Spatial and temporal variations in Pb concentrations and isotopic composition in road dust, farmland soil and vegetation in proximity to roads since cessation of use of leaded petrol in the UK

Results are presented for a study of spatial distributions and temporal trends in concentrations of lead (Pb) from different sources in soil and vegetation of an arable farm in central Scotland in the decade since the use of leaded petrol was terminated. Isotopic analyses revealed that in all of the samples analysed, the Pb conformed to a binary mixture of petrol Pb and Pb from industrial or indigenous geological sources and that locally enhanced levels of petrol Pb were restricted to within 10 m of a motorway and 3 m of a minor road. Overall, the dominant source of Pb was historical emissions from nearby industrial areas. There was no discernible change in concentration or isotopic composition of Pb in surface soil or vegetation over the decade since the ban on the sale of leaded petrol. There was an order of magnitude decrease in Pb concentrations in road dust over the study period, but petrol Pb persisted at up to 43% of the total Pb concentration in 2010. Similar concentrations and spatial distributions of petrol Pb and non petrol Pb in vegetation in both 2001 and 2010, with enhanced concentrations near roads, suggested that redistribution of previously deposited material has operated continuously over that period, maintaining a transfer pathway of Pb into the biosphere. The results for vegetation and soil transects near minor roads provided evidence of a non petrol Pb source associated with roads/traffic, but surface soil samples from the vicinity of a motorway failed to show evidence of such a source.     

Spatial variations in the fate and transport of metals in a mining-influenced stream, North Fork Clear Creek, Colorado

North Fork Clear Creek (NFCC) receives acid-mine drainage (AMD) from multiple abandoned mines in the Clear Creek Watershed. Point sources of AMD originate in the Black Hawk/Central City region of the stream. Water chemistry also is influenced by several non-point sources of AMD, and a wastewater treatment plant (WWTP). In-stream conditions immediately downstream from point-source inputs result in a visual and rapid precipitation of hydrous iron oxides (HFO). Hydrous manganese oxides (HMO) are seen to coat rocks further downstream during some seasons. Synoptic spatial sampling was used to assess the fate and transport of Cu, Fe, Mn, and Zn during different years and hydrological seasons. Visual-MINTEQ was used to compare observed and model-calculated percentage particulate Cu and Zn as influenced by sorption to both HFO and HMO and aqueous complexation with dissolved organic carbon (DOC). Over distance, Cu and Fe were transported predominantly in the particulate phase, Mn in the dissolved phase, and Zn was intermediate in its distribution, with generally about 50% being in each phase. Under higher flows, a larger fraction of the total metals was present in the dissolved phase, along with a lower total suspended sediment (TSS) concentration. This is consistent with the source of TSS being predominantly in-stream precipitation of metals, which might be kinetically limited under higher flows. Modeling results most closely represented observed percentage particulate Cu under lower flows; a strong seasonal trend was not evident for Zn. Model over-predictions of percentage particulate Cu suggest non-equilibrium with sorbent phases or that something in addition to DOC was keeping a portion of the Cu in solution; under-predictions for Zn suggest an additional sorbent. Differences between observed and modeled particulate varied significantly between sites and seasons; ranging from 1 to 54% for Cu and 1 to 34% for Zn overall.     

Observed and modeled seasonal trends in dissolved and particulate Cu, Fe, Mn, and Zn in a mining-impacted stream

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.     

Intra- and inter-annual variation of Cd, Zn, Mn and Cu in foliage of poplars on contaminated soil

