Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

Macroalgae and DGT as indicators of available trace metals in marine coastal waters near a lead–zinc smelter

The levels of Cd, Cu, Pb, and Zn were determined in the commonest species of green, red, and brown algae collected from five coastal sites in south-western Sardinia (Italy), an area with a long history of mining and smelting. The usefulness of employing Enteromorpha sp. and Padina pavonica (L.) Thivy to monitor metal pollution was evaluated, while diffusive gradients in thin films (DGT) devices were used to measure dissolved metals in seawater. Levels of Cd and Pb were high enough to be of environmental concern in the whole study area. A significant relationship was found between the content of Pb in P. pavonica and DGT-labile Pb in seawater, suggesting that gross elemental concentrations of nonessential metals such as Pb in algal tissues are apparently controlled by the abundance of dissolved metal species in the ambient seawater. The results pointed out the usefulness of using both DGT and algal methods for a better understanding of trace metal availability in coastal waters.     

Environmental hazard of cadmium, copper, lead and zinc in metal-contaminated soils remediated by sulfosuccinamate formulation

Accumulation of metals in soil at elevated concentrations causes risks to the environmental quality and human health for more than one hundred million people globally. The rate of metal release and the alteration of metal distribution in soil phases after soil washing with a sulfosuccinamate surfactant solution (Aerosol 22) were evaluated for four contaminated soils. Furthermore, a sequential extraction scheme was carried out using selective extractants (HAcO, NH(2)OH·HCl, H(2)O(2) + NH(4)AcO) to evaluate which metal species are extracted by A22 and the alteration in metal distribution upon surfactant-washing. Efficiency of A22 to remove metals varied among soils. The washing treatment released up to 50% of Cd, 40% of Cu, 20% of Pb and 12% of Zn, mainly from the soluble and reducible soil fractions, therefore, greatly reducing the fraction of metals readily available in soil. Metal speciation analysis for the solutions collected upon soil washing with Aerosol 22 further confirmed these results. Copper and lead in solution were mostly present as soluble complexes, while Cd and Zn were present as free ions. Besides, redistribution of metals in soil was observed upon washing. The ratios of Zn strongly retained in the soil matrix and Cd complexed with organic ligands increased. Lead was mobilized to more weakly retained forms, which indicates a high bioavailability of the remaining Pb in soil after washing. Comprehensive knowledge on chemical forms of metals present in soil allows a feasible assessment of the environmental impact of metals for a given scenario, as well as possible alteration of environmental conditions, and a valuable prediction for potential leaching and groundwater contamination.     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Redistribution of zinc, cadmium, and lead among soil fractions in a sandy calcareous soil due to application of poultry litter

This study was conducted to evaluate, using soil columns, the mobilization and redistribution of heavy metals (Zn, Cd, and Pb) among different soil fractions by soluble organic ligands within poultry litter. Uncontaminated soil was amended with Zn, Cd, and Pb to achieve concentration levels of 400, 8, and 200 mg kg⁻¹ soil, respectively. Columns repacked with this amended soil were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, or poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for exchangeable (EXC), carbonate (CARB) organic matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Considerable mobilization of Zn, Cd, and Pb occurred in soil during EDTA leaching. Leaching with PLE and CaCl₂ solutions significantly decreased Zn and Cd concentrations in the EXC, CARB, and OM fractions. These solutions significantly decreased Pb concentration in the EXC fraction, while PLE solubilized more Pb from EXC fraction than CaCl₂. Thus, the applied poultry litter may change Zn, Cd, and Pb fractions in metal-amended soil and possibly enhance metal mobility.     

Impaction collection and slurry sampling for the determination of arsenic, cadmium, and lead in sidestream cigarette smoke by inductively coupled plasma-mass spectrometry

The slurry sampling technique has been applied for the determination of arsenic, cadmium and lead in sidestream cigarette smoke condensate (SS CSC) by inductively coupled plasma mass spectrometry (ICP-MS). The smoke collection system consists of a "fishtail" chimney in conjunction with an impaction trap and a mixed cellulose ester (MCE) backup filter for the SS CSC collection. The smoke condensates, collected at three different regions of the system (i.e. the inner wall of the chimney, the impaction trap and the MCE filter), were individually prepared and analyzed and showed that about 70 and 20% of Cd and Pb, respectively, were trapped by the impaction trap and the MCE filter with less than 5% trapped by the chimney. In contrast, about 60% of As was trapped by the impactor and a relatively high percentage of As, about 30%, was deposited onto the inner wall of the chimney. The uneven distribution of trace metals at each collection stage strongly suggested that the composition of smoke aerosol and the associated physical form of the analytes may be different. The yields of As, Cd and Pb for the sidestream cigarette smoke of the 1R4F reference cigarette were 29.5 +/- 2.4, 421 +/- 6.6 and 46.4 +/- 0.9 ng cigarette(-1)(n= 3) respectively, when the cigarette was smoked according to the smoking regime: 45 mL puff volume of 2-s puff duration at an interval of 30 s with 50% ventilation holes covered. The analytical results for the slurry sampling technique were also compared with other sample preparation techniques and show good agreement.     

