Enhanced multi-metal extraction with EDDS of deficient and excess dosages under the influence of dissolved and soil organic matter

This study investigated the influence of dissolved and soil organic matter on metal extraction from an artificially contaminated soil. With high concentration of DOM, the extraction of Cu, Zn and Pb was enhanced by forming additional metal-EDDS complexes under EDDS deficiency. However, the enhancement of metal extraction under EDDS excess was probably due to the soil structure being disrupted owing to humic acid enhanced Al and Fe dissolution, which induced more metals dissolving from the soils. Fulvic acid was found to enhance metal extraction to a greater extent compared with humic acid because of its high content of the carboxylic functional group. Cu extraction from the soil with high organic matter content using EDDS was the lowest due to the high binding affinity of Cu to SOM, whereas Zn extraction became the highest because of a preference for EDDS to extract Zn due to the high stability constant of ZnEDDS.     

Release of trace metals, sulfate and complexed cyanide from soils contaminated with gas-purifier wastes: a microcosm study

Deposited gas-purifier wastes are commonly contaminated with trace metals, sulfate and cyanide (CN) compounds. We investigated their release from three soils contaminated with gas-purifier wastes into solution in microcosm experiments under varying redox conditions (E(H) 170-620 mV). The soils differed in pH (2.2; 4.9; 7.4) and featured low amounts of trace metals, but large amounts of total S and total CN. The pH governed trace metal release in the case of the acidic soil and CN release in the case of the slightly alkaline soil. The redox potential controlled trace metal and CN release in the case of the moderately acidic soil. Sources of dissolved SO(4)(2-) were dissolution of gypsum, desorption from Fe oxides and probably oxidation of elemental S. The geochemical behaviors of trace metals (soluble under acidic and reducing conditions) and CN (soluble under alkaline and oxidizing conditions) were diametrically opposed.     

Effects of incubation on solubility and mobility of trace metals in two contaminated soils

Much research has focused on changes in solubility and mobility of trace metals in soils under incubation. In this experiment, changes in solubility and mobility of trace metals (Pb, Cu and As) and Fe in two contaminated soils from Tampa, Florida and Montreal, Canada were examined. Soils of 30 g were packed in columns and were incubated for 3-80 days under water-flooding incubation. Following incubation, metal concentrations in pore water (water soluble) and in 0.01 M CaCl2 leachates (exchangeable+water soluble) were determined. While both soils were contaminated with Pb (1600-2500 mg kg(-1)), Tampa soil was also contaminated with As (230 mg kg(-1)). Contrast to the low pH (3.8) of Tampa soil, Montreal soil had an alkaline pH of 7.7 and high Ca of 1.6%. Concentrations of Fe(II) increased with incubation time in the Tampa soil mainly due to reductive Fe dissolution, but decreased in the Montreal soil possibly due to formation of FeCO3. The inverse relationship between concentrations of Pb and Fe(II) in pore water coupled with the fact that Fe(II) concentrations were much greater than those of Pb in pore water may suggest the importance of Fe(II) in controlling Pb solubility in soils. However, changes in concentrations of Fe(II), Pb, Cu and As in pore water with incubation time were similar to those in leachate, i.e. water soluble metals were positively related to exchangeable metals in the two contaminated soils. This research suggests the importance of Fe in controlling metal solubility and mobility in soils under water-flooded incubation.     

Evaluation of remediation process with plant-derived biosurfactant for recovery of heavy metals from contaminated soils

A washing process was studied to evaluate the efficiency of saponin on remediating heavy metal contaminated soils. Three different types of soils (Andosol: soil A, Cambisol: soil B, Regosol: soil C) were washed with saponin in batch experiments. Utilization of saponin was effective for removal of heavy metals from soils, attaining 90-100% of Cd and 85-98% of Zn extractions. The fractionations of heavy metals removed by saponin were identified using the sequential extraction. Saponin was effective in removing the exchangeable and carbonated fractions of heavy metals from soils. In recovery procedures, the pH of soil leachates was increased to about 10.7, leading to separate heavy metals as hydroxide precipitates and saponin solute. In addition recycle of used saponin is considered to be effective for the subsequent utilization. The limits of Japanese leaching test were met for all of the soil residues after saponin treatment. As a whole, this study shows that saponin can be used as a cleaning agent for remediation of heavy metal contaminated soils.     

