Scattered literature is harnessed to critically review the possible sources, chemistry, potential biohazards and best available remedial strategies for a number of heavy metals (lead, chromium, arsenic, zinc, cadmium, copper, mercury and nickel) commonly found in contaminated soils. The principles, advantages and disadvantages of immobilization, soil washing and phytoremediation techniques which are frequently listed among the best demonstrated available technologies for cleaning up heavy metal contaminated sites are presented. Remediation of heavy metal contaminated soils is necessary to reduce the associated risks, make the land resource available for agricultural production, enhance food security and scale down land tenure problems arising from changes in the land use pattern.

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Heavy Metals in Contaminated Soils: A Review of Sources, Chemistry, Risks and Best Available Strategies for Remediation

Remediation of heavy metal(loid)s contaminated soils - To mobilize or to immobilize?

In addition to the often-cited advantages of using Arabidopsis thaliana as a model system in plant biological research (1), Arabidopsis has many additional characteristics that make it an attractive experimental organism for studying lea d (Pb) accumulation and tolerance in plants. These include its fortuitous familial relationship to many known metal hyperaccumulators (Brassicaceae), as well as similar Pbaccumulation patterns to most other plants. Using nutrient-agar plates, hydroponic culture, and Pb-contaminated soils as growth media, we found significant variation in Arabidopsis thaliana ecotypes in accumulation and tolerance of Pb. In addition, we have found that Pb accumulation is not obligatorily linked with Pb tolerance, suggesti ng that different genetic factors control these two processes. We also screened ethyl methanesulfonate-mutagenized M2 populations and identified several Pb-accumulating mutants. Current characterization of these mutants indicates that their phenotypes are likely due to alteration of general metal ion uptake or translocation processes since these mutants also accumulate many other metals in shoots. We expect that further characterization of the ecotypes and mutants will shed light on the basic genetic and physiological underpinnings of plant-based Pb remediation. 7. Aromatic nitroreduction of acifluorfen in soils, rhizospheres, and pure cultures of rhizobacteria. Zablotowicz, R. M., Locke, M. A., and Hoagland, R. E. Phytoremediation of soil and water contaminants. Washington, DC : American Chemical Society, 1997. p. 38-53. NAL Call #: QD1.A45-no.664 Abstract: Reduction of nitroaromatic compounds to their corresponding amino derivatives is one of several pathways in the degradation of nitroxenobiotics. Our studies with the nitrodiphenyl ether herbicide acifluorfen showed rapid metabolism to am inoacifluorfen followed by incorporation into unextractable soil components in both soil and rhizosphere suspensions. Aminoacifluorfen was formed more rapidly in rhizospheres compared to soil, which can be attributed to higher microbial populations, espec ially of Gram-negative bacteria. We identified several strains of Pseudomonas fluorescens that possess nitroreductase activity capable of converting acifluorfen to aminoacifluorfen. Factors affecting acifluorfen nitroreductase activity in pure cultures an d cell-free extracts, and other catabolic transformations of acifluorfen, ether bond cleavage, are discussed. Plant rhizospheres should be conducive for aromatic nitroreduction. Nitroreduction by rhizobacteria is an important catabolic pathway for the ini tial degradation of various nitroherbicides and other nitroaromatic compounds in soils under Reduction of nitroaromatic compounds to their corresponding amino derivatives is one of several pathways in the degradation of nitroxenobiotics. Our studies with the nitrodiphenyl ether herbicide acifluorfen showed rapid metabolism to am inoacifluorfen followed by incorporation into unextractable soil components in both soil and rhizosphere suspensions. Aminoacifluorfen was formed more rapidly in rhizospheres compared to soil, which can be attributed to higher microbial populations, espec ially of Gram-negative bacteria. We identified several strains of Pseudomonas fluorescens that possess nitroreductase activity capable of converting acifluorfen to aminoacifluorfen. Factors affecting acifluorfen nitroreductase activity in pure cultures an d cell-free extracts, and other catabolic transformations of acifluorfen, ether bond cleavage, are discussed. Plant rhizospheres should be conducive for aromatic nitroreduction. Nitroreduction by rhizobacteria is an important catabolic pathway for the ini tial degradation of various nitroherbicides and other nitroaromatic compounds in soils under phytoremediation management. 