Effect of in situ soil amendments on arsenic uptake in successive harvests of ryegrass (Lolium perenne cv Elka) grown in amended As-polluted soils

Several iron-bearing additives, selected for their potential ability to adsorb anions, were evaluated for their effectiveness in attenuation of arsenic (As) in three soils with different sources of contamination. Amendments used were lime, goethite (alpha-FeOOH) (crystallised iron oxide) and three iron-bearing additives, iron grit, Fe(II) and Fe(III) sulphates plus lime, applied at 1% w/w. Sequential extraction schemes conducted on amended soils determined As, Cu, Zn and Ni fractionation. Plant growth trials using perennial ryegrass (Lolium perenne var. Elka) assessed shoot As uptake. This was grown in the contaminated soils for 4 months, during which time grass shoots were successively harvested every 3 weeks. Goethite increased biomass yields, but clear differences were observed in As transfer rates with the various iron oxides. In conclusion, whilst Fe-oxides may be effective in situ amendments, reducing As bioavailability, their effects on plant growth require careful consideration. Soil-plant transfer of As was not completely halted by any amendment.     

Batch and column studies of the stabilization of toxic heavy metals in dredged marine sediments by hematite after bioremediation

The management of dredged sediments is an important issue in coastal regions where the marine sediments are highly polluted by metals and organic pollutants. In this paper, mineral-based amendments (hematite, zero-valent iron and zeolite) were used to stabilize metallic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in a contaminated marine sediment sample. Mineral-based amendments were tested at three application rates (5 %, 10 %, and 15 %) in batch experiments in order to select the best amendment to perform column experiments. Batch tests have shown that hematite was the most efficient amendment to stabilize inorganic pollutants (As, Cd, Cu, Mo, Ni, Pb, and Zn) in the studied sediment. Based on batch tests, hematite was used at one application rate equal to 5 % to conduct column experiments. Column tests confirmed that hematite was able to decrease metal concentrations in leachates from stabilized sediment. The stabilization rates were particularly high for Cd (67 %), Mo (80 %), and Pb (90 %). The Microtox solid phase test showed that hematite could decrease significantly the toxicity of stabilized sediment. Based on batch and column experiments, it emerged that hematite could be a suitable adsorbent to stabilize metals in dredged marine sediment.     

The effects of chemical remediation treatments on the extractability and speciation of cadmium and lead in contaminated soils

Two rural soils contaminated by cadmium (Cd) and lead (Pb) were used to evaluate the effect of different chemical treatments on changes in speciation and extractability of Cd and Pb, and in phytoavailability to wheat. Triplicates of seven chemical treatments were tested to compare and evaluate the remediation techniques for contaminated soils using pot experiments. Treatments applied were calcium carbonate, a high quantity of phosphate salt, hog composts, iron oxide, manganese oxide, zeolite, and unamended control. Wheat (Triticum aestivum) was planted in the different amended soils for a further one month to evaluate the effectiveness of treatments on uptake of Cd and Pb by the wheat shoots. Results indicated that addition of calcium carbonate, manganese oxide, or zeolite reduces the extractability of Cd or Pb in both soils, and significantly reduce the uptake of Cd and Pb by wheat shoots. Changes in the extractability and metal sequential fractionations indicate that the exchangeable (or available) form of Cd and Pb in two soils can be transformed into unavailable forms after these amendments.     

A remediation strategy based on active phytoremediation followed by natural attenuation in a soil contaminated by pyrite waste

