Lead isotope ratios in lichen samples evaluated by ICP-ToF-MS to assess possible atmospheric pollution sources in Havana,Cuba

Epiphytic lichens, collected from 119 sampling sites grown over “Roistonea Royal Palm” trees, were used to assess the spatial distribution pattern of lead (Pb) and identify possible pollution sources in Havana (Cuba). Lead concentrations in lichens and topsoils were determined by flame atomic absorption spectrophotometry and inductively coupled plasma (ICP) atomic emission spectrometry, respectively, while Pb in crude oils and gasoline samples were measured by ICP-time of flight mass spectrometry (ICP-ToF-MS). Lead isotopic ratios measurements for lichens, soils, and crude oils were obtained by ICP-ToF-MS. We found that enrichment factors (EF) reflected a moderate contamination for 71% of the samples (EF > 10). The ²⁰⁶Pb/²⁰⁷Pb ratio values for lichens ranged from 1.17 to 1.20 and were a mixture of natural radiogenic and industrial activities (e.g., crude oils and fire plants). The low concentration of Pb found in gasoline (<7.0 μg L^?1) confirms the official statement that leaded gasoline is no longer used in Cuba.     

Roadside Rhododendron pulchrum leaves as bioindicators of heavy metal pollution in traffic areas of Okayama, Japan

The leaves of roadside Rhododendron pulchrum Sweet were examined as a bioindicator of traffic-related heavy metal pollution in Okayama. Total contents of heavy metals in roadside soil and the R. pulchrum leaves were determined. Results of correlation analyses showed significant correlations among Pb, Ni, and Zn contents of roadside soil and leaf samples. These results suggest that R. pulchrum is a useful bioindicator of heavy metal pollution in traffic areas. To identify traffic-related heavy metal pollution sources, traffic-related materials such as tires, asphalt pavement, and road paint were collected and analyzed. The results of analyses of our data show that Zn is emitted mainly from the abrasion of tires; Cr is emitted mainly from wear of the asphalt pavement. Furthermore, the respective lead isotope ratios in R. pulchrum leaves, soil, roadside dust, and traffic-related materials were measured using inductively coupled plasma mass spectrometry. The isotopic compositions of lead in R. pulchrum leaves were 207Pb/206Pb = 0.861-0.871 and 208Pb/206Pb = 2.093-2.127, which agrees well with ratios in automobile wheel balance weights, suggesting that lead-containing products associated with automobiles, such as wheel balance weights, contribute to traffic-related lead pollution.     

A 300 year history of lead contamination in northern French Alps reconstructed from distant lake sediment records

Lead concentrations and isotopic ratios were measured along two well-dated sediment cores from two distant lakes: Anterne (2100 m a.s.l.) and Le Bourget (270 m a.s.l.), submitted to low and high direct human impact and covering the last 250 and 600 years, respectively. The measurement of lead in old sediment samples (>3000 BP) permits, in using mixing-models, the determination of lead concentration, flux and isotopic composition of purely anthropogenic origin. We thus show that since ca. 1800 AD the regional increase in lead contamination was mostly driven by coal consumption ((206)Pb/(207)Pb approximately 1.17-1.19; (206)Pb/(204)Pb approximately 18.3-18.6), which peaks around 1915 AD. The increasing usage of leaded gasoline, introduced in the 1920s, was recorded in both lakes by increasing Pb concentrations and decreasing Pb isotope ratios. A peak around 1970 ((206)Pb/(207)Pb approximately 1.13-1.16; (206)Pb/(204)Pb approximately 17.6-18.0) corresponds to the worldwide recorded leaded gasoline maximum of consumption. The 1973 oil crisis is characterised by a drastic drop of lead fluxes in both lakes (from approximately 35 to <20 mg cm(-2) yr(-1)). In the late 1980s, environmental policies made the Lake Anterne flux drop to pre-1900 values (<10 mg cm(-2) yr(-1)) while Lake Le Bourget is always submitted to an important flux (approximately 25 mg cm(-2) yr(-1)). The good match of our distant records, together and with a previously established series in an ice core from Mont Blanc, provides confidence in the use of sediments as archives of lead contamination. The integration of the Mont Blanc ice core results from Rosman et al. with our data highlights, from 1990 onward, a decoupling in lead sources between the high elevation sites (Lake Anterne and Mont Blanc ice core), submitted to a mixture of long-distance and regional contamination and the low elevation site (Lake Le Bourget), where regional contamination is predominant.     

