A survey of zinc, copper and cadmium concentrations in salt marsh plants along the Dutch coast

In autumn 1986, plants and soil were collected from the lower and the higher salt marsh zones of salt marshes along the Dutch coast. The main purpose was to get an overview of Zn, Cu and Cd concentrations in six dominant species of salt marsh plants. The roots and shoots of the plants were analysed for Zn, Cu and Cd. The highest heavy metal concentrations were found in plants collected from salt marshes near harbour areas and/or that are known to receive contaminated fluvial sediment. Dicotyledonous plant species tended to have similar heavy metal concentrations in roots and shoots, whereas in monocotyledonous species the concentrations in the roots were two to three times higher than in the shoots. Differences in accumulation in the roots between elements and between plant species were found. Cd was accumulated more than Zn or Cu. Triglochin maritima shows a low Cd uptake by roots, whereas Spartina anglica and Scirpus maritimus tend to accumulate it. The fraction of soil particles smaller than 63 microm, loss on ignition and Zn, Cu and Cd concentrations were determined in soil samples. The highest Zn, Cu and Cd concentrations in the soil were found at salt marshes in the Western Scheldt area and were nine, five and 20 times higher than background levels, respectively.     

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.     

A comparison of the rhizosphere-based method with DTPA, EDTA, CaCl2, and NaNO3 extraction methods for prediction of bioavailability of metals in soil to barley

A rhizosphere-based method was compared with DTPA, EDTA, CaCl2, and NaNO3 extraction methods for the evaluation of bioavailability of heavy metals in soil to barley. The extractable amounts of Cr, Cu, Zn and Cd analyzed by the rhizosphere-based method correlated significantly with the metal content of barley roots. The extractable metals identified by DTPA, EDTA, CaCl2 and NaNO3 methods exhibited relatively poor or no correlation with the metal content of barley roots. The stepwise multiple regression equation of the rhizosphere-based method was the simplest one, as no soil properties needed to be entered, whereas the equations for the DTPA, EDTA, CaCl2 and NaNO3 extraction methods always require those variables. The most distinct feature of the rhizosphere-based method was that the proposed method was suitable for acidic, neutral and near alkaline soils. In contrast, the other extraction methods were restricted to soil types. In summary, the rhizosphere-based method is the most robust approach for evaluation of bioavailability of metals in soil to barley.     

Phytoextraction of metals from a multiply contaminated soil by Indian mustard

The effects of nitrilotriacetate (NTA) and citric acid applications on metal extractability from a multiply metal-contaminated soil, as well as on their uptake and accumulation by Indian mustard (Brassica juncea) were investigated. Desorption of metals from the soil increased with chelate concentration, NTA being more effective than citric acid in solubilising the metals. Plants were grown in a sandy soil collected from a contaminated field site and polluted by Cd, Cr, Cu, Pb and Zn. After 43 days of plant growth, pots were amended with NTA or citric acid at 5 mmol kg-1 soil. Control pots were not treated with any chelate. Harvest of plants was performed 1 week after chelate addition. Soil water-, NH4NO3- and DTPA-extractable Cd, Cu, Pb and Zn fractions were enhanced only in the presence of NTA. In comparison to unamended plants, Indian mustard shoot dry weights suffered significant reductions following NTA application. NTA treatment increased shoot metal concentrations by a factor of 2-3, whereas citric acid did not induce any difference compared to the control. Chromium was detected in the above-ground tissues only after NTA amendment. Due to differences in dry matter yield, a significant enhancement of metal uptake was observed in NTA-treated plants for Cu and Zn.     

Comparison of a rhizosphere-based method with other one-step extraction methods for assessing the bioavailability of soil metals to wheat