The uptake of trace metals in the leaves of fast-growing woody species is a crucial factor in ecological risk assessment and in the evaluation of phytoextraction potentials. In this study, we present a long-term data series of foliar Cd, Zn, Mn and Cu concentrations in poplar (Populus trichocarpa x P. deltoides). Leaves were collected every three weeks from 2001 until 2007 on three sites, (i) a new plantation on an alluvial soil polluted by river sediments, (ii) a new plantation on an unpolluted soil and (iii) a 10-year old plantation on a polluted dredged sediment soil. In addition, tree rings were measured on the alluvial soil in order to better assess growth over the past seven years. Foliar concentrations of Cd, Zn and Mn decreased considerably with time in the new plantation on polluted soil. Concentrations of Zn and Mn decreased in the new plantation on unpolluted soil as well. The older plantation on polluted soil did not show changes in foliar concentrations for Cd, Zn or Mn. Foliar Cu concentrations slightly increased for all sites. Within one growing season, foliar concentrations of Cd, Zn, Cu and Mn increased towards the end of the season. The tree ring data of the poplars on the alluvial soil indicated a strong decrease in growth due to declining tree condition from 2005 onwards, the same year that foliar Cd and Zn concentrations markedly decreased. Lower transpiration rates probably induced a lower uptake of dissolved trace metals. It is concluded that stand health and growth rate have a strong impact on the variation of foliar trace metal concentrations over time.     

Influence of pH and TOC concentration on Cu,Zn, Cd,and Al speciation in rivers

Dissolved ( < approximately 4 nm, dialysis in situ), colloidal ( < 0.45 microm filtered, minus dissolved) and particulate (total, minus < 0.45 microm filtered) concentrations of Cu, Zn, Cd, (Al) in eight (three) mining polluted rivers were determined by atomic absorption spectrometry (flame and graphite furnace). The metal size distribution in the rivers was compared to pH, Ca concentration, alkalinity, conductivity, and total organic carbon (TOC). Data plots based on the present and other studies also yielded information about the interrelations between TOC, pH and metal adsorption in rivers and lakes. Less than 10% of Cu, Zn, and Cd were sorbed on particles or colloids in two rivers with average pH at 3.1 and 5.1, whereas 46%, 21%, and 21% of Cu, Zn, and Cd, respectively, occurred in sorbed form in six pH neutral rivers. In three pH neutral rivers, on average 55% of Al was in colloidal form, whereas the dissolved and particulate fractions were 21% and 23%, respectively. Our data combined with data from similar studies support conclusions from other research suggesting that the percent fraction of metals adsorbed on particles rises steeply from almost zero to nearly 100% within a narrow and element specific pH range. Changes in TOC concentration seem capable of shifting the pH to % metal absorption curves in the order of one pH unit.     

Chemical and ecological effects of contaminated tunnel wash water runoff to a small Norwegian stream

Cleaning and washing of road tunnels are routinely performed and large volumes of contaminated wash water are often discharged into nearby recipients. In the present study, traffic related contaminants were quantified in tunnel wash water (the Nordby tunnel, Norway) discharged from a sedimentation pond to a nearby small stream, Årungselva. In situ size and charge fractionation techniques were applied to quantify traffic related metal species, while PAHs were quantified in total samples. All metals and several PAHs appeared at elevated concentrations in the discharged wash water compared with concentrations measured in Årungselva upstream the pond outlet, and to concentrations measured in the pond outlet before the tunnel wash event. In addition, several contaminants (e.g. Cu, Pb, Zn, fluoranthene, pyrene) exceeded their corresponding EQS. PAH and metals like Al, Cd, Cr, Cu, Fe and Pb were associated with particles and colloids, while As, Ca, K, Mg, Mo, Ni, Sb and Zn were more associated with low molecular mass species (< 10 kDa). Calculated enrichment factors revealed that many of the metals were derived from anthropogenic sources, originating most likely from wear of tires (Zn), brakes (Cu and Sb), and from road salt (Na and Cl). The enrichment factors for Al, Ba, Ca, Cr, Fe, K, Mg and Ni were low, suggesting a crustal origin, e.g. asphalt wear. Based on calculated PAH ratios, PAH seemed to originate from a mixture of sources such as wear from tires, asphalt and combustion. Finally, historical fish length measurement data indicates that the fish population in the receiving stream Årungselva may have been adversely influenced by the chemical perturbations in runoffs originating from the nearby roads and tunnels during the years, as the growth in summer old sea trout (Salmo trutta L.) in downstream sections of the stream is significantly reduced compared to the upstream sections.     