8. Ascorbate: a biomarker of herbicide stress in wetland plants. Lytle, T. F. and Lytle, J. S. Phytoremediation of soil and water contaminants. Washington, DC : American Chemical Society, 1997. p. 106-113. NAL Call #: QD1.A45-no.664 Abstract: In laboratory exposures of wetland plants to low herbicide levels (<0.1 micrograms/mL), some plants showed increased total ascorbic acid suggesting a stimulatory effect on ascorbic acid synthesis occurred; at higher herbicide conce ntrations (greater than or equal to 0.1 micrograms/mL) a notable decline in total ascorbic acid and increase in the oxidized form, dehydroascorbic acid occurred. Vigna luteola and Sesbania vesicaria were exposed for 7 and 21 days respectively to atrazine (0.05 to 1 microgram/mL); Spartina alterniflora 28 days at 0.1 micrograms/mL trifluralin; Hibiscus moscheutos 14 days at 0.1 and 1 microgram/mL metolachlor in fresh and brackish water. The greatest increase following low dosage occurred with S. alterniflo ra, increasing from <600 micrograms/g wet wt. total ascorbic acid to >1000 micrograms/g. Ascorbic acid may be a promising biomarker of estuarine plants exposed to herbicide runoff; stimulation of ascorbic acid synthesis may enable some wetland plant s used in phytoremediation to cope with low levels of these compounds. In laboratory exposures of wetland plants to low herbicide levels (<0.1 micrograms/mL), some plants showed increased total ascorbic acid suggesting a stimulatory effect on ascorbic acid synthesis occurred; at higher herbicide conce ntrations (greater than or equal to 0.1 micrograms/mL) a notable decline in total ascorbic acid and increase in the oxidized form, dehydroascorbic acid occurred. Vigna luteola and Sesbania vesicaria were exposed for 7 and 21 days respectively to atrazine (0.05 to 1 microgram/mL); Spartina alterniflora 28 days at 0.1 micrograms/mL trifluralin; Hibiscus moscheutos 14 days at 0.1 and 1 microgram/mL metolachlor in fresh and brackish water. The greatest increase following low dosage occurred with S. alterniflo ra, increasing from <600 micrograms/g wet wt. total ascorbic acid to >1000 micrograms/g. Ascorbic acid may be a promising biomarker of estuarine plants exposed to herbicide runoff; stimulation of ascorbic acid synthesis may enable some wetland plant s used in phytoremediation to cope with low levels of these compounds. 9. Atmospheric nitrogenous compounds and ozone--is NO(x) fixation by plants a possible solution. Wellburn, A. R. New phytol. 139: 1 pp. 5-9. (May 1998). NAL Call #: 450-N42 Descriptors: ozoneair-pollution nitrogen-dioxide nitric-oxide air-quality tolerancebioremediationacclimatizationnutrient-sources nutrient-uptake plantscultivarsgenetic-variation literature-reviews 10. Atrazine degradation in pesticide-contaminated soils: phytoremediation potential. Kruger, E. L., Anhalt, J. C., Sorenson, D., Nelson, B., Chouhy, A. L., Anderson, T. A., and Coats, J. R. Phytoremediation of soil and water contaminants. Washington, DC : American Chemical Society, 1997. p. 54-64. NAL Call #: QD1.A45-no. 664 Abstract: Studies were conducted in the laboratory to determine the fate of atrazine in pesticide-contaminated soils from agrochemical dealer sites. No significant differences in atrazine concentrations occurred in soils treated with atrazine i ndividually or combinations with metolachlor and trifluralin. In a screening study carried out in soils from four agrochemical dealer sites, rapid mineralization of atrazine occurred in three out of eight soils tested, with the greatest amount occurring i n Bravo rhizosphere soil (35% of the applied atrazine after 9 weeks). Suppression of atrazine mineralization in the Bravo rhizosphere soil did not occur with the addition of high concentrations of herbicide mixtures, but instead was increased. Plants had a positive impact on dissipation of aged Studies were conducted in the laboratory to determine the fate of atrazine in pesticide-contaminated soils from agrochemical dealer sites. No significant differences in atrazine concentrations occurred in soils treated with atrazine i ndividually or combinations with metolachlor and trifluralin. In a screening study carried out in soils from four agrochemical dealer sites, rapid mineralization of atrazine occurred in three out of eight soils tested, with the greatest amount occurring i n Bravo rhizosphere soil (35% of the applied atrazine after 9 weeks). Suppression of atrazine mineralization in the Bravo rhizosphere soil did not occur with the addition of high concentrations of herbicide mixtures, but instead was increased. Plants had a positive impact on dissipation of aged atrazine in soil, with significantly less atrazine extractable from Kochia-vegetated soils than from nonvegetated soils. 11. Bacterial inoculants of forage grasses that enhance degradation of 2-chlorobenzoic acid in soil. Siciliano, S. D. and Germida, J. J. Environ toxicol chem. 16: 6 pp. 1098-1104. (June 1997). NAL Call #: QH545.A1E58 Descriptors: polluted-soils bioremediationAbstract: Biological remediation of contaminated soil is an effective method of reducing risk to human and ecosystem health. Bacteria and plants might be used to enhance remediation of soil pollutants in situ. This study assessed the potential of bacteria (12 isolates), plants (16 forage grasses), and plant-bacteria associations (selected pairings) to remediate 2-chlorobenzoic acid (2CBA)-contaminated soil. Initially, grass viability was assessed in 2CBA-contaminated soil. Soil was contaminated wi th 2CBA, forage grasses were grown under growth chamber conditions for 42 or 60 d, and the 2CBA concentration in soil was determined by gas chromatography. Only five of 16 forage grasses grew in 2CBA-treated (816 mg/kg) soil. Growth of Bromus inermis had no effect on 2CBA concentration, whereas Agropyron intermedium, B. biebersteinii, A. riparum, and Elymus dauricus decreased 2CBA relative to nonplanted control soil by 32 to 42%. The 12 bacteria isolates were screened for their ability to promote the germ ination of the five grasses in 2CBA-contaminated soil. Inoculation of A. riparum with Pseudomonas aeruginos