Bioaccumulation of zinc,lead, copper,and cadmium from contaminated sediments by native plant species and Acrida cinerea in South China

This research was conducted to search and identify spontaneously growing heavy metal-tolerant plant species that are potentially useful for phytoremediation in contaminated sediment. Five sites were selected for collection of plants growing on polluted shore (river bank) sediment of the Xiang River, China. The concentrations of Zn, Pb, Cu and Cd in plants, sediments, and grasshoppers were determined using flame atomic absorption spectrophotometer (AAS700, Perkin-Elmer, USA). Considering translocation factor and bioaccumulation factor, Rumex crispus (Polygonaceae), Rumex dentatus (Polygonaceae), and Lagopsis supina (Labiatae) could be potentially useful for phytostabilization of metals. R. crispus can be considered potentially useful for phytoextraction of Cd. In light of the biomagnification factors, grasshoppers are deconcentrators for Pb and Cd, microconcentrators for Zn and macroconcentrators for Cu to the plants, respectively. To the best of our knowledge, the present study is the first report on Zn, Pb, Cu and Cd accumulation in R. crispus and L. supina, providing a pioneer contribution to the very small volume of data available on the potential use of native plant species from contaminated sediments in phytostabilization and phytoremediation technologies.     

Lead and cadmium concentrations in shorebirds from the Yeongjong Island, Korea

This study presents concentration levels of pollutants (lead, and cadmium) in tissues (livers, kidneys, muscles, and bones) of shorebirds (Kentish Plovers (n = 5), Mongolian Plovers (n = 2), Dunlins (n = 6), Great Knots (n = 10), Terek Sandpipers (n = 10)) from Yeongjong Island, Korea in the East Asian–Australian migration flyways during the autumn migration in 1994–1995. Lead concentrations in livers, in kidneys, in muscles, and in bones were significantly different among shorebird species. Lead concentrations in livers of Kentish Plovers (4.76 ± 2.72 μg/wet g), Mongolian Plovers (2.05 μg/wet g), Dunlins (3.77 ± 1.07 μg/wet g), and Great Knots (4.27 ± 3.19 μg/wet g) were less than the toxic level, and lead concentrations in livers of Terek Sandpipers (1.20 ± 0.94 μg/wet g) were at the background level. Cadmium concentrations in livers, in kidneys, in muscles, and in bones did not vary among shorebirds, and concentrations of cadmium in livers and in kidneys were at background level (respectively, approximate 1 μg/wet g, approximate 2.67 μg/wet g) in all shorebird species. We suggest that interspecific differences of lead and cadmium concentrations were attributed to differences in exposure time and differences of diet, microhabitats in wintering ground. In livers and kidney of shorebirds from Yeongjong Island, lead and cadmium concentrations were higher than other locations previously reported.     

Cadmium,zinc, lead,and copper in livers and kidneys of cattle in the neighbourhood of zinc refineries

Cattle in the Kempen area (in the province North-Brabant, the Netherlands) were investigated for cadmium, lead, zinc, and copper in livers and kidneys. The animals originated from farms located within a 20 km radius around several zinc refinery plants. The local soil is polluted with zinc and cadmium because of a thermal refining process used in the past.Mean cadmium organ concentrations were 2.5 times, and mean lead organ concentrations were 1.5 times higher than the concentrations found in controls. Copper levels tended to be decreased, but zinc levels did not differ from controls.The observed cadmium and lead organ concentrations did not indicate intoxication of the animals, but 22% of the kidneys and 3% of the livers investigated trespassed the maximum tolerance limit of cadmium with regard to human consumption.Continuous control of cadmium organ contents in organs from slaughtercattle kept in cadmium-polluted areas is recommended.     