There is no method recognized as a universal approach for evaluation of bioavailability of heavy metals in soil. Based on the simulation of the rhizosphere soil conditions and integration of the combined effects of root-soil interactions as a whole, a rhizosphere-based method has been proposed. Wet fresh rhizosphere soil was extracted by low-molecular-weight organic acids (LMWOAs) to fractionate metal fractions of soil pools, which were then correlated with the metal contents of wheat roots and shoots. The rhizosphere-based method was compared with other one-step extraction methods using DTPA, EDTA, CaCl2, and NaNO3 as extractants and the first step of the Community Bureau of Reference (BCR) method. Simple correlation and stepwise multiple regression analysis were used for the comparison. Simple correlation indicated that the extractable Cu, Zn, Cr, and Cd of soils by the rhizosphere-based method were significantly correlated with the metal contents of wheat roots. For DTPA, BCR1 and EDTA methods there was a relatively poor correlation between the extractable Cu, Zn and Cd of soil and metal contents of wheat roots. Stepwise multiple regression analysis revealed that the equation of the rhizosphere-based method was the simplest one, and no soil properties variables needed to be added. In contrast, the equations of other one-step extraction methods were more complicated, and soil properties variables needed to be entered. The most distinct feature of the rhizosphere-based method was that the recommended method was suitable for acidic, neutral and near alkaline soils. However, the DTPA and EDTA extraction methods were suitable for calcareous soils only-or-only for acidic soils. The CaCl2, and NaNO3 extraction methods were only suitable for exchangeable metals. In short, the rhizosphere-based method was the most robust approach for evaluation of bioavailability of heavy metals in soils to wheat.     

Plant accumulation of potentially toxic elements in sewage sludge as affected by soil organic matter level and mycorrhizal fungi.

Leek (Allium ameloprasum) was grown in pot trials in two clay loams of contrasting organic contents, with and without indigenous mycorrhizal propagules. Sewage sludges containing varying levels of Cd, Cu and Zn were added. Extractable soil metals, plant growth, major nutrient content and accumulation of metals, and soil microbial indices were investigated. The aim was to establish whether soil organic content and mycorrhizal status affected plant and microbial exposure to these metals. Extractable metals were higher and responses to inputs more pronounced in the arable, lower organic matter soil, although only Cd showed a soil difference in the CaCl2 fraction. There were no metal toxic effects on plants and some evidence to suggest that they promoted growth. Uptake of each metal was higher in the larger plants of the grassland, higher organic matter soil. Inoculation with arbuscular mycorrhizal fungi increased root Cd and Zn concentrations. With the exception of Cd (roots) and Zn (shoots), higher inputs of sludge metals did not increase plant metals. Zn and Cu, but not Cd, concentrations were higher in roots than in shoots.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

Extractable soil heavy metals following the cessation of biosolids application to agricultural soil

Changes in soil heavy metal extractability following the cessation of biosolids applications were studied in a long-term field experiment. Two anaerobically digested biosolids from wastewater treatment plants in Madrid (Sur and Viveros) were applied to cropland from 1983 to 1990. Soil samples were collected in the 1st, 5th and 9th year after the last biosolids application. Soil pH did not vary significantly after biosolids applications. Organic matter and total heavy metals (Zn, Pb, Cd, Ni, Cr and Cu) concentrations initially increased but then declined over time, mostly after the first 5 years following biosolids application. Metal extracted with DPTA increased in Sur treatments during the 1st year and diminished thereafter. However, in Viveros treatments, heavy metals extracted increased during the 1st year, declined in 1995, and showed a slight increase in 1999. These changes in heavy metal extractability were widely observed in the percentage of extractable metal recovery (EMR). The differences observed in the pattern of the two sources of biosolids applied could be due to the different rates of decomposition of their organic matter.     

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.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Risk assessment of heavy metal pollution for detritivores in floodplain soils in the Biesbosch, The Netherlands, taking bioavailability into account

Floodplains of the European rivers Rhine and Meuse are heavily polluted. We investigated the risk of heavy metal pollution (Cd, Cu, Pb, Zn) for detritivores living in a floodplain area, the Biesbosch, the Netherlands, affected by these rivers. Total soil, pore water and 0.01 M CaCl(2) extractable concentrations and concentrations in plant leaves, earthworms, isopods and millipedes were measured in two sites and compared with literature data to assess possible risks. Based on total metal concentrations in soil, serious effects on detritivores were expected. However, 0.01 M CaCl(2) extractable, pore water and plant leaf concentrations were similar to metal concentrations found in unpolluted areas. Concentrations of Cu and Cd in earthworms and Cu in millipedes were higher in the Biesbosch than in animals from reference areas. All other measured concentrations of heavy metals in earthworms, isopods and millipedes were similar to the ones found in reference areas. Despite high total soil concentrations, effects of Zn, Cu, Pb and Cd pollution on isopods are therefore not expected, while millipedes may only be affected by Cu. Since Cu and Cd levels in earthworms were increased compared to animals in unpolluted soils, this faunal group seems to be most at risk. Given the engineering role of earthworms in ecosystems, effects on the ecological functioning of floodplain soils therefore cannot be excluded.     

