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

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

Biochemical parameters and bacterial species richness in soils contaminated by sludge-borne metals and remediated with inorganic soil amendments

The effectiveness of two amendments for the in situ remediation of a Cd- and Ni-contaminated soil in the Louis Fargue long-term field experiment was assessed. In April 1995, one replicate plot (S1) was amended with 5% w/w of beringite (B), a coal fly ash (treatment S1+B), and a second plot with 1% w/w zerovalent-Fe iron grit (SS) (treatment S1+SS), with the aim of increasing metal sorption and attenuating metal impacts. Long-term responses of daily respiration rates, microbial biomass, bacterial species richness and the activities of key soil enzymes (acid and alkaline phosphatase, arylsulfatase, beta-glucosidase, urease and protease activities) were studied in relation to soil metal extractability. Seven years after initial amendments, the labile fractions of Cd and Ni in both the S1+B and S1+SS soils were reduced to various extents depending on the metal and fractions considered. The soil microbial biomass and respiration rate were not affected by metal contamination and amendments in the S1+B and S1+SS soils, whereas the activity of different soil enzymes was restored. The SS treatment was more effective in reducing labile pools of Cd and Ni and led to a greater recovery of soil enzyme activities than the B treatment. Bacterial species richness in the S1 soil did not alter with either treatment. It was concluded that monitoring of the composition and activity of the soil microbial community is important in evaluating the effectiveness of soil remediation practices.     

土壤重金属复合污染及其化学钝化修复技术研究进展

土壤重金属污染往往是2种或2种以上的多种重金属并存的复合污染。与单一污染相比，重金属复合污染中元素或化合物之间存在相互作用以及对生态效应的综合影响，对其污染土壤的修复具有挑战性。目前，土壤重金属污染的修复主要集中在单一元素上，而对土壤多种重金属并存的复合污染的同时修复研究较少。化学钝化修复是基于向土壤中添加稳定化剂，通...     

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.     

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 compost, pig slurry and lime on trace element solubility and toxicity in two soils differently affected by mining activities

The use of organic wastes as amendments in heavy metal-polluted soils is an ecological integrated option for their recycling. The potential use of alperujo (solid olive-mill waste) compost and pig slurry in phytoremediation strategies has been studied, evaluating their short-term effects on soil health. An aerobic incubation experiment was carried out using an acid mine spoil based soil and a low OM soil from the mining area of La Unión (Murcia, Spain). Arsenic and heavy metal solubility in amended and non-amended soils, and microbial parameters were evaluated and related to a phytotoxicity test. The organic amendments provoked an enlargement of the microbial community (compost increased biomass-C from non detected values to 35 μg g⁻¹ in the mine spoil soil, and doubled control values in the low OM soil) and an intensification of its activity (including a twofold increase in nitrification), and significantly enhanced seed germination (increased cress germination by 25% in the mine spoil soil). Organic amendments increased Zn and Pb EDTA-extractable concentrations, and raised As solubility due to the influence of factors such as pH changes, phosphate concentration, and the nature of the organic matter of the amendments. Compost, thanks to the greater persistence of its organic matter in soil, could be recommended for its use in (phyto)stabilisation strategies. However, pig slurry boosted inorganic N content and did not significantly enhance As extractability in soil, so its use could be specifically recommended in As polluted soils.     

Evaluation of metal mobility, plant availability and immobilization by chemical agents in a limed-silty soil

