Trace element availability and plant growth in a mine-spill contaminated soil under assisted natural remediation I. Soils

We evaluated the effects of different amendments and/or a plant cover on reclamation of a trace element contaminated soil. Seven treatments were established: four organic (leonardite (LEO), litter (LIT), municipal waste compost (MWC), biosolid compost (BC)), one inorganic (sugar beet lime (SL)) and two controls (control without amendment but with Agrostis (CTRP) and control without amendment and without Agrostis (CTR)). Results showed that total organic C was significantly higher in organic treatments in all samplings. Water-soluble C was lower in CTR compared to other treatments, but no significant differences were observed between organic treatments and SL and CTR. SL, BC and MWC treatments increased soil pH and reduced 0.01 M CaCl2-extractable Cd, Cu and Zn concentrations more efficiently, especially in the first 2 years. At the end of the experiment 0.01 M CaCl2-extractable trace element concentrations were similar in all treatments. 0.01 M CaCl2-extractable As and Pb were below the detection limit. Addition of amendments showed no clear reduction in 0.05 M EDTA-extractable trace element concentrations and some amendments even increased 0.05 M EDTA-extractable As and Cu with time. Pseudo-total trace element concentrations were higher for As in controls. On the other hand, mean values of Cu and Zn were higher in MWC treatment. BC and SL treatments also showed higher Zn mean concentration than controls. No amendment effect was observed for Cd and Pb.     

Assessment of fly ash-aided phytostabilisation of highly contaminated soils after an 8-year field trial: part 1. Influence on soil parameters and metal extractability

Sustainable management of large surface areas contaminated with trace elements is a real challenge, since currently applied remediation techniques are too expensive for these areas. Aided phytostabilisation appears to be a cost efficient technique to reduce metal mobility in contaminated soils and contaminated particle spread. In this context, this study aimed at evaluating the long-term efficiency of aided phytostabilisation on former agricultural soils highly contaminated with trace elements. The influence of afforestation and fly ash amendments to reduce metal mobility was investigated. Before being planted with a tree mix, the study site was divided into three plots: a reference plot with no amendment, the second amended with silico-aluminous fly ash and the third with sulfo-calcic fly ash. After eight years, some soil physico-chemical parameters, including cadmium (Cd), lead (Pb) and zinc (Zn) extractability were modified. In particular, pH decreased on the whole site while organic carbon content increased. The alteration of these parameters influencing trace element mobility is explained by afforestation. Over time, concentrations of CaCl₂-extractable metals increased and were correlated with the soil pH decrease. In the amended soils, extractable Cd, Pb and Zn concentrations were lower than in the reference soil. The results indicated that the two fly ashes buffered natural soil acidification due to vegetation development and limited trace element mobility and thus could limit their bioavailability. For long-term phytostabilisation, special attention should be focused on the soil pH, metal mobility and phytoavailability analysis.     

Mass balance and distribution of sludge-borne trace elements in a silt loam soil following long-term applications of sewage sludge

