Heavy metals (copper,lead, nickel,and cadmium) in the organic part of gray forest soils in the Buryat Republic

The levels of the accumulation of copper, lead, nickel, and cadmium in the parent material-soil-plants-soil organic matter system are given for gray forest soils in the Buryat Republic. The concentrations of copper, lead, and nickel in the parent materials do not exceed the corresponding clarkes, and cadmium is present in trace amounts. The concentrations of copper and nickel in the humus horizon are lower than those in the parent material; an opposite situation is observed for lead. The concentrations of copper, lead, and nickel in the soil organic matter and in the herbaceous plants correspond to their contents in the soil and do not exceed the background (clarke) values. Cadmium was not detected in the aboveground part of the plants, though it was found in the root mass and in the organic soil horizon. In the humus of gray forest soils, these heavy metals are mainly present in the acid filtrate remaining after the precipitation of humic acids.     

Heavy-Metal Bioavailability and Chelate Mobilization Efficiency in an Assisted Phytoextraction Process by Sesbania sesban (L.) Merr

Chelate-induced phytoextraction is an innovative technique for cleaning metal- contaminated soil. The present study evaluates the degree of metal mobilization in soil and enhancement of phytoextraction of cadmium (Cd), lead (Pb), and zinc (Zn) by Sesbania sesban (L.) Merr. from artificially contaminated soil by application of ethylenediaminetetraacetic acid (EDTA). After 30 days of plant growth, the pots were divided into three sets (0.0, 2.5, and 5.0 mmol EDTA per kg soil). Experimental results indicated that levels of diethylenetriaminepentaacetic acid (DTPA)–extractable metals and metals in the leachate decreased as the EDTA dose increased. Plant growth parameters and total chlorophyll contents in the plants with EDTA applied were less than those of control. However, EDTA application significantly reduced metal accumulation in root and increased metal accumulation in the shoot of plants; similar results were obtained for the bioconcentration factor and translocation factor. The application of 5 mmol EDTA kg^?1 to metal-spiked soil may be an efficient alternative for the chemically enhanced phytoextraction by S. sesban.     

The effect of sewage‐sludge on the heavy metal content of soils and plant tissue

Abstract

Domestic sewage sludge applied to farm fields at a rate of 44.9 kg/ha in a mixture with lime and sawdust was found to increase the soil levels of cadmium, chromium, copper, lead, mercury, nickel and zinc. The average levels in sludge treated soil were: 0.11, 0.56, 3.59, 2.72, 0.068, 1.49 and 2.57 ppm, respectively. The increases were small and the overall loading factors were well below recommended maximums. The uptake of these heavy metals by grass and legume plants was variable with cadmium, copper and zinc levels being higher in those plants growing in the sludge treated soils but only copper was significantly higher. The heavy metal contents found were all within the levels normally found in grass and legume plants. The higher mean concentration in plants growing on the sludge treated soils were cadmium 0.495; chromium 1.22; copper 12.3; lead 1.54; mercury 0.022; nickel 4.08 and zinc 28.4 ppm.     

Soil Surface Geochemical Anomaly Around the Copper-Nickel Metallurgical Smelter

The soils were sampled from the center of airborne contamination caused by long time activity of a copper/nickel smelter complex in the Kola Peninsula, Russia. The soil specimens were taken from an area about 250 km², which included the town of Monchegorsk, with frequency of 1 sample (plot) per 3 km² and heavy metals nickel, copper, cobalt, chromium, lead, cadmium, strontium, iron, manganese and arsenic were measured. The soil surrounding the Smelter, including the inhabited territory of the town, was found to be contaminated by nickel and copper to levels 450- and 250 times higher in comparison to the background, respectively. These soils were found to be extremely toxic and represented a severe threat to human health. Elevated concentrations of iron and arsenic caused by smelter emissions were found too.     

Effect of Organic Acids on Heavy-Metal Uptake and Growth of Canola Grown in Contaminated Soil

Heavy-metal pollution of soils causes many environmental, animal, and human health problems. Phytoextraction of heavy metals from contaminated soils is an effective and economic technique. Humic acids are naturally occurring phenol body polymerisates, which form chelate compounds with heavy metals. In the present study the influence of soil- applied humic, citric, and malic acids on the lead (Pb), cadmium (Cd), and chromium (Cr) uptake from a contaminated soil by canola plant was examined in a greenhouse experiment. The experiment was arranged in factorial design based on randomized complete blocks with three replications. The factors of experiment included three organic acids (humic, citric, and malic acid) as first factor and five concentrations [0, 0.001, 0.002, 0.003, and 0.004 (v/v)] as second factor. The results showed that increase in organic acid concentration significantly increased heavy-metal uptake by canola plant, which accumulated heavy metals in different parts of the plant. In addition, crop growth representing by plant height and plant dry weight as well as seed production significantly decreased. Based on these results, canola can be considered as effective crop for phytoextraction of heavy metals from contaminated soils.     