Metal-contaminated soils in the vicinity of industrial sites become of ever-increasing concern. Diagnostic criteria and ecological technologies for soil remediation should be calibrated for various soil conditions; actually, our knowledge of calcareous soil is poor. Silty soils near smelters at Evin (Pas de Calais, France) have been contaminated by non-ferrous metal fallout and regularly limed using foams. Therefore, the mobility, bioavailability, and potential phytotoxicity of Cd, Pb and Zn, were investigated using single soil extractions (i.e. water, 0.1 n Ca(NO(3))(2), and EDTA pH 7), and vegetation experiments, in parallel with a biological test based on (iso)-enzymes in leaves and roots, before and following soil treatment with chemical agents, i.e. Thomas basic slags (TBS), hydrous manganese oxide (HMO), steel shots (ST) and beringite. No visible toxicity symptoms developed on the above-ground parts of ryegrass, tobacco and bean plants grown in potted soil under controlled environmental conditions. Cd, Zn and Pb uptake resulted in high concentrations in the above-ground plant parts, but the enzyme capacities in leaves and roots, and the peroxidase pattern indicated that these metal concentrations were not phytotoxic for beans as test plants. The addition of chemical agents to the soil did not increase biomass production, but treatment with either HMO, ST or beringite markedly decreased the mobility of Cd, Zn and Pb. These agents were proven to be effective in mitigating the Cd uptake by plants. HMO and ST decreased either Pb or Zn uptake by ryegrass. TBS was effective in lowering Pb uptake by the same species. Beringite decreased Cd uptake by beans. If fallout could be restricted, the metal content of food crops in this area should be lowered by soil treatment. However, the differences in Cd uptake between plant species were not suppressed, regardless of the type of agents applied to the soil.     

Chelate-induced phytoextraction of metal polluted soils with Brachiaria decumbens

Chelate-induced phytoextraction with high biomass plant species has been proposed for the clean-up of heavy metal polluted soils. In the current work, the effect of the application of two different chelating agents, i.e. EDTA and EDDS, on the metal phytoextraction capacity of Brachiaria decumbens was studied. Although EDTA was, in general, more effective in soil metal solubilization, EDDS, a chelate less harmful to the environment, was more efficient inducing metal accumulation in B. decumbens shoots than EDTA. Indeed, in a moderately heavy metal polluted soil, EDDS caused a 2.54, 2.74 and 4.30-fold increase in Cd, Zn, and Pb shoot metal concentration, respectively, as compared to control plants. In this same soil, EDTA caused a 1.77, 1.11 and 1.87-fold increase in Cd, Zn, and Pb shoot metal concentration, respectively, as compared to control plants. EDDS was also more effective than EDTA in stimulating the translocation of metals from roots to shoots. B. decumbens plants were able to grow in the metal polluted soils showing no visible symptoms of phytotoxicity, which suggests their metal tolerance. Finally, B. decumbens, a fast-growing, high biomass, aluminum tolerant plant species, that has a well-established agronomic system, fulfills most of the requirements for chemically-induced phytoextraction.     

Response of kidney bean to concentration and chemical form of cadmium, zinc, and lead in polluted soils

Seven soils which had been polluted with heavy metals from a zinc smelter were sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined geochemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual fractions. Kidney beans were planted in the soils to examine the effect of concentration and chemical form of the metals in soil on the growth and metal uptake of the plants. The growth of kidney bean was restricted in heavy metal polluted soils compared with controls. Metal concentration and metal uptake by plants were correlated. The highest relationship was found between amount of metal uptake and the metal concentration in exchangeable + carbonate forms. The uptake of metals was according to their solubility sequence, i.e. Cd > Zn > Pb. The uptake rate of exchangeable + carbonate forms was the same for the three elements.     

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40 g kg⁻¹) and steel slag (3 and 6 g kg⁻¹) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.     

Simultaneous immobilization of metals and arsenic in acidic polluted soils near a copper smelter in central Chile

Introduction  

Acidic and metal(oid)-rich topsoils resulted after 34 years of continuous operations of a copper smelter in the Puchuncaví valley, central Chile. Currently, large-scale remediation actions for simultaneous in situ immobilization of metals and As are needed to reduce environmental risks of polluted soils. Aided phytostabilization is a cost-effective alternative, but adequate local available soil amendments have to be identified and management options have to be defined.     