Soil samples were collected at 15-cm increments to a depth of 75 cm from plots on a silt loam soil where until several years earlier and for 14 years, anaerobically digested sewage sludge had been annually applied by furrow irrigation. The study protocol consisted of four replications of 6.1 x 12.2-m plots with 0 (T0), 1/4-maximum (T1), 1/2-maximum (T2) and maximum (T3) sludge application rates randomized within blocks. When sludge applications were terminated, maximum sludge-treated plots had received 765 Mg ha-1 (dry weight equivalent) of sludge solids. Total soil concentrations of Cd, Cr, Cu, Ni, Pb and Zn had been significantly enhanced by all sludge application rates to a soil depth of 30 cm. Below the 30-cm depth, total soil Cd was increased to 75 cm, total Zn to 45 cm (T2 and T3 only), total Cr to 60 cm (T2 and T3 only), but total Cu, Pb, and Ni were not increased at depth. Despite the lack of significant increases in subsoil concentrations for some metals, mass balance calculations showed a relatively high proportion of all the above sludge-borne heavy metals to be unaccounted for in the soil profile for each application rate. Mass balance calculations of losses ranged from a high of 60% for Ni to a low of 36% for Cu and Pb. Similar losses were calculated from metal concentrations measured in soil samples taken at the time the sludge was applied. In soil surface samples (0-15 cm) from maximum sludge-treated plots, percentages of total metal concentration extracted with 4.0 M HNO3 ranged from a low of 31 for Zn to a high of 75 for Cu. Efficiency of metal extraction by HNO3 was inconsistent, depending on the soil horizon and sludge treatment, so that evaluation of HNO3-extractable metals is not a reliable method of estimating total metal retention in the profiles. In soil surface samples from maximum sludge-treated plots, the percentage of total metal contents extracted with DTPA ranged from a low of 0.03 for Cr to a high of 59 for Cd. The DTPA extractable levels of Cu, Ni, and Pb were higher in the subsoils of the sludge-treated soils, indicating that these metals had been redistributed from the surface layer to deeper zones in the profile of sludge-amended soil, despite the absence of elevated total concentrations of these three metals in the deeper subsoil.     

Arsenic pollution at the industrial site of Reppel-Bocholt (north Belgium)

An industrial site, polluted with As and heavy metals, was investigated by combining chemical (sequential extractions and pHstat leaching tests), physical and mineralogical characterization of soil samples and slag fragments, and by the analysis of soil porewater aimed at assessing the distribution, speciation and mobility of heavy metals and As. On the site itself, arsenic concentrations up to 3.6% in surficial soil samples and up to 22% in slag fragments were found, together with elevated concentrations (percentage level) of Cu, Co, Ni, Zn and Pb. High concentrations of arsenic (up to 38,000 microg/l) and heavy metals (up to 1700 microg/l Cu and 4700 microg/l Zn) were also found in the in situ sampled soil porewater, highlighting the considerable availability of As, Zn and Cu for uptake by plants and leaching to the ground water. Sequential extractions also indicated a high availability of arsenic and copper in most samples and slag fragments of the industrial site, although poorly reactive phases were encountered as well. pHstat leaching tests confirmed that the present leaching of contaminants is alarming. Moreover, soil acidification will enhance the leaching of contaminants, emphasizing that remediation of the industrial site is urgent. Small scale variability of total metal concentrations and metal speciation, both in the horizontal and vertical direction, and the occurrence of a camouflage layer underline the importance of elaborate sampling for pollution assessment on an industrial site.     

Copper and zinc adsorption onto poorly humified Sphagnum and Carex peat

Peat generally has a high adsorption capacity and has been suggested as an adsorbent for metals in polluted waters. However, the adsorption potential of peat can be expected to be strongly dependent on the chemical properties of the water. In this study, the effect of pH, ionic strength (CaCl2 and NaCl concentrations), and metal concentration on Cu and Zn adsorption onto poorly humified Sphagnum and Carex peat was investigated in batch experiments using a fractional factorial experimental design. The pH value was varied between 4 and 8, the CaCl2 and NaCl concentrations between 1.2-6.2 and 0.4-43 mM, respectively, and the Cu and Zn concentrations between 0.05 and 0.5 mM. The amount of Zn adsorbed increased more with increasing pH than the amount of Cu adsorbed. The effect of NaCl/CaCl2 concentration was minor. It was found that Zn adsorption in particular, but also Cu adsorption, increased more with pH onto Carex peat than onto Sphagnum peat. In the pH interval 4-8, the removal of Zn from the solution increased from 0% to 80% using Carex peat and from 10% to 65% using Sphagnum peat as the adsorbent. The Carex peat sample decreased the Cu concentration by 80% at pH 4 and by 95% at pH 8 and for Sphagnum peat a decrease of 85% was maintained in the pH range investigated. The differences between Sphagnum and Carex peat were attributed to the habitat conditions at the time of peat formation. Carex peat has higher ash, nitrogen and sulphur concentrations, while Sphagnum peat contains a higher amount of uronic acid. In treating polluted waters with peat, a higher degree of metal removal can be expected at high pH values than at low. The removal of Cu, which has a high affinity to the peat surface, was less dependent on pH than Zn removal. Poorly humified Carex peat should be chosen in treating wastewaters high in pH.     

