Experimental Assessment of Using Soluble Humic Substances for Remediation of Heavy Metal Polluted Soils

Since heavy metals are nondegradable and strongly bonded in soils, remediation of heavy metal polluted soils by extraction is difficult and current extraction techniques require harsh chemicals such as ethylenediaminetetraacetic acid (EDTA). However, use of EDTA is environmentally problematic because of costs, persistence, toxicity and deterioration of soil structure. Therefore, the potential of soluble natural humic substances (HS) to extract heavy metals from contaminated soils is tested as an environmentally friendly substitute for EDTA. A strongly polluted, calcareous urban soil (CRC soil) and a moderately polluted agricultural soil (CUP soil) were extracted at neutral pH in batch mode by three HS solutions from beech and Norway spruce litter (Beech-HS and Spruce-HS) and processed cow slurry (Bio-HS), all containing 25 mM dissolved organic carbon (DOC). After 10 extractions with a solution to soil ratio of 5:1 (L/kg), 8% to 39% of the total Cd, Cu, Ni and Pb soil contents, lowest for Ni and highest for Cu/Pb, were extracted. Natural and processed HS samples had comparable capacities to extract the heavy metals. A comparison of 100 mM DOC of Bio-HS and EDTA as extractants for Cu from the CRC soil showed extraction of 67% by EDTA and 41% by Bio-HS, indicating somewhat higher efficiency of EDTA than of HS. Sequential extraction of the CRC soil after Bio-HS and EDTA extraction showed removal of exchangeable, carbonate- and metal oxide-bound Cu but also of some residual Cu. It is therefore concluded that HS appears to be an attractive and promising alternative to EDTA as remediation agent for heavy metal polluted soils provided cheap HS of good quality is easily available.     

Enhanced phytoextraction: I. Effect of EDTA and citric acid on heavy metal mobility in a calcareous soil

Phytoextraction, the use of plants to extract heavy metals from contaminated soils, could be an interesting alternative to conventional remediation technologies. However, calcareous soils with relatively high total metal contents are difficult to phytoremediate due to low soluble metal concentrations. Soil amendments such as ethylene diaminetetraacetate (EDTA) have been suggested to increase heavy metal bioavailability and uptake in aboveground plant parts. Strong persistence of EDTA and risks of leaching of potentially toxic metals and essential nutrients have led to research on easily biodegradable soil amendments such as citric acid. In our research, EDTA is regarded as a scientific benchmark with which degradable alternatives are compared for enhanced phytoextraction purposes. The effects of increasing doses of EDTA (0.1,1,10 mmol kg(-1) dry soil) and citric acid (0.01, 0.05, 0.25, 0.442, 0.5 mol kg(-1) dry soil) on bioavailable fractions of Cu, Zn, Cd, and Pb were assessed in one part of our study and results are presented in this article. The evolution of labile soil fractions of heavy metals over time was evaluated using water paste saturation extraction (approximately soluble fraction), extraction with 1 M NH4OAc at pH 7 (approximately exchangeable fraction), and extraction with 0.5 M NH4OAc + 05 M HOAc + 0.02 M EDTA at pH 4.65 (approximately potentially bioavailable fraction). Both citric acid and EDTA produced a rapid initial increase in labile heavy metal fractions. Metal mobilization remained constant in time for soils treated with EDTA, but a strong exponential decrease of labile metal fractions was noted for soils treated with citric acid. The half life of heavy metal mobilization by citric acid varied between 1.5 and 5.7 d. In the following article, the effect of heavy metal mobilization on uptake by Helianthus annuus will be presented.     

