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.     

A comparison of antimony and lead profiles over the past 2500 years in Flanders Moss ombrotrophic peat bog, Scotland

Two cores collected in 2001 and 2004 from Flanders Moss ombrotrophic peat bog in central Scotland were dated (14C, 210Pb) and analysed (ICP-OES, ICP-MS) to derive and compare the historical atmospheric deposition records of Sb and Pb over the past 2500 years. After correction, via Sc, for contributions from soil dust, depositional fluxes of Sb and Pb peaked from ca. 1920-1960 A.D., with >95% of the anthropogenic inventories deposited post-1800 A.D. Over the past two centuries, trends in Sb and Pb deposition have been broadly similar, with fluctuations in the anthropogenic Sb/Pb ratio reflecting temporal variations in the relative input from emission sources such as the mining and smelting of Pb ores (in which Sb is commonly present, as at Leadhills/Wanlockhead in southern Scotland), combustion of coal (for which the Sb/Pb ratio is approximately an order of magnitude greater than in Pb ores) and exhaust emissions (Pb from leaded petrol) and abrasion products from the brake linings (Sb from heat-resistant Sb compounds) of automobiles. The influence of leaded petrol has been most noticeable in recent decades, firstly through the resultant minima in Sb/Pb and 206Pb/207Pb ratios (the latter arising from the use of less radiogenic Australian Pb in alkylPb additives) and then, during its phasing out and the adoption of unleaded petrol, complete by 2000 A.D., the subsequent increase in both Sb/Pb and 206Pb/207Pb ratios. The extent of the 20th century maximum anthropogenic enrichment of Sb and Pb, relative to the natural Sc-normalised levels of the Upper Continental Crust, was similar at approximately 50- to 100-fold. Prior to 1800 A.D., the influence of metallurgical activities on Sb and Pb concentrations in the peat cores during both the Mediaeval and Roman/pre-Roman periods was discernible, small Sb and Pb peaks during the latter appearing attributable, on the basis of Pb isotopic composition, to the mining/smelting of Pb ores indigenous to Britain.     

Identifying the sources and timing of ancient and medieval atmospheric lead pollution in England using a peat profile from Lindow bog, Manchester

A peat core from Lindow bog near Manchester, England, was precisely cut into 2 cm slices to provide a high-resolution reconstruction of atmospheric Pb deposition. Radiocarbon and (210)Pb age dates show that the peat core represents the period ca. 2000 BC to AD 1800. Eleven radiocarbon age dates of bulk peat samples reveal a linear age-depth relationship with an average temporal resolution of 18.5 years per cm, or 37 years per sample. Using the Pb/Ti ratio to calculate the rates of anthropogenic, atmospheric Pb deposition, the profile reveals Pb contamination first appearing in peat samples dating from ca. 900 BC which clearly pre-date Roman mining activities. Using TIMS, MC-ICP-MS, and SF-ICP-MS to measure the isotopic composition of Pb, the (208)Pb/(206)Pb and (206)Pb/(207)Pb data indicate that English ores were the predominant sources during the pre-Roman, Roman, and Medieval Periods. The study shows that detailed studies of peat profiles from ombrotrophic bogs, using appropriate preparatory and analytical methods, can provide new insight into the timing, intensity, and predominant sources of atmospheric Pb contamination, even in samples dating from ancient times.     

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.     

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.     

南极大气气溶胶中铅同位素比值的研究

通过对电感耦合等离子体质谱(ICP-MS)的工作条件和参数进行优化,建立了ICP-MS测定铅同位素比值的精确方法,测量了2007—2009年南极中山站采集到的气溶胶样品中208Pb/206Pb、207Pb/206Pb和206Pb/207Pb的比值。结果表明,南极大气气溶胶中铅同位素比值在逐年缓慢地发生线性变化,线性相关系数为0.996 2;气溶胶铅同位素示踪揭示南极附近国家(除南非)释放的铅可能成为南极大气中铅的重要来源。     

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.     