The importance of organic matter distribution and extract soil:solution ratio on the desorption of heavy metals from soils

The lability (mobility and bioavailability) of metals varies significantly with soil properties for similar total soil metal concentrations. We studied desorption of Cu, Ni and Zn, from 15 diverse, unamended soils. These studies included evaluation of the effects of soil:solution extraction ratio and the roles of soil properties on metal desorption. Dcsorption was examined for each metal by computing distribution coefficients (Kd) for each metal in each soil where Kd = [M]soil/[M]solution, Results from soil:solution ratio studies demonstrated that Kd values for the metals tended to increase with increasing soil:solution ratio. This result also held true for distribution of soil organic matter (SOM). Because the soil:solution ratio has a significant effect on measured metal distributions, we selected a high soil:solution ratio to more closely approach natural soil conditions. Copper showed strong affinity to operationally defined dissolved organic matter (DOM). In this study, DOM was operationally defined based on the total organic carbon (TOC) content in 0.45-microm or 0.22-microm filtrates of the extracts. The Kd of Cu correlated linearly (r2 = 0.91) with the Kd of organic matter (Kd-om) where the Kd-om is equal to SOM as measured by Walkley-Black wet combustion and converted to total carbon (TC) by a factor of 0.59. These values representing solid phase TC were then divided by soluble organic carbon as measured by TOC analysis (DOM). The conversion factor of 0.59 was employed in order to construct Kd-om values based on solid phase carbon and solution phase carbon. SOM plays a significant role in the fate of Cu in soil systems. Soil-solution distribution of Ni and Zn, as well as the activity of free Cu2+, were closely related to SOM, but not to DOM. Kd values for Ni, Zn and free Cu2+ in a particular soil were divided by the SOM content in the same soil. This normalization of the Kd values for Ni, Zn, and free Cu2+ to the SOM content resulted in significant improvements in the linear relationships between non-normalized Kd values and soil pH. The semi-empirical normalized regression equations can be used to predict the solubility of Ni and Zn and the activity of free Cu2+ as a function of pH.     

Metal extraction by Alyssum serpyllifolium ssp. lusitanicum on mine-spoil soils from Spain

The efficiency of Alyssum serpyllifolium ssp. lusitanicum (Brassicaceae) for use in phytoextraction of polymetallic contaminated soils was evaluated. A. serpyllifolium was grown on two mine-spoil soils (MS1 and MS2): MS1 is contaminated with Cr (283 mg kg(-1)) and MS2 is moderately contaminated with Cr (263 mg kg(-1)), Cu (264 mg kg(-1)), Pb (1433 mg kg(-1)) and Zn (377 mg kg(-1)). Soils were limed to about pH 6.0 (MS1/Ca and MS2/Ca) or limed and amended with NPK fertilisers (MS1/NPK and MS2/NPK). Biomass was reduced on MS2/Ca due to Cu phytotoxicity. Fertilisation increased biomass by 10-fold on MS1/NPK, but root growth was reduced by 7-fold compared with MS1/Ca. Plants accumulated Mn, Ni and Zn in shoots, and both metal content and transportation were generally greater in MS2 than in MS1. Zinc bioaccumulation factors (BF, shoot([metal])/soil([metal])) were significantly greater in MS2 than in MS1. However, metal yields were greatest in plants grown on MS1/NPK. Concentrations of EDTA-, NH(4)Cl- and Mehlich 3 (M3)-extractable Mn and Zn were greater after plant growth. Concentrations of M3-extractable Cr, Ni, Pb and Zn were increased at the rhizosphere. Sequential extractions showed changes in the metal distribution among different soil fractions after growth. This could reflect the buffering capacity of these soils or the plants' ability to mobilise metals from less plant-available soil pools. Results suggest that A. serpyllifolium could be suitable for phytoextraction uses in polymetallic-contaminated soils, provided Cu concentrations were not phytotoxic. However, further optimisation of growth and metal extraction are required.     

