An inter-laboratory study to test the ability of amendments to reduce the availability of Cd, Pb, and Zn in situ

An international inter-laboratory research program investigated the effectiveness of in situ remediation of soils contaminated by cadmium, lead and zinc, measuring changes in soil and soil solution chemistry, plants and soil microbiota. A common soil, from mine wastes in Jasper County MO, was used. The soil was pH 5.9, had low organic matter (1.2 g kg(-1) C) and total Cd, Pb, and Zn concentrations of 92, 5022, and 18 532 mg kg(-1), respectively. Amendments included lime, phosphorus (P), red mud (RM), cyclonic ashes (CA), biosolids (BIO), and water treatment residuals (WTR). Both soil solution and NH4NO3 extractable metals were decreased by all treatments. Phytotoxicity of metals was reduced, with plants grown in P treatments having the highest yields and lowest metal concentration (0.5, 7.2 and 406 mg kg(-1) Cd, Pb, and Zn). Response of soil micro-organisms was similar to plant responses. Phosphorus addition reduced the physiologically based extraction test Pb from 84% of total Pb extracted in the untreated soil to 34.1%.     

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.     

Bioconcentration and biokinetics of heavy metals in the earthworm

This study examines the steady state and non-steady state kinetics of five metals, cadmium, copper, lead, nickel, and zinc in earthworms. The steady state kinetics are based on field studies in which worms from contaminated and uncontaminated sites were collected and measurements were made of concentrations in the earthworms and soils. For each of the metals, evidence suggests that bioconcentration depends on the metal concentrations in the soil; bioconcentration is greater at lower soil concentrations. The studies of non-steady state kinetics involve uptake and elimination experiments in which worms are transferred from an uncontaminated soil to a contaminated soil (uptake studies) or from a contaminated soil to an uncontaminated soil (elimination studies). The voiding time is shown to be an important experimental variable in determining the measured levels of metal in earthworms because experimental measurements are usually made on a worm-soil complex (i.e. the soft tissue of the worm and the soil in the gut of the worm). Thus, for metals that are bioconcentrated in worm tissue, increasing the voiding period increases the concentration of the metal in the worm-soil complex. Conversely, for metals that are not bioconcentrated, increasing the voiding time leads to a decrease in concentrations in the worm-soil complex.     

In situ fixation of metals in soils using bauxite residue: chemical assessment

Contamination of soils with heavy metals and metalloids is a widespread problem all over the world. Low cost, non-invasive, in situ technologies are required for remediation processes. We investigated the efficiency of a bauxite residue (red mud) to fix heavy metals in two soils, one contaminated by industrial activities (French soil), and one by sewage sludge applications (UK soil). This Fe-oxide rich material was compared with lime, or beringite, a modified aluminosilicate that has been used for in situ fixation processes. Four different crop species were successively grown in pots. Metal concentrations in the soil pore waters were analyzed during the growing cycles. At the end of the experiment fluxes of heavy metals were measured using a diffusive gradient in thin film technique (DGT). Furthermore, a sequential extraction procedure (SEP) and an acidification test were performed to investigate the mechanisms of metal fixation by different soil amendments. In both soils, the concentrations of metals in the soil pore water and metal fluxes were greatly decreased by the amendments. An application of 2% red mud performed as well as beringite applied at 5%. Increasing soil pH was a common mechanism of action for all the amendments. However, the red mud amendment shifted metals from the exchangeable to the Fe-oxide fraction, and decreased acid extractability of metals. The results suggest that specific chemisorption, and possibly metal diffusion into oxide particles could also be the mechanisms responsible for the fixation of metals by red mud.     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Uptake of metals by food plants grown on soils 10 years after biosolids application

Potentially hazardous trace elements such as Cd, Cu, Cr, Ni and Zn are expected to accumulate in biosolids–amended soil and remain in the soil for a long period of time. In this research, uptake of metals by food plants including cabbage, carrot, lettuce and tomato grown on soils 10 years after biosolids application was studied. All the five metals were significantly accumulated in the biosolids-amended soils. The accumulation of metal in soil did not result in significant increase in concentrations of Cu, Cr and Ni in the edible plant tissues. However, the Cd and Zn concentrations of the edible tissues of plants harvested from the biosolids receiving soils were significantly enhanced in comparison with those of the unaffected soils. The plant uptake under Greenfield sandy loam soil was generally higher than those under the Domino clayey loam soil. The metal concentration of edible plant tissue exhibited increasing trends with respect to the concentrations of the ambulated metals. The extents of the increases were plant species dependent. The indigenous soil metals were absorbed by the plants in much higher rates than those of the biosolids–receiving soils. It appeared that the plant uptake of the indigenous soil-borne metal and the added biosolids-borne metals are independent of one another and mathematically are additive.     

