Risks of using membrane filtration for trace metal analysis and assessing the dissolved metal fraction of aqueous media--a study on zinc, copper and nickel

Membrane filtration is commonly performed for solid-liquid separation of aqueous solutions prior to trace metal analysis and when assessing “dissolved” metal fractions. Potential artifacts induced by filtration such as contamination and/or adsorption of metals within the membrane have been investigated for different membrane materials, metals, applied pressures and pre-cleaning steps. Measurements have been conducted on aqueous solutions including well-defined metal standards, ultrapure water, and on runoff water from corroded samples.Filtration using both non-cleaned and pre-cleaned filters revealed contamination and adsorption effects, in particular pronounced for zinc, evident for copper but non-significant for nickel. The results clearly show these artifacts to be non-systematic both for non-cleaned and pre-cleaned membranes. The applied pressure was of minor importance.Measurements of the labile fraction by means of stripping voltammetry clearly elucidate that membrane filtration followed by total metal analysis cannot accurately assess the labile or the dissolved metal fraction.     

Radionuclides and heavy metals in Borovac,Southern Serbia

BACKGROUND, AIM, AND SCOPE: The paper presents the complex approach to the assessment of the state of the environment in Southern Serbia, surroundings of Bujanovac, the region which is of great concern as being exposed to contamination by depleted uranium (DU) ammunition during the North Atlantic Treaty Organization (NATO) attacks in 1999. It includes studies on concentrations of radionuclides and heavy metals in different environmental samples 5 years after the military actions. MATERIALS AND METHODS: In October 2004, samples of soil, grass, lichen, moss, honey, and water were collected at two sites, in the immediate vicinity of the targeted area and 5 km away from it. Radionuclide ((7)Be, (40)K, (137)Cs, (210)Pb, (226)Ra, (232)Th, (235)U, (238)U) activities in solid samples were determined by standard gamma spectrometry and total alpha and beta activity in water was determined by proportional alpha-beta counting. Concentrations of 35 elements were determined in the samples of soil, moss, grass, and lichen by instrumental neutron activation analysis (INAA). RESULTS: The results are discussed in the context of a possible contamination by DU that reached the environment during the attacks as well as in the context of an environmental pollution by radionuclides and heavy metals in Southern Serbia. The results are compared to the state of environment in the region and other parts of the country both prior to and following the attacks. DISCUSSION: This is the first comprehensive study of the contents of radionuclides and heavy metals in Southern Serbia and consequently highly important for the assessment of the state of environment in this part of the country concerning possible effects of DU ammunition on the environment, as well as anthropogenic source of pollution by radionuclides and heavy metals and other elements. Also, the highly sensitive method of INAA was used for the first time to analyze the environmental samples from this area. CONCLUSIONS: The results of the study of radionuclides in the samples of soils, leaves, grass, moss, lichen, honey, and water in Southern Serbia (Bujanovac) gave no evidence of the DU contamination of the environment 5 years after the military actions in 1999. Activities of radionuclides in soils were within the range of the values obtained in the other parts of the country and within the global average. The ratio of uranium isotopes confirmed the natural origin of uranium. In general, concentrations of heavy metals in the samples of soils, plant leaves, mosses, and lichen are found to be less or in the lower range of values found in other parts of the country, in spite of the differences in plant and moss species or soil characteristics. Possible sources of heavy metal contamination were identified as a power coal plant in the vicinity of the sampling sites and wood and waste burning processes. RECOMMENDATIONS AND PERSPECTIVES: The collected data should provide a base for the health risk assessments on animals and humans in the near future. It should be emphasized that the sampling was carried out 5 years after the military action and that the number of samples was limited; therefore, the conclusions should be accepted only as observed tendencies and a detailed study should be recommended in the future.     