Investigations on the Relationship between Extracting (DTPA) Solutions and Plant (Phaseolus vulgaris) in the Uptake of Cadmium and Lead from Latosols

Given the relationship between the contents of heavy metals extracted from contaminated soil samples and dilution of these samples in diethylenetriaminepentacetic acid (DTPA) solution, the goal of this work was to test three soil–extractant solution ratios, namely 1:5, 1:10, and 1:15. The extracted contents from each solution were compared to those extracted by bean plants (Phaseolus vulgaris) cultivated in a greenhouse in two different soils: dystrophic red latosol (RLd) and humic red-yellow latosol (RYLh). Contents of cadmium (Cd) and lead (Pb) were greater in RYLh (lower amount of clay) for all soil–extractant ratios; 1:5 and 1:10 ratios differed negligibly from the plant result for the Cd extraction, while for Pb, the 1:15 soil–extractant ratio was the one that better correlated with the extractive behavior of sensitive indicator plants.     

粤西黄铁矿区铊-铅污染土壤的环境质量研究

以云浮硫铁矿开采场和尾渣堆放区为研究对象,采用HNO3-H2O2-HClO4-HF混酸-微波消解处理土壤样品,运用电感耦合等离子体质谱（ICP-MS）测定土壤样品中重金属的含量,研究了开采场附近土壤表层、尾渣堆放区土壤剖面的铊、铅、镍、铜、锌、镉等毒害重金属的含量。结果表明,云浮硫铁矿开采活动给矿区土壤环境带来了严重的危害。与中国土壤环境背景值相比,土壤中重金属含量最高可为背景值的35倍。运用Muller地积指数对土壤重金属污染现状进行了系统的环境风险评估,证实目前云浮矿区土壤中存在不同程度的铊、铅、铜、锌、镉等毒害重金属污染,其中,铊、铅的污染最为严重,镉、锌等达到中度污染至强污染,且污染已经渗透至土壤深层,特别是毒害性极强的重金属铊,生态环境受到严重危害。     

Biodegradation of rhamnolipid, EDTA and citric acid in cadmium and zinc contaminated soils

Rhamnolipid, a metal sequestering agent produced by Pseudomonas Sp., has been effective in the removal of metals in soil washing technologies. Rhamnolipid has a strong affinity for cadmium (Cd) compared to some other metals (e.g. cobalt (Co), nickel (Ni)) and might also be useful in chelate-assisted phytoextraction. There have been many studies investigating the formation of metal-rhamnolipid complexes and the ability of rhamnolipid to remove metals from soil. However, to date, the longevity of rhamnolipid in soil has not been measured. Therefore, this study investigated the rate of rhamnolipid degradation in soils of varying physicochemical properties and contaminated with varying concentrations of Cd and zinc (Zn). The rate of rhamnolipid degradation was compared with ethylene diamine tetraacetic acid (EDTA) and citric acid. Our results indicate that citric acid was rapidly degraded, with 20% degradation occurring between 1 and 4 d depending on the level of soil contamination and 70% degradation within 20 d. EDTA was more persistent in the soils; only 14% of the EDTA was degraded after 20 d. Rhamnolipid had cumulative degradation between those of citric acid and EDTA. In most contaminated soils, cumulative degradation of the chelates and ligands were lower than in the uncontaminated soils. These results show that rhamnolipid may remain in the soil long enough to enhance metal phytoextraction, but not remain long enough to raise concerns regarding metal transport in the long-term.     

Residual leachability of CCA-contaminated soil after treatment with biodegradable chelating agents and lignite-derived humic substances

Purpose

The aim of this study was to enhance the soil remediation of timber treatment sites; the potential application of biodegradable chelating agents and humic substances as enhancing agents was assessed in terms of the residual leachability of chromium, copper and arsenic (CCA).

Materials and methods

This study applied four leachability tests on a field-contaminated soil after 48-h washing with ethylenediamine-N,N-disuccinic acid (EDDS), glutamic-N,N-diacetic acid, ethylenediaminetetraacetic acid and humic substances derived from lignite and two other sources.