Acid sulphate soil disturbance and metals in groundwater: implications for human exposure through home grown produce

A significant emerging environmental problem is the disturbance and oxidation of soils with high levels of iron sulphide minerals resulting in acidification and causing the mobilization of metals into groundwater. This process is occurring in many parts of the world. In Western Australia, impacted groundwater is extracted by residents for domestic use. We sought to establish domestic use patterns of bore water and the concentration of metals. Sixty-seven domestic bore water samples clearly indicated oxidation of sulphidic materials with heavy metal concentrations ranging for aluminium (相似文献   

Green manure plants for remediation of soils polluted by metals and metalloids: Ecotoxicity and human bioavailability assessment

Borage, white mustard and phacelia, green manure plants currently used in agriculture to improve soil properties were cultivated for 10 wk on various polluted soils with metal(loid) concentrations representative of urban brownfields or polluted kitchen gardens. Metal(loid) bioavailability and ecotoxicity were measured in relation to soil characteristics before and after treatment. All the plants efficiently grow on the various polluted soils. But borage and mustard only are able to modify the soil characteristics and metal(loid) impact: soil respiration increased while ecotoxicity, bioaccessible lead and total metal(loid) quantities in soils can be decreased respectively by phytostabilization and phytoextraction mechanisms. These two plants could therefore be used for urban polluted soil refunctionalization. However, plant efficiency to improve soil quality strongly depends on soil characteristics.     

Determination of the applicability of CERCLA's petroleum exclusion at contaminated sites – focus on metals

Areas impacted by petroleum refining and handling operations may become subject to CERCLA enforcement. Because of CERCLA's petroleum exclusion clause, determining whether contamination in a CERCLA Site originated from petroleum products or hazardous wastes becomes important. Because certain metals are typically enriched in wastes relative to petroleum products and background soils, knowledge of metal contents in these potential end member metal sources is an important step towards contaminant source identification in soils and sediments. In LNAPL plumes, metal content, particularly lead, may be claimed to be the result of wastes mishandling and not due only to the presence of leaded gasoline in the plume. Analysis of the percent gasoline in the plume and accounting for weathering are steps to determining whether the lead content in an LNAPL plume is within the historical lead concentration ranges in gasolines. In addition to metals analyses, understanding of operational parameters such as the history of petroleum refining and handling operations, leaks, spills, and cleanup activities are needed for successful conclusion of the applicability of the petroleum exclusion.     

In situ fixation of metals in soils using bauxite residue: biological effects

Soils polluted with heavy metals can cause phytotoxicity and exhibit impared microbial activities. In this paper we evaluate the responses of different biological endpoints to in situ remediation processes. Three soil amendments (red mud, beringite and lime) were applied to two soils polluted by heavy metals. Oilseed rape, wheat, pea and lettuce were grown successively in pots on the untreated and amended soils and their yield and metal uptake were determined. A suite of microbial tests (lux-marked biosensors, Biolog and soil microbial biomass) were performed to determine the effect of the soil amendments on the functionality and size of the soil microbial community. In both soils all three amendments reduced phytotoxicity of heavy metals, enhanced plant yields and decreased the metal concentrations in plants. The red mud treatment also increased soil microbial biomass significantly. The microbial biosensors responded positively to the remediation treatments in the industrially-contaminated soil used in the experiment. Red mud applied at 2% of soil weight was as effective as beringite applied at 5%. The results also showed that since the biological systems tested respond differently to the alleviation of metal toxicity, a suite of biological assays should be used to assess soil remediation processes.     