Phytoremediation of metal-polluted soils can be promoted by the proper use of soil amendments and agricultural practices. A 4-year phytoremediation programme was applied to a site affected by the toxic spill of pyrite residue at Aznalcóllar (Spain) in 1998, contaminated with heavy metals (Zn, Cu, Pb, Cd) and arsenic. This consisted of active phytoremediation, using organic amendments (cow manure and compost) and lime and growing two successive crops of Brassica juncea (L.) Czern., followed by natural attenuation without further intervention. Changes in soil pH, extractable metal and As concentrations, organic carbon content and microbial biomass was evaluated. The initial oxidation of metal sulphides from pyrite residues released soluble metals and reduced soil pH to extremely acidic values (mean 4.1, range 2.0-7.0). The addition of lime (up to 64 t ha(-1)) increased soil pH to adequate values for plant growth, resulting in a significant decrease in DTPA-extractable metal concentrations in all plots. The natural attenuation phase showed also a decrease in extractable metals. Organic treatments increased the soil total organic carbon, which led to higher values of microbial biomass (11.6, 15.2 and 14.9 g kg(-1) TOC and 123, 170 and 275 microg g(-1) biomass-C in control, compost and manure plots, respectively). Active phytoremediation followed by natural attenuation, was effective for remediation of this pyrite-polluted soil.     

Remediation of contaminated agricultural soils near a former Pb/Zn smelter in Austria: batch, pot and field experiments

Metal contaminated crops from contaminated soils are possible hazards for the food chain. The aim of this study was to find practical and cost-effective measures to reduce metal uptake in crops grown on metal contaminated soils near a former metal smelter in Austria. Metal-inefficient cultivars of crop plants commonly grown in the area were investigated in combination with in-situ soil amendments. A laboratory batch experiment using 15 potential amendments was used to select 5 amendments to treat contaminated soil in a pot study using two Barley (Hordeum vulgare L.) cultivars that differed in their ability to accumulate cadmium. Results from this experiment identified 3 of these amendments for use in a field trial. In the pot experiment a reduction in ammonium nitrate extractable Cd (<41%) and Pb (<49%) compared to the controls was measured, with a concurrent reduction of uptake into barley grain (Cd<62%, Pb<68%). In the field extractable fractions of Cd, Pb, and Zn were reduced by up to 96%, 99%, and 99%, respectively in amended soils.     

The effects of biochars from rice residue on the formation of iron plaque and the accumulation of Cd, Zn, Pb, As in rice (Oryza sativa L.) seedlings

A historically multi-metal contaminated soil was amended with biochars produced from different parts of rice plants (straw, husk and bran) to investigate how biochar can influence the mobility of Cd, Zn, Pb and As in rice seedlings (Oryza sativa L.). Rice shoot concentrations of Cd, Zn and Pb decreased by up to 98%, 83% and 72%, respectively, due to biochar amendment, though that of As increased by up to 327%. Biochar amendments significantly decreased pore water concentrations (C_pw) of Cd and Zn and increased that of As. For Pb it depended on the amendment. Porewater pH, dissolved organic carbon, dissolved phosphorus, silicon in pore water and iron plaque formation on root surfaces all increased significantly after the amendments. The proportions of Cd and Pb in iron plaque increased by factors 1.8-5.7 and 1.4-2.8, respectively; no increase was observed for As and Zn. Straw-char application significantly and noticeably decreased the plant transfer coefficients of Cd and Pb. This study, the first to investigate changes in metal mobility and iron plaque formation in rice plants due to amending a historically contaminated soil with biochar, indicates that biochar has a potential to decrease Cd, Zn and Pb accumulations in rice shoot but increase that of As. The main cause is likely biochar decreasing the C_pw of Cd and Zn, increasing the C_pw of As, and increasing the iron plaque blocking capacity for Cd and Pb.     

Effect of chemical amendments on the concentration of cadmium and lead in long-term contaminated soils

The availability of metal in contaminated soil can be reduced by the addition of soil amendments. The objectives of this study are to study the effects of applying different soil amendments on the concentration of Cd and Pb in soil solution, DTPA or EDTA extractable Cd and Pb, and the uptake of Cd and Pb by wheat (Triticum vulgare) when growing in long-term Cd and Pb-contaminated soils, more than 20 years. The soil amendments, including check, compost, zinc oxide, calcium carbonate, calcium carbonate mixed with zinc oxide, and calcium carbonate mixed with compost, were conducted in a four replicates pot cultural study. The amended soils were incubated for six months under 60% of water holding capacity. Following incubation, wheat was grown for four months in greenhouse. Analyses of Cd concentration demonstrated a significant decrease in soil solution concentration and DTPA or EDTA extractable in soils amended with calcium carbonate or calcium carbonate mixed with ZnO (or compost) (p<0.01). These amendments can significantly reduce the Cd concentration in the grain, leaf and stem, or reduce the total Cd uptake in all parts of wheat species grown in highly contaminated soil amended with calcium carbonate or calcium carbonate mixed with ZnO (or compost) (p<0.01). The concentration of Cd in soil solution and extracted with DTPA or EDTA can predict the Cd concentration in wheat, especially for soil solution.     