Assessment of metals in down feathers of female common eiders and their eggs from the Aleutians: arsenic, cadmium, chromium, lead, manganese, mercury, and selenium

Concentrations of arsenic, cadmium, chromium, lead, manganese, mercury and selenium were examined in the down feathers and eggs of female common eiders (Somateria mollissima) from Amchitka and Kiska Islands in the Aleutian Chain of Alaska to determine whether there were (1) differences between levels in feathers and eggs, (2) differences between the two islands, (3) positive correlations between metal levels in females and their eggs, and (4) whether there was more variation within or among clutches. Mean levels in eggs (dry weight) were as follows: arsenic (769 ppb, ng/g), cadmium (1.49 ppb), chromium (414 ppb), lead (306 ppb), manganese (1,470 ppb), mercury (431 ppb) and selenium (1,730 ppb). Levels of arsenic were higher in eggs, while chromium, lead, manganese, and mercury were higher in feathers; there were no differences for selenium. There were no significant interisland differences in female feather levels, except for manganese (eider feathers from Amchitka were four times higher than feathers from Kiska). Levels of manganese in eggs were also higher from Amchitka than Kiska, and eider eggs from Kiska had significantly higher levels of arsenic, but lower levels of selenium. There were no significant correlations between the levels of any metals in down feathers of females and in their eggs. The levels of mercury in eggs were below ecological benchmark levels, and were below human health risk levels. However, Aleuts can seasonally consume several meals of bird eggs a week, suggesting cause for concern for sensitive (pregnant) women.     

Regional monitoring of lead and cadmium contamination in a tropical grazing land site,Thailand

An investigation was carried out to monitor Pb and Cd contamination in grazing land located near a highway. Environmental media at different distances fromhighway (soil, grass, water, cow's forage, fertilizer,manure and milk samples) were collected from three samplinglocations. Soil and grass were characterized by high metalmobility (soil with Pb: 5.25±0.71–14.59±1.17 mgkg^-1, dry mass and Cd: 0.038–0.33±0.04 mg kg^-1, dry mass and grass with Pb: 0.76±0.05–6.62±0.18 mg kg^-1, dry mass and Cd: 0.17±0.01–0.73±0.09 mg kg^-1, dry mass). One-way analysis of variane (ANOVA) was applied to find out the correlation between metal (total and bioavailable) concentrationsin the soil and the distance from roadside. In most cases, the finding showed that plants growing nearer to the highway are usually exposed to more heavy metal accumulations than those awayfrom the highway. In addition, a correlation was established between plant available metal concentrations and plant metaluptake concentrations.Analysis of fertilizer and manure showed considerable amountof metals (fertilizer with Pb: 1.53±0.06 mg kg^-1 andCd: 0.038 mg kg^-1 and manure with Pb: 2.55–3.34 mgkg^-1 and Cd: 0.14–0.31 mg kg^-1). Long termsimultaneous application of fertilizer and manure on thecommercial farm showed higher metal accumulation in the soiland plants than those of co-operative farm Considerableconcentrations of metals (Pb: 1.60–2.94 mg kg^-1 andCd: 0.025–0.19 mg kg^-1) were observed in fodder. The finding clearly demonstrated that there are seasonalvariation in total daily metal intake by individual cow (Pb:109.37 mg day^-1 (dry), 273.47 mg day^-1 (rainy) andCd: 2.02 mg day^-1 (dry), 19.62 mg day^-1 (rainy)).The provisional tolerable weekly intake of heavy metals incows is 390 g Pb and 28 g Cd per kg bodyweight in the rainy season and 156 g Pb and 2 gCd per kg body weight in the dry season. The levels of metals (Pb: 0.014 mg L^-1 and Cd: not detectable) and bio-transferfactor (10^-5–10^-4) in raw milk were found to be well below the Codex Alimentarius Commissions Draft (1997). Ouranalysis revealed that improvements on farm management give significant reduction in elevated levels of Pb and Cdin soil and plants, and however leads to minimize the amountof Pb and Cd in consumed milk.     