不同土壤重金属复合污染的有效态离子冲量表征

选择红壤、黄棕壤和潮土为对象，依据中国土壤环境质量二级和三级标准确定土壤重金属铜、锌、镉的污染浓度，通过生物盆裁试验研究在重金属Cu、Zn、Cd复合污染条件下牧草（黑麦草、紫花苜蓿）体内重金属含量和土壤中重金属有效态含量的相关性，结果表明，在3种不同性质的污染土壤上，牧草体内重金属的离子冲量与其对应土壤中重金属有效态的离子冲量之间均存在明显的相关性。校正土壤pH、牧草品种等因素后，土壤有效态离子冲量可以有效表征不同土壤-牧草系统的重金属复合污染。     

Effects of metals on life cycle parameters of the earthworm Eisenia fetida exposed to field-contaminated, metal-polluted soils

Two control and eight field-contaminated, metal-polluted soils were inoculated with Eisenia fetida (Savigny, 1826). Three, 7, 14, 21, 28 and 42 days after inoculation, earthworm survival, body weight, cocoon production and hatching rate were measured. Seventeen metals were analysed in E. fetida tissue, bulk soil and soil solution. Soil organic carbon content, texture, pH and cation exchange capacity were also measured. Cocoon production and hatching rate were more sensitive to adverse conditions than survival or weight change. Soil properties other than metal concentration impacted toxicity. The most toxic soils were organic-poor (1-10 g C kg(-1)), sandy soils (c. 74% sand), with intermediate metal concentrations (e.g. 7150-13,100 mg Pb kg(-1), 2970-53,400 mg Zn kg(-1)). Significant relationships between soil properties and the life cycle parameters were determined. The best coefficients of correlation were generally found for texture, pH, Ag, Cd, Mg, Pb, Tl, and Zn both singularly and in multivariate regressions. Studies that use metal-amended artificial soils are not useful to predict toxicity of field multi-contaminated soils.     

The effect of heavy metals on dinitrogen fixation by Rhizobium-white clover in a range of long-term sewage sludge amended and metal-contaminated soils

An investigation was conducted to determine whether effective strains of Rhizobium leguminosarum biovar. trifolii capable of symbiotic N2 fixation with white clover (Trifolium repens) were present in a range of metal-contaminated soils. A number of historically sewage-amended sites (including experimental, pasture grassland and arable sites) were selected and compared with highly contaminated samples from abandoned heavy metal mines. Many sites had metal concentrations above the limits established by the UK Government, based on those developed by the European Commission (EC) for sludge-amended soils. Acetylene reduction activity (ARA) was used to screen the samples for effective N2 fixation. When the host plant was indigenous to the sward, rhizobia were found in the nodules and in the soil rhizosphere at all the sites tested. They were shown to be capable of effective symbiosis and N2 fixation, even though metal concentrations greatly exceeded the soil metal limits in some cases. However, nodulation failed to occur in some cases where T. repens was not indigenous to metal-contaminated soils. This indicated either that an ineffective rhizobial population was present, or that effective cells were absent from the soil. The influence of individual metals on ARA could not be determined conclusively because of the confounding effects of soil physicochemical variability and the presence of different metals at high concentrations together in the soil. However, Cd concentrations appeared to be particularly important in determining the presence of effective ARA in soils with no indigenous clover. In contrast to previous studies, the results presented here suggest that heavy metals may have had a quantitative effect on the free-living population of rhizobia, rather than a genetic effect.     

Relationship of surface changes to metal leaching from tungsten composite shot exposed to three different soil types

Physical changes that occur on the surface of fired shots due to firing and impact with soil may increase the dissolution of muniton metals. Increased metal dissolution could potentially increase metal transport and leaching, affecting metal concentrations in surface and groundwater. This research describes the relationship between the surface changes on fired tungsten-nickel-iron (94% W:2% Ni:4% Fe) composite shots and metals leaching from those shots. Tungsten composite shot was fired into, and aged in, three soil types (Silty Sand, Sandy Clay, and Silt) in mesoscale rainfall lysimeters to simulate live-fire conditions and subsequent interactions between the metals of the composite and soil. Leachate, runoff, and soil samples were collected from the lysimeters and analyzed for metal content. The shots were analyzed using scanning electron microscopy (SEM) to evaluate surface changes. SEM results indicated that a soil’s particle size distribution initially affected the amount of metal that was sheared from the surface of the fired W-composite shots. Shearing was greatest in soils with larger soil particles (sand and gravel); shearing was least in soils composed of small soil particles (fines). Increased metallic shearing from the shot’s surface was associated with increased W dissolution, compared to controls, following a simulated 1 year soil aging.     