Pollution of montane soil with Cu, Zn, As, Sb, Pb, and nitrate in Kanto, Japan

Soil cores and rainwater were sampled under canopies of Cryptomeria japonica in four montane areas along an atmospheric depositional gradient in Kanto, Japan. Soil cores (30 cm in depth) were divided into 2-cm or 4-cm segments for analysis. Vertical distributions of elemental enrichment ratios in soils were calculated as follows: (X/Al)_i/(X/Al)_BG (where the numerator and denominator are concentration ratios of element-X and Al in the i- and bottom segments of soil cores, respectively). The upper 14-cm soil layer showed higher levels of Cu, Zn, As, Sb, and Pb than the lower (14-30 cm) soil layer. In the four areas, the average enrichment ratios in the upper 6-cm soil layer were as follows: Pb (4.93) ≥ Sb (4.06) ≥ As (3.04) > Zn (1.71) ≥ Cu (1.56). Exogenous elements (kg/ha) accumulated in the upper 14-cm soil layer were as follows: Zn (26.0) > Pb (12.4) > Cu (4.48) ≥ As (3.43) ≥ Sb (0.49). These rank orders were consistent with those of elements in anthropogenic aerosols and polluted (roadside) air, respectively, indicating that air pollutants probably caused enrichment of these elements in the soil surface layer. Approximately half of the total concentrations of As, Sb, and Pb in the upper 14-cm soil layer were derived from exogenous (anthropogenic) sources. Sb showed the highest enrichment factor in anthropogenic aerosols, and shows similar deposition behavior to NO₃⁻, which is a typical acidic air pollutant. There was a strong correlation between Sb and NO₃⁻ concentrations in rainfall (e.g., in the throughfall under C. japonica: [NO₃⁻] = 21.1 [dissolved Sb], r = 0.938, p < 0.0001, n = 182). Using this correlation, total (cumulative) inputs of NO₃⁻ were estimated from the accumulated amounts of exogenous Sb in soils, i.e., 16.7 t/ha at Mt. Kinsyo (most polluted), 8.6 t/ha at Mt. Tsukuba (moderately polluted), and 5.8 t/ha at the Taga mountain system (least polluted). There are no visible ecological effects of these accumulated elements in the Kanto region at present. However, the concentrations of some elements are within a harmful range, according to the Ecological Soil Screening Levels determined by the U.S. Environmental Protection Agency.     

Sources of Cd,Cu, Pb and Zn in biowaste

Biowaste, the separately collected organic fraction of municipal solid waste, can be reused for soil conditioning after composting. In this way, environmentally harmful waste management strategies, such as landfilling or incineration, can be reduced. However, frequent application of composts to soil systems may lead to the accumulation of heavy metals in soils, and therefore legal criteria were laid down in a decree to guarantee the safe use of composts. The heavy metal content of biowaste-composts frequently exceeds the legal standards, and thus raises a conflict between two governmental policies: the recycling of solid waste on the one hand, and the protection of natural ecosystems and public health on the other hand. In this study, the heavy metal content (Cd, Cu, Pb and Zn) of biowaste was compared with the natural background content of Cd, Cu, Pb and Zn in the different constituents of biowaste. For this, the physical entities of biowaste were physically fractionated by wet-sieving and subsequent water-elutriation. In this way, organic and inorganic fractions of different particle sizes were obtained and the content of Cd, Cu, Pb and Zn and the organic matter content of the different fractions were determined. On the basis of particle size, density and visual appearance, the particle-size fractions were assigned to various indoor and outdoor origins of the biowaste. It was found that a large amount of biowaste was not organic, but over 50% was made up of soil minerals due to the collection of biowaste constituents from gardens. The heavy metal content of the various fractions in biowaste was compared with the natural background contents of heavy metals in the constituents of biowaste, i.e. food products, plant material, soil organic matter and soil minerals, by collecting literature data. The heavy metal content in the fractionated physical entities of biowaste corresponded with the natural background concentration of its constituents and indicated that biowaste was not contaminated by other sources. However, the natural background content of biowaste constituents will result in heavy metal contents for biowaste-compost that will exceed the legal standards. It is advised that the legal standards for composts should be critically re-examined. The protection of soil systems could be better guaranteed if the input of heavy metals was evaluated for all inputs of fertilisers and soil conditioners, i.e. animal manures, various types of compost and artificial fertilisers.     