Potential of Brassic rapa, Cannabis sativa, Helianthus annuus and Zea mays for phytoextraction of heavy metals from calcareous dredged sediment derived soils

Remediation of soil pollution is one of the many current environmental challenges. Anthropogenic activity has resulted in the contamination of extended areas of land, the remediation of which is both invasive and expensive by conventional means. Phytoextraction of heavy metals from contaminated soils has the prospect of being a more economic in situ alternative. In addition, phytoextraction targets ecotoxicologically the most relevant soil fraction of these metals, i.e. the bioavailable fraction. Greenhouse experiments were carried out to evaluate the potential of four high biomass crop species in their potential for phytoextraction of heavy metals, with or without with the use of soil amendments (EDTA or EDDS). A calcareous dredged sediment derived surface soil, with high organic matter and clay content and moderate levels of heavy metal pollution, was used in the experiments. No growth depression was observed in EDTA or EDDS treated pots in comparison to untreated controls. Metal accumulation was considered to be low for phytoextraction purposes, despite the use of chelating agents. The low observed shoot concentrations of heavy metals were attributed to the low phytoavailability of heavy metals in this particular soil substrate. The mobilising effects induced by EDTA in the soil were found to be too long-lived for application as a soil amendment in phytoextraction. Although EDDS was found to be more biodegradable, higher effect half lives were observed than reported in literature or observed in previous experiments. These findings caution against the use of any amendment, biodegradable or otherwise, without proper investigation of its effects and the longevity thereof.     

Microbial indicators of heavy metal contamination in urban and rural soils

Urban soils and especially their microbiology have been a neglected area of study. In this paper, we report on microbial properties of urban soils compared to rural soils of similar lithogenic origin in the vicinity of Aberdeen city. Significant differences in basal respiration rates, microbial biomass and ecophysiological parameters were found in urban soils compared to rural soils. Analysis of community level physiological profiles (CLPP) of micro-organisms showed they consumed C sources faster in urban soils to maintain the same level activity as those in rural soils. Cu, Pb, Zn and Ni were the principal elements that had accumulated in urban soils compared with their rural counterparts with Pb being the most significant metal to distinguish urban soils from rural soils. Sequential extraction showed the final residue after extraction was normally the highest proportion except for Pb, for which the hydroxylamine-hydrochloride extractable Pb was the largest part. Acetic acid extractable fraction of Cd, Cu, Ni, Pb and Zn were higher in urban soils and aqua regia extractable fraction were lower suggesting an elevated availability of heavy metals in urban soils. Correlation analyses between different microbial indicators (basal respiration, biomass-C, and sole C source tests) and heavy metal fractions indicated that basal respiration was negatively correlated with soil Cd, Cu, Ni and Zn inputs while soil microbial biomass was only significantly correlated with Pb. However, both exchangeable and iron- and manganese-bound Ni fractions were mostly responsible for shift of the soil microbial community level physiological profiles (sole C source tests). These data suggest soil microbial indicators can be useful indicators of pollutant heavy metal stress on the health of urban soils.     

Potentials and drawbacks of chelate-enhanced phytoremediation of soils.

Chelate-enhanced phytoremediation has been proposed as an effective tool for the extraction of heavy metals from soils by plants. However, side-effects related to the addition of chelates, e.g. metal leaching and effects on soil micro-organisms, were usually neglected. Therefore, greenhouse and lysimeter studies were conducted to study the phytoremedation potential of EDGA and citric acid and to evaluate its effects on microbial activity and leaching of Cd, Zn Cu and Pb. Grass, lupine and yellow mustard were grown on a moderately polluted acid (pH 4.5) sandy soil that contained 2 mg kg(-1) Cd and 200 mg kg(-1) Zn. Citric acid appeared to be degraded microbially within a few days after addition which limited its potential for long-lasting remediation studies. EDGA enhanced metal solubility but plant uptake did not increase accordingly. The metal shoot:root ratio increased upon addition of EDGA but it also reduced the net shoot and root biomass production of both lupine and yellow mustard. Bacterial biomass was higher in both the citric and EDGA treated pots but bacterial activity remained unaffected. The number of microbivorous nematodes was greatly reduced upon addition of EDGA which was most likely related to the reduced biomass production and, to a smaller extent, to the changes in the composition of the available food. Furthermore, EDGA enhanced metal leaching in the lysimeter study which could lead to groundwater pollution. To prevent these unwanted side-effects, careful management of phytoremediation methods, therefore, seems necessary.     