Phytoextraction of copper from contaminated soil by Elsholtzia splendens as affected by EDTA, citric acid, and compost

Phytoextraction of copper (Cu) from contaminated soils greatly depends on the metal bioavailability in the soils and metal uptake ability of the plant. In this study, the effects of chelators [ethylenediamine tetraacetic acid (EDTA), citric acid (CA)] and compost amendments on Cu phytoextraction potential by a tolerant and accumulating plant species (E. splendens) were examined in two types of contaminated soils, ie., the mined soil from Cu-mined area (MS) and a paddy soil polluted by Cu refining (PS). The results showed that EDTA application at 2.5-5.0 mmol kg(-1) increased phytoextraction of Cu by four- and eight-fold from both MS and PS, respectively, which is mainly attributed to increased H2O extractable Cu in the soil. The Cu amount extracted by the shoots of E. splendens reached 800-1000 microg Cu plant(-1) from the MS and 400-700 microg Cu plant(-1) from the PS at EDTA application rates of 2.5-5.0 mmol kg(-1). The application of CA at 5.0 mmol kg(-1) had minimal effects on Cu extractability in both soils and slightly decreased Cu extraction efficiency by E. splendens. Plant biomass production was enhanced by CA at 0.25 mmol L(-1) in nutrient solution, but inhibited by CA at 5.0 mmol kg(-1) in both MS and PS. Increasing the compost rate significantly decreased H2O extractable Cu in the MS, but raised H2O-extractable Cu in the PS, which resulted mainly front the reduced exchangeable Cu in the MS and the increased exchangeable and organic fractions of Cu in the PS by compost. At high compost rate (5%), the shoots of E. splendens extracted 3.6-fold higher Cu from the PS than from the MS. These results indicate that, among the soil amendments, efficiency of Cu phytoextraction is enhanced mostly by 2.5-5.0 mmol kg(-1) EDTA, followed by 5% (w:w) compost, whereas < 5.0 mmol kg(-1) CA has minimal effects on Cu phytoextraction by E. splendens in the PS. As for the MS, only 2.5-5.0 mmol kg(-1) EDTA can elevate the efficiency of Cu, while 5% compost amendment and < 5.0 mmol kg(-1) CA application have no marked effects on Cu phytoextraction by E. splendens.     

The chelating effect of citric acid,oxalic acid,amino acids and Pseudomonas fluorescens bacteria on phytoremediation of Cu,Zn, and Cr from soil using Suaeda vera

Phytoextraction is a green technique for the removal of soil contaminants by plants uptake with the subsequent elimination of the generated biomass. The halophytic plant Suaeda vera Forssk. ex J.F.Gmel. is an native Mediterranean species able to tolerate and accumulate salts and heavy metals in their tissues. The objective of this study was to explore the potential use of S. vera for soil metal phytoextraction and to assess the impact of different chelating agents such as natural organic acids (oxalic acid [OA], citric acid [CA]), amino acids (AA) and Pseudomonas fluorescens bacteria (PFB) on the metal uptake and translocation. After 12 months, the highest accumulation of Cu was observed in the root/stem of PFB plots (17.62/8.19 mg/kg), in the root/stem of CA plots for Zn (31.16/23.52 mg/kg) and in the root of OA plots for Cr (10.53 mg/kg). The highest accumulation of metals occurred in the roots (27.33–50.76 mg/kg). Zn was the metal that accumulated at the highest rates in most cases. The phytoextraction percentages were higher for Cu and Zn (～2%) with respect to Cr (～1%). The percentages of metal removal from soil indicate the need to monitor soil properties, to recognize the influence of each treatment and to increase the concentration of bioavailable metals by the use of agricultural management practices aimed at promoting plant growth.     