EXAFS speciation and phytoavailability of Pb in a contaminated soil amended with compost and gypsum

Due to unregulated uses of lead pellets for hunting purposes in Japan, soils and sediments in some river basins and wetlands have become highly contaminated with Pb. Deterioration of natural vegetation has occurred sporadically in these areas, and therefore revegetation is needed for ecological restoration. The objectives of the present study were to assess the effects of surface applications of compost and gypsum amendments on Pb availability to a watercress plant (Nasturtium officinale W.T. Aiton) and molecular-scale speciation of Pb in soil solid phases. The compost and gypsum amendments significantly decreased dissolved Pb and Sb in pore water. The concentration of Pb in aboveground plant tissues was 190 mg kg^− 1 in the control soil and was reduced to < 20 mg kg^− 1 in the compost and gypsum-amended soils. The concentration of Sb in plants grown in the control soil was 13 mg kg^− 1, whereas that in the soils receiving compost and gypsum decreased below detectable levels. Redox potential was higher in vegetated soils (ave. 349 mV) than in the unvegetated soils (ave. 99 mV) due to oxygen introduced by plant roots. Extended X-ray absorption fine structure (EXAFS) spectroscopy illustrated that Pb occurred as Pb sorbed on birnessite and/or ferrihydrite (Pb-Mn/Fe, ~ 60%) and Pb sorbed on organic matter (Pb-org, ~ 15%), and galena (PbS, ~ 10%) in the vegetated and unvegetated control soils. The compost amendment increased the proportion of Pb-org by 2-fold than in the control soils. The amended soils with plant growth decreased the proportion of Pb-Mn/Fe phases by half of that without plant growth. Galena and anglesite (PbSO₄) were not detected in compost-amended soils and even in gypsum-amended soils since a significant soil reduction to anoxic levels did not occur in the entire soil. The present study indicated that, under flooded conditions, surface applications of compost and gypsum amendments reduced plant Pb uptake from the Pb contaminated soil.     

Responses of aquatic organisms to metal pollution in a lowland river in Flanders: a comparison of diatoms and macroinvertebrates

The role of macroinvertebrates and diatoms as indicator for metal pollution was investigated by assessing both biota along a metal gradient in the Belgian river the Dommel. Macroinvertebrates and diatoms were sampled in summer and winter and physical-chemical characteristics of the water were measured at four different sample periods and related to sediment characteristics. Although metal concentrations, except cadmium, in the water nowhere exceeded water quality standards, high metal concentrations were measured in the sediment, indicating historical contamination of the Dommel. At the sites that were situated downstream of the pollution source, high levels of conductivity and chloride were measured in the water. Redundancy Analysis (RDA) indicated pH, phosphate and zinc as the significant environmental variables explaining each respectively 7.7%, 11.6% and 22.6% of the macroinvertebrate community composition. Two clusters could be separated, with Gammarus pulex, Leptocerus interruptus, Baetis rhodani and Cloeon dipterum associated with low zinc concentrations and Tubificidae, Asellus aquaticus, Erpobdella sp. and Chironomus thummi-plumosus associated with higher zinc concentrations. Ammonium (10.6%), conductivity (16.5%), chloride (11.4%) and zinc (5.9%) turned out to be significant variables explaining the diatom community structure. Based on physical-chemical differences and species composition, three different groups could be separated. With this Tabellaria flocculosa and Fragilaria capucina var. rumpens were associated with low metal concentrations, Gomphonema parvulum and Nitzschia palea with elevated concentrations and Eolimna minima and Sellaphora seminulum with high zinc concentrations. In conclusion, the diatom community best reflected the metal gradient. With regard to water quality indices, those based on macroinvertebrates best followed the metal pollution gradient and were most strongly correlated with physical-chemical variables of water and sediment. This study indicated that to assess the effect of metal pollution in lowland rivers, the combined use of macroinvertebrates and diatoms is more appropriate than the use of both biota separately.     

