SOURCES OF TRACE METALS IN STREAMS AND HEADWATER LAKES IN FINLAND

Distributions of Mn, Zn, Cu, Ni, Cr, Pb, As, and Cd in Finnish surface waters were studied by comparing two data sets: samples from 154 headwater lakes collected by the Water and Environment Administration in 1992 and samples from 1165 headwater streams collected during the environmental geochemical mapping program of the Geological Survey of Finland in 1990. It was expected that headwater lakes with catchments smaller than 1 km² and high lake percentage (ratio of lake area to catchment size) would be more influenced by atmospheric trace metal deposition than the streams, with average catchment size of 30 km². The lakes with highest arsenic concentrations lie in an area with greenstones and arsenic-rich black schists. The same lakes have high copper concentrations, which evidently are derived from the Cu-rich greenstones of the catchment. The high copper concentrations of streams and lakes in the industrialized region of the southwest coast are due to several anthropogenic sources. The highest concentrations of chromium occur in brown stream and lake waters rich in humic matter, while manganese and zinc concentrations, which are controlled by acidity, tend to be elevated in low-pH waters. The high nickel concentrations in lakes in southwestern Finland probably are due to anthropogenic input, while Ni anomalies in stream and lake water in eastern Finland are correlated with high Ni contents of glacial till. The lead concentrations in lakes are mainly of airborne anthropogenic origin. The pattern of atmospheric deposition is reflected in the concentrations of Cd, As, Cu, Zn, and Ni in headwater lakes, but land-use, the natural distribution of metals in the overburden, water acidity, and the amount of humic substances influence the distribution of trace metals in both lakes and streams. Thus the trace metal distribution in headwater lakes cannot be used alone to estimate the contribution of anthropogenic atmospheric deposition to metal anomalies in Finnish surface waters.     

Temporal and spatial trends in metal loads to sediments of Lake Simcoe,Ontario

Metal loads to sediments of Lake Simcoe were partitioned into three components, which were attributable to natural background, accelerated erosion, and point + atmospheric sources. These loads were calculated over time using metal concentration profiles together with pre-settlement sedimentation rates based on sonar and time-variable sedimentation rates based on ²¹⁰Po profiles in cores. Concentrations of metals significantly higher than pre-settlement concentrations were observed in all cores in the case of Pb, back to 80 yr BP on average, and in at least 75% of cores, back to 60 yr BP for Cd and Zn and 30 to 45 yr BP for Cu, Ni, and Cr. Total metal loads increased 3 × for Cu and Ni, 4 × for Zn and Cr, 11 × for Cd and nearly 20 × for Ph from pre-1800 to 0 to 10 yr BP. At present about 90% of the anthropogenic loads of Pb and Cd, and 60 to 70% of the anthropogenic Cu, Ni, Zn, and Cr, are from point + atmospheric sources, the balance being from increased erosion. The direct atmospheric input of Cd is relatively high, approximately 77% of point + atmospheric inputs, while inputs of Cr and Ni are low at 1% and 9%, and inputs of Cu, Zn, and Pb are intermediate at 20 to 40% of point + atmospheric inputs. Two significant findings on spatial distribution of metals were the large increases in metal loads to Cook Bay following the drainage of 33 km² of marshes for agricultural use and the widespread dispersal of Cr from point source(s) in Kempenfelt Bay.     

Variation in the geochemistry of recent lake sediments along a west east pollution gradient in the Bergen area, Norway

Twenty nine lakes were sampled on a 62 km long west-east transect near Bergen, Norway from Sotra in the west to Norheimsund in the east. Top and bottom samples of 29 sediment cores, 20–40 cm long, were collected and 17 chemical elements were measured. Sphaeroidal carbonaceous particles from fossil fuel origin were counted in the surface sediments. The study was designed to answer two questions: (1) Does lake-sediment composition reflect variations in local atmospheric pollution? (2) What factors explain the observed variation in concentration of chemical elements along this transect? Ca, Cr, Mg, and Ni concentrations along the transect appear to result from differences in the content of these elements in bedrock. Hg, Pb, and Zn concentrations in the top sediments are dominated by input from anthropogenic sources. Variation of Cd, Fe, and Zn in the top sediments seems to be dependent on variation in lake-water pH. Hg and Zn from anthropogenic sources probably result from long-transported pollution. Pb and carbonaceous particles from anthropogenic sources possibly have a local origin.     