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.     

Labile pools of Pb in vegetable-growing soils investigated by an isotope dilution method and its influence on soil pH

Pollution of Pb in the surface of agricultural soils is of increasing concern due to its serious impact on the plant growth and the human health through the food chain. However, the mobility, activity and bioavailability of Pb rely mainly on its various chemical species in soils. In the present study, E and L values, the labile pools of isotopically exchangeable Pb, were estimated using the method of isotope dilution in three vegetable-growing soils. The experiments involved adding a stable enriched isotope ((206)Pb > 96%) to a soil suspension and to soils in which plants are subsequently grown, the labile pools of Pb were then estimated by measuring the isotopic composition of Pb in soil solutions and in the plant tissues, respectively. In addition, the correlation of E values and soil pH was investigated at the ranges of pH 4.5-7.0. The amount of labile Pb in soils was also estimated using different single chemical extractants and a modified BCR approach. The results showed that after spiking the enriched isotopes of (206)Pb (>96%) for 24 hours an equilibration of isotopic exchanges in soil suspensions was achieved, and the isotope ratios of (208)Pb/(206)Pb measured at that time was used for calculating the E(24 h) values. The labile pools of Pb by %E(24 h) values, ranging from 53.2% to 61.7% with an average 57%, were found to be significantly higher (p < 0.05) than the values estimated with L values, single chemical extractants and the Σ(BCR) values obtained with the BCR approach, respectively. A strong negative correlation (R(2) = 0.984) between E(24 h) values and soil pH was found in the tested soil sample. The results indicate that the %E(24 h) value can more rapidly and easily predict the labile pools of Pb in soils compared with L values, but it might be readily overestimated because of the artificial soil acidity derived from the spiked isotopic tracer and the excess of spiked enriched isotopes. The results also suggest that the amounts of Pb extracted with EDTA and the Σ(BCR) values extracted with the modified BCR approach are helpful to detect the labile pools of Pb in soils. In addition, the negative correlation between soil pH and the labile pools of Pb in soils may be useful for further remediation to reduce the bioavailability of Pb in contaminated soils.     

Evolution of lead concentration in the particulate matter of Santiago,Chile, since 1978

Santiago is a city of over 4.5 million inhabitants and about 415000 motor vehicles using leaded gasoline. Twenty-four-hour samples were taken of total and fractionated particulate matter using a low-volume system and two Andersen cascade impactors, between 1978 and 1989 at different sites of the city of Santiago. Lead concentrations were determined by atomic absorption spectrophotometry. The results show that Pb concentrations vary greatly depending on the site selected. Higher values are always detected near the city center. An annual variation with the highest value during the autumn-winter period (May–July) is clearly observed. Lead concentrations versus size are clearly biased to particles smaller than 2 µm. A correlation is observed between Pb concentrations and the suspended particulate matter under 3 µm at different sites of the city. The curves of Pb concentration versus size of the aerosols emitted by the gas exhaust of motor vehicles using leaded gasoline are similar to those of the atmospheric aerosols.     

Chronological trends in trace metals recorded by a tree bark pocket in Yakushima Island, Japan

Bark included within the trunk of a 200-year-old Japanese cedar tree harvested in Yakushima Island, Japan, a World Natural Heritage Site located 150 km south of mainland Japan and 800 km east of Shanghai, China, was analysed for trace metals by ICP-MS providing a chronology of atmospheric pollution. The concentration of V, As and Pb in decadal sections of the bark pocket increased 30 to 50 fold from 1900-09 to 1960-69, indicating increased atmospheric deposition of these metals. The trend coincided with the establishment and expansion of heavy industries in Kyushu, Japan, resulting in locally high levels of air pollution. V, As and Pb subsequently declined, reflecting lower industrial emissions following air pollution control legislation from the late 1960's and decline in heavy industries. Ni, Cu and Zn showed a relatively small, 7 to 10 fold increase over time. Lead isotope ratios in the bark pockets shifted from about 0.84 to 0.86 for 207Pb/206Pb and from 2.04 to 2.10 for 208Pb/206Pb, showing that the origin of atmospheric lead changed over time from coal to more diverse sources.     