Phytoremediation : 植物による環境/土壌浄化

Plant growth promoting rhizobacteria and endophytes accelerate phytoremediation of metalliferous soils

Hydroxyl radicals based advanced oxidation processes (AOPs) for remediation of soils contaminated with organic compounds: A review

http://ira.lib.polyu.edu.hk/bitstream/10397/2581/1/B33%20Phyto%20Chelant%20Review%202008.pdf

The use of chelating agents in the remediation of metal-contaminated soils: A review

Synthetic chelates such as ethylene diamine tetraacetic acid (EDTA) have been shown to enhance phytoextraction of some heavy metals from contaminated soil. In a soil column study, we examined the effect of EDTA on the uptake of Pb, Zn and Cd by Chinese cabbage (Brassica rapa), mobilization and leaching of heavy metals and the toxicity effects of EDTA additions on plants. The most effective was a single dose of 10 mmol EDTA kg−1 soil where we detected Pb, Zn and Cd concentrations that were 104.6, 3.2 and 2.3-times higher in the aboveground plant biomass compared to the control treatments. The same EDTA addition decreased the concentration of Pb, Zn and Cd in roots of tested plants by 41, 71 and 69%, respectively compared to concentrations in the roots of control plants. In columns treated with 10 mmol kg−1 EDTA, up to 37.9, 10.4 and 56.3% of initial total Pb, Zn and Cd in soil were leached down the soil profile, suggesting high solubility of heavy metals-EDTA complexes. EDTA treatment had a strong phytotoxic effect on the red clover (Trifolium pratense) in bioassay experiment. Moreover, the high dose EDTA additions inhibited the development of arbuscular mycorrhiza. The results of phospholipid fatty acid analyses indicated toxic effects of EDTA on soil fungi and increased environmental stress of soil microfauna.