Atmospheric bulk deposition of trace metals to the Seine river Basin, France: concentrations, sources and evolution from 1988 to 2001 in Paris

Concentrations of Cd, Cu, Ni, Pb and Zn were determined in bulk atmospheric deposition collected at five stations in the Seine River basin (France), to evaluate sources and fluxes of atmospheric trace metals. Bulk deposition (wet + dry) was sampled weekly from March 2001 to February 2002 for 4 sites and from March to December 2001 for the last one. The concentrations of the elements in bulk deposition (dissolved + particulate form) followed the order: Zn > Pb > Cu > Ni > Cd. Concentrations of Zn, Pb and Ni were highly correlated with one another, suggesting a common source, related to the combustion of coal and heavy fuel. Metal concentrations in bulk deposition did not exhibit a high degree of temporal variability over the annual cycle and were not obviously related to meteorological parameters (rainfall, wind). Estimates of the total annual direct atmospheric deposition of metals to the Seine Estuary ranged from 16 kg yr^{? 1} for Cd to 5600 kg yr^{? 1} for Zn. Loadings of Cd, Cu and Ni from direct atmospheric inputs were less than 1% of those contributed by the Seine River and loadings of Pb and Zn represented 1.27% and 1.56% of the Seine contribution. Direct atmospheric inputs are negligible compared to fluvial inputs, but the indirect atmospheric deposition to the estuary was not estimated. Based on these results, trace metal concentrations in Paris have decreased by a factor of 4.6 for Zn and by a factor of 50 for Ni from 1988 to 2001. Of particular interest is the continued decrease in bulk deposition of Pb during this period, underlining the impact of policy initiatives concerning the reduction of lead on emissions in France.     

Wet Deposition of Trace Metals in Singapore

The concentrations of 12 trace metals (Al, Cd, Cr, Cu, Co, Fe,Mn, Ni, Pb, Zn, V, and Ti) in wet depositions are reported. Eighty four rainwater samples were collected using an automated wet-only sampler in Singapore for one year (2000) and subjected to chemical analysis using ICP-MS. Based on the volume-weighted meanconcentrations measured, the trace metals were classified into three groups: Al and Fe with an average concentration of largerthan 15 μg L^-1, Cr, Cu, Mn, Ni, Pb, Zn, V, and Ti withconcentrations between 1 and 10 μg L^-1, and finally Co and Cd with concentrations lower than 1 μg L^-1. Elementenrichment factors were calculated to distinguish between naturaland anthropogenic sources. The calculation of crustal enrichmentfactors with Al as the reference element indicated that while Ti,Fe and Mn originated from crustal sources, the remaining trace metals (Cd, Cr, Co, Cu, Ni, Pb, Zn and V) were mainly derived from anthropogenic sources. The removal of the trace metals from the atmosphere by precipitation was influenced by the rainfall amount as well as pH. The magnitude of the measured average annual wet deposition fluxes of Al, Fe, and combustion-generatedelements such as V, Ni, and Cu is higher than that reportedfor other sites outside Singapore, owing to abundant rainfallthroughout the year in this region.     