Potentially toxic metals in ombrotrophic peat along a 400 km English-Scottish transect

Four samples of ombrotrophic peat were collected from each of 10 upland locations in a transect from the southern Pennines to the Highland Boundary Fault, a total distance of ca. 400 km. Bulk compositions and other properties were determined. Total contents of Al and heavy metals (Ni, Cu, Zn, Cd, Pb) were determined following digestion with hydrofluoric acid, and concentrations of metals extractable with dilute nitric acid were also measured. Supernatants obtained from aqueous extractions of the peat samples were analysed for pH, major cations and anions, dissolved organic carbon and dissolved metals, and concentrations of free metal ions (Al(3+), Ni(2+), etc.) were estimated by applying a chemical speciation model. Both total and HNO(3)-extractable metal concentrations varied along the transect, the highest values being found at locations close to industrial and former mining areas. The HNO(3)-extractable soil metal contents of Ni, Cu and Cd were appreciably lower than lowest-observed-effect-concentrations (LOEC) for toxicity towards microorganisms in acid, organic rich soils. However, the contents of Zn at two locations, and of Pb at five locations exceeded LOECs, suggesting that they may be exerting toxic effects in the peats. Soil solution concentrations of free heavy metal ions (Cu(2+), Zn(2+), Cd(2+), Pb(2+)) were substantially lower than LOECs for toxicity towards vascular plants, whereas concentrations of Al(3+) were near to toxic levels at two locations.     

The effects of soil amendments on heavy metal bioavailability in two contaminated Mediterranean soils

Two heavy metal contaminated calcareous soils from the Mediterranean region of Spain were studied. One soil, from the province of Murcia, was characterised by very high total levels of Pb (1572 mg kg(-1)) and Zn (2602 mg kg(-1)), whilst the second, from Valencia, had elevated concentrations of Cu (72 mg kg(-1)) and Pb (190 mg kg(-1)). The effects of two contrasting organic amendments (fresh manure and mature compost) and the chelate ethylenediaminetetraacetic acid (EDTA) on soil fractionation of Cu, Fe, Mn, Pb and Zn, their uptake by plants and plant growth were determined. For Murcia soil, Brassica juncea (L.) Czern. was grown first, followed by radish (Raphanus sativus L.). For Valencia soil, Beta maritima L. was followed by radish. Bioavailability of metals was expressed in terms of concentrations extractable with 0.1 M CaCl2 or diethylenetriaminepentaacetic acid (DTPA). In the Murcia soil, heavy metal bioavailability was decreased more greatly by manure than by the highly-humified compost. EDTA (2 mmol kg(-1) soil) had only a limited effect on metal uptake by plants. The metal-solubilising effect of EDTA was shorter-lived in the less contaminated, more highly calcareous Valencia soil. When correlation coefficients were calculated for plant tissue and bioavailable metals, the clearest relationships were for Beta maritima and radish.     

Reduction of bioavailability and leachability of heavy metals during vermicomposting of water hyacinth

Vermicomposting of water hyacinth is a good alternative for the treatment of water hyacinth (Eichhornia crassipes) and subsequentially, beneficial for agriculture purposes. The bioavailability and leachability of heavy metals (Zn, Cu, Mn, Fe, Ni, Pb, Cd, and Cr) were evaluated during vermicomposting of E. crassipes employing Eisenia fetida earthworm. Five different proportions (trials 1, 2, 3, 4, and 5) of cattle manure, water hyacinth, and sawdust were prepared for the vermicomposting process. Results show that very poor biomass growth of earthworms was observed in the highest proportion of water hyacinth (trial 1). The water soluble, diethylenetriaminepentaacetic acid (DTPA) extractable, and leachable heavy metals concentration (percentage of total heavy metals) were reduced significantly in all trials except trial 1. The total concentration of some metals was low but its water soluble and DTPA extractable fractions were similar or more than other metals which were present in higher concentration. This study revealed that the toxicity of metals depends on bioavailable fraction rather than total metal concentration. Bioavailable fraction of metals may be toxic for plants and soil microorganisms. The vermicomposting of water hyacinth by E. fetida was very effective for reduction of bioavailability and leachability of selected heavy metals. Leachability test confirmed that prepared vermicompost is not hazardous for soil, plants, and human health. The feasibility of earthworms to mitigate the metal toxicity and to enhance the nutrient profile in water hyacinth vermicompost might be useful in sustainable land renovation practices at low-input basis.     