Heavy metal fluxes at the sediment-water interface of three coastal ecosystems from south-west of the Iberian Peninsula

Concentrations of the heavy metals Cr, Cu, Fe and Mn were measured in sediments and porewater samples collected in three coastal ecosystems southwest of the Iberian Peninsula: the Odiel and Barbate River Salt Marshes and the Bay of Cadiz. Both the sediment and the porewater metal concentrations in the Odiel River Salt Marshes are higher than the values found in the Bay of Cadiz and Barbate River Salt Marsh, particularly for copper, a metal associated with mining activity. In porewater, the profiles were not the same as those in the solid phase and reflect the different behaviours of the elements in relation to the redox conditions. The heavy metals Cr and Cu show a typical enrichment in the porewater of the oxic zone. The heavy metals Mn and Fe show an increase in the porewater at the depths where the maximum nitrate and phosphate concentrations occur, respectively. Significant differences between background levels for each heavy metal in the various studied zones exist. Iron and Cu showed larger background levels in the Odiel River Salt Marshes than those in the Cadiz Bay and the Barbate River Salt Marshes. In the Bay of Cadiz the background levels are also high, particularly for Cr. At the Odiel River Salt Marshes the diffusive flux of Cu is high (1.3-230.1 microg cm(-2) year(-1)), which suggests that the Odiel River Salt Marshes are subject to strong contamination by Cu, which is presumably introduced to the sediment in particulate form. In the Bay of Cadiz, Cr is the only metal with positive diffusive flux (2.15 microg cm(-2) year(-1)). It is higher than those obtained in other coastal ecosystems including the Odiel River Salt Marshes. The positive diffusive flux of Cr has been associated with the input of this metal by the naval industry and the manufacturing of car and aircraft components.     

Evaluation of metal concentrations in edible vegetables grown in compost amended soil

Agricultural uses of compost usually have a positive effect on the yield of vegetable crops for human consumption. However, compost that contains heavy metals can transfer these components to soils and plants. To evaluate the contamination levels of metals in soil, compost, and edible vegetables, the Mn, Zn, Pb, Cd, Cu, and Ni total contents were measured. Metal availability in soils, as well as other variables – the pH, CEC (cation exchange capacity), total nitrogen, organic carbon, particle size distribution and mineralogy of the clay fraction – were examined in the soil samples. The analysed compost samples were produced from urban solid waste, cattle manure, and edible vegetable and tree pruning residues. The values of pH, CEC, total nitrogen, organic matter, exchangeable hydrogen and carboxylic groups were measured in the compost samples. Of the six metals examined in the soils, in general, Mn and Zn attained the highest concentrations, followed by Cu. Relatively high Mn, Zn, Cu, Cd and Pb concentrations were found in the soils. Metal concentrations extracted with DTPA were below the critical levels in soils, i.e. the levels above which toxicity is likely. In general, Zn, Pb, Cd, Cu and Ni concentrations in compost were lower than those reported by other workers, while Mn levels were within the range for this metal in compost. The results showed that there was an effect of the vegetable type (p < 0.01) for all the parameters examined. High Pb concentrations were found in lettuce and chive as compared with the tolerance limit for this metal in fresh vegetables in Brazil. Cadmium concentrations were also enhanced in the fresh vegetables compared with the typical concentrations of metals in plants. Zinc, Cu, Cd, and Ni concentrations were lower than the tolerance limits established for foods by the Brazilian legislation.     