Chelate-assisted phytoextraction using canola (Brassica napus L.) in outdoors pot and lysimeter experiments

Phytoextraction is an emerging technology for non-destructive remediation of heavy metal-polluted soils. This study was conducted to test chelate-assisted phytoextraction of Cu, Pb and Zn using EDTA and canola (Brassica napus L. cv. Petranova) on a moderately polluted industrial soil (loamy sand) in the sub-continental climate of Eastern Austria. The effects of the rate (up to 2.1 g kg^–1 soil) and mode (single versus split) of EDTA application on the biomass, water contents and metal concentrations in shoots and roots were investigated along with changes of metal lability in soil and leaching from the root zone in parallel outdoors pot and lysimeter experiments. Labile (1 M NH₄NO₃-extractable) metal concentrations in soil increased considerably upon application of EDTA, indicating enhanced phytoavailability. However, this was also associated with enormously increased metal concentrations in the leachates collected below the root zone. Enhanced metal labilities and leachate concentrations persisted for more than 1 year after harvest. Metal lability was more enhanced by EDTA in rhizosphere relative to bulk soil, indicating interactions of EDTA with root activities. Shoot biomass and water contents of canola were virtually unaffected by EDTA, revealing that canola can tolerate excessive metal concentrations in soil pore water. Metal concentrations in shoots were increased considerably, but were insufficient to obtain reasonable extraction rates. Split applications were generally more effective than the same amounts of EDTA added at once. Metal concentrations in roots decreased after each application of EDTA, possibly indicating metal removal from roots by free protonated EDTA, but increased again within several days. As the application of chelate-assisted phytoextraction is limited by the risk of groundwater pollution, further work should focus on natural, continuous phytoextraction technologies.     

Solubility and accumulation of metals in Chinese brake fern, vetiver and rostrate sesbania using chelating agents

Greenhouse experiments were conducted to study the effects of chelating agents on the growth and metal accumulation of Chinese brake fern (Pteris vittata L.), vetiver (Vetiveria zizanioides L.), and rostrate sesbania (Sesbania rostrata L.) in soil contaminated with arsenic (As), Cu, Pb, and Zn. Among the five chelating agents used [ethylenediaminetriacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), oxalic acid (OA), and phytic acid (PA)], OA was the best to mobilize As, EDTA to mobilize Cu and Pb, and HEDTA to mobilize Zn from soil, respectively. The biomass of vetiver was the highest, followed by rostrate sesbania. All chelating agents inhibited the growth of Chinese brake fern and rostrate sesbania, but HEDTA significantly increased the aboveground biomass of vetiver. Dry weights of both Chinese brake fern and rostrate sesbania decreased with increasing EDTA concentrations amended in the soil, especially in treatments with high EDTA concentrations. EDTA and HEDTA enhanced Cu, Zn, and Pb, but lowered As accumulation in all three plant species, except for As in vetiver, while OA significantly enhanced As accumulation in the aboveground part of vetiver. Concentrations of Cu, Zn, and Pb in the aboveground parts of plants increased significantly with the increase of EDTA concentrations and treatment time. In addition to As, Chinese brake fern also accumulated the highest Cu, Pb, and Zn in its aboveground parts among the three plant species grown in metal-contaminated soil with EDTA/HEDTA treatments. This species, therefore, can be used to simultaneously clean up As, Cu, Pb, and Zn from contaminated soils with the aid of EDTA or HEDTA.     

Counter-Current Metal Leaching and Precipitation for Soil Remediation

Chemical acid leaching is an effective technique for extracting toxic metals from the finest fractions of polluted soils. Nevertheless, the use of large quantities of reagents and process water results in prohibitive operating costs. The purpose of this study was to evaluate the technical and economic advantages of recirculating water in a counter-current leaching process (CCLP). Five 1-h sulfuric acid extraction steps (at pH = 1.5) followed by three 5-min water-washing steps were applied to the fine particle fraction (<0.125 mm) of an industrial soil polluted by Cd (13.2 mg·kg^?1), Cu (3 100 mg·kg^?1), Mn (685 mg kg^?1), Pb (550 mg·kg^?1), and Zn (2 840 mg·kg^?1). The leaching experiments were carried out at ambient temperature using a 10% soil suspension and in 1-L working volume stirred tank reactors. This paper presents results of conventional and counter-current leaching process (CCLP) tests and shows that the CCLP yields removal results for Cu (85%), Zn (86%), Mn (75%), and Cd (90%) that are similar to those obtained using the conventional leaching process. Moreover, the CCLP uses half of the quantity of acid and one-eighth of the amount of water that the conventional process uses. Metal precipitation with NaOH and Ca(OH)₂ was applied to treat the acidic leachates, and good metal removal yields were achieved with both reagents. However, the large consumption of chemicals implies high operating costs. In addition, the precipitation causes considerable sludge production, particularly when using Ca(OH)₂. Overall, the CCLP coupled to metal precipitation using NaOH and water recycling appears to be the most attractive option for the removal of toxic metals from this industrial soil.     