Date palm (Phoenix dactylifera L.) leaves as biomonitors of atmospheric metal pollution in arid and semi-arid environments

The leaves of date palms were evaluated as a possible biomonitor of heavy metal contamination in Ma’an city, Jordan. Concentrations of (Fe), (Pb), (Zn), (Cu), (Ni), and (Cr) were determined in washed and unwashed leaves and soil samples collected from different sites with different degrees of metal contamination (urban, suburban, industrial, highway and rural sites); separate leaves were taken from outside the city to be used as a control sample. Samples collected from industrial sites were found to have high concentrations of all metals except those of Cu, Ni and Pb, which were found at high levels in the highway site samples which is associated with the road traffic. The difference between unwashed and washed samples showed that metal pollutants exist as contaminants, particularly Pb, Zn and Ni, which varied in concentration, depending on the source of the metal.     

The importance of biological factors affecting trace metal concentration as revealed from accumulation patterns in co-occurring terrestrial invertebrates

As physicochemical properties of the soil highly influence the bioavailable fraction of a particular trace metal, measured metal body burdens in a particular species are often assumed to be more reliable estimators of the contamination of the biota. To test this we compared the Cd, Cu and Zn content of three spiders (generalist predators) and two amphipods (detritivores), co-occurring in seven tidal marshes along the river Schelde, between each other and with the total metal concentrations and the concentrations of four sequential extractions of the soils. Correlations were significant in only one case and significant site x species interactions for all metals demonstrate that factors affecting metal concentration were species and site specific and not solely determined by site specific characteristics. These results emphasize that site and species specific biological factors might be of the utmost importance in determining the contamination of the biota, at least for higher trophic levels. A hypothetical example clarifies these findings.     

Direct and indirect effects of metal contamination on soil biota in a Zn-Pb post-mining and smelting area (S Poland)

Effects of metal contamination on soil biota activity were investigated at 43 sites in 5 different habitats (defined by substratum and vegetation type) in a post-mining area. Sites were characterised in terms of soil pH and texture, nutrient status, total and exchangeable metal concentrations, as well as plant species richness and cover, abundances of enchytraeids, nematodes and tardigrades, and microbial respiration and biomass. The concentrations of total trace metals were highest in soils developed on mining waste (metal-rich dolomite), but these habitats were more attractive than sandy sites for plants and soil biota because of their higher content of organic matter, clay and nutrients. Soil mesofauna and microbes were strongly dependent on natural habitat properties. Pollution (exchangeable Zn and Cd) negatively affected only enchytraeid density; due to a positive relationship between enchytraeids and microbes it indirectly reduced microbial activity.     

Relation between heavy metal concentrations in salt marsh plants and soil

The aim of the research reported here was to investigate the relation between heavy metal concentrations in salt marsh plants, extractability of the metals from soil and some soil characteristics. In April 1987, Spartina anglica and Aster tripolium plants and soil were collected from four salt marshes along the Dutch coast. The redox potential of the soil between the roots of the plants and at bare sites was measured. Soil samples were oven-dried and analyzed for chloride concentration, pH, fraction of soil particles smaller than 63 microm (f < 63 microm), loss on ignition (LOI) and ammonium acetate and hydrochloric acid extractable Cd, Cu and Zn concentrations. The roots and shoots of the plants were analyzed for Cd, Cu and Zn. Because drying of the soil prior to chemical analysis might have changed the chemical speciation of the metals, and therefore the outcome of the ammonium acetate extraction, a second survey was performed in October 1990. In this survey A. tripolium plants and soil were collected from two salt marshes. Fresh and matched oven-dried soil samples were analyzed for water, ammonium acetate and diethylene triaminepentaacetic acid (DTPA) extractable Cd, Cu and Zn concentrations. The soil samples were also analyzed for f < 63 microm, LOI and total (HNO(3)/HCl digestion) metal concentrations. Soil metal concentrations were correlated with LOI. Drying prior to analysis of the soil had a significant effect on the extractability of the metals with water, ammonium acetate or DTPA. Plant metal concentrations significantly correlated only with some extractable metal concentrations determined in dried soil samples. However, these correlations were not consistently better than with total metal concentrations in the soil. It was concluded that extractions of metals from soil with water, ammonium acetate or DTPA are not better predictors for metal concentrations in salt marsh plants than total metal concentrations, and that a major part of the variation in metal concentrations in the plants cannot be explained by variation in soil composition.     

Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Evaluation of heavy metal lability in polluted soils by a cation exchange batch procedure

A new extraction procedure with cationic exchange resins is proposed for the assessment of heavy metal lability in polluted soils. This method classifies soluble metal compounds in three levels according to their lability: very labile, moderately labile and non-labile. The concept of lability is based on the use of resins with different ability to interact with metals. The proposed procedure was applied to five samples of polluted soils. In the five soils, soluble Cd was found to be very labile, soluble Ni and Pb were mostly non-labile, Mn and Zn lability depended on the soil, while Cu had a fraction of moderately labile forms in four of the five soils. The resin extraction procedure was compared with the DTPA and CaCl2 extractions.     

Residual metal concentrations in soils and leaf accumulations in tobacco a decade following farmland application of municipal sludge

The objectives of this investigation were to examine the long-term residual effects of metal loading through sewage sludge applications on the total vs. diethylene triamine pentacetic acid (DTPA) extractable metal concentrations in soil and leaf accumulations in tobacco. Maryland tobacco (Nicotiana tabacum L.), cv. 'MD 609', was grown in 1983 and 1984 at two sites in Maryland that had been amended in 1972 with dewatered, digested sewage sludge from washington, DC, at rates equal to 0, 56, 112 and 224 mg ha(-1). The metal concentrations in the sludge, in mg kg(-1) dry weight, were: 1300 Zn, 570 Cu, 280 Pb, 45 Ni and 13 Cd. Soil samples collected from the surface horizon and composite leaf samples of cured tobacco were analyzed for total Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations. The soil samples were also examined for soil pH and DTPA extractable metals. Equations were generated using polynomic and stepwise regression analyses which described the relationships between total vs. DTPA extractable soil metals, and between DTPA soil and soil pH vs. plant metal concentrations, respectively. Significant increases were observed for both total and DTPA extractable metal concentrations for all metals, with all but total Mn and Ni being significant for linear and quadratic effects regarding sludge rates. However, linear relationships were found between DTPA extractable vs. total soil concentrations for all elements except Pb and Ni which were quadratic. Significant increases in plant Zn, Cu, Mn, Ni and Cd and decreases in Fe were observed with increased sludge rates. Plant Pb levels were unaffected by sludge applied Pb. Linear relationships were observed between plant Zn and Cd and DTPA soil metal levels: however, Mn and Cu levels were described by quadratic and cubic relationship, respectively. Relationships between plant Fe and Pb and DTPA extractable concentrations were nonsignificant. Additional safeguards to protect crop contamination from heavy metals such as Cd were discussed.     

Toxicity and heavy metal contamination of surficial sediments from the Bay of Thessaloniki (Northwestern Aegean Sea) Greece

Surficial sediments (the fraction < 2000 microm) from the Bay of Thessaloniki, in the Northwestern Aegean Sea, Greece were examined for heavy metal and organic carbon contents, as well as for acute LUMIStox toxicity of pore waters (PWs), wet sediment elutriates (WSEs) and dry sediment elutriates (DSEs) obtained from the solid material remaining after PW extraction. WSEs where not toxic. EC20/50 values could be measured in some DSE and PW samples. In all sediment samples, the DSE toxicity was greater than the corresponding PW toxicity. Sediment concentrations of total and labile Cd, Pb, Cu, Cr, Zn, Mn, Ni and Fe were determined and evaluated in relation to sediment quality guidelines. Pollution levels ranged from low to high for certain metals. A misfit between sediment toxicities calculated from heavy metal concentrations and those biologically measured was observed. Toxicity values were in general poorly correlated with sediment's heavy metal or organic carbon content. As significant correlation was however found between the DSE toxicity with total Ni and labile Fe, as well as for the PW toxicity with total Ni, labile Fe and labile Cr.     