Distribution and behavior of trace metals in the sediment and porewater of a tropical coastal wetland

Vertical profiles (0-30 cm below surface) of four trace metals-Cadmium (Cd), Chromium (Cr), Lead (Pb) and Zinc (Zn)-in the sediment and sediment porewater of an ecologically important intertidal mudflat in the Mai Po and Inner Deep Bay Ramsar Site were thoroughly studied over a period of 10 months (from March 1999 to January 2000). Two surveys, one in summer and another in winter, involving a total of eight sampling stations were conducted to study the seasonal variation of the remobilization characteristics of these trace metals in the mudflat sediment. The range of depth averaged concentration of these trace metals in the mudflat sediment was: 0.3-0.8 microg/g (Cd); 9.8-91.0 microg/g (Cr); 7.3-69.1 microg/g (Pb); and 39.5-192.0 microg/g (Zn), while that in the sediment porewater was: 0.3-121.1 microg/l (Cd); 3.0-2704.1 microg/l (Cr); 2.6-105.6 microg/l (Pb); and 32.6-4238.3 microg/l (Zn). In general, levels of dissolved trace metals in the sediment porewater were much higher in the summer than in the winter while their concentrations in the sediment were more or less the same throughout the year. Enrichment of Cd, Pb and Zn in the sediment porewater of the upper oxic layer and that of Cr in the oxic-sub-oxic boundary was generally observed. Regions in the vicinity of the Mai Po mangroves and the river mouths of Shenzhen River and Shan Pui River were found to be hotspots of trace metal pollution. Benthic diffusive fluxes of trace metals from the mudflat sediment were also estimated. Of the four trace metals, cadmium showed the greatest tendency toward remobilization from the sediment phase to the more bio-available porewater phase.     

Localised remobilization of metals in a marine sediment

Trace metals and Fe and Mn were measured at vertical spatial resolutions of 2.5 and 5 mm in the top 35 cm of the profundal sediment of a Scottish sea-loch using DGT (diffusive gradients in thin films) technique. DGT probes lower adjacent metal concentrations in pore waters and induce a flux of metal from the solid phase to porewater. The concentrations of metals in porewaters at the interface of the probe were measured during its deployment in a box core. These measurements reflect porewater concentrations of metals and their rates of resupply from the local solid phase of a very small volume (25 microl) of sediment. There was pronounced horizontal and vertical structure in the interfacial concentrations. Horizontal variations were shown by results from adjacent DGT assemblies being markedly different in detail, while vertical structure was measured directly by the DGT-depth profiles. Iron and Mn varied systematically with depth, with both broad and detailed features of Co aligning with those of Mn. There was, however, evidence of additional localised sources of Co that were apparently unrelated to the redox behaviour that Mn typifies, but associated with the remobilization of Ni, possibly from mineral dissolution. Arsenic(III) was remobilized in well-defined zones. Detailed correspondence of As(II) with some Fe features suggest that its release is mechanistically-related to iron oxide dissolution, but the 3 orders of magnitude higher concentrations of Fe may sometimes obscure the association. These results demonstrate that, within sediments, metals may be released in discrete locations that are not measured by conventional porewater sampling techniques due to their horizontal averaging.     

Sorption and bioavailability of heavy metals in long-term differently tilled soils amended with organic wastes

In this study, bioavailability and enrichment studies were focused on Cd, Zn and Cu in two different soils (sandy loam and silt loam), which were treated with compost and sewage sludge, respectively, both under conventional tillage (CT) and no tillage (NT). Long-term NT resulted in a significant increase in Cd and Zn extracted by aqua regia in a soil profile (0-25 cm), especially in the 0-3 cm layer. In the sandy loam, a slight increase in cadmium due to sewage sludge application was observed. Results from EDTA-extractable heavy metal analyses were not consistent but NH(4)NO(3)-extractable concentrations were significantly lower in the NT soil. Bioavailability of heavy metals was reduced in the long-term NT, resulting in lower uptake of Cd and Zn by plants and accumulation in the soil. The effect of tillage on enrichment of heavy metals in soils was more significant than the impact of the fertilisation by means of legally allowable application rates of organic wastes. This work suggests that non-tilled soils enriched in heavy metals should not be amended with organic waste in the long term.     