EDTA enhanced heavy metal phytoextraction: metal accumulation, leaching and toxicity

Using a soil column experiment, we compared the effect of a single dose and weekly additions of ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedissuccinate (EDDS) on the uptake of Pb, Zn, and Cd by Chinese cabbage [Brassica rapa L. subsp. pekinensis (Lour.) Hanelt], and on the leaching of heavy metals through the soil profile. The analysis of plant material revealed that both chelates increased the concentrations of Pb and, to a lesser extent, also of Zn and Cd in the leaves of the test plant. The most effective applications were single doses of 10 mmol EDTA and EDDS kg(-1) soil, which caused the concentrations of Pb in the shoots to increase 94.2- and 102.3-fold, respectively, relative to the control. The same dose of EDTA increased the concentration of Zn and Cd in the leaves 4.3- and 3.8-fold and of EDDS 4.7- and 3.5-fold, respectively. In treatments with weekly additions and lower concentrations of both chelates, EDTA was more effective than EDDS in increasing the plant uptake of Pb. In soil columns treated with weekly additions of 10 mmol kg(-1) EDTA, on average 22.7, 7.0, and 39.8% of initial total Pb, Zn, and Cd in the soil were leached through the soil profile. The same amount of EDDS caused much lower leaching of Pb and Cd--only 0.8 and 1.5% of initial total concentrations. Leaching of Zn, 6.2% of the total concentration, was comparable with the EDTA treatment. A biotest with red clover (Trifolium pratense L.) indicated a greater phytotoxic effect of EDTA than EDDS addition. EDDS was also less toxic to soil fungi, as determined by phospholipid fatty acid (PLFA) analysis, and caused less stress to soil microorganisms, as indicated by the trans to cis PLFA ratio. Chelate addition did not prevent the development of arbuscular mycorrhiza on red clover.

Ethylenediaminedissuccinate as a new chelate for environmentally safe enhanced lead phytoextraction.

Chelate-induced remediation has been proposed as an effective tool for the extraction of lead (Pb) from contaminated soils by plants. However, side-effects, mainly mobilization and leaching of Pb, raise environmental concerns. Biodegradable, synthetic organic chelate ethylenediaminedisuccinic acid (EDDS), and commonly used ethylenedimanetetraacetic acid (EDTA) were used for induced phytoextraction with a test plant Brassica rapa and in situ washing of soil contaminated with 1350 mg/kg of Pb. Horizontal permeable barriers were placed 20 cm deep in soil columns and tested for their ability to prevent leaching of Pb. The reactive materials in the barriers were nutrient enriched vermiculite, peat or agricultural hydrogel, and apatite. EDTA and EDDS addition increased Pb concentrations in the test plant by 158 and 89 times compared to the control, to 817 and 464 mg/kg, respectively. In EDTA treatments, approximately 25% or more of total initial soil Pb was leached in single cycle of chelate addition. In EDDS treatments, 20% of the initial Pb was leached from columns with no barrier, while barriers with vermiculite or hydrogel and apatite decreased leaching by more than 60 times, to 0.35%. 11.6% of total initial Pb was washed from the soil above the barrier with vermiculite and apatite, where almost all leached Pb was accumulated. Results indicate that use of biodegradable chelate EDDS and permeable barriers may lead to environmentally safe induced Pb phytoextraction and in situ washing of Pb.

Domen Lestan

Papers

The use of chelating agents in the remediation of metal-contaminated soils: A review

EDTA enhanced heavy metal phytoextraction: metal accumulation, leaching and toxicity

Ethylenediaminedissuccinate as a new chelate for environmentally safe enhanced lead phytoextraction.

Induced phytoextraction/soil washing of lead using biodegradable chelate and permeable barriers.

Chelator induced phytoextraction and in situ soil washing of Cu.