Evaluation of heavy metal availability in polluted soils by two sequential extraction procedures using factor analysis

Superficial soil and grass samples from 13 locations affected by several anthropogenic sources (mining, metal factory, traffic emissions) were collected in Gipuzkoa, northern Spain. The more labile metal fractions, the mobile (extracted by 0.01 mol l(-1) CaCl(2)) and the mobilisable (extracted by 0.005 mol l(-1) DTPA), were evaluated using a short sequential procedure with two steps. From the results a short-medium term potential lability of Cd, Cu, Zn and Pb can be concluded. The labile levels were compared with the results obtained using the Tessier sequential procedure. Factor analysis was used to check the associations between the total metal contents in soil and grass, as well as between the levels of the different sequential fractions and the total content in grass. Cd, Cu and Zn labile levels were related to total metal grass contents indicating its suitability for the availability studies in polluted soil-plant system.     

DGT use in contaminated site characterization. The importance of heavy metal site specific behaviour

The objective of this study is to provide an insight into the techniques for measuring the lability of heavy metals in solid-phase pool of soils in order to assess the environmental risk arising from pollution. The technique of diffusive gradients in thin films (DGT) and a sequential extraction procedure were used to quantify the labile pools of Cu, Fe, Mn and Ni. These results were compared to metal concentrations in groundwater, measured directly using the in situ piezometers, and to the total concentration of metal in the soils. High concentrations of metal in the directly analysed soil solution compared to DGT measurement were attributed to the presence of colloidal metal. The use of DGT allowed only to calculate leaching parameters of the free ions and labile fractions of the metals. For this reason DGT technique needs preliminary investigation on metal speciation in soil solution before its application as a good tool in the characterization procedure of contaminated sites.     

A link between lead and cadmium kinetic speciation in seawater and accumulation by the green alga Ulva lactuca

In this work, studies on the bioaccumulation of Cd and Pb by Ulva lactuca at different sites of Gulf San Jorge (Patagonia, Argentina) are presented. Higher values of bioaccumulated Cd were found in Punta Maqueda - a site believed to serve as a control - in comparison to those in Punta Borja, a place highly exposed to urban and industrial activities. Consequently; the labile fractions of Cd and Pb in seawater were determined with a flow injection-preconcentration manifold interfaced to a graphite furnace-atomic absorption spectrometer (FI-GFAAS). The results obtained by kinetic speciation showed that the variable that correctly explains heavy metals accumulation in the alga, is the labile metal fraction in seawater. We propose to use an enhancement ratio - on the basis of the kinetically labile metal fraction - for calculation of the metal accumulated by the alga relative to its environment.     

Aging and temperature effects on DOC and elemental release from a metal contaminated soil

The combined effect of time and temperature on elemental release and speciation from a metal contaminated soil (Master Old Site, MOS) was investigated. The soil was equilibrated at 10, 28, 45, 70 and 90 degrees C for 2 days, 2 weeks, and 2 months in the laboratory. Dissolved organic carbon (DOC), total soluble elements (by ICP), and labile metals (by DPASV) were determined in the filtered (0.22 microm) supernatants. For the samples equilibrated at 90 degrees C, DOC fractions were size fractionated by filtration and centrifugation; a subsample was only centrifuged while another was also filtered through a 0.45 microm filter. Analyses of the supernatants (ICP, DPASV, DOC) were performed on all size fraction subsamples. Dissolved organic carbon (DOC) increased both with temperature and incubation time; however, metal behavior was not as uniform. In general, total soluble metal release (ICP) paralleled the behavior of DOC, increasing with both time and temperature, and confirming the importance of soil organic matter (SOM) in metal retention. Voltammetric analysis (dpasv) of Cu and Zn showed that very little of these metals remains labile in solution due, presumably, to complexation with dissolved organic matter. Labile concentrations of Cd, on the other hand, constituted a significant portion (50%) of total soluble Cd. Copper and Al increased in solution with time (up to 2 months) and temperature up to 70 degrees C; however, at 90 degrees C the soluble concentration declined sharply. The same behavior was observed after equilibration for longer periods of time (550 days) at lower temperatures (23 and 70 degrees C). While concentrations of labile Cu and total soluble Cu and Al increased in the unfiltered samples, the trend remained the same. DPASV analysis showing shifts in labile Cu complexes with temperature and time, together with the results from the unfiltered samples, lead to the hypothesis that Cu was complexing with large polymers that could form at the elevated temperature, and thus be removed from the analyzed solution. It is possible that Cu and Al released by SOM oxidation has re-sorbed or complexed to more recalcitrant organic matter or to mineral phases. Variations in the relative molecular size fractions present within the DOC pool produced by increased time and temperature may influence the element-DOC complexes present in solution and their behavior in soil environments.     