The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants

The experiments were done to investigate the effect of soil pH and organic matter content on EDTA-extractable heavy metal contents in soils and heavy metal concentrations in rice straw and grains. EDTA-extractable Cr contents in soils and concentrations in rice tissues were negatively correlated with soil pH, but positively correlated with organic matter content. The combination of soil pH and organic matter content would produce the more precise regression models for estimation of EDTA-Cu, Pb and Zn contents in soils, demonstrating the distinct effect of the two factors on the availability of these heavy metals in soils. Soil pH greatly affected heavy metal concentrations in rice plants. Furthermore, inclusion of other soil properties in the stepwise regression analysis improved the regression models for predicting straw Fe and grain Zn concentrations, indicating that other soil properties should be taken into consideration for precise predicting of heavy metal concentrations in rice plants.     

Recombinant luminescent bacterial sensors for the measurement of bioavailability of cadmium and lead in soils polluted by metal smelters

Environmental hazard of heavy metals in soils depends to a large extent on their bioavailability. The approach used in this study enables the determination of bioavailable metals in solid-phase samples. Two recombinant bacterial sensors, one responding specifically to cadmium and the other to lead and cadmium by increase of luminescence (firefly luciferase was used as a reporter) were used to determine the bioavailability of these metals in soil-water suspensions (a contact assay) and respective particle-free extracts. Fifty agricultural soils sampled near zinc and lead smelters in the Northern France containing up to (mg/kg) 20.1 of Cd, 1050 of Pb and 1390 of Zn were analysed. As the soil matrix interferes with the assay, recombinant luminescent control bacteria lacking the metal recognizing protein and corresponding promoter (thus, being not metal-inducible) but otherwise comparable to the sensor bacteria (the same host bacterium and plasmid encoding luciferase) were used in parallel to take into account the possible quenching and/or stimulating effects of the sample on the luminescence of the sensor bacteria. Both, chemical and sensor analysis showed that only microg/l levels of metals were extracted from the soil into the water phase (0.1% of the total Cd, 0.07% of Pb and 0.5% of Zn). However, 115-fold more Cd and 40-fold more Pb proved bioavailable if the sensor bacteria were incubated in soil suspensions (i.e., in the contact assay). The bioavailability of metals in different soils varied (depending probably on soil type) ranging from 0.5% to 56% for cadmium and from 0.2% to 8.6% for lead.     

Difference of lead,copper and zinc concentrations between interiors and exteriors of peds in some contaminated soils

Solute transport of elements in soils depends on the soil structural and hydraulic properties, and it is controlled by sorption and diffusion, which both limit the mobility and distribution of elements in soils. This study was conducted to compare lead (Pb), copper (Cu) and zinc (Zn) concentrations between ped exteriors and interiors of some contaminated soils. The results show that the differences of the heavy metals between exteriors and interiors decreased in the order clayey soil, clayey loam soil, loam soil. For same soils, the differences decreased from Pb to Cu to Zn. The differences in readily extractable concentrations of the three metals between ped exteriors and interiors were much larger than the differences in their total metals, this may indicate that extractable metals were more recently deposited. The higher Pb and Cu concentrations in the ped exteriors than interiors may additionally be explained by anthropogenic input, movement and downward through preferential flow.     

Heavy metal contamination from mining sites in South Morocco: 1. Use of a biotest to assess metal toxicity of tailings and soils