Chemically Assisted Phytoextraction: A Review of Potential Soil Amendments for Increasing Plant Uptake of Heavy Metals

The contamination of soils by trace metals has been an unfortunate sideeffect of industrialization. Some of these contaminants can interfere with vulnerable enduses of soil, such as agriculture or nature, already at relatively low levels of contamination. Reversely, conventional civil–technical soil-remediation techniques are too expensive to remediate extended areas of moderately contaminated soil. Phytoextraction has been proposed as a more economic complementary approach to deal with this specific niche of soil contamination. However, phytoextraction has been shown to be a slow-working process due to the low amounts of metals that can be annually removed from the soil under normal agronomic conditions. Therefore, extensive research has been conducted on process optimization by means of chemically improving plant availability and the uptake of heavy metals. A wide range of potential amendments has been proposed in the literature, with considerable attention being spent on aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA). However, these compounds have received increasing criticism due to their environmental persistence and associated risks for leaching. This review presents an overview of potential soil amendments that can be employed for enhancing metal uptake by phytoextraction crops, with a distinct focus on more degradable alternatives to persistent compounds such as EDTA.     

Bio-Acidification and Leaching of Metals,Nitrogen, and Phosphorus from Soil and Sludge Mixtures

Soil and wastewater treatment sludge are commonly brought together in mixtures for a variety of beneficial purposes. The mixtures contain bioacidifying (i.e., sulfur-oxidizing) microorganisms that can easily be activated through providing the appropriate substrate and environmental conditions. In this study, contaminated soil and sludge mixtures were subjected to controlled bio-acidification and the impacts of the process on the partitioning of heavy metals, nitrogen, and phosphorus were examined. Three successive bio-acidification cycles resulted in significant leaching of metals from sludge. The leaching results, expressed as fraction of total mass of metals in the sludge, averaged 67% for Cr, 96% for Ni, 24% for Zn; 16% for Cu; 23% for Cd; and 96% for Pb. Bio-acidification of the sludge also converted 28 to 45% of the organic nitrogen into ammonia and increased the soluble orthophosphates fraction of total phosphorus by approximately 18 to 20%. Bio-acidification also resulted in significant metals leaching from the contaminated soils in the soil/sludge mixtures. Soil/sludge mixtures were prepared using six soil particle sizes (less than 0.075?mm to 2.38?mm) contaminated with 22,500?mg/kg Zn, 14,000?mg/kg Pb, 1500?mg/kg Cr, 9500?mg/kg Cu, 1000?mg/kg Ni, and 1000?mg/kg Cd. The addition of metals to the soil inhibited the sulfur-oxidizing microorganisms, preventing bio-acidification in the mixtures containing 4 to 50?g soil in 130?ml sludge, and considerably slowing bio-acidification in the mixtures containing 1 to 3?g soil. Using a mixture that contained 2-g soil samples, three successive bio-acidification cycles resulted in significant cumulative metals leaching results. The leaching results, expressed as percentage of the mass of metals added to the soil, were in the range of 56 to 98% for Cr, 77 to 95% for Zn, 33 to 66% for Ni, 64 to 82% for Cu, and 10 to 33% for Pb, with the higher results in each range belonging to the larger size soil particles. On the other hand, only Cr was leached in neutralized soil samples. The results confirmed the potential for inhibition of the sulfur-oxidizing microorganisms and bio-acidification in contaminated soil/sludge mixtures, and the significant impacts of bio-acidification on the mobility of metals, nitrogen, and phosphorus. In addition, the results confirmed the potential for using controlled bioacidification for removing heavy metals from contaminated soil using the indigenous sulfur oxidizing microorganisms in sludge.     