Fractionation and bioavailability of Cu in soil remediated by EDTA leaching and processed by earthworms (<Emphasis Type="Italic">Lumbricus terrestris</Emphasis> L.)

Background, aim, and scope  

Soil remediation with ethylenediamine tetraacetic acid (EDTA) leaching is capable of removing only part of the total metal concentration in the soil, mostly the labile, bioavailable metal species (metal bioavailability stripping). However, reintroduction of remediated soil in the environment exposes the soil to various environmental factors, which could potentially shift nonlabile residual metals back to labile bioavailable forms. We studied the effect of autochthonous earthworm species as model biotic environmental factor on the fractionation and bioavailability of Cu residual in soil after remediation.     

Heavy metal contamination characteristic of soil in WEEE (waste electrical and electronic equipment) dismantling community: a case study of Bangkok,Thailand

Sue Yai Utit is an old community located in Bangkok, Thailand which dismantles waste electrical and electronic equipment (WEEE). The surface soil samples at the dismantling site were contaminated with copper (Cu), lead (Pb), zinc (Zn), and nickel (Ni) higher than Dutch Standards, especially around the WEEE dumps. Residual fractions of Cu, Pb, Zn, and Ni in coarse soil particles were greater than in finer soil. However, those metals bonded to Fe-Mn oxides were considerably greater in fine soil particles. The distribution of Zn in the mobile fraction and a higher concentration in finer soil particles indicated its readily leachable character. The concentration of Cu, Pb, and Ni in both fine and coarse soil particles was mostly not significantly different. The fractionation of heavy metals at this dismantling site was comparable to the background. The contamination characteristics differed from pollution by other sources, which generally demonstrated the magnification of the non-residual fraction. A distribution pathway was proposed whereby contamination began by the deposition of WEEE scrap directly onto the soil surface as a source of heavy metal. This then accumulated, corroded, and was released via natural processes, becoming redistributed among the soil material. Therefore, the concentrations of both the residual and non-residual fractions of heavy metals in WEEE-contaminated soil increased.     

Informal e-waste recycling: environmental risk assessment of heavy metal contamination in Mandoli industrial area,Delhi, India

Nowadays, e-waste is a major source of environmental problems and opportunities due to presence of hazardous elements and precious metals. This study was aimed to evaluate the pollution risk of heavy metal contamination by informal recycling of e-waste. Environmental risk assessment was determined using multivariate statistical analysis, index of geoaccumulation, enrichment factor, contamination factor, degree of contamination and pollution load index by analysing heavy metals in surface soils, plants and groundwater samples collected from and around informal recycling workshops in Mandoli industrial area, Delhi, India. Concentrations of heavy metals like As (17.08 mg/kg), Cd (1.29 mg/kg), Cu (115.50 mg/kg), Pb (2,645.31 mg/kg), Se (12.67 mg/kg) and Zn (776.84 mg/kg) were higher in surface soils of e-waste recycling areas compared to those in reference site. Level exceeded the values suggested by the US Environmental Protection Agency (EPA). High accumulations of heavy metals were also observed in the native plant samples (Cynodon dactylon) of e-waste recycling areas. The groundwater samples collected form recycling area had high heavy metal concentrations as compared to permissible limit of Indian Standards and maximum allowable limit of WHO guidelines for drinking water. Multivariate analysis and risk assessment studies based on total metal content explains the clear-cut differences among sampling sites and a strong evidence of heavy metal pollution because of informal recycling of e-waste. This study put forward that prolonged informal recycling of e-waste may accumulate high concentration of heavy metals in surface soils, plants and groundwater, which will be a matter of concern for both environmental and occupational hazards. This warrants an immediate need of remedial measures to reduce the heavy metal contamination of e-waste recycling sites.     