The potential of elemental and isotopic analysis of tree bark for discriminating sources of airborne lead contamination in the UK

Samples of tree bark, which accumulate airborne material, were collected from seven locations in the UK to provide an indication of the magnitude and source of lead pollution. Measurement of the Pb content and 206/207Pb stable isotope ratio by inductively coupled plasma mass spectrometry revealed significant differences between the sites. The concentration of Pb varied over almost four orders of magnitude from 7.2 to 9,600 micrograms g-1, the maximum values being found near a 'secondary' Pb smelter. The 206/207Pb isotope ratios varied from 1.108 +/- 0.002 to 1.169 +/- 0.001. The lowest Pb concentrations and highest isotope ratios were detected in bark samples from the Scilly Isles, reflecting the low-level of industry and road traffic. In contrast, samples obtained from a city centre (Sheffield) and near a motorway (M1) contained 25-46 micrograms g-1 Pb and recorded the lowest 206/207Pb ratios. Higher concentrations in the vicinity of a coal-fired power station recorded a 206/207Pb ratio of 1.14, suggesting a significant contribution from fly-ash. The relative contribution of lead from petrol (206/207Pb = 1.08) and other sources such as coal (206/207Pb = 1.18) were thus estimated using mass balance equations. Tree bark near the lead smelter recorded an intermediate 206/207Pb ratio of 1.13 reflecting the processing of material of mixed origin.     

Lead contamination of an agricultural soil in the vicinity of a shooting range

In this study, coupled Pb concentration/Pb isotope data were used to evaluate the effect of a shooting range (operational for over 30 years) on Pb contamination of adjacent agricultural soils and the associated environmental risks. Lead was mainly concentrated in the arable layer of the contaminated agricultural soils at total concentrations ranging from 573 to 694 mg kg^???1. Isotopic analyses (²⁰⁶Pb/²⁰⁷Pb) proved that Pb originated predominantly from the currently used pellets. Chemical fractionation analyses showed that Pb was mainly associated with the reducible fraction of the contaminated soil, which is in accordance with its predominant soil phases (PbO, PbCO₃). The 0.05 M EDTA extraction showed that up to 62% of total Pb from the contaminated site is potentially mobilizable. Furthermore, Pb concentrations obtained from the synthetic precipitation leaching procedure extraction exceeded the regulatory limit set by the United States Environmental Protection Agency for drinking water. Ion exchange resin bags showed to be inefficient for determining the vertical distribution of free Pb^2?+? throughout the soil profile. Increased Pb concentrations were found in the biomass of spring barley (Hordeum vulgare L.) sampled at the studied site and two possible pathways of Pb uptake have been identified: (1) through passive diffusion-driven uptake by roots and (2) especially through atmospheric deposition, which was also proved by analyses of a bioindicator species (bryophyte Hypnum cupressiforme Hedw.). This study showed that shooting ranges can present an important source of Pb contamination of agricultural soils located in their close vicinity.     

Environmental monitoring of the role of phosphate compounds in enhancing immobilization and reducing bioavailability of lead in contaminated soils

Lead is a highly toxic element and forms stable compounds with phosphate, which is commonly used to immobilize Pb in soils. However, few studies have monitored the long-term stability of immobilized Pb, which is a critical factor in determining the effectiveness of the in situ stabilization technique. Both soluble and insoluble phosphate compounds were tested for Pb immobilization, and its subsequent mobility and bioavailability in a contaminated soil from a shooting range. Adding tricalcium phosphate, hydroxyapatite, rock phosphate and potassium dihydrogen phosphate reduced the concentration of ammonium-nitrate-extractable Pb in the contaminated soil by 78.6%, 48.3%, 40.5% and 80.1%, respectively. Insoluble phosphate amendments significantly reduced leached Pb concentration from the column while soluble potassium dihydrogen phosphate compound increased P and Pb concentrations in the leachate. Rock phosphate reduced Pb accumulation in earthworms by 21.9% compared to earthworms in the control treatment. The long-term stability of immobilized Pb was evaluated after 2 years' incubation of the contaminated soil with rock phosphate or soluble phosphate compounds. Bioavailable Pb concentration as measured by simple bioavailability extraction test (SBET) showed the long-term stability of immobilized Pb by P amendments. Therefore, Pb immobilization using phosphate compounds is an effective remediation technique for Pb-contaminated soils.     