Reduction of heavy metal content in Hiroshima Bay oysters (Crassostrea gigas) by purification

Cultured oysters from Hiroshima Bay were analysed to determine the content of nine trace elements, cadmium (Cd), lead (Pb), chromium (Cr), arsenic (As), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), and iron (Fe) and compared with oysters treated for 48 h in both artificial sea water and a solution of 0.5% ethylenediaminetetraacetic acid (EDTA) in artificial sea water. It was found that the values of As and Fe in both groups of treated oysters were significantly lower than in the untreated oysters and that the Pb and Mn levels tended to be lower. It was also found that oysters treated in 0.5% EDTA solution in artificial sea water had lower levels of Cd and Cu than the oysters treated only in artificial sea water.     

Heavy metal leaching from coal fly ash amended container substrates during Syngonium production

Coal fly ash has been proposed to be an alternative to lime amendment and a nutrient source of container substrates for ornamental plant production. A great concern over this proposed beneficial use, however, is the potential contamination of surface and ground water by heavy metals. In this study, three fly ashes collected from Florida, Michigan, and North Carolina and a commercial dolomite were amended in a basal substrate. The formulated substrates were used to produce Syngonium podophyllum Schott 'Berry Allusion' in 15-cm diameter containers in a shaded greenhouse. Leachates from the containers were collected during the entire six months of plant production and analyzed for heavy metal concentrations. There were no detectable As, Cr, Hg, Pb, and Se in the leachates; Cd and Mo were only detected in few leachate samples. The metals constantly detected were Cu, Mn, Ni, and Zn. The total amounts of Cu, Mn, Ni, and Zn leached during the six-month production period were 95, 210, 44, and 337 microg per container, indicating that such amounts in leachates may contribute little to contamination of surface and ground water. In addition, plant growth indices and fresh and dry weights of S. podophyllum 'Berry Allusion' produced from fly ash and dolomite-amended substrates were comparable except for the plants produced from the substrate amended with fly ash collected from Michigan which had reduced growth indices and fresh and dry weights. Thus, selected fly ashes can be alternatives to commercial dolomites as amendments to container substrates for ornamental plant production. The use of fly ashes as container substrate amendments should represent a new market for the beneficial use of this coal combustion byproduct.     

Enhanced solubilization of arsenic and 2,3,4,6 tetrachlorophenol from soils by a cyclodextrin derivative

The application of extracting aqueous solutions with cyclodextrins in several soil remediation technologies has been increasingly studied but little is known about their removal capacities toward the inorganic species. Herein, the effectiveness of cyclodextrins (CDs) in extracting arsenic, copper, and iron from a mining soil is presented. In a preliminary test of four types of CD aqueous solutions, only the addition of carboxylmethyl-beta-cyclodextrin CMCD (a cyclodextrin derivative) led to a significant enhancement in arsenic removal. An increase in the concentration of copper and iron in the leachates was also observed with CMCD. Kinetic study of arsenic release was carried out at two temperatures (20 and 35 degrees C). The arsenic concentration in the leachates increases with increasing cyclodextrin concentration. At an 80 mM CMCD concentration, arsenic, copper, and iron released in filtrates were about 20-, 1,000-, and 4,000-fold greater, respectively, than that obtained using deionized water. In the soil system, the CMCD capacity removal was found to be higher for cations than for arsenic. Because the tetrachlorophenol can co-occur with arsenic and copper in several contaminated sites, its solubilization by CMCD was also investigated. Extraction experiments were performed to extract 2,3,4,6 tetrachlorophenol (TeCP) in spiked soil with CMCD. The results of batch experiments have shown that CMCD could significantly increase the TeCP extraction from soil. CD sorption on soils as quantified by a fluorescence technique was low, indicating no significant loss of CD during the leaching experiments. The use of CMCD as a flushing agent to enhance the removal of both inorganic and organic pollutants from mixed-contaminated soils appears as a promising remediation method.     