石灰干化污泥对土壤重金属稳定化处理的效果

以采自湖南省嘉禾县重金属复合污染土壤为研究对象,采用城市污水处理石灰干化污泥作为稳定剂,对污染土壤进行稳定化处理,并采用TCLP和BCR连续提取法对稳定化效果进行分析和评价。研究结果表明,单独使用石灰干化污泥,TCLP浸出浓度随着干化污泥质量分数的增加而显著减少,干化污泥的质量分数为40%时,稳定化率最大为Zn-98.92%、Cd-99.06%、Pb-96.84%;但是干化污泥的高pH值导致稳定后土壤中As的浸出增加。为了恢复植物生长功能,经过亚铁盐和磷酸调节pH后,石灰干化污泥稳定过的土壤pH有效降低,同时亚铁盐和磷酸有利于促进Pb和Zn的稳定效果;但是对Cd的稳定有负面影响;另外,亚铁盐的加入同时可以减少As的浸出浓度。经处理后土壤中重金属形态由不稳定态转为稳定态,使重金属的浸出浓度明显降低,减少了土壤重金属的浸出毒性。该研究结果表明,石灰干化污泥可以作为资源回收利用,应用于重金属污染土壤的修复中,并能改善稳定后土壤适宜植物生长的理化性质。     

Effect of coal mine soil contamination on the elemental uptake and distribution in two edible Amaranthus species, A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

Degradability of ethylenediaminedisuccinic acid (EDDS) in metal contaminated soils: implications for its use soil remediation

Previous research has identified ethylenediaminedisuccinate (EDDS) as a promising biodegradable alternative for persistent compounds such as EDTA for application in soil washing or enhanced phytoextraction of heavy metals. This study examines heavy metal mobilization in three polluted soils varying in soil composition, with specific attention for competitive behaviour for complexation between the various metals and major elements, such as Al, Fe, Mn, Ca and Mg. In addition, amendment biodegradability was compared between the different soil types. The selected soils included a moderately contaminated calcareous clayey soil, a dredged sediment derived surface soil with similar soil characteristics yet more heavily polluted with Cd, Cr and Zn, and a sandy soil moderately contaminated by historical smelter activity (atmospheric deposition). Biodegradability of EDDS in the three soils varied distinctly. This was mainly expressed in the duration of the lag phase prior to metal complex degradation, and not so much in the half life when degradation effectively did set in. Differences in the lag phase were attributed to differences in soil pollution. However, EDDS was fully degraded within a period of 54 d in all soils regardless of initial delay. Assessment of the cation mobilisation patterns in the three soils under study revealed that mainly Ca, Fe and Al can reduce effectiveness of heavy metal mobilisation by competition for complexation.     

Microbial cellulose decomposition in soils from a rifle range contaminated with heavy metals

The objective of this study was to assess the effects of heavy metals on microbial decomposition of cellulose in heavy metal-contaminated soils using a cotton strip assay. The assay is a measure of the potential of soil microorganisms to decompose the plant polymer, cellulose. Cellulolytic activity in soil was assessed by determining the reduction in tensile strength of the buried cotton strips over a 25- and 45-day period. Soils were obtained from a rifle range that contain high levels of lead, copper and zinc. The site has been used for approximately 50 years, resulting in metal levels of up to 30,000 mg/kg of lead, 4000 mg/kg of copper and 600 mg/kg of zinc in the most contaminated soils. All the metal-contaminated soils had lower degradation rates than the uncontaminated soils tested. Among the contaminated soils, however, the heavy metal concentration was not the major factor in determining the loss in tensile strength of the cotton strips, where cellulose decomposition was governed by other soil physicochemical properties. Soil with a higher cation exchange capacity, readily oxidisable material and volatile solids content had the greatest loss in tensile strength of cotton strips. Microbial adaptation to the presence of high concentrations of soil heavy metals and reduced bioavailability of metals is the likely explanation for this phenomenon.     

Trace metal speciation and bioavailability in urban soils

Urban soils often contain concentrations of trace metals that exceed regulatory levels. However, the threat posed by trace metals to human health and the environment is thought to be dependent on their speciation in the soil solution rather than the total concentration. Three inactive railway yards in Montréal, Québec, were sampled to investigate the speciation and bioavailability of Cd, Cu, Ni, Pb and Zn. Soil solutions were obtained by centrifuging saturated soil pastes. In the soil solutions, up to 59% of the dissolved Cd was in its free ionic form. For Cu, Pb and Zn, organic complexes were the predominant species. Over 40% of Ni was present as inorganic complexes if the solution pH exceeded 8.1. Multiple regression analyses showed that pH and total metals in soil were significantly correlated with the activities of free metal ions, except for Cd(2+), which only had a weak correlation with soil pH. Free, dissolved and total soil metals were tested for their ability to predict metal uptake by plants in the field. However, none of these metal pools were satisfactory predictors. The results indicated that in these urban soils, trace metals were mainly in stable forms and bioavailability was extremely low.     