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

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

Using public participation to sample trace metals in lake surface sediments: the OPAL Metals Survey

Members of the public in England were invited in 2010 to take part in a national metals survey, by collecting samples of littoral sediment from a standing water body for geochemical analysis. To our knowledge, this is the first national sediment metals survey using public participation and reveals a snapshot of the extent of metals contamination in ponds and lakes across England. Hg, Ni, Cu, Zn and Pb concentrations exceeding sediment quality guidelines for the health of aquatic biota are ubiquitous in ponds and lakes, not just in areas with a legacy of industrial activity. To validate the public sampling approach, a calibration exercise was conducted at ten water bodies selected to represent a range of lakes found across England. Sediment concentrations of Hg, Ni, Cu, Zn and Pb were measured in samples of soil, stream and littoral and deep water sediment to assess inputs. Significant differences between littoral sediment metal concentrations occur due to local variability, but also organic content, especially in upland, peat soil catchments. Variability of metal concentrations between littoral samples is shown to be low in small (<20 ha) lowland lakes. Larger and upland lakes with more complex inputs and variation in organic content of littoral samples have a greater variability. Collection of littoral sediments in small lakes and ponds, with or without voluntary participation, can provide a reliable sampling technique for the preliminary assessment of metal contamination in standing waters. However, the heterogeneity of geology, soils and history/extent of metal contamination in the English landscape, combined with the random nature of sample collection, shows that systematic sampling for evaluating the full extent of metal contamination in lakes is still required.     

Surface water quality assessment of the Vatinsky Egan River catchment, West Siberia

Stream water chemistry were analyzed across Vatinsky Egan River Catchment (West Siberia). The objective of the study is to reveal the spatial and seasonal variations of the water quality and to assess the anthropogenic chemical inputs into the river system. Stream chemistry were monitored in 24 sampling sites for a period extended from January 2002 to December 2005. Spatial distribution of constituents in the Vatinsky Egan River basin indicated pollution from non-point sources associated with oil development. Data revealed that ion concentrations of river waters are usually negatively correlated with stream discharge. The major spatial variations of the hydrochemistry are related to the salinity. Chloride exhibited wide and high concentration range. A comparison with another rivers of West Siberia reveals that Vatinsky Egan River is the most saline and regional impacts further out in the watershed. The salinity of the river water increases substantially as it crosses Samotlor oil field. Many Cl(-) concentrations in the middle and lower parts of the catchment exceed the world average river values by one or more orders of magnitude. For 38% of sampling events, total petroleum hydrocarbons (TPH) concentrations were above the recommended water quality standards.     

Fit-for-purpose phosphorus management: do riparian buffers qualify in catchments with sandy soils?

Hillslope runoff and leaching studies, catchment-scale water quality measurements and P retention and release characteristics of stream bank and catchment soils were used to better understand reasons behind the reported ineffectiveness of riparian buffers for phosphorus (P) management in catchments with sandy soils from south-west Western Australia (WA). Catchment-scale water quality measurements of 60 % particulate P (PP) suggest that riparian buffers should improve water quality; however, runoff and leaching studies show 20 times more water and 2 to 3 orders of magnitude more P are transported through leaching than runoff processes. The ratio of filterable reactive P (FRP) to total P (TP) in surface runoff from the plots was 60 %, and when combined with leachate, 96 to 99 % of P lost from hillslopes was FRP, in contrast with 40 % measured as FRP at the large catchment scale. Measurements of the P retention and release characteristics of catchment soils (<2 mm) compared with stream bank soil (<2 mm) and the <75-μm fraction of stream bank soils suggest that catchment soils contain more P, are more P saturated and are significantly more likely to deliver FRP and TP in excess of water quality targets than stream bank soils. Stream bank soils are much more likely to retain P than contribute P to streams, and the in-stream mixing of FRP from the landscape with particulates from stream banks or stream beds is a potential mechanism to explain the change in P form from hillslopes (96 to 99 % FRP) to large catchments (40 % FRP). When considered in the context of previous work reporting that riparian buffers were ineffective for P management in this environment, these studies reinforce the notion that (1) riparian buffers are unlikely to provide fit-for-purpose P management in catchments with sandy soils, (2) most P delivered to streams in sandy soil catchments is FRP and travels via subsurface and leaching pathways and (3) large catchment-scale water quality measurements are not good indicators of hillslope P mobilisation and transport processes.     