粘土矿物修复重金属污染土壤

简要介绍了我国土壤重金属污染的现状与危害.通过粘土矿物在重金属污染土壤中净化功能的阐述,提出利用粘土矿物修复土壤重金属污染的观点.继而从天然和改性粘土矿物特性,叙述了粘土矿物修复土壤重金属污染的机制与应用进展及其影响因素.最后讨论了粘土矿物在修复土壤重金属污染过程中值得注意的几个问题,并展望了粘土矿物在该领域应用中的发展方向.     

Decomposition of heavy metal contaminated nettles (Urtica dioica L.) in soils subjected to heavy metal pollution by river sediments

Two incubation experiments were conducted to evaluate differences in the microbial use of non-contaminated and heavy metal contaminated nettle (Urtica dioica L.) shoot residues in three soils subjected to heavy metal pollution (Zn, Pb, Cu, and Cd) by river sediments. The microbial use of shoot residues was monitored by changes in microbial biomass C, biomass N, biomass P, ergosterol, N mineralisation, CO(2) production and O(2) consumption rates. Microbial biomass C, N, and P were estimated by fumigation extraction. In the non-amended soils, the mean microbial biomass C to soil organic C ratio decreased from 2.3% in the low metal soil to 1.1% in the high metal soils. In the 42-d incubation experiment, the addition of 2% nettle residues resulted in markedly increased contents of microbial biomass P (+240%), biomass C (+270%), biomass N (+310%), and ergosterol (+360%). The relative increase in the four microbial properties was similar for the three soils and did not show any clear heavy metal effect. The contents of microbial biomass C, N and P and ergosterol contents declined approximately by 30% during the incubation as in the non-amended soils. The ratios microbial biomass C to N, microbial biomass C to P, and ergosterol to microbial biomass C remained constant at 5.2, 26, and 0.5%, respectively. In the 6-d incubation experiment, the respiratory quotient CO(2)/O(2) increased from 0.74 in the low metal soil to 1.58 in the high metal soil in the non-amended soils. In the treatments amended with 4% nettle residues, the respiratory quotient was constant at 1.13, without any effects of the three soils or the two nettle treatments. Contaminated nettle residues led generally to significantly lower N mineralisation, CO(2) production and O(2) consumption rates than non-contaminated nettle residues. However, the absolute differences were small.     

EDTA and HEDTA effects on Cd, Cr, and Ni uptake by Helianthus annuus

Phytoremediation has shown great potential as an alternative treatment for the remediation of heavy-metal-contaminated soils and groundwater. However, the lack of a clear understanding pertaining to metal uptake/translocation mechanisms, enhancement amendments, and external effects on phytoremediation has hindered its full-scale application. The objective of this research was to investigate the ability of synthetic chelators for enhancing the phytoremediation of cadmium-, chromium- and nickel-contaminated soil. Ethylenediaminetriacetic acid (EDTA) and N-(2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) were applied to the soil at various dosages to elevate metal mobility. Uptake into and translocation within Helianthus annuus was determined. It was found that EDTA at a rate of 0.5 g/kg significantly increased the shoot concentrations of Cd and Ni from 34 and 15 to 115 and 117 mg/kg, respectively. The total removal efficiency for EDTA was 59 microg/plant. HEDTA at the same application rate resulted in a total metal uptake of 42 microg/plant. These research demonstrated that chelator enhancement is plant- and metal-specific and is subjective to inhibition when multiple heavy metals are present. Results also showed that chelator toxicity reduced the plant's biomass, thereby decreasing the amount of metal accumulation.     