Solubility of lead, zinc and copper added to mineral soils

Elevated levels of heavy metals in soils are a result of industrial activities, atmospheric deposition, and the land application of sewage sludges and industrial by-products. Their persistence in the soil environment has created interest in the possible changes in solubility. In this study, total dissolved concentrations of Pb, Zn, and Cu were monitored in seven metal-amended soils (a calcareous and six acid mineral soils). Single metal solutions were added to soils and equilibrated (aged) for 40 days. During the 40 days the soil was allowed to air-dry and was rewetted in cycles of about 5 days. At the end of this reaction period, metal solubility was measured (by atomic absorption spectrometry and direct current plasma spectrometry) at the initial soil pH and at decreased pH values which were induced by addition of small aliquots of acid. As expected, solubility of added Pb, Zn, and Cu increased with a decrease in pH. Furthermore, the results showed that the solubility relationship with pH was similar in all non-calcareous soils. This suggests that metal solubility may be controlled by similar soil components, presumably involving soil characteristics such as pH, organic matter content, and soil mineralogy. For each metal, an approximate pH value was found at which solubility deviated from the solubility of metals when they occur in soils at typical (natural) values. This pH was about (pH+/-0.2): 5.2 for Pb, 6.2 for Zn, and 5.5 for Cu. Thus, pH values below these thresholds may enhance metal mobility, biological availability and toxicity in soils. Metals dissolved at higher pH in the calcareous soil (18.8 g kg(-1) inorganic carbon, initial pH 8.2). In a calcareous soil, a significant fraction of these metals react with carbonates, and decreased pH results in much higher metal dissolution. Yet, metal solubility in soils is not determined by the formation and dissolution of single metal compounds.     

Effects of low-molecular-weight organic acids and residence time on desorption of Cu, Cd, and Pb from soils

Effects of low-molecular-weight organic acids (LMWOAs) and residence time on desorption of Cu, Cd, and Pb from two typical Chinese soils were studied. Citric, malic, and acetic acids were chosen as representatives of LMWOAs commonly present in soils. CaCl(2) and NaNO(3) were used in desorption as they were main soil background electrolytes for comparison. Desorption of Cu, Cd, and Pb from both soils followed the descending order: citric acid>malic acid>acetic acid>CaCl(2)>NaNO(3), which was consistent with the order of stability of Cu-, Cd-, and Pb-LMWOAs complexes from large to small and ion exchange ability of Ca(2+) and Na(+). Desorption of metals by inorganic salts decreased with increasing desorption solution pH. Whereas desorption of metals by LMWOAs showed different trend in response to pH change due to their different complexing abilities. Malic and acetic acids released less metals at low pH 3.1 compared with citric acid at pH 7, indicating that pH was not the dominant factor governing the release of metals. In addition, all LMWOAs desorbed more metals than inorganic salts, CaCl(2) and NaNO(3). Therefore, organic ligands played a dominant role in desorption of heavy metals. More metals were released from Jiangxi soil than from Heilongjiang soil due to lower soil pH, CEC, organic matter content and manganese oxide of Jiangxi soil. Generally, desorption of metals decreased with increasing residence time of metals in soils.     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Use of bone meal amendments to immobilise Pb, Zn and Cd in soil: A leaching column study

The aim of this study is to test the stabilisation of metals in contaminated soils via the formation of low-solubility metal phosphates. Bone apatite, in the form of commercially available bone meal, was tested as a phosphate source on a mine waste contaminated made-ground with high levels of Pb, Zn and Cd. Triplicate leaching columns were set up at bone meal to soil ratios of 1:25 and 1:10, in addition to unamended controls, and were run for 18 months. The columns were irrigated daily with a synthetic rain solution at pH of 2, 3, and 4.4. After 100 days, the leachate Pb, Zn and Cd concentrations of all amended columns were significantly reduced. For 1:10 treatments, release of these metals was suppressed throughout the trial. For 1:25 treatments, Zn and Cd concentrations in the leachates began to increase after 300 days. DTPA and water extractions showed that Pb and Cd were more strongly held in the amended soils. This study concludes that the complexity of soil processes and the small quantities of metals sequestered precluded determination of a metal immobilisation mechanism.     