Identifying the Sources and Contamination Status of Potentially Toxic Trace Elements in Agricultural Soils

Elevated concentrations of potentially toxic trace elements in agricultural soils contribute to soil pollution affecting food quality and safety. We assessed pollution levels in agricultural systems, lowland rice (LL) and highland cash crops (HL), by comparing with non-agricultural soils (NA). Correlation analysis and principal component analysis (PCA) were performed, and geo-accumulation index (I_geo) and pollution loading index (PLI) were calculated. Zinc in LL, and Cd in LL and HL, were significantly higher than in NA. The I_geo values of cooper (Cu), lead (Pb), nickel (Ni), zinc (Zn), and cadmium (Cd) ranged from uncontaminated to moderately contaminated (Class 0 to 2) for LL, HL, and NA. Overall, trace element levels were categorized as unpolluted based on PLI. Soil properties significantly correlated with Cu, Pb, Ni, and Zn concentrations but not with Cd. Based on PCA, sources of origin for Cu, Pb, Ni, and Zn were lithogenic, while the sources for Cd was anthropogenic in the studied agricultural soils.     

Trace metals in sediments and aquatic plants from the Xiangjiang River, China

Purpose

The metal concentrations and Pb isotopic composition in sediments and plants from the Xiangjiang River, China, were investigated to understand the contamination and potential toxicity of metals in sediments; to determine the accumulation and distribution of metals in plant tissues; and to trace the possible pollution source of Pb in sediments and plants.

Materials and methods

Sediments and plants were collected from 43 sampling sites in the study region. After sediments were air-dried and passed through a 63-??m sieve, they were acid-digested and DTPA-extracted for determination of total and bioavailable metals. The plants were separated into roots, leaves, and stems; dried; cut into pieces; and digested with HNO₃?CH₂O₂. Metals (As, Cd, Cr, Cu, Ni, Pb, and Zn) and Pb isotopic composition were analyzed by inductively coupled plasma-mass spectrometry.

Results and discussion

Maximum As, Cd, Cr, Cu, Ni, Pb, and Zn concentrations in sediments were 47.18, 55.81, 129.5, 161.6, 160.4, 430.7, and 1,098.8?mg?kg^?1, respectively. The bioavailable fractions of As, Cd, Cu, Pb, and Zn had significant linear relationship with their corresponding total contents in sediments while no significant relationship was observed between bioavailable and total contents of Cr and Ni. In general, plant tissues showed higher As, Cd, Cu, Pb, and Zn concentrations and lower Cr and Ni concentrations compared with sediments. The ²⁰⁶Pb/²⁰⁷Pb ratios decreased in the order of total > bioavailable > stems ?? leaves > roots. A strong linear correlation was observed between the ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁷Pb ratios of the plant tissues, sediments, and the possible pollution sources of Pb in the Xiangjiang River.

Conclusions

As, Cd, Cu, Pb, and Zn demonstrated higher contamination levels in sediments and plants compared with Cr and Ni. Cd had highest potential ecological risk. The Pb from anthropogenic sources with low ²⁰⁶Pb/²⁰⁷Pb ratios was preferentially associated with the bioavailable fractions in sediments and accumulated in roots. The Pb in plant tissues is mainly derived from the Pb in sediment and is taken up through the sediment-to-root pathway.     

Identification of the sources of metals and arsenic in river sediments by multivariate analysis and geochemical approaches

Purpose

Frequent mining activities and higher background values in soil have led to the contamination of the sediments of some rivers in southwest China by several metals and arsenic (As). This study combined multivariate analysis with geochemical approaches to differentiate mining activity from other sources, which may aid to evaluate the effectiveness of reducing mining release.

Materials and methods

Sixteen sediment samples were collected along the Yuan River, China. The total concentrations of lead (Pb), zinc (Zn), copper (Cu), cadmium (Cd), chromium (Cr), mercury (Hg), and As were measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The Pb isotopic composition was measured using a thermal ionization mass spectrometer (TIMES). Both geochemical approaches and multivariate statistical analysis were used to identify the sources of these metals. The fractionation of Pb was determined through a Community Bureau of Reference (BCR) sequential extraction procedure to aid the identification of the sources.