Results and discussion

It was noteworthy that the reduction in the total metal concentrations after soil washing was not predictive of the leaching behaviour. When assessed by toxicity characteristic leaching procedure (TCLP) and waste extraction test (WET), Cu and As leachability was decreased as a result of their extraction by soil washing. By contrast, when assessed by synthetic precipitation leaching procedure (SPLP) and European Council Waste Acceptance Criteria (ECWAC) tests, Cu and As leachability was found to increase, probably because the effect of destabilization of residual metals during soil washing was more observable in unbuffered leaching solutions. On the other hand, Cr leachability was acceptably low in TCLP and WET but still exceeded drinking water standard in SPLP and ECWAC tests.

Conclusions

The three chelating agents were able to meet the criteria for Cu in all leachability tests, while the limits of As concentrations could only be met by EDDS in TCLP test. The three humic substances reduced the leachate concentrations of Cu and As without destabilizing the residual metals; however, the reduction was insufficient to meet the required limits in all leachability tests considered.     

Chemical Fractionation and Phytoavailability of Heavy Metals in a Soil Amended with Metal Salts or Metal-Spiked Poultry Manure

Chemical fractionation patterns and plant tissue concentrations were used to assess nickel, copper, zinc, cadmium, and lead phytoavailability to maize in a soil amended with metal salts or poultry manure. A sandy loam was treated with 80–400 mg kg^?1 doses of a quinternary mixture of the metal nitrates either directly or as spiked poultry manure. The European Communities Bureau of Reference sequential extraction procedure partitioned the metals among three operationally defined pools in the soil. Metal mobilities were lower in the poultry manure–amended than the metal salt–treated soil, indicating the manure's ability to fix the metals in soil. Pot experiments revealed high metal transferabilities with no apparent phytotoxic symptoms in maize at the doses applied, suggesting some degree of tolerance to the metals. Heavy-metal concentrations in maize increased linearly with metal doses in metal salt–treated soil, but were less phytoavailable in soil amended with poultry manure. Heavy-metal concentrations in maize were reasonably predicted from soil parameters using stepwise multivariate regression models. The findings are useful in the assessment and remediation of heavy metal–contaminated soils.     

Use of Drinking Water Treatment Residuals in Reducing Bioavailability of Metals in Biosolid-Amended Alkaline Soils

This greenhouse study evaluated the use of drinking-water-treatment residuals (WTRs) to reduce the bioavailability of metals in the biosolid-amended agricultural alkaline soils. Results showed that increasing the application rate of biosolids increased the accumulation of lead (Pb), nickel (Ni), copper (Cu), and cadmium (Cd) in corn (Zea mays cv. single hybride 10), with greater metal concentrations in roots than in shoots. However, the addition of WTRs (1–4%, w/w) to the soil amended with 3% biosolids significantly (P < 0.05) decreased the concentrations of soil diethylenetriaminepentaacetic acid (DTPA)–extractable metals. The accumulation of Pb, Ni, Cu, and Cd in corn significantly correlated with the DTPA-extractable metal concentrations in the soils. Plant metal concentrations were significantly affected by the soil type, application rates of biosolids and WTRs, and the ratio of WTRs to biosolids in the soils. The 1:1 application ratio of WTRs to biosolids at the 3% application rate effectively reduced the accumulation of metals in corn tissues.     

Surfactant-Enhanced Removal of Cu (II) and Zn (II) from a Contaminated Sandy Soil

Batch tests were conducted to know the effectiveness of using surfactants only and surfactants with a complexing agent to remove Cu (II) and Zn (II) from an artificially contaminated sandy soil. SDS (sodium dodecyl sulfate), AOT (alpha-olefin sulfonate) and Tx-100 (Triton X-100) were the surfactants selected as the washing liquids. Complexing agent EDTA (ethylenediaminetetraacetic acid) was also selected for washing the soil. To avoid external factors from interfering with the cleaning process, artificial soil formed by a mixture of clean sand and bentonite was used to form contaminated soil samples. The amount of organic matter present was insignificant. Compared to extraction by distilled water, tests indicated that a six-fold increase in copper extraction occurred due to the presence of surfactants and/or the complexing agent EDTA. Compared to extraction by distilled water, zinc extraction by surfactants and or the complexing agent EDTA was nearly 1.2 to 1.3 times more. Effects of competition as well as interference associated with the adsorption and desorption of these metals are also very briefly reported.     

