tundra soils. In the peat cores, long-range atmospheric fallout appeared to be the main source of Pb as indicated by temporal trends that followed the known European pollution history, i.e. accelerated fallout at the onset of industrialization and peak fallout around the 1960s-70s. The Pb isotopic composition of the O-horizon of podzolic tundra soil ((206)Pb/(207)Pb=1.170 ± 0.002; mean ± SD) overlapped with that of the peat ((206)Pb/(207)Pb=1.16 ± 0.01) representing a proxy for atmospheric aerosols, but was clearly different from that of the parent soil material ((206)Pb/(207)Pb=1.22-1.30). This finding indicated that long-range fallout of atmospheric Pb is the main driver of Pb accumulation in podzolic tundra soil. In O-horizons of tundra soil weakly affected by cryoturbation (cryosols) however, the input of Pb from the underlying mineral soil increased as indicated by (206)Pb/(207)Pb ratios of up to 1.20, a value closer to that of local soil minerals. Nevertheless, atmospheric Pb appeared to be the dominant source in this soil compartment. We conclude that Pb concentrations in the O-horizon of studied tundra soils - despite being much lower than in boreal soils and representative for one of the least exposed sites to atmospheric Pb contaminants in Europe - are mainly controlled by atmospheric inputs from distant anthropogenic sources.

Mechanisms controlling lateral and vertical porewater migration of depleted uranium (DU) at two UK weapons testing sites.

Uranium associations with colloidal and truly dissolved soil porewater components from two Ministry of Defence Firing Ranges in the UK were investigated. Porewater samples from 2-cm depth intervals for three soil cores from each of the Dundrennan and Eskmeals ranges were fractionated using centrifugal ultrafiltration (UF) and gel electrophoresis (GE). Soil porewaters from a transect running downslope from the Dundrennan firing area towards a stream (Dunrod Burn) were examined similarly. Uranium concentrations and isotopic composition were determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Multi-Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS), respectively. The soils at Dundrennan were Fe- and Al-rich clay-loam soils whilst at Eskmeals, they were Fe- and Al-poor sandy soils; both, however, had similar organic matter contents due to the presence of a near-surface peaty layer at Eskmeals. These compositional features influenced the porewater composition and indeed the associations of U (and DU). In general, at Dundrennan, U was split between large (100kDa-0.2µm) and small (3-30kDa) organic colloids whilst at Eskmeals, U was mainly in the small colloidal and truly dissolved fractions. Especially below 10cm depth, association with large Fe/Al/organic colloids was considered to be a precursor to the removal of U from the Dundrennan porewaters to the solid phase. In contrast, the association of U with small organic colloids was largely responsible for inhibiting attenuation in the Eskmeals soils. Lateral migration of U (and DU) through near-surface Dundrennan soils will involve both large and small colloids but, at depth, transport of the smaller amounts of U remaining in the porewaters may involve large colloids only. For one of the Dundrennan cores the importance of redox-related processes for the re-mobilisation of DU was also indicated as Mn(IV) reduction resulted in the release of both Mn(II) and U(VI) into the truly dissolved phase.

Scottish peat bog records of atmospheric vanadium deposition over the past 150 years: comparison with other records and emission trends.

Cores from four Scottish ombrotrophic peat bogs were used to reconstruct the historical record of atmospheric vanadium (V) deposition in Scotland over the last 150 years. The general similarity of V and Pb concentration profile trends in (210)Pb-dated cores from each of the sites strongly suggested that V, like Pb, is essentially immobile in ombrotrophic peat. After allowance via use of the conservative element Ti for the contribution of soil dust V, the deposition of anthropogenic V was found to be greatest (∼ 1.3 to 2.0 mg m(-2) y(-1)) in the mid-20(th) century before decreasing to 0.1-0.3 mg m(-2) y(-1) in the early years of the 21(st) century. The latter values were in good agreement with directly measured atmospheric V fluxes at nearby sites, a finding also observed in the case of Pb. The decline in peat-core-derived fluxes for both V and Pb from 1970 to 2004, however, was not as large as the decline in official UK emission estimates for the two metals during this period. This, along with an order of magnitude discrepancy between the anthropogenic V/Pb ratios at the peat core surface and the higher values of the ratio for UK emissions in the early 2000s, suggests that the recently revised UK emissions data for V may perhaps still be overestimated and/or that some previously deposited Pb is being resuspended in the atmosphere.

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.

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 (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.

Historical accumulation rates of mercury in four Scottish ombrotrophic peat bogs over the past 2000 years.

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 (210)Pb- and (14)C-dated cores up to 2000 years old. Average pre-industrial rates of mercury accumulation of 4.5 and 3.7 microg 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 85 microg m(-2) y(-1), recorded at different times possibly reflecting local/regional influences during the first 70 years of the 20th century, at the four sites (TM, FM, RM, CM), before declining to a mean value of 27+/-15 microg 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 (206)Pb/(207)Pb isotopic ratio of lead in the (210)Pb-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.