Results and discussion

The concentrations and enrichment factors (EFs) of Pb, Zn, Cu, Cd, and As in the middle reach of the river were higher than those at the other sites, indicating anthropogenic sources. The factor analysis (FA) extracted “mining and smelting,” “mixture of anthropogenic and natural,” and “natural” factors. The Pb isotope composition of metal ores was similar (²⁰⁶Pb/²⁰⁷Pb?<?1.190 and ²⁰⁸Pb/²⁰⁶Pb?>?2.023) to that found in the sediments in the middle reach, indicating anthropogenic sources of mining activities. Compared with the narrow ranges of the δ³⁴S ratios in the bedrock (+8.5 to +9.3?‰) and the metal ores (?1.4 to +1.9?‰), the sediment samples presented a relatively wide range of δ³⁴S ratios from ?2.6 to +9.2?‰ with a mean of +2.6?‰, which suggests a mixed composition. The BCR sequential extraction procedure revealed that the proportion of the extractable fraction in the sediments in the middle reach was higher than that in other sites, suggesting anthropogenic sources as the cause of contamination in the study area.

Conclusions

Lead, Zn, Cu, Cd, Cr, Hg, and As are mainly derived from natural materials in the upstream region. In the middle reach, these elements are the result of anthropogenic activities, particularly activities associated with the mining industry. In the downstream region, the origin of these elements is considered to be a mixture of anthropogenic and natural sources. In addition to geochemical approaches and multivariate statistical analysis, the BCR sequential extraction method is an effective procedure for the identification of the anthropogenic sources of sediment-associated metals.     

抚仙湖重金属污染强度、历史及来源的沉积记录

This study focused on the concentration change of heavy metals of sediment cores in heavily polluted north area and less polluted middle area of Fuxian Lake in Southwest China.On the basis of the analysis of Cu,Ni,Ti,V,Pb,Cd,and Zn concentration-depth profiles,the pollution history of heavy metals was studied using ¹³⁷cesium (¹³⁷Cs) dating.The sources of heavy metals were distinguished by normalization of their profiles to aluminum and analysis of heavy metal concentrations of potential source materials.Geoaccumulation index (I_geo) was used to quantify their contamination intensity.The results showed that all the heavy metals found in the Fuxian Lake sediments originated naturally before 1980s.Cu,Ni,Ti,and V were still mainly natural in the north lake after 1980s,Cu,Ni,Ti,V,and Pb were mainly natural in the middle lake at all time,but the concentrations of Pb and Zn in the north lake were influenced by industrial wastes from the phosphorus fertilizer factory and cement plants.In all the lake,the contaminations of Cd and Zn were the results of agricultural cultivation using a large amount of fertilizers and the atmospheric fallouts of dusts from cement plants.At present,the geoaccumulation indices showed that the Fuxian Lake sediments were moderately to strongly polluted by Cd in the middle lake,and unpolluted to moderately polluted by Pb and Zn and strongly polluted by Cd in the north lake.Moreover,the pollution intensities of Cd,Zn,and Pb have been increased since 1980s.     

historical deposition rates of Cd,Cu, Pb,and Zn in Norway and Sweden estimated by 210Pb dating and measurement of trace elements in cores of peat bogs

From six ombrotrophic mires located far from distinct local sources in Sweden and Norway, a core was sampled in bog hummocks in 1988 and dated by 210_Pb. Ten slices from each core were analyzed for Cd, Cu, Pb, and Zn. Based on the datings, the accumulation rates of Cd, Cu, Pb, and Zn have been estimated for the last 150 years. A reasonable agreement exists in the comparison between the recent deposition in the peat bog and nearby bulk deposition measurements. Highest deposition has been measured in southern Norway and the western part of Sweden. Generally, deposition has increased during the last 150 years, except at a station on the east coast of Sweden. In a study in Sweden where heavy metals have been measured in mosses every five years time since 1970, significant decreases in the concentrations of heavy metals have been found. Similar decreases have not been measured in the present study, although both methods are expected to reflect atmospheric deposition. Several studies have indicated that peat bogs are not suitable for measuring the historical evolution of trace metals. However, despite the disagreement, the recent literature suggests that it can be done with reasonable accuracy when performed with samples from hummocks in the peat bog.     