Potential Effects of Metals in Reacidified Limed Water Bodies in Norway and Sweden

The goal of this work was to assess risk of chemical andbiological effects of metals in reacidified, limed water bodiesin Norway and Sweden. The risk assessment is based on aliterature review and evaluations of water chemical data fromthe 1995 Nordic Lake Survey. Compared to the pre-liming period,it us unlikely that enhanced remobilization of inorganicaluminium (Al) or other toxic metals (metal bomb hypothesis)from the catchment, the lake sediment and/or the streambed willoccur when limed waters reacidify. Rather, the concentrationsin surface waters are expected to be lower than before limingstarted, because of reduced atmospheric inputs of both strongacids and metals as Cd, Hg, Pb, and Zn during the last 10–20 yr. The concentrations in lakes relative to the biologicaleffect levels, as well as the chemical properties of thedifferent metals suggest that the potential biological risksassociated to reacidification of limed lakes decrease in theorder Al > Cd > Pb. The risks associated with Cr, Cu, Fe, Mn, Ni and Zn are very low and do not have to be consideredexcept in waters with known concentrations larger than the lowest biological risk level. Such waters are very rare (<2%). Aluminium is the metal that should be used to set the limit for judging the risk of biological damage due to reacidification of limed surface waters.     

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.     

Concentrations of dissolved herbicides and pharmaceuticals in a small river in Luxembourg

Urban and agricultural areas affect the hydraulic patterns as well as the water quality of receiving drainage systems, especially of catchments smaller than 50 km(2). Urban runoff is prone to contamination due to pollutants like pesticides or pharmaceuticals. Agricultural areas are possible sources of nutrient and herbicide contamination for receiving water bodies. The pollution is derived from leaching by subsurface flow, as well as wash-off and erosion caused by surface runoff. In the Luxembourgish Mess River catchment, the pharmaceutical and pesticide concentrations are comparable with those detected by other authors in different river systems worldwide. Some investigated pesticide concentrations infringe current regulations. The maximum allowable concentration for diuron of 1.8 μg l(?-?1) is exceeded fourfold by measured 7.41 μg l(?-?1) in a flood event. The load of dissolved pesticides reaching the stream gauge is primarily determined by the amount applied to the surfaces within the catchment area. Storm water runoff from urban areas causes short-lived but high-pollutant concentrations and moderate loads, whereas moderate concentrations and high loads are representative for agricultural inputs to the drainage system. Dissolved herbicides, sulfonamides, tetracyclines, analgesics and hormones can be used as indicators to investigate runoff generation processes, including inputs from anthropogenic sources. The measurements prove that the influence of kinematic wave effects on the relationship between hydrograph and chemographs should not be neglected in smaller basins. The time lag shows that it is not possible to connect analysed substances of defined samples to the corresponding section of the hydrograph.     

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.     

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the ²⁰³Tl/²⁰⁵Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios (²⁰⁷Pb/²⁰⁶Pb) found were 0.85073?±?0.0004~0.85373?±?0.0003 for the main stream, while they were 0.83736?±?0.0010 for the tributary and 0.84393?±?0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60 %. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.     

Impacts of groundwater metal loads from bedrock fractures on water quality of a mountain stream

Acid mine drainage and metal loads from hardrock mines to surface waters is a significant problem in the western USA and many parts of the world. Mines often occur in mountain environments with fractured bedrock aquifers that serve as pathways for metals transport to streams. This study evaluates impacts from current and potential future groundwater metal (Cd, Cu, and Zn) loads from fractures underlying the Gilt Edge Mine, South Dakota, on concentrations in Strawberry Creek using existing flow and water quality data and simple mixing/dilution mass balance models. Results showed that metal loads from bedrock fractures to the creek currently contribute <1% of total loads. Even if background water quality is achieved upstream in Strawberry Creek, fracture metal loads would be <5%. Fracture loads could increase substantially and cause stream water quality standards exceedances once groundwater with elevated metals concentrations in the aquifer matrix migrates to the fractures and discharges to the stream. Potential future metal loads from an upstream fracture would contribute a small proportion of the total load relative to current loads in the stream. Cd has the highest stream concentrations relative to standards. Even if all stream water was treated to remove 90% of the Cd, the standard would still not be achieved. At a fracture farther downstream, the Cd standard can only be met if the upstream water is treated achieving a 90% reduction in Cd concentrations and the median stream flow is maintained.     

