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.

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.

Multiple profiling of soil microbial communities identifies potential genetic markers of metal-enriched sewage sludge.

The long-term impacts of Cu- and Zn-rich sewage sludge additions on the structure of the microbial community in a field under pasture were investigated using a combination of multiplex-terminal restriction fragment length polymorphism (M-TRFLP) and T-RFLP profiling approaches. Changes in the community structure of bacteria, fungi, archaea and actinobacteria were observed in soils that had previously received Cu- (50-200 mg kg(-1) soil) and Zn- (150-450 mg kg(-1) soil) rich sewage sludge additions. Changes in the structure of all microbial groups measured were observed at Cu and Zn rates below the current EU guidelines (135 mg kg(-1) Cu and 300 mg kg(-1) Zn). The response of the fungal community, and to a lesser extent the bacterial and archaeal community, to Cu was dose dependent. The fungal community also showed a dose-dependent response to Zn, which was not observed in the other microbial groups assessed. Redundancy analysis demonstrated that individual terminal restriction fragments responded to both Cu and Zn and these may have potential as genetic markers of long-term metal effects in soil.

Is there a future for sequential chemical extraction?

Since their introduction in the late 1970s, sequential extraction procedures have experienced a rapid increase in use. They are now applied for a large number of potentially toxic elements in a wide range of sample types. This review uses evidence from the literature to consider the usefulness and limitations of sequential extraction and thereby to assess its future role in environmental chemical analysis. It is not the intention to provide a comprehensive survey of all applications of sequential extractions or to consider the merits and disadvantages of individual schemes. These aspects have been covered adequately in other, recent reviews. This review focuses in particular on various key issues surrounding sequential extractions such as nomenclature, methodologies, presentation of data and interpretation of data, and discusses typical applications from the recent literature for which sequential extraction can provide useful and meaningful information. Also covered are emerging developments such as accelerated procedures using ultrasound- or microwave energy-assisted extractions, dynamic extractions, the use of chemometrics, the combination of sequential extraction with isotope analysis, and the extension of the approach to non-traditional analytes such as arsenic, mercury, selenium and radionuclides.

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.

Sequential extraction combined with isotope analysis as a tool for the investigation of lead mobilisation in soils: application to organic-rich soils in an upland catchment in Scotland.

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.

Lead in grass in the Scottish uplands: deposition or uptake?

If it is assumed that the Pb collected in grass samples is derived mainly from atmospheric deposition then grass samples can be used as a convenient and easily analysed monitor for Pb deposition, in particular to establish the isotopic composition of current deposition in remote locations. As some studies have demonstrated a strong correlation between soil and grass Pb concentrations, it was considered important to establish the proportion of soil Pb in the grasses used to monitor atmospheric deposition at upland locations in Scotland. Consideration of earlier studies provided evidence that very little, if any, Pb in grass was derived from soil. Lead isotope analysis, by thermal ionisation mass spectrometry, of grasses grown on soils spiked with enriched (207)Pb in the field situation allowed the relative contribution of atmospheric deposition and soil to the grass Pb to be calculated. In most cases, >80% of Pb in grass was derived from atmospheric deposition and in recent years this value was >90%. Recalculation of the (206)Pb/(207)Pb ratio in grass samples showed that there was very little error in the results, published previously, which were based on the assumption that all the Pb collected with grass was derived from the atmosphere. The trends established by measuring the (206)Pb/(207)Pb ratio in grasses were confirmed and remain valid.

Investigation of the concentration and isotopic composition of inputs and outputs of Pb in waters at an upland catchment in NE Scotland.

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.

Reproducibility of the BCR sequential extraction procedure in a long-term study of the association of heavy metals with soil components in an upland catchment in Scotland.

Humic iron podzol soils from three different plots at the Glensaugh Research Station, Aberdeenshire have been sampled on an annual basis since 1990 and analysed using both total digestion and the original BCR sequential extraction procedure. Particular care was required during the oxidation of these organic soils to prevent loss of material. The residue from the sequential extraction was analysed so that the values for total concentration derived from the total digestion and from the sum of the concentrations in the fractions of the extraction procedure could be compared. The comparison was good for all three soils indicating that not only did the sequential extraction give good recovery but that this was reproducible over a period of several years. The proportion of metals extractable at each step remained relatively constant thereby demonstrating the reproducibility of the procedure and the stability of the metals in the soils over the time scale of the sampling used. Whereas the total concentrations of Cr, Cu and Ni were highest in the soil from a roadside plot, this was not the case for Cd, Pb and Zn. In the case of Pb, concentrations in soils (0-25-cm depth) well away from the road were over 100 mg/kg and well above the expected background level. The distribution of metals between each of the extracted fractions varied not only between each metal but also between each of the three soils indicating that both metal and soil influenced the measured distribution. The distribution of Pb in the roadside soil was different from those in the other two soils and over 10% was extracted in the first, acetic acid soluble, fraction.