Predicting Heavy Metal Concentrations in the Surface Sediments of Norwegian Headwater Lakes from Atmospheric Deposition: An Application of a Simple Sediment-Water Partitioning Model

Data from 96 headwater lakes from Norway are used to model heavy metal concentrations in surficial lake sediments in relation to atmospheric deposition. The study evaluates the application of sediment-water partitioning models at the field scale and finds optimum values for the partition coefficients. The impact of environment (sediment type, lake water pH, etc.) on K_Dvalues is explored directly by comparing K_Destimates with environmental variables. K_Dvalues for each metal are found by optimising the fit between predicted and observed surface-sediment concentrations. The sensitivity of the K_Destimates to data structure is examined by bootstrapping. K_Dvalues of 10^5.8and 10^6.2were calculated for cadmium (Cd) and lead (Pb), respectively, comparable to recent direct observations. Biogenic silica influenced K_Dvalues for Cd, Pb and Zn, whereas lake depth influenced Pb. pH did not have any detectable effect. K_Dfor zinc (Zn) was less well defined, but higher than indicated by published experimental measurements. The results suggest that sediment-water partitioning models have an important contribution to make to field-scale lake studies of sediment heavy metals, and have important implications for palaeolimnological evaluations of heavy metal deposition.     

Predicting heavy metal transfer from soil to plant: potential use of Freundlich‐type functions

Soil‐plant transfer of metals is a nonlinear process. We therefore aimed at evaluating the potential of Freundlich‐type functions (c_Plant = b × c_Soil^a) to predict Cd, Cu, Pb, and Zn concentrations in wheat (Triticum aestivum L.) grain and leaf (c_Plant) from soil concentrations (c_Soil). Wheat plants and soil A horizons, mainly developed from Holocene sediments, were sampled at 54 agricultural sites in Slovakia. Metals were extracted from soils with 0.025 M EDTA at pH 4.6 and concentrated HNO₃/HClO₄ (3:1); plant samples were digested with concentrated HNO₃. Total metal concentrations of soil samples were 0.07—25 mg Cd kg^—1, 9.3—220 mg Cu kg^—1, 14—1827 mg Pb kg^—1, and 34—1454 mg Zn kg^—1. On average, between 20 % (Zn) and 80 % (Cd) of the total concentrations were EDTA‐extractable. The total metal concentrations of grain samples were < 0.01—1.3 mg Cd kg^—1, 1.3—6.6 mg Cu kg^—1, < 0.05—0.30 mg Pb kg^—1, and 8—104 mg Zn kg^—1. The leaves contained up to 3.2 mg Cd kg^—1, 111 mg Cu kg^—1, 4.3 mg Pb kg^—1, and 177 mg Zn kg^—1. Linear regression without data transformation was precluded because of the nonnormal data distribution. The Freundlich‐type function was suitable to predict Cd (grain: r = 0.71, leaf: 0.86 for the log‐transformed data) and Zn concentrations (grain: 0.69, leaf: 0.68) in wheat grain and leaf from the EDTA‐extractable metal concentrations. The prediction of Cu and Pb concentrations in grain (Cu: r = 0.44, Pb: 0.41) was poorer and in leaf only possible for Pb (0.50). We suggest to use the Freundlich‐type function for defining threshold values instead of linear regression because it is more appropriate to simulate the nonlinear uptake processes and because it offers interpretation potential. The results suggest that the coefficient b of the Freundlich‐type function depends on the intensity of metal uptake, while the coefficient a reflects the plants' capability to control the heavy metal uptake. The latter is also sensitive to metal translocation in plants and atmospheric deposition.<?show $6#>     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