Accumulation of Pb, Cu, and Zn in native plants growing on a contaminated Florida site

Contamination of heavy metals represents one of the most pressing threats to water and soil resources as well as human health. Phytoremediation can be potentially used to remediate metal-contaminated sites. This study evaluated the potential of 36plants (17species) growing on a contaminated site in North Florida. Plants and the associated soil samples were collected and analyzed for total metal concentrations. While total soil Pb, Cu, and Zn concentrations varied from 90 to 4100, 20 to 990, and 195 to 2200mg kg(-1), those in the plants ranged from 2.0 to 1183, 6.0 to 460, and 17 to 598mg kg(-1), respectively. None of the plants were suitable for phytoextraction because no hyperaccumulator was identified. However, plants with a high bioconcentration factor (BCF, metal concentration ratio of plant roots to soil) and low translocation factor (TF, metal concentration ratio of plant shoots to roots) have the potential for phytostabilization. Among the plants, Phyla nodiflora was the most efficient in accumulating Cu and Zn in its shoots (TF=12 and 6.3) while Gentiana pennelliana was most suitable for phytostabilization of sites contaminated with Pb, Cu and Zn (BCF=11, 22 and 2.6). Plant uptake of the three metals was highly correlated, whereas translocation of Pb was negatively correlated with Cu and Zn though translocation of Cu and Zn were correlated. Our study showed that native plant species growing on contaminated sites may have the potential for phytoremediation.     

The spatial and temporal trends of Cd, Cu, Hg, Pb and Zn in Seine River floodplain deposits (1994-2000)

Fresh floodplain deposits (FD), from 11 key stations, covering the Seine mainstem and its major tributaries (Yonne, Marne and Oise Rivers), were sampled from 1994 to 2000. Background levels for Cd, Cu, Hg, Pb, and Zn were established using prehistoric FD and actual bed sediments collected in small forested sub-basins in the most upstream part of the basin. Throughout the Seine River Basin, FD contain elevated concentrations of Cd, Cu, Hg, Pb and Zn compared to local background values (by factors>twofold). In the Seine River Basin, trace element concentrations display substantial downstream increases as a result of increasing population densities, particularly from Greater Paris (10 million inhabitants), and reach their maxima at the river mouth (Poses). These elevated levels make the Seine one of the most heavily impacted rivers in the world. On the other hand, floodplain-associated trace element levels have declined over the past 7 years. This mirrors results from contemporaneous suspended sediment surveys at the river mouth for the 1984-1999 period. Most of these temporal declines appear to reflect reductions in industrial and domestic solid wastes discharged from the main Parisian sewage plant (Seine Aval).     

Multiple site study of recent atmospheric metal (Pb, Zn and Cu) deposition in the NW Iberian Peninsula using peat cores