Adsorption and cosorption of cadmium and glyphosate on two soils with different characteristics

Glyphosate [N-(phosphonomethyl)glycine] (GPS; H3G) is a widely used pesticide throughout the world. It affects metal behaviors in soil-plant system due to its functional groups, which react with metal ions to form metal complexes. Adsorption and cosorption of cadmium and glyphosate on a Wushan soil (WS soil, Anthrosol) and a Zhuanhong soil (ZH soil, Udic Ferrisol) as affect by solution pH were studied by means of batch adsorption experiments. It indicated that the adsorption quantity of Cd or glyphosate was highly relevant to soil characteristics. The WS soil had higher adsorption capacity of Cd than the ZH soil, due to its high organic matter content and cation exchange capacity (CEC). In contrast, the adsorption quantity of glyphosate on the WS soil was less than that on the ZH soil, because the WS soil has lower iron and aluminum oxides content but higher pH than the ZH soil. The herbicide glyphosate affected Cd adsorption on the two soils when they coexisted in a same soil solution, which was attributed to a glyphosate-induced pH-decrease and the corresponding decline in negative surface charges of the soil. Beside that, glyphosate reacted with solution Cd to form the water-soluble complexes that had lower affinity to soil surface in comparison with Cd itself. On the other hand, the presence of Cd in the soil solution also affected the adsorption of glyphosate on the soils. The presence of Cd increased adsorption quantity of glyphosate on the WS and ZH soils, which was resulted from the decrease of equilibrium solution pH caused by Cd2+ exchange with H+ ions of soil surface. In addition to that, glyphosate adsorption possibly takes place on sites where Cd was previously adsorbed and acted as a bridge between the soil and glyphosate.     

Recycling EDTA solutions used to remediate metal-polluted soils

The objective of this research was to investigate the recycling of ethylenediamine-tetraacetic acid (EDTA) used for the removal of trace metals from contaminated soils. We successfully used Na2S combined with Ca(OH)2 to precipitate the trace metals allowing us to recycle the EDTA. The results of batch and column leaching experiments show that both Ca-EDTA and Na-EDTA are powerful chelating agents with a similar soil remediation potential. The major advantage of Ca-EDTA is the preservation of soil organic matter. We found that Na2S was capable of separating the metals Cd, Cu and Pb from EDTA; however, the precipitation of Zn required the addition of Ca(OH)2. After reusing the reclaimed EDTA seven times, over a 14-day period, EDTA reagent losses ranged from 19.5% to 23.5%. Successive washing cycles enhanced the removal of trace metals from contaminated soils. The metal sulfide precipitates contain high concentrations of metals and could potentially be recycled.     

Mobility of Pb, Cu, and Zn in the phosphorus-amended contaminated soils under simulated landfill and rainfall conditions

Phosphorus-bearing materials have been widely applied in immobilization of heavy metals in contaminated soils. However, the study on the stability of the initially P-induced immobilized metals in the contaminated soils is far limited. This work was conducted to evaluate the mobility of Pb, Cu, and Zn in two contrasting contaminated soils amended with phosphate rock tailing (PR) and triple superphosphate fertilizer (TSP), and their combination (P?+?T) under simulated landfill and rainfall conditions. The main objective was to determine the stability of heavy metals in the P-treated contaminated soils in response to the changing environment conditions. The soils were amended with the P-bearing materials at a 2:1 molar ratio of P to metals. After equilibrated for 2 weeks, the soils were evaluated with the leaching procedures. The batch-based toxicity characteristic leaching procedure (TCLP) was conducted to determine the leachability of heavy metals from both untreated and P-treated soils under simulated landfill condition. The column-based synthetic precipitation leaching procedure (SPLP) were undertaken to measure the downward migration of metals from untreated and P-treated soils under simulated rainfall condition. Leachability of Pb, Cu, and Zn in the TCLP extract followed the order of Zn?>?Cu?>?Pb in both soils, with the organic-C- and clay-poor soil showing higher metal leachability than the organic-C- and clay-rich soil. All three P treatments reduced leachability of Pb, Cu, and Zn by up to 89.2, 24.4, and 34.3 %, respectively, compared to the untreated soil, and TSP revealed more effectiveness followed by P?+?T and then PR. The column experiments showed that Zn had the highest downward migration upon 10 pore volumes of SPLP leaching, followed by Pb and then Cu in both soils. However, migration of Pb and Zn to subsoil and leachate were inhibited in the P-treated soil, while Cu in the leachate was enhanced by P treatment in the organic-C-rich soil. More than 73 % P in the amendments remained in the upper 0–10 cm soil layers. However, leaching of P from soluble TSP was significant with 24.3 % of P migrated in the leachate in the organic-C-poor soil. The mobility of heavy metals in the P-treated soil varies with nature of P sources, heavy metals, and soils. Caution should be taken on the multi-metal stabilization since the P amendment may immobilize some metals while promoting others’ mobility. Also, attention should be paid to the high leaching of P from soluble P amendments since it may pose the risk of excessive P-induced eutrophication.     