Physico-chemical and biological parameters determine metal bioavailability in soils

The Netherlands Stimulation program on System-oriented Ecotoxicological Research focused on three study areas, including two floodplains and a peaty grassland. All three areas were polluted with metals, with total soil concentrations often exceeding Dutch Intervention Values. The floodplain areas showed a homogeneous distribution of metal pollution, while pollution in the peaty area was more heterogeneous. This study aimed at establishing possible general trends in metal bioavailability by combining results obtained at the three different study sites. Available metal concentrations, measured as pore water or 0.01 M CaCl₂ extractable concentrations in soil, were lowest in the floodplain soils, probably due to the high pH (> 7.0) and high organic matter (8-30%) and clay contents (13-42%). In the peaty soil, having a lower soil pH (4.5-6.5) but higher organic matter contents (38-60%), in some but not all samples Cu concentrations in pore water and Cu and Pb concentrations in 0.01 CaCl₂ extracts were higher than in non-polluted reference areas. Plants in the floodplain areas had only low metal concentrations in their leaves, but soil invertebrates and small mammals did contain elevated concentrations in their body. Cd showed high levels in earthworms, snails and small mammals, while also Cu levels were sometimes increased in earthworms, millipedes and small mammals from the floodplain areas. Earthworms from the peaty area contained increased levels of Cu and Pb. These results suggest that metal bioavailability cannot be predicted from available concentrations in pore water or 0.01 M CaCl₂ soil extracts, but requires measurement of biota and more insight into the biodynamics of metal uptake.     

Metal content of dandelion (Taraxacum officinale) leaves in relation to soil contamination and airborne particulate matter.

The global distribution of the common dandelion (Taraxacum officinale Weber, sensu lato; Asteraceae), along with its ability to tolerate a wide range of environmental conditions, make this 'species' a particularly attractive candidate to evaluate for its value as a biological monitor of environmental metal contamination. To examine the metal content of dandelion leaves in relation to environmental metal levels, the concentrations of eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were analyzed in leaf and soil samples collected at 29 sites in the mid-western United States differentially impacted by pollution. Sites were chosen primarily to cover a range of annual mean 24-h airborne particulate matter < or = 10 microm (hereafter, PM10) exposure, with PM10 levels varying from those found in isolated rural areas to levels typical of the most industrialized urban locations in the mid-western United States. A positive. significant correlation was detected between soil concentrations of each metal and measures of PM10 at a site, signifying that airborne particulate matter is a good indicator of soil metal contamination. Leaf concentrations of four of the eight metals (Cr, Mn, Pb and Zn) examined were found to increase significantly as the soil levels of these metals increased, but the percentage of the total variation explained by the relationship in these cases was generally low. This latter finding, along with the lack of a significant relationship between leaf and soil concentrations for the four other metals, indicate that the factors affecting metal absorption from the soil by dandelions are complex and that, aside from soil metal concentrations, other soil, plant and/or other environmental factors affect metal uptake. There was also no evidence that leaf metal concentrations were positively correlated with PM10. In addition, the concentrations of some metals (Cu, Fe, Mn, Pb and Zn) were significantly higher in leaves collected in the fall compared to those collected at the same sites in the spring. These findings suggest that dandelions may not be a particularly effective tool for quantifying levels of environmental metal contamination, at least on the scale of pollution typifying industrialized urban areas of the mid-western United States.     