Heavy Metals and Polycyclic Aromatic Hydrocarbons (PAHs) in a Rural Community Leewards of a Waste Incineration Plant

In a rural community (Stephanskirchen, Southern Germany) near a waste incineration plant 7 soils, sewage sludge, waste incineration residues, the gutter sediment of a family home, and mosses were sampled to determine the total concentrations of Cd, Pb, Zn and 20 PAHs. Representative samples were used to measure NH₄NO₃- and EDTA-extractable Cd, Pb, and Zn as well as 20 PAHs in particle size separates (clay, silt, fine and coarse sand). Sites near the main road, hill top, and forested sites contain up to 1.24 mg Cd, 888 mg Pb, and 279 mg Zn per kg. The heavy metal concentrations of the sewage sludge, the gutter sediment, and especially the waste incineration residues are extremely high (up to 57 mg Cd, 3300 mg Pb, and 5700 mg Zn per kg). The extractability of Pb and Zn with NH₄NO₃ is low (< 5%), that with EDTA is high (up to 71.2% of total Cd, 82.5% of total Pb, and 47.2% of total Zn). The sum concentrations of PAHs range between 0.4 and 470 mg kg^?1. The silt has the highest PAH concentrations of the particle size separates. High saturation of organic matter with PAHs in the sand indicates high recent PAH deposition. Selected ratios of single PAHs reveal diesel and gasoline exhausts as main sources for PAH. Principal component and cluster analysis show that the pollutant pattern depends on the C_org concentration and on the time passed since deposition. There is no significant influence of the waste incineration emissions on the heavy metal and PAH concentrations.     

Verhalten von Schwermetallen in Böden. 2. Extraktion mobiler Schwermetalle mittels CaCl2 und NH4NO3

Behaviour of heavy metals in soils. 2. Extraction of mobile heavy metals with CaCl₂ and NH₄NO₃ 156 soil samples from arable fields, grassland and forest stands were analysed for the CaCl₂^? and NH₄NO₃^? extractable contents of Cd, Zn, Mn, Cu and Pb. The average amounts of Cd, Zn, Cu and Pb extracted with CaCl₂ are higher compared with NH₄NO₃ whereas the relation for Mn is vice versa. The proportion of the NH₄NO₃^? extractable contents in percent of the CaCl₂^? extractable contents of Cd, Zn and Pb decrease with increasing pH, whereas the contents of Mn and Cu increase. Inspite of a differing extraction behaviour of the two salt solutions the CaCl₂^? and NH₄NO₃^? extractable amounts of Cd, Mn, Zn und Pb are highly correlated and can be converted one into another. The mobile (CaCl₂, NH₄NO₃) proportion of the corresponding total, EDTA and DTPA heavy metal contents is in close relation to the pH of the soils. Using CaCl₂ solution the threshold pH values for an increasing mobility decrease in the order Cd > Mn > Zn > Cu > Pb, using NH₄NO₃ as extractant the order is Mn > Cd > Zn > Cu > Pb. In the case of CaCl₂ as extractant soluble chloro-Cd-complexes will be formed so that the Cd mobility in soils will be overestimated in most cases.     

The effect of pH and atmospheric deposition on concentrations of trace elements in acidified freshwaters: A statistical approach