EDTA-assisted phytoextraction of heavy metals by turfgrass from municipal solid waste compost using permeable barriers and associated potential leaching risk

A column experiment with horizontal permeable barriers was conducted to investigate phytoextraction of heavy metals by Lolium perenne L. from municipal solid waste compost following EDTA application, as well as to study the effects of L. perenne and permeable barriers on preventing metal from leaching. In columns with barriers, EDTA addition yielded maximum concentrations of Cu, Zn and Pb of 155, 541 and 33.5 mg kg⁻¹ in shoot, respectively. This led to 4.2, 2.1 and 7.4 times higher concentrations of Cu, Zn and Pb compared to treatment with no chelating agent, respectively. In treatments with 10 mmol kg⁻¹ EDTA, the barriers reduced leaching of Cu, Zn and Pb by approximately three times, respectively, resulting in leaching of total initial Cu, Zn and Pb by 27.3%, 25.2% and 28.8%, respectively, after four times’ irrigation. These results indicate that L. perenne and permeable barriers are effective to reduce leaching of heavy metals and minimize the risk of contaminating groundwater in EDTA-enhanced phytoremediation. Thus these findings highlight that turfgrass and permeable barriers can effectively prevent metal leaching.     

Evaluation of Different Amendments to Stabilize Cadmium,Zinc, and Copper in a Contaminated Soil: Influence on Metal Leaching and Phytoavailability

The contamination of soils with heavy metals is a global disaster that is related to human activities. Phytostabilization basically refers to the use of metal-tolerant plants and inexpensive mineral or organic soil amendments to reduce the concentrations or toxic effects of contaminants in the environment. Here, we tested the effects of four cost-effective amendments (CaCO₃, phosphate rock, activated carbon, and exhausted olive cake ash) on Cd, Zn, and Cu leaching and uptake by ryegrass (Lolium perenne L.). The results showed that all amendments reduced Cd, Zn, and Cu leaching, mainly due to the alkalinity increase. Among all amendments tested, CaCO₃ was the most effective treatment in decreasing both the heavy-metal leaching and concentrations in ryegrass shoots. Results obtained suggest the efficacy of several amendments, but further work is needed to gain insight into their possible synergetic effects.     

Heavy Metal Accumulation and Ecological Responses of Turfgrass to Rubbish Compost with EDTA Addition