Our work was conducted to investigate the heavy metal toxicity of tailings and soils collected from five metal mines located in the south of Morocco. We used the MetPAD biotest Kit which detects the toxicity specifically due to the heavy metals in environmental samples. This biotest initially developed to assess the toxicity of aquatic samples was adapted to the heterogeneous physico-chemical conditions of anthropogenic soils. Contrasted industrial soils were collected from four abandoned mines (A, B, C and E) and one mine (D) still active. The toxicity test was run concurrently with chemical analyses on the aqueous extracts of tailings materials and soils in order to assess the potential availability of heavy metals. Soil pH was variable, ranging from very acidic (pH 2.6) to alkaline values (pH 8.0-8.8). The tailings from polymetallic mines (B and D) contained very high concentrations of Zn (38,000-108,000 mg kg(-1)), Pb (20,412-30,100 mg kg(-1)), Cu (2,019-8,635 mg kg(-1)) and Cd (148-228 mg kg(-1)). Water-extractable metal concentrations (i.e., soil extracts) were much lower but were highly toxic as shown by the MetPAD test, except for soils from mines A, E and site C3 from mine C. The soil extracts from mine D were the most toxic amongst all the soils tested. On this site, the toxicity of soil water extracts was mainly due to high concentrations of Zn (785-1,753 mg l(-1)), Cu (1.8-82 mg l(-1)) and Cd (2.0-2.7 mg l(-1)). The general trend observed was an increase in metal toxicity measured by the biotest with increasing available metal contents in tailings materials and soils. Therefore, the MetPAD test can be used as a rapid and sensitive predictive tool to assess the heavy metal availability in soils highly contaminated by mining activities.     

Retention and distribution of heavy metals in mangrove soils receiving wastewater

The distribution and chemical fractionation of heavy metals retained in mangrove soils receiving wastewater were examined by soil column leaching experiments. The columns, filled with mangrove soils collected from two swamps in Hong Kong and the People's Republic of China, were irrigated three times a week for 150 days with synthetic wastewater containing 4 mg l(-1) Cu, 20 mg l(-1) Zn, 20 mg l(-1) Mn and 0.4 mg l(-1) Cd. Soil columns leached with artificial seawater (without any heavy metals) were used as the control. At the end of the leaching experiments, soil samples from each column were divided into five layers according to its depth viz. 0-1, 1-3, 3-5, 5-10 and > 10 cm, and analyzed for total and extractable heavy metal content. The fractionation of heavy metals in the surface soil samples (0-1 cm) was investigated by the sequential extraction technique. In both types of mangrove soils, the surface layer (0-1 cm) of the columns receiving wastewater had significantly higher concentrations of total Cu, Cd, Mn and Zn than the control. Concentrations declined significantly with soil depth. The proportion of exchangeable heavy metals in soils receiving wastewater was significantly higher than that found in the control, about 30% of the total heavy metals accumulated in the soil masses of the treated columns were extracted by ammonium acetate at pH 4. The sequential extraction results show that in native mangrove soils (the soils without any treatment), the major portion of Cu, Zn, Mn and Cd was associated with the residual and precipitated fractions with very low concentrations in more labile phases. However, in mangrove soils receiving wastewater, a significantly higher percentage of Mn, Zn and Cd was found in the water-soluble and exchangeable fractions. Copper appeared to be more strongly adsorbed in mangrove soils than the other heavy metals. In general, heavy metal accumulation in the surface mangrove soils collected in Hong Kong was higher than those in the PRC, although the metals in the latter soil type were more strongly bound. These findings suggest that whether the heavy metal retained in managrove soils becomes a secondary source or a permanent sink would depend on the kinds of heavy metals and also the types of mangrove soils.     

Lead and cadmium in indoor air and the urban environment

The present study was conducted to find potential terrestrial biomonitors for heavy metals in indoor air in an urban environment. TSP, PM(10), and PM(2.5) were collected in three retirement facilities in the urban area of Vienna. In addition, particulate matter and soil, vegetation, and isopods (Porcellio scaber L.) were collected in the adjacent garden areas. Aerosols were sampled with a low-volume air sampler. The sampled materials were wet ashed and total lead and cadmium contents were determined. Water-soluble heavy metal concentrations were measured in aqueous extracts from air exposed filters, soil, and vegetation. Lead and cadmium were analyzed by graphite furnace AAS. Lead contents in the vegetation were inferred from water-soluble lead in soils. Lead in isopods generally reflected the contents in vegetation. Cadmium in plants probably derived from soil solutions as well as from atmospheric input. Isopods reflected the total cadmium contents in soils. Particulate matter was dominated by PM(2.5), both with respect to mass concentrations and to heavy metal contents. The indoor aerosol was found to be influenced by human activity, indoor sources, and outdoor particles. Relationships between indoor airborne heavy metals and the contents in vegetation (lead and cadmium: positive) and isopods (lead: negative) were identified to have the potential for biomonitoring indoor air quality.