Progress in assisted natural remediation of an arsenic contaminated agricultural soil

A contaminated soil was collected in a field adjacent to a derelict As((III)) smelter in Reppel (Bocholt, Belgium). A single soil treatment (% by soil weight) based on either iron grit (SS, 1%), beringite (B, 5%), or iron grit (1%) + beringite (5%) (BSS) was applied. Untreated and treated Reppel soils and a control soil were placed in lysimeters inside a greenhouse and cropped annually. The efficiency of soil treatments in decreasing As and metals in exposure sources and restoring soil functions was assessed 6 years after the treatments commenced. Decreases in extractable Cd, Mn, Zn and As occurred in the BSS soil. Only BSS treatment reduced both As and metal concentrations in leachates. BSS treatment produced best growth of lettuce and cabbage, the highest shoot and pod yields for dwarf bean, the lowest As, Cd and Zn concentrations in plant tissues, and partly restored Rhizobium nodulation on bean roots. The epigeic earthworm (Dendrobaena octaedra) could only survive in the BSS soil. Depurated living worms from the BSS soil had Cd concentration similar to those in control worms, but higher As, Ca, Fe, and Zn concentrations. Based on physiologically based extraction test (PBET), As bioaccessibility was reduced from 12% (untreated soil) to 7.4% (BSS) and 3% (SS), but only the SS treatment decreased the bioaccessibility of Cd (-30%) and Pb (-35%). The range of chemical and biological indicators suggested that BSS amendment was the most effective treatment for restoration of normal soil functions 6 years after initial treatment of the Reppel soil.     

Metals and arsenic in soils and corresponding vegetation at Central Elbe river floodplains (Germany)

Floodplain soils at the Elbe river are frequently polluted with metals and arsenic. High contents of these pollutants were detected down to subsoil layers. NH4NO3-extractable (phytoavailable) Cd, Ni, and Zn were elevated in horizons with high acidity. Among five common floodplain plant species, Artemisia vulgaris showed highest concentrations of Cd, Cu, and Hg, Alopecurus pratensis of As and Phalaris arundinacea of Ni, Pb, and Zn. Relationships were weak between metal concentrations in plants and phytoavailable stocks in soil. As and Hg uptake seems to be enhanced on long submerged soils. Enrichments of Cd and Hg are linked to a special plant community composition. Grassland herbage sampled in July/August revealed higher concentrations of As (+122%), Hg (+124%), and Pb (+3723%) than in May. To limit harmful transfers into the food chain, low-lying terraces and flood channels revealing highest contaminations or phytoavailabilities should be excluded from mowing and grazing.     

Influence of flooding and metal immobilising soil amendments on availability of metals for willows and earthworms in calcareous dredged sediment-derived soils

Soil amendments previously shown to be effective in reducing metal bioavailability and/or mobility in calcareous metal-polluted soils were tested on a calcareous dredged sediment-derived soil with 26 mg Cd/kg dry soil, 2200 mg Cr/kg dry soil, 220 mg Pb/kg dry soil, and 3000 mg Zn/kg dry soil. The amendments were 5% modified aluminosilicate (AS), 10% w/w lignin, 1% w/w diammonium phosphate (DAP, (NH₄)₂HPO₄), 1% w/w MnO, and 5% w/w CaSO₄. In an additional treatment, the contaminated soil was submerged. Endpoints were metal uptake in Salix cinerea and Lumbricus terrestris, and effect on oxidation-reduction potential (ORP) in submerged soils. Results illustrated that the selected soil amendments were not effective in reducing ecological risk to vegetation or soil inhabiting invertebrates, as metal uptake in willows and earthworms did not significantly decrease following their application. Flooding the polluted soil resulted in metal uptake in S. cinerea comparable with concentrations for an uncontaminated soil.     