Domestic rubbish compost is a complex-polluted system, containing multiple heavy metals,which limits its application. In the present study, Cr, Mn, Ni, Cu, Zn, Cd, and Pb accumulation and ecological responses of turfgrass to rubbish compost were investigated following the addition of EDTA. The results showed that the addition of EDTA significantly increased heavy metal accumulation in Lolium perenne L.and Festuca arundinacea L. Most heavy metal concentrations in L. perenne increased with increasing EDTA supply. The concentrations of Cr, Mn, Ni, Cu, and Cd in L. perenne were highest following the addition of 30 mmol/kg EDTA and the concentrations of Cr and Ni at this point reached concentrations of1914.17 and 521.25 μg/g, respectively. When the EDTA level was ＜ 20 mmol/kg, the accumulation of most heavy metals in F. arundinacea increased with increasing EDTA supply, but showed a tendency to decrease at EDTA concentrations ＞20 mmol/kg. The highest concentrations of Mn, Ni, Cu, and Zn in F.arundinacea reached 268.01, 110.94, 161.52 and 1 354.97 μg/g, respectively, following the addition of 20mmol/kg EDTA. The EDTA-induced increase in the accumulation of heavy metals in turfgrass was plantand metal-specific. L. perenne had a relatively high ability to accumulate Cr, Ni, and Zn. The highest Zn concentration was 2 979.58 μg/g and, following the addition of EDTA, the concentrations of the three metals were increased 26.23, 20.03, and 10.49-fold, respectively, compared with control. However, F. arundinacea showed a high ability to accumulate Cr, with the highest concentration (596.02 μg/g) seen following the addition of 30 mmol/kg EDTA; the concentration of Cr increased 15.51-fold compared with control. With EDTA addition, ecological responses of both turfgrass species showed that EDTA at concentrations ＜10mmol/kg increased seed germination and aboveground net primary production (ANP) of L. perenne and slightly inhibited those of F.arundinacea, but EDTA at concentrations ＞20 mmol/kg inhibited these parameters significantly for both species. Moreover, EDTA increased the chlorophyll and proline content at all concentrations tested. On the basis of the synthetic remediation index, the optimal EDTA concentration for turfgrass remediation of heavy metals in compost is approximately 10 mmol/kg.     

铜尾矿区土壤与凤丹植株重金属富集研究

对安徽铜陵铜尾矿区凤丹种植地的土壤和凤丹中重金属污染状况进行了研究.结果表明,尾矿库区种植地极端贫瘠,有机质含量仅1.1～3.4g·kg^-1,而土壤Cu、Cd、Pb、Zn含量皆高于对照土壤,其中Cu含量达587.43～1176.44mg·kg^-1,Cd含量达3.08～5.16mg·kg^-1,约达国家土壤二级标准的10倍.凤丹各部位的Cu、Cd和Pb含量均超过了药用植物的限量标准,尤其是根皮部位Cu含量达31.50～64.00mg·kg^-1,Cd含量达0.98～1.45mg·kg^-1,超出标准1.6～3.6倍,表明种植地和凤丹都受到严重污染.凤丹不同部位中的Zn、Cd、Pb和Cu分别以茎、叶、叶和根皮中的含量最高.凤丹对Cd、Zn的富集比Cu和Pb高,但在根皮中的富集系数均较小.     

Leaching Behavior of Heavy Metals and Transformation of Their Speciation in Polluted Soil Receiving Simulated Acid Rain

Heavy metals that leach from contaminated soils under acid rain are of increasing concern. In this study, simulated acid rain (SAR) was pumped through columns of artificially contaminated purple soil. Column leaching tests and sequential extraction were conducted for the heavy metals Cu, Pb, Cd, and Zn to determine the extent of their leaching as well as to examine the transformation of their speciation in the artificially contaminated soil columns. Results showed that the maximum leachate concentrations of Cu, Pb, Cd, and Zn were less than those specified in the Chinese Quality Standards for Groundwater (Grade IV), thereby suggesting that the heavy metals that leached from the polluted purple soil receiving acid rain may not pose as risks to water quality. Most of the Pb and Cd leachate concentrations were below their detection limits. By contrast, higher Cu and Zn leachate concentrations were found because they were released by the soil in larger amounts as compared with those of Pb and Cd. The differences in the Cu and Zn leachate concentrations between the controls (SAR at pH 5.6) and the treatments (SAR at pH 3.0 and 4.5) were significant. Similar trends were observed in the total leached amounts of Cu and Zn. The proportions of Cu, Pb, Cd, and Zn in the EXC and OX fractions were generally increased after the leaching experiment at three pH levels, whereas those of the RES, OM, and CAR fractions were slightly decreased. Acid rain favors the leaching of heavy metals from the contaminated purple soil and makes the heavy metal fractions become more labile. Moreover, a pH decrease from 5.6 to 3.0 significantly enhanced such effects.     