Copper and zinc retention by an organically amended soil

This paper describes changes in retention of Cu and Zn in laboratory experiments by a sandy soil that had been amended in the field with different composted wastes. The amounts of the metals retained increased as a result of the amendments, especially after two years. Desorption of the sorbed metals was always negligible, regardless of the treatment. The proportion of Cu retained was considerably higher than that of Zn, suggesting a higher affinity of the soil for the former. The greater sorption in the amended soils indicates a build-up of fresh sites for metal retention.The use of 'log(activity) vs. pH' plots showed that the nature of the surfaces retaining metals on the untreated and amended soils is different. At comparable pH values, the amended soils gave higher solution metal concentrations. Some of the possible environmental consequences of the use of these amendments for remediation purposes are discussed.     

Effects of Cd and Pb on soil microbial community structure and activities

Background, aim, and scope  

Soil contamination with heavy metals occurs as a result of both anthropogenic and natural activities. Heavy metals could have long-term hazardous impacts on the health of soil ecosystems and adverse influences on soil biological processes. Soil enzymatic activities are recognized as sensors towards any natural and anthropogenic disturbance occurring in the soil ecosystem. Similarly, microbial biomass carbon (MBC) is also considered as one of the important soil biological activities frequently influenced by heavy metal contamination. The polymerase chain reaction–denaturing gradient gel electrophoresis (DGGE) has recently been used to investigate changes in soil microbial community composition in response to environmental stresses. Soil microbial community structure and activities are difficult to elucidate using single monitoring approach; therefore, for a better insight and complete depiction of the soil microbial situation, different approaches need to be used. This study was conducted in a greenhouse for a period of 12 weeks to evaluate the changes in indigenous microbial community structure and activities in the soil amended with different application rates of Cd, Pb, and Cd/Pb mix. In a field environment, soil is contaminated with single or mixed heavy metals; so that, in this research, we used the selected metals in both single and mixed forms at different application rates and investigated their toxic effects on microbial community structure and activities, using soil enzyme assays, plate counting, and advanced molecular DGGE technique. Soil microbial activities, including acid phosphatase (ACP), urease (URE), and MBC, and microbial community structure were studied.     

Changes in pH,dissolved organic matter and Cd species in the rhizosphere soils of Cd phytostabilizer Athyrium wardii (Hook.) Makino involved in Cd tolerance and accumulation

Phytostabilization has great practical significance and flexibility in the ecological restoration of mining tailings and remediation of heavy metals polluted soils. However, potential use of metallophytes in phytostabilization is limited by a lack of knowledge of many basic plant processes. A mining ecotype (ME) Athyrium wardii, Pb/Cd phytostabilizer, and a non-mining ecotype (NME) A. wardii were grown in a pot experiment to investigate the chemical characteristics of the rhizosphere when exposed to the Cd polluted soils. Rhizobags were used to collect rhizosphere and bulk soils, separately. The results indicated that the ME A. wardii was more efficient in Cd accumulation in the root than NME after growing in Cd polluted soils for 50 days in a green house. Soil solution pH and dissolved organic carbon (DOC) concentration in the rhizosphere of ME A. wardii were higher than in the bulk soil and initial values (before planting), whereas the increment in the ME A. wardii were greater than NME. Owing to the increasing of rhizosphere soil pH, exchangeable Cd significantly decreased, whereas the other Cd species were increased with increasing soil DOC values. It is assumed that the ME A. wardii was effective in stabilizing Cd from the mobile fraction to non-mobile fractions. Results from this study suggest that rhizosphere alkalinization and the exudation of high amounts of dissolved organic matter (DOM) to reduce heavy metal mobility might be the two important mechanisms involved in the metal tolerance/accumulation of ME A. wardii.