Soil arsenic availability and the transfer of soil arsenic to crops in suburban areas in Fujian Province, southeast China

The bioavailability, soil-to-plant transfer and associated health risks of arsenic in soils collected from paddy rice fields and vegetable fields in suburban areas of some major cities of Fujian Province were investigated. The total soil concentrations of arsenic ranged from 1.29 to 25.28 mg kg(-)(1) with a mean of 6.09 mg kg(-)(1). Available (NaH(2)PO(4)-extractable) arsenic content accounted for 0.7-38.2% of total soil arsenic and was significantly correlated with total soil arsenic content. For the vegetable soils, the available fraction (ratio of available As to total As) of arsenic decreased with decreasing silt (particle size 0.02-0.002 mm) and free iron (DCB extractable) contents and with increasing soil pH and organic matter content. The available fraction of arsenic in the paddy rice soils increased with increasing free iron and organic matter contents and decreasing soil pH and silt content. The correlation of NaH(2)PO(4)-extractable arsenic with the arsenic concentration of the vegetables was much better than that of total As. The transfer factor based on the soil available arsenic (TF(avail)) was chosen to compare the accumulation ability of the various crops. The TF(avail) values of rice grains (air-dried weight basis) ranged between 0.068 and 0.44 and were higher than those of the vegetables, ranging from 0.001 to 0.12. The accumulation ability of the crops decreased in the order of rice>radish>water spinach>celery>onion>taro>leaf mustard>fragrant-flowered garlic>pakchoi>Chinese cabbage>lettuce>garlic>cowpea>cauliflower>bottle gourd>towel gourd>eggplant. Daily consumption of rice and other As-rich vegetables could result in an excessive intake of arsenic, based on the provisional tolerable intake for adults for arsenic recommended by WHO.     

An ecotoxicity assessment of contaminated forest soils from the Kola Peninsula

Point source copper and nickel contamination emanating from smelters of the Kola Peninsula, NW Russia, has been observed since the mid-1960s. Previous studies have concentrated on the spatial distribution of heavy metals and their effects on forest ecology and indigenous mammals and birds. Soil is perceived as the major repository for the metal pollutants but there is a need to link the soil concentration of pollutants on the Kola Peninsula with biological parameters. Many standard methods currently used in soil ecotoxicology are developed and refined with artificial amendments and rarely modified for use in historically contaminated environments. In this study, forest soils were sampled along a 34 km transect from the smelter and analysed both chemically and with a range of ecologically relevant biological tests. Soil respiration, total nematode count, microbial heterotrophic numbers and minimal inhibitory concentrations to copper and nickel were carried out on bulk soil. The soil pore water was tested with bacterial and fungal bioluminescence-based biosensors. The heterotrophic numbers and their inhibitory concentration showed strong correlation with heavy metal concentrations while decreasing biosensor luminescence was related to increasing copper concentrations present in the pore waters. Overall, there were considerable impacts on some microbial parameters but other measures including respiration and nematode populations were insensitive to pollutant levels. While chemical analysis of heavy metals proved essential in defining the extent of contamination, environmentally relevant ecotoxicological tests complemented these data by demonstrating pollutant impact. Ecotoxicological approaches that study both the bulk soil and pore water may represent the key to understanding the fate of heavy metal in soils.     

A simplified equilibrium model for sorption of heavy metal ions from aqueous solutions on chitosan

The amounts of sorption of Cu2 , Ni2+, and Zn2+ from water on cross-linked chitosan were measured. Experiments were performed as a function of initial pH (2-5), total metal concentration (0.77-17 mol/m3), and metal concentration ratio (0.25-4) at 25 degrees C in single- and binary-metal systems. The sorption was so highly pH dependent that the isotherm could not be described by one specific equation. A simplified equilibrium model was thus proposed considering competitive sorption of proton and metal ions. The number of active sites on chitosan bound with one metal ion was adjustable and model parameters could be graphically determined. Given initial metal concentrations and solution pH, the proposed model could predict the amounts of sorption of proton and metals as well as the equilibrium pH. In general, application of the model parameters calculated in single-metal systems to the prediction of sorption in binary-metal systems was not satisfactory due to a remarkable effect of competitive sorption.     