Enhanced Soil Washing for the Remediation of a Brownfield Polluted by Pyrite Ash

Soil from an abandoned/disused fertilizer plant polluted with pyrite ash containing heavy metal(loid)s (As, Cu, Pb, and Zn) was treated by means of physical and chemical washing. We first performed an exhaustive characterization of the soil-pollutant interaction, which allowed us to determine the chemical nature (complex oxyhydroxides), potential mobility and bioavailability of the pollutants (very low), as well as the grain size fractions of preferential accumulation (silt-clay fraction comprises more than 60% of the material and revealed contents well above 2.000 ppm of Cu, Zn and Pb). Soil/ash samples were subjected to a number of chemical washing trials, including leaching with 2 M HCl, 2 M NaOH and acidic process water (pH around 0). The fraction below 63 µm was mechanically separated and exposed to additional leaching tests e.g. chloridizing roasting with NaCl plus water leaching. Of all the tested procedures, the latter proved the most effective, particularly with regard to Cu and Zn recovery (recoveries up to 40% and 34%, respectively). The information gathered offers an insight into the modes and rates at which metals can be leached from pyrite ashes after chloridizing roasting as a prelude to more extensive soil washing feasibility studies focused on potential metal recovery.     

Transfer of selected mineral nutrients and trace elements in the host–hemiparasite association, Cistus–Odontites lutea, growing on and off metal-polluted sites

The role of a hemiparasitic life-style in plant resistance to toxic trace elements in polluted soils is unclear. Restriction of metal uptake by the host, restriction of metal transfer from host to parasite, or transformation of metals into a less toxic form may play a role. This study analysed the transfer of selected mineral elements from soil to host ( Cistus spp . ) and from host to hemiparasite ( Odontites lutea) at locations with different metal burdens: a Cu-rich serpentine site, Pb–Ba mine spoil and an unpolluted soil. Highest soil-to-host transfer factors for K, Mg, Ca, Zn, Cu and Pb were observed on the unpolluted soil. Statistically significant differences among locations of host-to-parasite transfer factors were only found for Ca and Pb. Restriction of transfer of unfavourable Ca/Mg ratios, characteristic at the serpentine site, and of high Pb and Zn concentrations at the Pb–Ba mine occurred mainly at the soil–host, and not at the host–parasite, level. Odontites lutea was able to withstand enhanced Zn and Pb concentrations and low Fe/Cu ratios in shoot tissue without developing toxicity symptoms. This could be caused by specific metal resistance mechanisms in this hemiparasite and/or the transformation and transfer of these metals into a less toxic form by the metal-tolerant host.     

Plant uptake and the leaching of metals during the hot EDDS-enhanced phytoextraction process

Using pot experiments, the effect of the application of the biodegradable chelating agent S,S-ethylenediaminedisuccinic acid (EDDS) in hot solutions at 90 degrees C on the uptake of Cu, Pb, Zn, and Cd by corn (Zea mays L. cv. Nongda No. 108) and beans (P vulgaris L. white bean), and the potential leaching of metals from soil, were studied. When EDDS was applied as a hot solution at the rate of 1 mmol kg(-1), the concentrations and total phytoextraction of metals in plant shoots exceeded or approximated those in the shoots of plants treated with normal EDDS at the rate of 5 mmol kg(-1). On the other hand, the leaching of Cu, Pb, Zn, and Cd after the application of the hot EDDS solution at the rate of 1 mmol kg(-1) was reduced by 46%, 21%, 57%, and 35% in comparison with that from the application of normal EDDS at 5 mmol kg(-1), respectively. For treatment with 1 mmol kg(-1) of EDDS, the leached metals decreased to the levels of the control group (that without EDDS amendment) 14 d after the application of EDDS. The soil amendment with biodegradable EDDS in hot solutions may provide a good alternative to chelate-enhanced phytoextraction in enhancing metal uptake by plants and limiting metals from leaching out of the soil.     