The use of X-ray fluorescence to detect lead contamination of carpeted surfaces

The recognition of the hazards to young children of low-level lead intoxication and the widespread distribution of lead in the urban environment have resulted in massive federal, state, and local lead awareness and abatement programs. Two of the most significant exposure routes of lead to young children are the soils and dusts found within the child's home. Most state and federal lead abatement programs deal with lead-based paint contamination but often do not address the issue of soft-surface contamination, such as that of carpets, furniture, and draperies. Carpets can be a reservoir of contaminated soils and dusts; currently, there exists no standard method to test carpeted surfaces for lead contamination. This paper describes a study that uses X-ray fluorescence (XRF) to test carpeted surfaces for lead contamination. XRF technology is the standard technology used in lead-based paint testing and is known to be an accurate technique to test for lead in soils. This study uses a controlled laboratory atmosphere to evaluate this technology; the objectives are to determine: (1) a lower limit of detection for the instrument; and (2) whether soil loading levels can be differentiated by XRF using trace elements also present in the soil. Results indicate that XRF can easily differentiate soil loading levels (g soil/m² carpet). The lower limit of detection of soil lead concentration on the carpet is a function of both soil lead concentration and soil loading; therefore, lead loading (mg Pb/m²) is a better indicator of detection limit than soil lead concentration. Lead loading detection levels from 108–258 mg Pb/m² were obtained, as compared to a level of 10 000 mg/m² (1 mg/cm²) for lead on painted surfaces as required by theLead-Based Paint Poisoning Prevention Act. XRF technology has the potential to be a fast, inexpensive screening technique for the evaluation of lead contamination on carpeted surfaces.     

Metal Contamination in Urban Soils of Coastal Tuscany (Italy)

Urban soils are often contaminated by metals deriving from human activities. Urban polluted soils can affect human health through direct physical contact or through the food chain. The behaviour of metals is affected by chemical and physical soil properties. Heavy metal concentration was determined in some soils of three medium sized towns of coastal Tuscany, Central Italy. Soil samples were collected in roadsides, urban agricultural soils (allotments), playgrounds and public parks. The analysis included total metal content (Pb, Cu, Zn, Ni, Cd), and sequential extraction. Lead reached the highest levels in the soils and was higher near roads. In urban agricultural soils and in allotments Cu was present in noticeable quantities (300 mg kg⁻¹). The presence of Cu in urban soils seems to be typical of soils used for a long period as agricultural land, especially vineyards in the area covered by this study. Sequential extraction was performed to evaluate the mobility of the metals and to better understand the impact of the anthropogenic activity on urban sites. In the present study principal components analysis (PCA) is employed to describe the characteristics of urban soils.     

Field measurement of lead in workplace air and paint chip samples by ultrasonic extraction and portable anodic stripping voltammetry

On-site measurement of lead in workplace air filter samples and paint chip samples by ultrasonic extraction and anodic stripping voltammetry (UE-ASV) was evaluated in the field during renovation and remodeling activities in residences having leaded paint. Aerosol and paint samples were collected using standard techniques, and the samples were analyzed on-site for lead content by portable UE-ASV. Lead in sample extracts was subsequently determined by atomic absorption (AA) spectrometry in a fixed-site laboratory. The remaining sample extracts plus undissolved material (air filters or paint particles) were then subjected to hot plate digestion in concentrated nitric acid-30% hydrogen peroxide prior to AA analysis for lead. Field UE-ASV lead data were thereby compared to UE-AA and hot plate digestion-AA results from fixed-site laboratory lead measurement. Determination of lead in air filter samples by UE-ASV (over the range of 5 microg to approximately 800 microg Pb per sample) was extremely well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, a significant negative bias associated with ASV measurement was observed, and this was attributed to a matrix effect. Lead measurement in paint chip samples by UE-ASV (over the range of approximately 10 to approximately 550 microg Pb g(-1)) was well correlated with lead measurement by UE-AA and hot plate digestion-AA procedures. However, correlation and precision were lower for lead measurement in paint samples as compared to aerosol samples, and a negative bias was also observed. Lead measurements by UE-AA were compared to lead determinations by hot plate digestion-AA; these data were highly correlated and demonstrated no significant bias. Thus it was concluded that the ultrasonic extraction procedure performed equivalently to hot plate digestion. It was reasoned that matrix effects due to the preparation and analysis of paint chip particles resulted in greater imprecision as well as negative bias by ASV measurement. Despite significant negative bias in this sample set, UE-ASV offers promise for on-site measurement of lead in samples of interest in occupational and environmental health.     