Retention of As and Sb in ombrotrophic peat bogs: records of As, Sb, and Pb deposition at four Scottish sites.

Possible postdepositional As migration in ombrotrophic peat bogs was investigated by comparing depth profiles of As with those of Sb and Pb, two elements considered to be essentially immobile in peat, and those of redox-sensitive, potentially mobile nutrient elements such as Mn, Fe, P, and S in 210Pb-dated cores from four Scottish bogs. Concentration profiles of As were similar to those of Sb and Pb rather than these other elements, indicating that As is bound strongly to organic matter and is relatively immobile in ombrotrophic peat. Historical records of atmospheric anthropogenic As, Sb, and Pb deposition during the industrial and postindustrial periods were derived, site-specific maxima (up to 1.55, 1.33, and 45 mg m(-2) y(-1), respectively) occurring between the late 1890s and 1960s, reflecting emissions from diverse sources such as mining and smelting, coal combustion, and also, in the case of Pb, exhaust emissions from the use of leaded gasoline. Since the mid-1980s, fluxes of Pb decreased (4-7 fold) more rapidly than those of As and Sb (2-3 fold), attributable to both the gradual elimination of leaded gasoline and recent new sources of the latter elements. Relative trends in derived anthropogenic As, Sb, and Pb deposition largely agreed with other Scottish peat and moss archive records, direct measurements of deposition, and UK emissions, i.e., four different types of data source.

Strategies for improving human health in contaminated situations: a review of past, present and possible future approaches.

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.

An integrated colloid fractionation approach applied to the characterisation of porewater uranium-humic interactions at a depleted uranium contaminated site.

Methods for the fractionation of aquatic colloids require careful application to ensure efficient, accurate and reproducible separations. This paper describes the novel combination of mild colloidal fractionation and characterisation methods, namely centrifugal ultrafiltration, gel electrophoresis and gel filtration along with spectroscopic (UV-visible) and elemental (Inductively Coupled Plasma-Optical Emission Spectroscopy, Inductively Coupled Plasma-Mass Spectrometry) analysis, an approach which produced highly consistent results, providing improved confidence in these methods. Application to the study of the colloidal and dissolved components of soil porewaters from one soil at a depleted uranium (DU)-contaminated site revealed uranium (U) associations with both large (100 kDa-0.2 microm) and small (3-30 kDa) humic colloids. For a nearby soil with lower organic matter content, however, association with large (100 kDa-0.2 microm) iron (Fe)-aluminium (Al) colloids in addition to an association with small (3-30 kDa) humic colloids was observed. The integrated colloid fractionation approach presented herein can now be applied with confidence to investigate U and indeed other trace metal migration in soil and aquatic systems.

Distribution and partitioning of depleted uranium (DU) in soils at weapons test ranges - investigations combining the BCR extraction scheme and isotopic analysis.

Depleted uranium (DU) has become a soil contaminant of considerable concern in many combat zones and weapons-testing sites around the world, including locations in Europe, the Middle East and the USA, arising from its dispersion via the application of DU-bearing munitions. Once DU is released into the environment its mobility and bioavailability will, like that of other contaminants, largely depend on the type of associations it forms in soil and on the nature of the soil components to which it binds. In this study we used the BCR sequential extraction scheme to determine the partitioning of DU amongst soil fractions of texturally varying soils from locations affected by weapons-testing activities. Isotopic analyses (MC-ICP-MS and alpha-spectrometry) were performed to verify the presence of DU in whole soils and soil fractions and to determine any preferential partitioning of the contaminant. Results identified soil organic matter as being consistently the most important component in terms of DU retention, accounting for 30-100% of DU observed in the soils examined. However, at greater distances from known contamination points, DU was also found to be largely associated with the exchangeable fraction, suggesting that DU can be mobilised and transported by surface and near-surface water and does remain in an exchangeable (and thus potentially bioavailable) form in soils.

Depleted uranium mobility across a weapons testing site: isotopic investigation of porewater, earthworms, and soils.

The mobility and bioavailability of depleted uranium (DU) in soils at a UK Ministry of Defence (UK MoD) weapons testing range were investigated. Soil and vegetation were collected near a test-firing position and at eight points along a transect line extending approximately 200 m down-slope, perpendicular to the firing line, toward a small stream. Earthworms and porewaters were subsequently separated from the soils and both total filtered porewater (<0.2 microm) and discrete size fractions (0.2 microm-100 kDa, 100-30 kDa, 30-3 kDa, and <3 kDa)obtainedvia centrifugal ultrafiltration were examined. Uranium concentrations were determined by inductively coupled plasma optical emission spectrometry (ICP-OES) for soils and ICP-mass spectrometry (MS) for earthworms and porewaters, while 235U:238U atom ratios were determined by multicollector (MC)-ICP-MS. Comparison of the porewater and earthworm isotopic values with those of the soil solids indicated that DU released into the environment during weapons test-firing operations was more labile and more bioavailable than naturally occurring U in the soils at the testing range. Importantly, DU was shown to be present in soil porewater even at a distance of approximately 185 m from the test-firing position and, along the extent of the transect was apparently associated with organic colloids.