A study on the effects of lead, cadmium and phosphorus on the lead and cadmium uptake efficacy of Viola baoshanensis inoculated with arbuscular mycorrhizal fungi

The effect of indigenous arbuscular mycorrhizal (AM) fungi on lead (Pb) and cadmium (Cd) uptake by the hyperaccumulator plant Viola baoshanensis was studied in greenhouse pot experiments. Seedlings of V. baoshanensis inoculated without or with indigenous AM fungi were grown in paddy soil with the addition of Pb at 0, 500, 1000 and 1500 mg kg(-1), or of Cd at 0, 50,100, 200 mg kg(-1), or in mine soil with the addition of phosphorus at 0, 50, 250, 500 mg kg(-1). AM colonization increased shoot biomass at low phosphorus levels, and this beneficial effect was diminished or reversed by high phosphorus availability. AM colonization decreased shoot Cd concentrations regardless of the availability of Cd and phosphorus, but the mechanisms involved varied with Cd availability. At low Cd bioavailability, reduced Cd uptake was due to decreased Cd translocation from the roots to the shoots, whereas that was attributed to reduced root uptake at high Cd bioavailability. In contrast, the effect of AM colonization on shoot Pb varied with the availability of phosphorous and Pb. Our results show that the interactions between V. baoshanensis and indigenous AM fungi were modified by the availability of Pb, Cd and phosphorus.     

Copper, zinc, and cadmium body concentrations in Hexaplex trunculus collected from the Tunisian coast

Copper, Zn, and Cd were analyzed in the soft tissues of the edible gastropod Hexaplex trunculus collected from seven localities along the Tunisian coast. The body concentration of these metals was significantly different depending on the gender and site. Copper and Zn varied, respectively, from 47.70 to 343.64 μg/g dry weight (dw) and 149.46 to 530.44 μg/g dw, being higher in males. Cadmium varied from 0.22 to 18.95 μg/g dw and was always higher in females. Overall, the highest concentrations of the three metals were all recorded in Gabès fishing harbor. Comparison of metal concentrations with the European standards compiled by the Food and Agriculture Organization showed that values exceeded standards in several localities. Imposex had been previously recorded in H. trunculus along the Tunisian coast; however, it does not seem to be related with Cu, Zn, and Cd pollution because the body concentration of these metals is not correlated with imposex degree. Nevertheless, interactive effects resulting from the combination of different pollutants and other stressors cannot be disregarded.     

Mercury, cadmium, lead, and selenium in fish from a Norwegian fjord and off the coast, the importance of sampling locality

Hepatic levels of mercury, cadmium, lead, and selenium and levels of mercury and selenium in muscle tissue were analysed in tusk from the Nordfjord in Norway. With the exception of selenium in the muscle tissue, the metal levels were significantly higher in the fjord fish than in fish caught off the coast. No local source is known to explain the difference in levels, and this indicates that the fjord efficiently accumulates atmospheric contaminants. The present results demonstrate the importance of sampling area when determining levels of metals in marine organisms far from point sources. The liver was increasingly used as a storage compartment for mercury and selenium with increasing exposure.     

Distributions of lead and cadmium in dust in the vicinity of a sewage sludge incinerator

The content of lead and cadmium in surface dust within a 4 km radius of a sewage sludge incinerator has been investigated. Particular attention was given to Pb and Cd in different size fractions of dust, an aspect not explored in previous studies, and the differences between expressions of contamination as concentration or loading were examined. Despite suggestions from reports that sludge incinerators may have difficulty in complying with emission standards, the present investigation found little evidence for a major contribution to local pollution by the incinerator. Certainly, the highest Cd level was found some 2.2 km downwind of the prevailing wind direction from the incinerator, suggesting some resultant contamination, although the levels do not appear to be excessive. Similar observations apply to Pb contamination of the area. While data of the type produced in this study contribute to an understanding of environmental quality, both loadings and levels need to be considered, as the implications of only consideration one of these may be limited and even misleading.     

Bioavailability of copper,cadmium, zinc,and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes

The technique of diffusion gradient in thin films (DGT) for assessing bioavailable metals has not been tested under field conditions. We assessed the relationships of DGT- and cation exchange resin-membrane-measured concentrations of Cd, Cu, Pb, and Zn with plant uptake of the metals under greenhouse and field conditions. In the greenhouse, the effective concentrations of Cu, Pb, and Zn by DGT correlated significantly with uptake by sorghum (Sorghum bicolor), but cation exchange resin-membrane-measured concentrations of Cd, Pb, and Zn did not correlate with sorghum uptake. In the field, the DGT-measured concentrations of Cd, Pb, and Zn were not linearly related to uptake Cd, Pb, and Zn by lettuce (Lactuca sativa) except for Cu uptake (r = 0.87, p < 0.05). Similarly, it was only the resin-membrane-extractable Pb that correlated with Pb uptake by lettuce (r = 0.77; p < 0.05). However, fitting non-linear regression models improved the plant metal uptake predictions by DGT-measured bioavailable Cd, Cu, Pb, and Zn under field conditions. In conclusion, the DGT technique was fairly predictive of bioavailability in the greenhouse, but not in the field.