Isotopic characterisation of lead in contaminated soils from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria.

Soil samples from the vicinity of a non-ferrous metal smelter near Plovdiv, Bulgaria contained very high concentrations of cadmium, lead and zinc (up to 140, 4900 and 5900 mg kg(-1), respectively). A roadside soil in a relatively uncontaminated area also contained high concentrations of the same metals (24, 1550 and 1870 mg kg(-1), respectively) indicating that the transport of ores could be a source of contamination. Even though the lead isotope ratios in all the samples fell within a very narrow range (for example, 1.186-1.195 for (206)Pb/(207)Pb), the samples could be differentiated into three distinct groups: ores ((206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.1874-1.1884 and 2.4755-2.4807, respectively), current deposition (1.1864 and 2.4704-2.4711, respectively) and local background (1.1927-1.1951 and 2.4772-2.4809, respectively). Although most of the current deposition has its origin in the ores used at the smelter, up to 12% could be from other sources such as petrol lead.

Origin of lead associated with different reactive phases in Scottish upland soils: an assessment made using sequential extraction and isotope analysis.

Soil samples (0-25 cm) have been taken annually since 1991 from three protected plots set up at an upland location at Glensaugh in Aberdeenshire, Scotland. The soils were analysed using the original BCR sequential extraction procedure and the lead isotopic composition was determined in each of the fractions, as well as the unfractionated soil using thermal ionisation mass spectrometry (TIMS). The lead concentrations in all the soils, including those well away from the road, were much higher than typical background values indicating that the whole area has been subject to deposition of anthropogenic lead. The distribution of lead between the different fractions was similar for the two non-roadside soils with most lead present in the oxidizable fraction. Although most lead in the roadside soil was also present in the oxidizable fraction, a substantial proportion (about 10%) was in the easily soluble fraction suggesting that roadside lead could be more mobile than lead in the other soils. Good reproducibility was obtained for the isotope analyses in all the fractions. The ratios calculated for the bulk soil from the ratios in the individual fractions agreed very closely with those measured directly in the unfractionated soil thereby demonstrating both reproducibilty and accuracy. The lowest (206)Pb/(207)Pb ratios were found in the roadside soil consistent with the recent deposition of petrol lead. The (206)Pb/(207)Pb ratios in all fractions of the other soils fell into a narrow band and it was necessary to use (204)Pb ratios to differentiate between lead in the extractable fractions and lead in the residual component. It is probable that lead in the non-roadside soils was deposited a considerable time ago and is characterised by a relatively high (206)Pb/(207)Pb ratio. Use of the (204)Pb ratios showed that the residual components in each of the three soils were isotopically distinct.

Isotopic characterisation of lead deposited 1989-2001 at two upland Scottish locations.

The isotopic composition of lead collected with grass samples taken over the period 1989-2001 from plots at two upland locations (Glensaugh in north east and Hartwood in central Scotland) has been determined using thermal ionisation mass spectrometry. Although marked reductions in lead concentrations in grass were observed at Glensaugh in the initial three years, subsequently concentrations have remained relatively constant (1-3 microg g(-1)) in all plots to the present day. The one exception was a roadside plot at Hartwood which showed a large reduction from 1.0 microg g(-1) in 1999 to 0.2 microg g(-1) in 2000 following the abolition of petrol lead in the UK at the beginning of 2000. The total concentrations at this plot were consistently lower than those found at plots away from road traffic but exposed to the prevailing wind direction. The 206Pb/207Pb ratio increased steadily at all the plots throughout the period of the study indicating the reducing influence of petrol lead but the changes were not as great as might be expected with the decrease in the use of leaded petrol. Assuming the collected lead had only two sources, petrol lead and a diffuse background "industrial" lead, the proportion of petrol lead was only in the range 17-69% for roadside samples and 0-39% in other samples. A substantial proportion of deposited lead, therefore, now has its origin other than in petrol. Mixing curves indicate that whereas the lead deposited at Glensaugh could be defined by only two end members, that at Hartwood needs more than two components in the mixture. The results also suggest that although petrol lead has been eliminated, traffic is still a source of lead and another source defined as "traffic lead" should be considered.