Photometric application of the MTT- and NRR-assays as biomarkers for the evaluation of cytotoxicity ex vivo in Eisenia andrei

In soils, the toxicity of noxious substances such as metals is determined by a number of different factors of chemical, physical, biological, and environmental origin. Addressing these factors as a sum of different parameters, we studied these effects in soil-dwelling indicator species by using ‘sub-cellular’ biomarkers, to see if they can provide an early stage response to environmental disturbances. ‘Sub-cellular’ biomarkers such as the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and the Neutral Red Retention (NRR) assays are well established for the assessment of cytotoxicity of toxicants on cell cultures. Both assays can be carried out in 96-well microplates and evaluated photometrically. To be able to assess the risk potential of contaminated soils using these assays, without changing the soils chemically or physically to accommodate cell cultures, the assays were adapted for ex vivo use. The assays were performed on coelomic liquid extracted from exposed earthworms. Eisenia andrei was exposed in a standardized laboratory soil substrate (OECD soil) spiked with cadmium at a range of concentrations known to be cytotoxic to earthworms. Earthworms were also exposed to ultramafic soils as field-relevant soil substrates, containing high concentrations of a mixture of metals of natural origin such as chromium, cobalt, manganese, and nickel. A significant response was measured with both assays in the coelomocytes of the earthworms exposed to the Cd-spiked OECD soil as well as to the ultramafic soils. It was shown that as biomarkers for the assessment of ‘sub-cellular’ toxicity, the photometrical application of the MTT and the NRR assay promised to be rapid, objective, and easily conductible tools.     

Mikrosondenuntersuchungen an unterschiedlich stark mit Schwermetallen belasteten Böden. 2. Gehalte an Schwermetallen und anderen Elementen in Huminstoffaggregationen,Streustoffen und Holzkohlepartikeln

Electron microprobe studies on soil samples with varying heavy metal contamination. 2. Contents of heavy metals and other elements in aggregations of humic substances, litter residues and charcoal particles EMA point analysis show that the organic matter constituents of heavy metal contaminated soils are highly enriched with heavy metals. The maximal trace element accumulation were for Cu up to 13,000 mg/kg, for Zn up to 48,000 mg/kg, for Cd up to 2,100 mg/kg and for Pb up to 193,000 mg/kg. The affinity for the accumulation of the different heavy metals in aggregations of humic substances can be described by the sequence Cu > Pb ? Cd > Zn ? Ni > Co. In very strongly acidified humic top soil horizons the Pb and Cd accumulation in the organic matter constituents is in competition with the accumulation in Fe and Mn oxides. The heavy metal contents (especially of Cu) of the organic matter are often correlated with the content of organically bound calcium. The EMA results also show that high heavy metal amounts occur in combination with Ca-accumulations in the epidermis and the outer bark parenchym of decayed roots. EMA point analysis of the interior of fungus sclerotias show that sclerotias can contain high amounts of heavy metals, in particular lead (up to 49,700 mg Pb/kg). From statistical results of EMA point analysis follows that lead and other heavy metals attached to humic substances are not only bound as metal organic complexes but also as organic metal phosphate complexes. Also charcoal particles of polluted soils contain high amounts of heay metals. The accumulation affinity is quite similar to that of humic substances.     

Examining the Effects of the Destroying Ammunition,Mines, and Explosive Devices on the Presence of Heavy Metals in Soil of Open Detonation Pit: Part 1—Pseudo-total Concentration

This paper presents the results of determining the pseudo-total concentration of five heavy metals in the soil on which the destruction of ammunition, mines, and explosive devices is carried out by the method of open detonation. In the analyzed area, the concentrations of cadmium, lead, nickel, copper, and zinc were determined, while from the physical properties of the soil were determined the granulometric composition and the pH. The aim of the study is to determine the origin and total load on heavy metals and, based on that, to assess the dangers and impact of the site in terms of the soil pollution by heavy metals. In accordance with the regulations of Bosnia and Herzegovina, the results of the soil testing showed a significant load of copper (up to seven times) and cadmium (up to six times), and exceeding the allowed values for nickel and zinc in some places. Lead was the only metal whose concentration was within the maximum allowed and according to that the soil was classified as unpolluted. A sample of soil from the edge of the pit is the only sample in which all heavy metals, except Ni, were within the maximum allowable concentration. In regard to the concentration of the examined metals, the soil of the pit is classified as medium polluted from the aspect of copper, cadmium, and nickel and highly contaminated with zinc. The concentrations of copper and zinc in the examination area correspond to contaminated soil that represents ecological risk, which requires soil remediation.     