Site environmental assessment to an old paint factory in China

High ethyl-benzene and total petroleum hydrocarbons (TPHs) were found in the soil samples and groundwater samples during a site environmental assessment for an old paint factory in the city Changchun, Jilin province of China. The target old paint plant had been in operation for near 30 years by manufacturing resin and house paint. Driving force for this study was to identify potential environmental contamination existing in this paint factory which is located next to a new resident area under construction. The assessment result would be used as baseline environmental data input for remediation plan when the factory site will be changed into potential resident area in near future. The analytical data from the soil samples from different area of the factory which had high exposure to operation showed that solid waster storage area was contaminated with high heavy metals (Cd, Pb, and Zn) and waster paint storage areas were contaminated with ethyl-benzene, xylene and C9-C30 aromatic hydrocarbon solvent. The analytical data from the groundwater samples from different area of the factory showed that resin plant area and waster paint storage areas were contaminated with high concentration of naphthalene, ethyl-benzene and xylene which exceed the reference standard. Remediation action is recommended.     

Possible Routes for Lead Accumulation in Feral Pigeons (Columba Livia)

This study examined possible routes for lead (Pb) accumulation in resident pigeons collected from rural, urban, and four industrial sites in Korea. The accumulation pattern of Pb was comparable to the study sites. The highest Pb concentration was found in the bone, followed by kidney, liver, and lung of pigeons. Highest Pb residues in bones were found in urban (Seoul), and two industrial complex areas (Busan and Ulsan), which were about 15 times higher than rural area (Duckjuk island), and followed by Ansan and Yochon industrial areas. Regional Pb variations in liver, kidney, and lung tissues were also similar pattern with the bone Pb difference. These findings indicate that Pb accumulation in tissues of pigeons may be affected by the Pb exposure in their respective habitats. Crop contents and gizzard materials were investigated as representing the ingested items. No difference of Pb concentration was observed in major foods (maize and/or wheat) of crop contents in the study sites except Busan, whereas variations of Pb levels in gizzard materials were indicative of a similar pattern with tissue Pb differences. The Pb concentration in tissues of pigeons did not correspond well to the atmospheric Pb levels. With regard to possible Pb sources, ingested items especially materials present in the gizzard are important sources for Pb contamination to pigeons because Pb-containing sources may be expected to present in roadside particles, dusts, paint chips and building flakes. However, air Pb value being low may not affect significant as the regional variations in tissues of pigeons.     

Possible routes for lead accumulation in feral pigeons (Columba livia)

This study examined possible routes for lead (Pb) accumulation in resident pigeons collected from rural, urban, and four industrial sites in Korea. The accumulation pattern of Pb was comparable to the study sites. The highest Pb concentration was found in the bone, followed by kidney, liver, and lung of pigeons. Highest Pb residues in bones were found in urban (Seoul), and two industrial complex areas (Busan and Ulsan), which were about 15 times higher than rural area (Duckjuk island), and followed by Ansan and Yochon industrial areas. Regional Pb variations in liver, kidney, and lung tissues were also similar pattern with the bone Pb difference. These findings indicate that Pb accumulation in tissues of pigeons may be affected by the Pb exposure in their respective habitats. Crop contents and gizzard materials were investigated as representing the ingested items. No difference of Pb concentration was observed in major foods (maize and/or wheat) of crop contents in the study sites except Busan, whereas variations of Pb levels in gizzard materials were indicative of a similar pattern with tissue Pb differences. The Pb concentration in tissues of pigeons did not correspond well to the atmospheric Pb levels. With regard to possible Pb sources, ingested items especially materials present in the gizzard are important sources for Pb contamination to pigeons because Pb-containing sources may be expected to present in roadside particles, dusts, paint chips and building flakes. However, air Pb value being low may not affect significant as the regional variations in tissues of pigeons.     