A model for evaluation of the phytoavailability of trace elements to vegetables under the field conditions

Currently, several single extraction methods are used for the evaluation of the phytoavailability of metals using pot experiments. A systematic comparison, however, is lacking. It is especially true for the field studies. This study was to investigate the phytoavailability of trace elements to vegetables grown on metal-contaminated soils under the field conditions. All soils collected were typical calcareous soils in northern China. Four frequently used methods using CaCl2, diethylenetriaminepentaacetic acid (DTPA), CH3COOH, and water as extractants were compared for phyto-availability. The concentrations of metals extracted by these four extraction methods ranged from 3.42 to 815, 1.51- 6965, 0.732-24473, 0.688-7863, 0.246-685, 1.99-5337 0.203-4649 ng/g for Cr, Ni, Zn, Cu, Cd, Pb and REEs, respectively. Simple correlation analysis indicated that a significant correlation (Cr: r = 0.5411**; Zn: r = 0.6352**; Cd: r = 0.6979**; Pb: r = 0.5537** and REEs: r = 0.5185** -0.6684**) was observed between the CaCl2-extractable metals in soil solution and that in Chinese cabbage. In addition, soil pH, organic matter (OM), and cation exchange capacity (CEC) also affect the phytoavailability. An empirical model was developed to express the combined effect of soil properties on the phytoavailability. The stepwise multiple regression analysis demonstrated that the phytoavailability of trace elements strongly correlated with the extractable fraction by CaCl2, total metal concentration in soils, and soil pH, OM, CEC. This model can describe approximately 75-95% of the variability of metal uptake and the r2 values ranged from 0.741** to 0.954**, which were much better than the single correlation analysis. For celery and cole, a strong correlation was obtained for Cr, Ni, Zn, Cu, Cd, La, Ce, Pr and Nd. For spinach and Chinese cabbage, however, a positive correlation was only observed for 1 and 3 metals, respectively. Generally, the developed empirical model can integrate the combined effects of soil properties, extractable metal fractions in soil solutions and plant species on the phytoavailability of metals to vegetables in the field conditions.     

The use of NTA and EDDS for enhanced phytoextraction of metals from a multiply contaminated soil by Brassica carinata

The potential of nine different species to grow in the presence of metals (As, Cd, Cu, Pb and Zn) and to accumulate them in the shoots was assessed for each metal separately by germination and root length tests, and successively by hydroponic experiments. Of the nine species tested, Brassica carinata was the species that accumulated the highest amounts of metals in shoots without suffering a significant biomass reduction. To further evaluate the potential of B. carinata for chelant-enhanced phytoextraction of a natural, multiply metal-polluted soil (As, Cd, Cu, Pb and Zn), both hydroponic and pot experiments were carried out with nitrilotriacetic acid (NTA) or (S,S)-ethylenediamine disuccinic acid (EDDS) as complexing agents. The hydroponic study with solutions containing the five metals together showed that accumulation of Cd, Cu, Pb and Zn in shoots was higher following EDDS addition compared to NTA. EDDS was more effective than NTA in desorbing Cu, Pb and Zn from the soil, whereas As and Cd were poorly extracted. B. carinata plants were grown for 4 weeks in the multiply metal-contaminated soil and then the soil was amended with 5 mmol kg(-1) NTA or EDDS. All plants were harvested 1 week after amendment. In comparison to NTA, EDDS was more effective in enhancing the concentrations of Cu, Pb and Zn in B. carinata shoots (2- to 4-fold increase compared to the control). One week after chelant addition, the DTPA-extractable metal concentrations in the polluted soil were lower in the EDDS treatment in comparison with the NTA amendment. Even though B. carinata showed a reduced growth and a relatively low metal uptake, it demonstrated the ability to survive and tolerate the presence of more metals simultaneously.     