Suitability of selected bioindicators of atmospheric pollution in the industrialised region of Ostrava,Upper Silesia,Czech Republic

This study is a continuation of our preceding research identifying suitable environmental samples for the tracing of atmospheric pollution in industrial areas. Three additional types of environmental samples were used to characterise contamination sources in the industrial area of Ostrava city, Czech Republic. The region is known for its extensive metallurgical and mining activities. Fingerprinting of stable Pb isotopes was applied to distinguish individual sources of anthropogenic Pb. A wide range of ²⁰⁶Pb/²⁰⁷Pb ratios was observed in the investigated samples: ²⁰⁶Pb/²⁰⁷Pb = 1.168–1.198 in mosses; ²⁰⁶Pb/²⁰⁷Pb = 1.167–1.215 in soils and ²⁰⁶Pb/²⁰⁷Pb = 1.158–1.184 in tree cores. Black and brown coal combustion, as well as metallurgical activities, is the two main sources of pollution in the area. Fossil fuel burning in industry and households seems to be a stronger source of Pb emissions than from the metallurgical industry. Concentration analyses of tree rings showed that a significant increase in As concentrations occurred between 1999 and 2016 (from 0.38 mg kg^?1 to 13.8 mg kg^?1). This shift corresponds to the use of brown coal from Bílina, Czech Republic, with an increased As concentration. The burning of low-quality fuels in households remains a problem in the area, as small ground sources have a greater influence on the air quality than do industrial sources.     

Spatial distribution,temporal variation,and sources of heavy metal pollution in groundwater of a century-old nonferrous metal mining and smelting area in China

This study first presents the spatial distribution, temporal variation, and sources of heavy metal pollution in groundwater of a nonferrous metal mine area in China. Unconfined groundwater was polluted by Pb, Zn, As, and Cu, in order, while confined karst water in the mines showed pollution in the following sequence: Zn, Cd, Cu, Pb, and As. Pollution by Pb was widespread, while Zn, As, Cu, and Cd were found to be high in the north–central industrial region and to decrease gradually with distance from smelters and tailings. Vertically, more Pb, Zn, Cu, and Cd have accumulated in shallow Quaternary groundwater, while more As have migrated into the deeper fracture groundwater in the local discharge area. Zn, Cd, and Cu concentrations in groundwater along the riverside diminished owing to reduced wastewater drainage since 1977, while samples in the confluence area were found to have increasing contents of Pb, Zn, As, Cu, and Cd since industrialization began in the 1990s. Sources of heavy metals in groundwater were of anthropogenic origin except for Cr. Pb originated primarily from airborne volatile particulates, wastewater, and waste residues and deposited continuously, while Zn, Cd, and Cu were derived from the wastewater of smelters and leakage of tailings, which corresponded to the related soil and surface residue researches. Elevated As values around factories might be the result of chemical reactions. Flow patterns in different hydrogeological units and adsorption capability of from Quaternary sediments restricted their cross-border diffusion.     

Contamination from historic metal mines and the need for non-invasive remediation techniques: a case study from Southwest England

The UK is legally required by the EU Water Framework Directive (WFD) to improve the environmental quality of inland and coastal waters in the coming years. Historic metal mine sites are recognised as an important source of some of the elements on the WFD priority chemicals list. Despite their contamination potential, such sites are valued for their heritage and for other cultural and scientific reasons. Remediating historic mining areas to control the contamination of stream waters, whilst also preserving the integrity of the mine site, is a challenge but might be achieved by novel forms of remediation. In this study, we have carried out environmental monitoring at a historic, and culturally-sensitive, lead-silver mine site in southwest England and have undertaken a pilot experiment to investigate the potential for a novel, non-invasive remediation method at the site. Concentrations of Pb and Zn in mine spoil were clearly elevated with geometric mean concentrations of 6,888 and 710 microg g(-1), respectively. Mean concentrations of Pb in stream waters were between 21 and 54 microg l(-1), in exceedance of the WFD environmental quality standard (EQS) of 7.2 microg l(-1) (annual average). Mean Zn concentrations in water were between 30 and 97 microg l(-1), compared to the UK EQS of 66.5 microg l(-1) (average). Stream sediments within, and downstream from, the mining site were similarly elevated, indicating transport of mine waste particles into and within the stream. We undertook a simple trial to investigate the potential of hydroxyapatite, in the form of bonemeal, to passively remove the Pb and Zn, from the stream waters. After percolating through bonemeal in a leaching column, 96-99% of the dissolved Pb and Zn in stream water samples was removed.