Movement of water and heavy metals (Zn, Cu, Pb and Ni) through sand and sandy loam amended with biosolids under steady-state hydrological conditions

New guidelines for using biosolids in UK agriculture favour the use of enhanced treated biosolids, such as dried and composted cakes, due to concerns about the potential for transfer of pathogens into the food chain. However, there is a need to ensure that their use is environmentally acceptable and does not increase the risk to potable water supplies or the food chain from other contaminants such as heavy metals and xenobiotic organic chemicals. The objective of this study was to determine whether the use of composted and dried mesophilic anaerobically digested dewatered (MADD) biosolids would increase the risk of heavy metal leaching from cultivated horizons when compared to more conventionally used MADD cake. Three biosolids (MADD sewage sludge cake - fresh, dried and composted) were mixed with a sand (typic quartzipsamments, %OM = 3.0, pH = 6.5) or a sandy loam (typic hapludalf, %OM = 4.8, pH = 7.6) at an application rate equivalent to 250 kg N/ha/y resulting in loadings of approximately Zn: 6 microg, Cu: 2 microg, Pb: 5 microg and Ni: 0.2 microg/g of soil dry weight basis. These amended soils were repacked into columns (0.4 m by 0.1 m internal diameter) and leaching of Zn, Cu, Pb and Ni was investigated following application of two 24 h simulated rainfall events of 4.5 mm/h. Water balance data and the use of conservative tracers (Cl- and Br ) showed that the hydrological regimes of each core were comparable and, thus, unlikely to account for differences in metal leaching observed. Although no significant difference (P = 0.05) was observed between biosolid amended and control soils, those amended with composted sludge consistently gave higher loss of all metals than did the control soils. Total losses of metals from compost amended soil over the two rainfall events were in the ranges, Zn:20.5-58.2, Cu:9.0-30.5, Pb:24.2-51.2 and Ni:16.0-39.8 microg metal/kg amended soil, compared with Zn:16.4-41.1, Cu:6.2-25.3, Pb:16.9-41.7, and Ni:3.7-25.4 microg metal/kg soil from the control soils. Losses of Zn, Cu, Pb and Ni from fresh MADD cake amended soils (19.8-41.3, 3.2-25.8, 21.6-51.6 and 7.6-36.5 microg metal/kg amended soil, respectively) and from dry MADD cake amended soils (10.7-36.7, 1.8-23.8, 21.2-51.2 and 6.8-39.2 microg metal/kg amended soil, respectively) were similar to the controls. Generally, quantities of metals leached followed the order Zn = Pb > Cu > Ni, which was consistent with the levels of metals in the original sludge/soil mixtures. These results suggest that composting or drying MADD biosolids is unlikely to increase the risk of groundwater contamination when compared to the use of MADD cake; therefore, the changes in UK sludge use in agriculture guidelines are satisfactory in this respect.     

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

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.     

Effects of three chelating agents,EDTA, NTA,and TPP,on the concentration of elements in rat tissues

Ethylene diamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and tripolyphosphate (TPP) sodium salts were given orally to rats at the dose of 1 mmol/kg/d for 35 d. The concentrations of Na, K, Ca, Mg, P, S, Fe, Sr, Cu, and Zn were determined in blood, plasma, brain, heart, muscle, liver, kidney, duodenum, and bone of control rats and of the rats receiving EDTA, NTA, and TPP. The main effect induced by EDTA, NTA, and TPP was a decrease of the concentrations of several elements Ca, Mg, Fe, P in the duodenum. Otherwise, EDTA induced an increase of Zn in the kidney (+ 20%), NTA, an increase of Fe in liver (+ 29%), and particularly an increase of Zn in bone (+ 44%). TPP induced a slight decrease of Zn and Cu in liver. In conclusion, EDTA, NTA, and TPP taken orally at the dose of 1 mmol/kg/d for 35 d induced moderate changes of the concentrations of some elements in rat tissues, but without signs of toxicity.