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.     

Effects of past sewage sludge additions on heavy metal availability in light textured soils: implications for crop yields and metal uptakes

The effect of heavy metal additions in past sewage sludge applications on soil metal availability and the growth and yield of crops was evaluated at two sites in the UK. At Gleadthorpe, sewage sludges enriched with salts of zinc (Zn), copper (Cu) and nickel (Ni) had been applied to a loamy sand in 1982 and additionally naturally contaminated Zn and Cu sludge cakes in 1986. At Rosemaund, sewage sludges naturally contaminated with Zn, Cu, Ni and chromium (Cr) had been applied in 1968-1971 to a sandy loam. From 1994 to 1997, the yields of both cereals and legumes at Gleadthorpe were up to 3 t/ha lower than the no-sludge control where total topsoil Zn and Cu concentrations exceeded 200 and 120 mg/kg, respectively, but only when topsoil ammonium nitrate extractable metal levels also exceeded 40 mg/kg Zn and 0.9 mg/kg Cu. At Rosemaund, yields were only decreased where total topsoil Cu concentrations exceeded 220 mg/kg or 0.7 mg/kg ammonium nitrate extractable Cu. These results demonstrate the importance of measuring extractable as well as total heavy metal concentrations in topsoils when assessing likely effects on plant yields and metal uptakes, and setting soil quality criteria.     

Microbial processes in the rhizosphere soil of a heavy metals-contaminated Mediterranean salt marsh: a facilitating role of AM fungi

We investigated the relationship of the zonal pattern followed by the vegetation in a polluted Mediterranean salt marsh, in semiarid south-eastern Spain, with the microbiological and biochemical properties (labile C fractions, oxidoreductases and hydrolases) of the rhizosphere soil of two halophyte species, Arthrocnemum macrostachyum and Sarcocornia fruticosa, and with the degree of arbuscular mycorrhizal (AM) colonisation in their rhizospheres. Levels of plant biomass and cover were inversely related to heavy metal contents and salinity. The concentrations of Fe, Cu, Mn and Pb extracted with DTPA hardly varied among the different zones of the salt marsh. The dehydrogenase and phosphatase activities, the soluble C and water-soluble carbohydrates concentrations and the extent of root colonisation were greater in the salt marsh zones of lower soil salinity and lower metal concentration. Urease and beta-glucosidase activities were not detected in the salt marsh. Plant biomass and cover showed positive relationships with mycorrhizal colonisation (R=0.773, P<0.001; R=0.874, P<0.001, respectively). Mycorrhizal colonisation was negatively correlated with the contents of Pb and Zn in plant tissues. This work supports the view that reduced plant uptake of toxic metals, particularly lead, could be involved in the beneficial effects of AM fungi on plant development in Mediterranean salt marshes contaminated with mining wastes.     

Chemical speciation and extractability of Zn,Cu and Cd in two contrasting biosolids-amended clay soils

An incubation experiment was conducted to study the chemical speciation and extractability of three heavy metals in two contrasting biosolids-amended clay soils. One was a paddy soil of pH 7.8 and the other was a red soil of pH 4.7 collected from a fallow field. Anaerobically digested biosolids were mixed with each of the two soils at three rates: 20, 40 and 60 g kg(-1) soil (DM basis), and unamended controls were also prepared. The biosolids-amended and control soils were incubated at 70% of water holding capacity at 25 degrees C for 50 days. Separate subsamples were extracted with three single extractants and a three-step sequential extraction procedure representing acetic acid (HOAc)-soluble, reducible and oxidisable fractions to investigate the extractability and speciation of the heavy metals. As would be expected, there were good relationships between biosolids application rate and metal concentrations in the biosolids-amended soils. The three heavy metals had different extractabilities and chemical speciation in the two biosolids-amended soils. Ethylene diamine tetraacetic acid extracted more Cu, Zn and Cd than did the other two single extractants. The oxidisable fraction was the major fraction for Cu in both biosolids-amended soils and the HOAc-soluble and reducible fractions accounted for most of the Zn. In contrast, Cd was present mainly in the reducible fraction. The results are discussed in relation to the mobility and bioavailability of the metals in polluted soils.