Effect of Coal Mine Soil Contamination on the Elemental Uptake and Distribution in Two Edible Amaranthus Species,A. dubius and A. hybridus

The impact of coal mine dump contaminated soil on the elemental uptake by two edible plants, namely, Amaranthus dubius (red herbs) and Amaranthus hybridus (green herbs), was studied by investigating their response and ability to tolerate and accumulate varying levels of elements in their roots and shoots. The vegetation was grown on varying amounts of contaminated soil, viz. 0%, 5%, 15%, 25% w/w using coal mine dump soil. The soil was analyzed for soil pH, cation exchange capacity (CEC), soil organic matter (SOM), moisture content, and selected heavy metals. The distribution of six metals, namely, Pb, Cd, Hg, Ni, Mn, and Fe, in roots, stem, and leaves of the plants was determined in two stages of growth after 5 weeks and 10 weeks. All soil and plant samples were microwave digested and subjected to heavy metal analysis using the ICP-OES, GFAAS, and CVAAS. The pH of the coal mine dump contaminated soil decreased with an increase in contamination. Both the SOM and CEC values decreased, which increases the availability of elements, by providing more binding sites in the soil. Relatively, the red herbs had higher elemental concentrations than the green herbs. Both plants recorded high manganese accumulation. No mercury was detected in the soils or plants.     

The effects of multiple metal contamination on ectomycorrhizal Scots pine (Pinus sylvestris) seedlings

Experiments were conducted to investigate the effects of single and multiple metal contamination (Cd, Pb, Zn, Sb, Cu) on Scots pine seedlings colonised by ectomycorrhizal (ECM) fungi from natural soil inoculum. Seedlings were grown in either contaminated field soil from the site of a chemical accident, soils amended with five metals contaminating the site, or in soil from an uncontaminated control site. Although contaminated and metal-amended soil significantly inhibited root and shoot growth of the Scots pine seedlings, total root tip density was not affected. Of the five metals tested in amended soils, Cd was the most toxic to ECM Scots pine. Field-contaminated soil had a toxic effect on ECM fungi associated with Scots pine seedlings and caused shifts in ECM species composition on ECM seedlings. When compared to soils amended with only one metal, soils amended with a combination of all five metals tested had lower relative toxicity and less accumulation of Pb, Zn and Sb into seedlings. This would indicate that the toxicity of multiple metal contamination cannot be predicted from the individual toxicity of the metals investigated.     

EDTA及其回收溶液治理重金属污染土壤的研究

试验结果表明,EDTA能够有效地萃取土壤重金属,由于其价格较贵和不易被降解等特点,限制了它的广泛运用.在运用MINTEQA2模型对萃取液中重金属离子形态分析的基础上,选用Na2S沉淀法将重金属从EDTA萃取液中有效分离.同时将回收的EDTA连续进行萃取土壤重金属,由于回收EDTA浓度下降的原因,其效果比新鲜EDTA的要稍微差一点,但从经济和效率上来说,仍旧可以用来治理重金属污染的土壤.     

Using biochar for remediation of soils contaminated with heavy metals and organic pollutants

Soil contamination with heavy metals and organic pollutants has increasingly become a serious global environmental issue in recent years. Considerable efforts have been made to remediate contaminated soils. Biochar has a large surface area, and high capacity to adsorb heavy metals and organic pollutants. Biochar can potentially be used to reduce the bioavailability and leachability of heavy metals and organic pollutants in soils through adsorption and other physicochemical reactions. Biochar is typically an alkaline material which can increase soil pH and contribute to stabilization of heavy metals. Application of biochar for remediation of contaminated soils may provide a new solution to the soil pollution problem. This paper provides an overview on the impact of biochar on the environmental fate and mobility of heavy metals and organic pollutants in contaminated soils and its implication for remediation of contaminated soils. Further research directions are identified to ensure a safe and sustainable use of biochar as a soil amendment for remediation of contaminated soils.