A statistical evaluation of 5 338 analysis of freshwaters from little polluted stream basins in the Czech Republic indicated a relationship between the Pb, Cu, Zn, Cd, Be, As, Mn, Sr, F^? and Fe concentrations and the pH, over a range of pH 3.6 to 9.6. Except for Sr, the median concentrations of all the trace metals increase with decreasing pH, but the increase never extends over the whole studied acidic range (pH 3.6 to 7.0). Acid deposition related mobilization of Mn and Be into freshwaters explains the sharp increase in their concentrations with decreasing pH. Cadmium and Zn are also mobilized n strongly acidic environment. The concentrations of Be, As, F^? and Mn in strongly acidic waters and those of Zn and Cd in weakly acidic ones are considerably higher in areas receiving a higher atmospheric loading. For Be and Mn, the higher concentrations are caused by higher acid deposition rates, while for As and F^?, the concentrations are probably greater due to higher atmospheric deposition of these elements over more intensely acontaminated areas of the Czech Republic. In extremely acidic waters (pH < 4.2), the concentrations of Mn, Be, Cd, Zn and Al no longer increase with decreasing pH; on the contrary, those of Mn and Be actually decrease. This seems to be primarily caused by a decrease in their concentrations within the surface horizons of soils and vegetation induced by prolonged leaching. The Cd and Zn concentrations are independent of pH over an interval of pH 5.4 to 6.0 and thus the increase in the mean concentrations of Cd and Zn with decreasing pH involves two separate stages, at pH > 6.0 and at pH < 5.4. The concentrations of Cu in acid freshwaters are controlled by both the presence of high molecular weight organics plus biota uptake and by their atmospheric deposition levels; the concentrations of As and Pb are in addition controlled by sorption on Fe - oxyhydroxides. These elements accumulate in the topsoil, even under conditions of severe acidification. The surprisingly lower concentrations of Pb and Cu were found in acidic waters of more contaminated areas.     

Heavy metal pollution by long range atmospheric transport in natural soils of Southern Norway

Natural surface soils in Southern Norway are strongly contaminated by metals from atmospheric deposition. Except from local pollution with Cu, Ni and to a limited extent Pb around the town of Kristiansand, this large-scale contamination can be ascribed to long-range atmospheric transport from other parts of Europe. Zinc, As, Cu, and Pb are all found in excessive concentrations in the surface layer of natural soils throughout the region, and in particular within a zone of about 20 to 40 km from the coast. In this zone the elements appear at the following concentrations or higher in the A₀ layer (typical levels in other parts of Norway little affected by air pollution in parantheses): Zn, 120(30) mg kg^?1; As, 4(0.5) mg kg^?1; Cd, 2(0.2) mg kg^?1; Pb, 160(15) mg kg^?1. Possible harmful effects to soil biological processes of this contamination cannot be excluded.     

Effects of Phosphorus Additions on Lead,Cadmium, and Zinc Bioavailabilities in a Metal-Contaminated Soil

The use of phosphorus (P) to reduce lead (Pb)bioavailability is being proposed as an alternative to excavationand disposal as a remedial technology for Pb-contaminated soilsin residential areas. The objective of this study was todetermine the influence of P sources and rates andCaCO₃additions on the bioavailabilities of Pb, cadmium (Cd), and zinc(Zn) in a contaminated soil material using plants, a sequentialextraction procedure, and ion activities in equilibrium solutionas indicators. A contaminated soil containing 370 mg kg^-1 Cd, 2800 mg kg^-1 Pb and 29100 mg kg^-1 Zn was amended ina factorial arrangement of CaCO₃ (0 or 2000 mg kg^-1) and P as rock phosphate or KH₂PO₄ at 0:1, 2:1 or 4:1P:Pb mole ratios. A pot study was conducted using sorghum-sudangrass (Sorghum bicolor L. Moench). The addition of P did not influence Pb concentrations in plant tissue and had little effect on Cd concentrations. An interaction between P source and level of P addition was found for Zn concentrations in plant tissue; concentrations increased with increasing amounts of P from KH₂PO₄ anddecreased with increasing amounts of P from rock phosphate. Sequential extraction results suggested a much greater reduction in Pb bioavailability from treatment withKH₂PO₄ than with rock phosphate and that P influencedthe fractionations of Cd and Zn. Activities of Cd²⁺,Pb²⁺, and Zn²⁺ in equilibrium solutions generally weredecreased by rock phosphate and increased by KH₂PO₄. Saturation indices suggested the addition ofKH₂PO₄shifted the soil equilibrium from octavite to hydroxypyromorphite, whereas solid-phase control of Cd²⁺ andZn²⁺ was not influenced by soil amendments. A soluble Psource was more effective in reducing Pb bioavailability thanrock phosphate but had variable effects on Cd and Znbioavailabilities.     