Differences in the responses of native and transplanted mosses to atmospheric pollution: a possible role of selenium

Native and transplanted mosses of the species Scleropodium purum were used to study the possible adaptation of the former to atmospheric contamination. A total of seven assays were carried out with transplanted moss exposed at sites around a thermal power station for 28 and 56 days, and native moss collected from the sites at the same time. Irrigated moss bags were used in order to maintain stable conditions throughout the exposure periods. Determinations were made of levels of Co, Cr, Cu, K, Ni, Pb, Se and Zn in the mosses. No significant differences were found, throughout the exposure time studied, in metal bioconcentration in the native mosses, whereas in the transplanted mosses the differences were significant for all metals except Ni. The degree of bioconcentration was higher at the start of the exposure period and later became more stable. The high levels of Se found in the native mosses compared to the transplanted mosses indicates a possible mechanism of adaptation by detoxification.     

Towards the characterisation of heavy metals in dredged canal sediments and an appreciation of 'availability': two examples from the UK.

Canal sediments can act as sinks for a wide range of contaminants including heavy metals from various sources (e.g. industrial and waste water discharges). Dredging of canals is required to maintain navigational depth and prevent flooding. The sediments removed from canals are often disposed of to land, being deposited either straight on to the banks of the canal or, in recent years, in licensed disposal sites. The aim of this work was to investigate the nature of dredged sediment-derived soils and the heavy metals present in them. Two disposal sites in the United Kingdom (UK) were investigated and soil samples taken. A variety of analytical techniques were used, including Aqua regia digestion and sequential extraction, in order to assess the concentrations and associations of metals present. Diethylene triaminepenta-acetic acid extracts, performed to illustrate plant-available metal concentrations, reveal that up to 40% of the total extracted metals were in an 'available' form. Variations in metal concentrations with depth in the soil cores show a significant correlation with total organic carbon content.     

Measurement of dynamic mobilization of trace metals in sediments using DGT and comparison with bioaccumulation in Chironomus riparius: first results of an experimental study

Sediments in aquatic ecosystems are often contaminated as a result of anthropogenic activities. Sediments and benthic organisms have been used to monitor trace metals contamination. However, due to the high variability of contaminant bioavailability, the attempt to link metal concentration in sediments and contamination of the organisms or ecotoxicological effect often lead to disappointing results. The technique of diffusive gradients in thin films (DGT) has been proposed as a relevant tool to study metal bioavailability, for example for accumulation in plants. In the present study, laboratory microcosm experiments were conducted with six contaminated sediments to compare metal accumulation in DGT and bioaccumulation in a chironomid (Chironomus riparius) for Cu, Cd and Pb . Metal accumulation in DGT was measured over time then modelled to determine two parameters of the dynamic response of the metals to DGT deployment: the size of the particulate labile pool and the kinetic of the solid-dissolved phase exchange. The mobility of metals was found metal and sediment dependent. A significant relationship between metal accumulated in DGT and bioaccumulated in chironomids was found for Cu and Pb. However, total metals in sediments were the best predictors of bioaccumulation. Nevertheless, the knowledge of the metals dynamic enhanced our ability to explain the different biological uptake observed in sediments of similar total metal concentrations.