Occurrence of phthalic acid esters in Gomti River Sediment, India

Cadmium and lead are important environmental pollutants with high toxicity to animals and human. Soils, though have considerable metal immobilizing capability, can contaminate food chain via plants grown upon them when their built-up occurs to a large extent. Present experiment was carried out with the objective of quantifying the limits of Pb and Cd loading in soil for the purpose of preventing food chain contamination beyond background concentration levels. Two separate sets of pot experiment were carried out for these two heavy metals with graded levels of application doses of Pb at 0.4–150 mg/kg and Cd at 0.02–20 mg/kg to an acidic light textured alluvial soil. Spinach crop was grown for 50 days on these treated soils after a stabilization period of 2 months. Upper limit of background concentration levels (C _ul) of these metals were calculated through statistical approach from the heavy metals concentration values in leaves of spinach crop grown in farmers’ fields. Lead and Cd concentration limits in soil were calculated by dividing C _ul with uptake response slope obtained from the pot experiment. Cumulative loading limits (concentration limits in soil minus contents in uncontaminated soil) for the experimental soil were estimated to be 170 kg Pb/ha and 0.8 kg Cd/ha. Based on certain assumptions on application rate and computed cumulative loading limit values, maximum permissible Pb and Cd concentration values in municipal solid waste (MSW) compost were proposed as 170 mg Pb/kg and 0.8 mg Cd/kg, respectively. In view of these limiting values, about 56% and 47% of the MSW compost samples from different cities are found to contain Pb and Cd in the safe range.     

Assessment of heavy metal toxicants in the roadside soil along the N-5, National Highway, Pakistan

The assessment of the toxicants in roadside soil on regular basis has become extremely essential with the increase in awareness for the metal toxicity in the environment. The present study investigates the presence of toxic metals along National Highway (N-5), Pakistan. Averages of about 1.3 million per month of automobile vehicles ply on this route. Lead (Pb), zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), cobalt (Co), manganese (Mn), mercury (Hg), and iron (Fe) were analyzed by atomic absorption spectrophotometry in roadside soil at the nine selected locations along the highway. Strong Pearson correlations (α = 0.05) were found between Pb and Zn (r(2)?= 0.887), Fe and Mn (r(2)?= 0.880), Hg and Cd (0.864), Cu and Zn (0.838), and Cu and Pb (0.814). The correlation between the elemental compositions of the main automobile components revealed vehicular traffic as the main non-point source of roadside soil pollution. Extremely high level of mercury, 144.05 mg kg(-1), was found at S5. It was revealed that the unregulated incineration and dumping sites of hazardous waste material along N-5 were also responsible for these contaminations. Multivariate analysis on the obtained data also disclosed the same interpretation. Cluster analysis of the data grouped Pb, Zn, and Cu at 85.23% similarity, whereas, Cd, Hg, and Ni were grouped at 78.75% similarity basis. The findings need swift action against the root cause of soil pollution.     

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.     

Evaluating the Applicability of Regulatory Leaching Tests for Assessing Lead Leachability in Contaminated Shooting Range Soils

The toxicity characteristic leaching procedure (TCLP) is the current US-EPA standard protocol to evaluate metal leachability in wastes and contaminated soils. However, application of TCLP to assess lead (Pb) leachability from contaminated shooting range soils may be questionable. This study determined Pb leachability in the range soils using TCLP and another US-EPA regulatory leaching method, synthetic precipitation leaching procedure (SPLP). Possible mechanisms that are responsible for Pb leaching in each leaching protocol were elucidated via X-ray diffraction (XRD). Soil samples were collected from the backstop berms at four shooting ranges, with Pb concentrations ranging from 5,000 to 60,600 mg kg⁻¹ soil. Lead concentrations in the TCLP leachates were from 3 to 350 mg l⁻¹, with all but one soil exceeding the USEPA non-hazardous waste disposal limit of 5 mg l⁻¹. However, continued dissolution of metallic Pb particles from spent Pb bullets and its re-precipitation as cerussite (PbCO₃) prevented the TCLP extraction from reaching equilibrium at the end of the standard leaching period (18 h). Thus, the standard one-point TCLP test would either over- or under-estimate Pb leachability in shooting range soils. Lead concentration in the SPLP leachates ranged from 0.021 to 2.6 mg l⁻¹, with all soils above the USEPA regulatory limit of 0.015 mg l⁻¹. In contrast to TCLP, SPLP leaching had reached equilibrium, with regard to both pH and Pb concentrations, within the standard 18 h leaching period, and the analytical SPLP results were in good agreement with those derived from modeling. Thus, we concluded that SPLP is a more appropriate alternative than TCLP for assessing lead leachability in range soils.