Heavy Metals in Freshly Deposited Stream Sediments of Rivers Associated with Urbanisation of the Ganga Plain,India

Freshly deposited stream sediments from six urban centres of the Ganga Plain were collected and analysed for heavy metals to obtain a general scenery of sediment quality. The concentrations of heavy metals varied within a wide range for Cr (115–817), Mn (440–1 750), Fe (28 700–61 100), Co (11.7–29.0), Ni (35–538), Cu (33–1 204), Zn (90–1 974), Pb (14–856) and Cd (0.14–114.8) in mg kg^-1. Metal enrichment factors for the stream sediments were <1.5 for Mn, Fe and Co; 1.5–4.1 for Cr, Ni, Cu, Zn and Pb; and 34 for Cd. The anthropogenic source in metals concentrations contributes to 59% Cr, 49% Cu, 52% Zn, 51% Pb and 77% Cd. High positive correlation between concentrations of Cr/Ni, Cr/Cu, Cr/Zn, Ni/Zn, Ni/Cu, Cu/Zn, Cu/Cd, Cu/Pb, Fe/Co, Mn/Co, Zn/Cd, Zn/Pb and Cd/Pb indicate either their common urban origin or their common sink in the stream sediments. The binding capacity of selected metals to sediment carbon and sulphur decreases in order of Zn > Cu > Cr > Ni and Cu > Zn > Cr > Ni, respectively. Stream sediments from Lucknow, Kanpur, Delhi and Agra urban centres have been classified by the proposed Sediment Pollution Index as highly polluted to dangerous sediments. Heavy metal analysis in the <20-μm-fraction of stream sediments appears to be an adequate method for the environmental assessment of urbanisation activities on alluvial rivers. The present study reveals that urban centres act as sources of Cr, Ni, Cu, Zn, Pb and Cd and cause metallic sediment pollution in rivers of the Ganga Plain.     

Distribution of Heavy Metals in Near-Shore Sediments of the Swan River Estuary,Western Australia

Estuarine systems adjacent to urban areas are at risk of contamination by contaminants from anthropogenic sources, such as heavy metals. We anticipated that the sediments of the Swan River estuary, which runs through metropolitan Perth in Western Australia, would show metal contamination related to industrialization and inputs of stormwater. Total Cu, Pb and Cd concentrations, and Cu, Pb, Cr and Zn inoperationally-defined fractions, were determined inseparate sampling exercises in near-shore sediments ofthe upper Swan River estuary.Total metal concentrations in sediments were not high (maximum values of 297 mg kg^-1 for Cu, 184 mg kg^-1 for Pb and 0.9 mg kg^-1 for Cd) when compared with Australian environmental assessmentguidelines for soils. On the basis of linear regressions between sediment metal concentrations andphysicochemical properties of the sediments (pH, organic carbon, particle size distribution), no single parameter could explain the variation in metal concentrations for all metals. Sediment organic carbon content was positively correlated with Cu concentration; Cu concentrations also increased significantly with increasing clay content anddecreasing sand content. Pb concentrations showed a significant increase with increasing sediment pH, and were approximately three-fold higher in sediments adjacent to stormwater drain outfalls than in sediments remote from drains; no such effect was observed for Cu or Cd. No effect of distance downstream was observed. Sequential extraction of sediments showed that most of the metals were in relatively immobile forms, for example bound to Feoxides, or only extractable by aqua regia. The enhanced concentrations of Pb near stormwater outfalls suggest that vehicle-derived Pb may be an important contributor of Pb to the estuary.