A lead isotopic assessment of tree bark as a biomonitor of contemporary atmospheric lead.

The outermost bark layer of trees, predominantly Scots pine (Pinus sylvestris), was sampled at 82 non-urban locations from six arbitrarily designated areas (Northwest, Northeast, Central Highlands, Central and East, Central and Southwest, Southeast), throughout Scotland during 2002-2003 and analysed for lead concentration and stable lead isotopes by flame atomic absorption spectrometry (AAS) and inductively coupled plasma-mass spectrometry (ICP-MS), respectively. The mean lead concentration and mean (206)Pb/(207)Pb ratio (+/-1 standard deviation, SD) for bark samples from the areas were as follows: Northwest (8.0 mg kg(-1), 1.121+/-0.014, n=17), Northeast (8.9 mg kg(-1), 1.117+/-0.012, n=12), Central Highlands (11.3 mg kg(-1), 1.130+/-0.010, n=11), Central and East (35.3 mg kg(-1), 1.120+/-0.007, n=10), Central and Southwest (20.6 mg kg(-1), 1.125+/-0.018, n=22) and Southeast (34.4 mg kg(-1), 1.120+/-0.005, n=10), with an overall mean lead concentration of 18.5 mg kg(-1) (range 0.6-146 mg kg(-1), median 8.4 mg kg(-1)) and an overall mean (206)Pb/(207)Pb ratio of 1.122+/-0.014 (range 1.089-1.168, median 1.122). The overall mean (206)Pb/(207)Pb ratio for bark was therefore significantly lower (p<0.01, t test) than the mean atmospheric (206)Pb/(207)Pb ratio of 1.154+/-0.006 (range 1.144-1.167, n=50) and 1.154+/-0.010 (range 1.134-1.171, n=26) as determined in rainwater collected routinely at Glensaugh, Central Highlands, during 2002 and 2003, respectively. The bark (206)Pb/(207)Pb values, 90% of which lay between 1.10 and 1.14, were more akin to those recorded for the atmosphere (via rainwater, atmospheric particulates, moss, etc.) at various locations throughout Scotland during the 1990s, a decade over which the use of leaded petrol (mean (206)Pb/(207)Pb ratio=1.076+/-0.011) declined markedly before its complete withdrawal in 2000. This strongly suggests that the lead content and isotopic composition of tree bark from Scots pine, which reputedly sheds its outer layers every couple of years or so, reflect exposure to atmospherically deposited lead (in the atmosphere or soil) over a much longer time period than just the previous 2-3 years of exposure to contemporary atmospheric lead. The possible influence of soil lead upon tree bark through external attachment was not observed in a comparative sub-set study of 27 paired bark (mean (206)Pb/(207)Pb ratio=1.122+/-0.016) and surface (0-2 cm) soil (mean (206)Pb/(207)Pb ratio=1.145+/-0.022) samples, in only six cases (i.e. 22%) of which did the corresponding (206)Pb/(207)Pb ratios agree within +/-2 SD. Likewise, bark (206)Pb/(207)Pb values exhibited no discernible trend with distance from the nearest road, with similar average values for 0-20 m (1.123+/-0.015, n=34) and 20-700 m (1.122+/-0.012, n=48), although the corresponding mean (and median) lead concentration of 23.5 (10) mg kg(-1) vs. 14.9 (7.5) mg kg(-1) was slightly higher for the former. The influence of airborne dusts from waste deposits related to former mining/smelting of Wanlockhead/Leadhills lead ores ((206)Pb/(207)Pb=1.170+/-0.003) could be seen, however, in the sycamore bark lead concentrations of up to 3050 mg kg(-1) and (206)Pb/(207)Pb ratios (1.168-1.171) observed at a distance of 0.5 km away.

Assessing depleted uranium (DU) contamination of soil, plants and earthworms at UK weapons testing sites.

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.

Using size fractionation and Pb isotopes to study Pb transport in the waters of an organic-rich upland catchment.

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.

Identifying source correlation parameters for hydrocarbon wastes using compound-specific isotope analysis.

A preliminary evaluation of compound-specific isotope analysis (CSIA) as a novel, alternative method for identifying source correlation compounds in soils contaminated with residual heavy or weathered petroleum wastes is presented. Oil-contaminated soil microcosms were established using soil (sandy-loam, non-carbonaceous cley) amended with ballast-, crude- or No.6 fuel oil. Microcosms were periodically sampled over 256 days and delta(13)C values (which express the ratio of (13)C to (12)C) determined at each time point for five n-alkanes and the isoprenoid norpristane using gas chromatography-isotope ratio mass spectrometry (GC-IRMS). Although some temporal variation was observed, no significant temporal shifts in the delta(13)C values for the five n-alkanes were measured in all three oils. Isoprenoid isotope ratios (delta(13)C) appeared to be least affected by biotransformation, especially in the No.6 fuel oil. The research suggests that the delta(13)C of isoprenoids such as norpristane, may be of use as source correlation parameters.