Characterization of humic substances obtained from calcareous soils from Greece with various extractants. II. Physical characterization

Humic substances from the Ah horizons of five differently calcareous soils from Greece were successively extracted with organic solvents and/or 0.1 N NaOH and they were characterized by UV/VIS/IR spectroscopy and differential thermal analysis (DTA). Diethylether, acetone and dioxane extracts contained non-humic substances such as aliphatic and aromatic ethers, esters, alcoholes and long aliphatic chains, while low molecular weight humic substances were found in the ethanol extracts. All the extracts were found to contain phenolic and ?-acceptor compounds. Some differences in the physical characteristics of the humic substances were associated with the kinds of vegetation. The IR-spectra showed no essential differences between HA's and FA's extracted directly with NaOH or after previous soil extraction with organic solvents. HA's extracted directly by NaOH from soil samples under grass had a higher degree of condensation and thermal stability and generally higher carbon contents than those from soils under pine, cultivation and sedges.     

Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

Use of Single Extraction Methods to Predict Bioavailability of Heavy Metals in Polluted Soils to Rice

Human exposure to toxic heavy metals via dietary intake is of increasing concern. Heavy-metal pollution of a rice production system can pose a threat to human health. Thus, it was necessary to develop a suitable extraction procedure that would represent the content of metal available to rice plants (Oryza sativa L.). The aim of this study was to predict, on the basis of single extraction procedures of soil heavy metals, the accumulation of heavy metals (cadium, lead, copper, and zinc) in rice plants. Six extracting agents [Mehlich 1, Mehlich 3, EDTA (ethylenediaminetetraacetic acid), DTPA–TEA (diethylenetriaminepentaacetic acid–triethanolamine), ammonium acetate (NH₄OAc), and calcium chloride (CaCl₂)] were tested to evaluate the bioavailability of heavy metals from paddy soils contaminated with lead–zinc mine tailings to rice. The extraction capacity of the metals was found to be of the order EDTA > Mehlich 3 > Mehlich 1 > DTPA–TEA > NH₄OAc > CaCl₂. The correlation analysis between metals extracted with different extractants and concentrations of the metals in the grain and stalk of the plant showed positive correlations with all metals. The greatest values of correlation coefficients were determined between the NH₄OAc- and CaCl₂-soluble fractions of soil and contents in plants in all four metals studied. Therefore, NH₄OAc and CaCl₂ were the most suitable extractants for predicting bioavailability of heavy metals in the polluted soils to rice. The results suggested that uptake of heavy metals by rice was mostly from exchangeable and water-soluble fractions of the metals in the soils. Soil-extractable metals were more significantly correlated with metal accumulation in the stalk than in the grain. The pH had more significant influence on availability of heavy metals in the soils than total content of metals and other soil properties. The bioavailability of metals for rice plants would be high in acidic soils.     

冻融-化学淋洗法协同修复重金属Cd和Pb污染黏性土

针对质地黏重、低渗透性黏性土的淋洗效率低下,该文提出冻融协同化学淋洗的修复方案,并以某冶炼厂受Cd、Pb污染场地黏性土为研究对象,选用乙二胺四乙酸二钠(ethylene diaminetetraacetic acid disodium salt,EDTA)为淋洗剂,进行了冻融-淋洗土柱的实证试验。结果表明,土体的反复冻融(冻胀-吸水、融沉-排水)破坏土体颗粒原有结构,有助于淋洗液与污染物充分接触,淋洗效果明显,经7次冻融后,Cd、Pb去除率分别达到77.24%、37.78%。采用改进的BCR(European Communities Bureau of Reference)连续提取法分析了土柱中Cd、Pb的赋存特征,经7次冻融后,土壤中弱酸提取态、可还原态、残渣态结合的Cd质量分数较淋洗前分别降低了41.46%、63.02%、26.33%,而土壤中可还原态和残渣态结合的Pb质量分数分别降低了32.32%、67.36%。冻融协同化学淋洗修复技术的淋洗剂用量远小于传统淋洗法,为今后利用寒区冻融交替现象,大规模对季冻区重金属污染土壤的异位修复提供了新的思路。     

Dissolving Heavy Metals from Soils with Acids in order to Approximate Total Element Content

The average percentages of copper, zinc and nickel extracted with 2 N HNO₃ from typical slightly contaminated Swiss soils resulted in 59, 68 and 58% of the total, respectively. The amounts rose to 85% for zinc and to 69% for nickel using 3 N HCl. Copper, however, showed no higher solubility in this solvent. Possible reasons for the different solubility patterns of heavy metals are discussed on the basis of results obtained from X-ray and infrared investigations of soil colloids.