Effect of ageing on the availability of heavy metals in soils amended with compost and biochar: evaluation of changes in soil and amendment properties

Remediation strategies using soil amendments should consider the time dependence of metal availability to identify amendments that can sustainably reduce available pollutant concentrations over time. Drying-wetting cycles were applied on amendments, soils and soil + amendment mixtures, to mimic ageing at field level and investigate its effect on extractable Cd, Cu, Ni, Pb and Zn concentrations from three contaminated soils. The amendments investigated were municipal waste organic compost and biochars. The amendments, soils and mixtures were characterised by their physicochemical properties at different ageing times. The amendments were also characterised in terms of sorption capacity for Cd and Cu. The sorption capacity and the physicochemical properties of the amendments remained constant over the period examined. When mixed with the soils, amendments, especially the compost, immediately reduced the extractable metals in the soils with low pH and acid neutralisation capacity, due to the increase in pH and buffering capacity of the mixtures. The amendments had a relatively minor impact on the metal availability concentrations for the soil with substantially high acid neutralisation capacity. The most important changes in extractable metal concentrations were observed at the beginning of the experiments, ageing having a minor effect on metal concentrations when compared with the initial effect of amendments.

     

Heavy metal immobilization by chemical amendments in a polluted soil and influence on white lupin growth

The effects of chemical amendments (zeolite, compost and calcium hydroxide) on the solubility of Pb, Cd and Zn in a contaminated soil were determined. The polluted soil was from the Southwest Sardinia, Italy. It showed very high total concentrations of Pb (19663 mgkg(-1) d.m.), Cd (196 mgkg(-1) d.m.) and Zn (14667 mgkg(-1) d.m.). The growth and uptake of heavy metals by white lupin (Lupinus albus L., cv. Multitalia) in amended soils were also studied in a pot experiment under greenhouse conditions. Results showed that the amendments increased the residual fraction of heavy metals in the soils, and decreased the heavy metals uptake by white lupin compared with the unamended control. Among the three amendments, compost and Ca(OH)2 were the most efficient at reducing Pb and Zn uptake, while zeolite was the most efficient at reducing Cd uptake by the plants. White lupin growth was better in amended soils than in unamended control. The above ground biomass increased with a factor 1.8 (soil amended with zeolite), 3.6 (soil amended with compost) and 3.1 (soil amended with Ca(OH)2) with respect to unamended soil. The roots biomass increased with a factor 1.4 (soil amended with zeolite), 5.6 (soil amended with compost) and 4.8 (soil amended with Ca(OH)2). Results obtained suggest that the soil chemical treatment improved the performance of crops by reducing bioavailability of metals in the soils. However it would be therefore interesting to find a suitable mixture of these amendments to contemporarily immobilize the three main pollutants in the polluted soils.     

Effects of heavy metals on growth and arsenic accumulation in the arsenic hyperaccumulator Pteris vittata L

The effects of Cd, Ni, Pb, and Zn on arsenic accumulation by the arsenic hyperaccumulator Pteris vittata were investigated in a greenhouse study. P. vittata was grown for 8 weeks in an arsenic-contaminated soil (131 mg As kg(-1)), which was spiked with 50 or 200 mg kg(-1) Cd, Ni, Pb, or Zn (as nitrates). P. vittata was effective in taking up arsenic (up to 4100 mg kg(-1)) and transporting it to the fronds, but little of the metals. Arsenic bioconcentration factors ranged from 14 to 36 and transfer factors ranged from 16 to 56 in the presence of the metals, both of which were reduced with increasing metal concentration. Fern biomass increased as much as 12 times compared to the original dry weight after 8 weeks of growth (up to 19 g per plant). Greater concentrations of Cd, Ni, and Pb resulted in greater catalase activity in the plant. Most of the arsenic in the plant was present as arsenite, the reduced form, indicating little impact of the metals on plant arsenic reduction. This research demonstrates the capability of P. vittata in hyperaccumulating arsenic from soils in the presence of heavy metals.     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验,测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣,并为矿区重金属污染土壤的修复提供技术支持,采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理;通过浸出毒性实验对固化/稳定化处理效果进行综合分析,试图寻求一种最佳的稳定剂。结果表明,无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加,样品浸出液的pH都有升高,As、Cd的浸出浓度都有明显下降,而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中,粉煤灰混合堆肥化污泥的处理效果最好,浸出液的pH值达到7.82,As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳,同时具有以废治污的资源化生态效能。     