In order to estimate atmospheric metal deposition in Southern Europe since the beginning of the Industrial Period (~ 1850 AD), concentration profiles of Pb, Zn and Cu were determined in four ²¹⁰Pb-dated peat cores from ombrotrophic bogs in Serra do Xistral (Galicia, NW Iberian Peninsula). Maximum metal concentrations varied by a factor of 1.8 for Pb and Zn (70 to 128 μg g⁻¹ and 128 to 231 μg g⁻¹, respectively) and 3.5 for Cu (11 to 37 μg g⁻¹). The cumulative metal inventories of each core varied by a factor of 3 for all analysed metals (132 to 329 μg cm⁻² for Pb, 198 to 625 μg cm⁻² for Zn and 22 to 69 μg cm⁻² for Cu), suggesting differences in net accumulation rates among peatlands. Although results suggest that mean deposition rates vary within the studied area, the enhanced ²¹⁰Pb accumulation and the interpretation of the inventory ratios (²¹⁰Pb/Pb, Zn/Pb and Cu/Pb) in two bogs indicated that either a record perturbation or post-depositional redistribution effects must be considered. After correction, Pb, Zn and Cu profiles showed increasing concentrations and atmospheric fluxes since the mid-XX^th century to maximum values in the second half of the XX^th century. For Pb, maximum fluxes were observed in 1955-1962 and ranged from 16 to 22 mg m⁻² yr⁻¹ (mean of 18 ± 1 mg m⁻² yr⁻¹), two orders of magnitude higher than in the pre-industrial period. Peaks in Pb fluxes in Serra do Xistral before the period of maximum consumption of leaded petrol in Europe (1970s-1980s) suggest the dominance of local pollutant sources in the area (i.e. coal mining and burning). More recent peaks were observed for Zn and Cu, with fluxes ranging from 32 to 52 mg m⁻² yr⁻¹ in 1989-1996, and from 4 to 9 mg m⁻² yr⁻¹ in 1994-2001, respectively. Our results underline the importance of multi-core studies to assess both the integrity and reliability of peat records, and the degree of homogeneity in bog accumulation. We show the usefulness of using the excess ²¹⁰Pb inventory to distinguish between differential metal deposition, accumulation or anomalous peat records.     

Determination and speciation of copper and lead in sediments of a Mediterranean river (River Tenes, Catalonia, Spain)

Total concentrations of Cu and Pb and the speciation of these metals in sediments of the River Tenes are studied in order to establish the extent to which they are polluted and their capacity of remobilization. Five samples taken along the river were analyzed, major components of the sediments were studied using XRF and total Pb and Cu content were determined by AAS. In order to test the accuracy of the digestion methods used (triacid attack with nitric, perchloric and hydrofluoric acids or diacic attack with nitric and hydrochloric acids) for the determination of total trace metal, a standard reference material was also analyzed. Triacid attack is proposed to obtain good results. The results show a highly polluted area (1556 mg kg⁻¹ Cu and 1555 mg kg⁻¹ Pb) in the last sampling site analyzed. For metal speciation, the sequential scheme of Tessier et al. was used. From the results obtained, it can be concluded that Cu content in non-residual fraction is bonded mainly to organic matter, whereas non-residual Pb is mainly associated to iron and manganese oxides.     

Distribution of species of Cu, Pb, Zn and Cd in a water profile of the Yarra river estuary

The behaviour of Cu, Pb, Zn and Cd in a highly stratified estuary was examined. The distribution of ionic and ‘organically bound” forms of the metals was determined by differential pulse anodic stripping voltammetry (dpasv) before and after u.v. irradiation. The two forms of the metals were compared with the water characteristics of salinity, temperature, turbidity, flow, and inorganic and organic carbon.Irradiation increased the concentration of all four elements detectable by dpasv. The greatest increase was for Cu in the 1 m depth river water which yielded 7.5 μg l⁻¹ before irradiation and 29 μg l⁻¹ after irradiation. Cu and Cd showed minimum concentrations in the seawater layer at 4 m depth, corresponding to the fresh seawater flowing upstream below the halocline. The concentrations of Cu and Cd were higher in the river water than in the underlying seawater. Zn concentration in the river water was lower than in the seawater. Relationships between the trace metal concentrations and the characteristics of the water column are not clear, but the direction of water movement is a major influence.     

The physicochemical speciation of Cd, Pb, Cu, Fe and Mn in the final effluent of a sewage treatment works and its impact on speciation in the receiving river

A scheme for the speciation of metals in freshwaters has been applied to the analysis of the final effluent from a sewage treatment plant and to the receiving river upstream and downstream of the effluent outfall. The treatment plant was selected because of the high influent and effluent concentrations of Cd. The metal speciation patterns in the effluent are interpreted primarily in terms of organic interactions, which appear to be exerting a solubilizing effect on Cd and Cu, but not on the Pb and Fe which are principally associated with the particulate size fraction (> 12 μm). The influx of metals with the sewage effluent alters the speciation pattern in the river. A large part of the Cd is added to the smallest size fraction (< 0.015 μm). However, the major part of each metal, with the exception of Mn, is associated with the colloidal and particulate size fractions, thus minimising the immediate toxic significance to aquatic life.     