Development of multimetal binding model and application to binary metal biosorption onto peat biomass

Biosorption of Cr(3+), Cu(2+) and Cd(2+) from binary metal solutions onto peat in the batch systems was investigated at pH 4. The order of maximum uptake was Cr>or=Cu>Cd and maximum uptake levels of ca. 0.4 mmol/g were observed for chromium and copper while cadmium was taken up to a maximum of ca. 0.2 mmol/g. Co-ion competition resulted in up to 70 percent decrease of primary metal uptake. A novel approach to multicomponent sorption modelling involving regression to the total metal taken up was adopted. Two extended Langmuir-type models were found to exhibit good fit to the experimental data. Using the simpler model of these, three-dimensional sorption surfaces were generated which describe the metal uptake as a function of equilibrium concentrations of both metals. These methods allow prediction of metal uptakes over a continuum of concentrations of both metals in binary systems.     

The potential of Lolium perenne for revegetation of contaminated soil from a metallurgical site

A greenhouse study was carried out to determine the possibility of using Lolium perenne for revegetation of soil from a former ferrous metallurgical plant (Naples, South Italy) contaminated by Cu, Pb and Zn at levels above current Italian regulatory limits. Surface soil samples (0-40 cm) from the facility area where raw minerals were disposed (RM1 and RM2), from a nearby unpolluted cultivated soil (C) as control and a 1:3 mixture of the control with the polluted ones (RM1+C and RM2+C) were utilized for the experiment. Revegetation trials were conducted in the greenhouse. At 90 days from seeding, shoot length, chlorophyll content, biomass yield, plant metal uptake and changes of organic carbon content and metal distribution among soil extractable phases defined by sequential extraction were determined. In the mixed substrates (RM1+C and RM2+C) concentrations of Cu, Pb and Zn were still two to three times higher than the Italian regulatory limits. Plants were healthy with 100% survival in all substrates, with no macroscopic symptoms of metal toxicity. The high pH of the soil could be one of the most important parameters responsible for the limited plant availability of the metals. On RM1, RM2 and mixed media, plants experienced retarded growth, reduced shoot length and biomass yield and higher total chlorophyll content compared to those cropped on the control soil, without any evident phytotoxic symptoms. In RM1 and RM2, the plant contents of Cu (19.3 and 12.6 mg kg(-1)), Pb (0.98 and 0.67 mg kg(-1)) and Zn (99 and 88 mg kg(-1)) were higher than that of plants grown on non-contaminated soil (Cu 10.1, Pb < 0.2, Zn 79 mg kg(-1)), but still in the range of physiologically acceptable levels. The distribution of metals in soil was slightly affected by Lolium growth with changes only regarding the organic-bound Cu and Zn pool, with reduction up to 24%. Results indicated that an acceptable healthy vegetative cover can be achieved on the contaminated soil by the proposed revegetation approach and that metals will remain stable over the study period with slight variation of the more available metal forms.     

Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants

Sewage sludges obtained from seven wastewater treatment plants from the province of Salamanca, Spain, were periodically sampled to determine seasonal and time variation of their elemental composition over 2000 to 2002. The aim of this paper was to provide additional insight to evaluate the potential environmental impact following soil incorporation of these materials as amendments. Aqua regia extractable metals (pseudo total content) of Cd, Cr, Cu, Ni, Pb and Zn were determined and furthermore, the main chemical forms of metals within the sludge were evaluated using a five-step fractionation procedure. All the studied sludges displayed high fertility properties due to their richness of OC, P and K. Total mean concentrations of Cd, Cr, Cu, Ni, Pb and Zn in the sludges were within the regulation of the Spanish legislation. Using an multifactor analysis of variance, significant differences between Cr, Cu, Ni, Pb and Zn pseudo total contents (p<0.01) of sludges at different sites were found while the Cd content was statistically similar. Also significant differences were found between these pseudo total contents of heavy metals in samples collected along the time after three years (0.001相似文献