钝化剂在烟草植物修复铅镉污染土壤中的作用

重金属钝化剂可以改变土壤中重金属的形态,降低其在土壤中的有效浓度、植物毒性及生物有效性,影响污染土壤中植物的生长及其对重金属的吸收。在温室盆栽条件下研究了施加羟基磷灰石（HA）、纳米羟基磷灰石（nHA）、纳米零价铁（nFe0）和纳米TiO2（nTiO2）对烟草植物修复铅镉污染土壤的作用。结果表明,HA降低土壤中Ph、cd的有效性、促进烟草生长、增加了烟草叶、茎、根中cd的吸收量和根系中Pb的吸收量,有利于Ph、cd的钝化和植物修复。nHA也可以降低土壤中Pb、cd的有效性,增加了烟草叶中cd的吸收量,有利于Pb、cd的钝化和cd的植物提取。nFe0和nTiO2：对于土壤Pb和cd的钝化作用和植物修复均没有显著影响。综合来看,HA最适合应用于烟草植物修复铅镉污染土壤。     

Lead and zinc bioavailability to Eisenia fetida after phosphorus amendment to repository soils

Four phosphorus forms were investigated as potential soil amendments to decrease the bioavailability of Pb and Zn in two repository soils to the earthworm, Eisenia fetida. Treatments were evaluated by examining differences in bioaccumulation factors between amended and non-amended soils. Triple super phosphate at 5000 mg P/kg decreased both Pb and Zn bioavailability in both soils. Rock phosphate at 5000 mg P/kg decreased Zn bioavailability, but not Pb bioavailability in both repository soils. Monocalcium phosphate and tricalcium phosphate at 5000 mg P/kg did not significantly decrease Pb or Zn bioavailability to earthworms in either repository soil. In order to optimize phosphorus amendments, additional phosphorus (up to 15,000 mg P/kg) and lowered pH were used in a series of tests. The combination of lowering the pH below 6.0 and increasing phosphorus concentrations caused complete mortality in all triple super phosphate amended soils and partial mortality in the highest rock phosphate amended soils. Results indicate that triple super phosphate and rock phosphate are viable soil amendments, but care should be taken when optimizing amendment quantity and pH so that adverse environmental effects are not a by-product.     

Heavy metal pollution in vegetables grown in the vicinity of a multi-metal mining area in Gejiu,China: total concentrations,speciation analysis,and health risk

A field survey was conducted to investigate the present situation and health risk of arsenic (As), lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) in soils and vegetables in a multi-metal mining area, Gejiu, China. Furthermore, three vegetables (water spinach, potato, and summer squash) containing high metal concentrations were selected to further analyze metal speciation. The results showed that the average concentrations of five metals in soil exceeded the limiting values, and their bioavailable concentrations were significantly positively correlated to the total ones. Heavy metals in the edible parts of vegetables also exceeded the corresponding standards. The leaves of pakchoi, peppermint, and coriander had a strong metal-accumulative ability and they were not suitable for planting. Except the residue forms, the main forms of metals in the edible parts of three selected vegetables were ethanol-, NaCl-, and HAc-extractable fractions for As, Pb, and Cd, respectively; however, Cu was mainly presented as NaCl-extractable and Zn as HAc-extractable fractions. A high proportion of ethanol-extractable As showed that As bioactivity and toxic effects were the highest. Although the total and bioavailable Cd were high in soil, its speciation in vegetables was mainly presented as HAc-extractable fraction, which has a relatively low bioactivity. Lead and arsenic were imposing a serious threat on the local residents via vegetable consumption.