Anthropogenic impacts in North Poland over the last 1300 years — A record of Pb, Zn, Cu, Ni and S in an ombrotrophic peat bog

Lead pollution history over Northern Poland was reconstructed for the last ca. 1300 years using the elemental and Pb isotope geochemistry of a dated Polish peat bog. The data show that Polish Pb-Zn ores and coal were the main sources of Pb, other heavy metals and S over Northern Poland up until the industrial revolution. After review of the potential mobility of each element, most of the historical interpretation was based on Pb and Pb isotopes, the other chemical elements (Zn, Cu, Ni, S) being considered secondary indicators of pollution. During the last century, leaded gasoline also contributed to anthropogenic Pb pollution over Poland. Coal and Pb-Zn ores, however, remained important sources of pollution in Eastern European countries during the last 50 years, as demonstrated by a high ²⁰⁶Pb/²⁰⁷Pb ratio (1.153) relative to that of Western Europe (ca. 1.10). The Pb data for the last century were also in good agreement with modelled Pb inventories over Poland and the Baltic region.     

Enrichment of Cu,Ni, Zn,Pb and As in an ombrotrophic peat bog near a Cu-Ni smelter in southwest Finland

The accumulation of selected trace elements (Cu, Ni, Zn, Pb, As) in the surface peat layer of an ombrotrophic bog 2.4 km from a Cu-Ni smelter at Harjavalta, Finland was studied using a peat core. A reference core was taken from an ombrotrophic bog at a background site, Hietaj?rvi, in eastern Finland. Element concentrations were analysed from 1-cm slices and enrichment factors (EF) were calculated. The enrichment factors of both Cu and Ni in the Harjavalta peat bog are extremely high compared to the Hietaj?rvi site. However, only the 6-cm surface peat Pb values are higher in Harjavalta compared to Hietaj?rvi. Precipitation was collected during 1992-1996, in the vicinity of the Harjavalta smelter, in order to estimate the current atmospheric deposition load. Comparison between the precipitation and peat data reveals that at Harjavalta the surface peat is relatively much more polluted than the current precipitation. The variation in EF of the Harjavalta peat core with respect to depth shows two patterns: Cu and Pb are similar, as are Ni, Zn and As. The vertical gradient in Harjavalta Cu EF suggests that Cu supplied to the peat by atmospheric deposition is very well preserved by the bog.     

Partitioning and speciation of chromium, copper, and arsenic in CCA-contaminated soils: influence of soil composition

This study focused on the influence of soil composition and physicochemical characteristics on the retention and partitioning of Cu, Cr and As in nine chromated copper arsenate (CCA) artificially contaminated soils. A statistical mixture design was used to set up the number of soils and their respective composition. Sequential extraction and modified solvent extraction were used to assess Cu and Cr partitioning and As speciation [As(III) or As(V)]. It was found that peat had a strong influence on CEC (232 meq/100 g), on buffer capacity and on Cu and Cr retention, whereas kaolinite's contribution to the CEC was minor (38 meq/100 g). Average metal retention in mineral soils was low (58% for Cu and 23% for Cr) but increased dramatically in highly organic soils (96% for Cu and 78% for Cr). However, both organic and mineral soils demonstrated a very high sorption of added As (71-81%). Levels of Cu and Cr in a soluble or exchangeable form (F1) in highly organic soils were very low, whereas the levels strongly bound to organic matter were much higher. Conversely, in mineral soils, 47% of Cu and 18% of Cr were found in F1. As a result, Cr and Cu in moderately and highly organic contaminated soils were present in less mobile and less bioavailable forms, whereas in mineral soils, the labile fraction was higher. The modified method used for selective determination of mineral As species in CCA-contaminated soils was found to be quantitative and reliable. Results revealed that arsenic was principally in the pentavalent state. Nevertheless, in organic soils, arsenite was found in significant proportions (average value of 29% in highly organic soils). This indicates that some reduction of arsenate to arsenite occurred since the original species in CCA is As(V).