Leaching of Cu,Cd, Pb,and phosphorus and their availability in the phosphate-amended contaminated soils under simulated acid rain

Environmental Science and Pollution Research - Phosphate amendments have been used to immobilize heavy metal-contaminated soils. However, phosphate amendments contain large amounts of phosphorus,...     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.     

Impact of the earthworm Lumbricus terrestris (L.) on As, Cu, Pb and Zn mobility and speciation in contaminated soils

To assess the risks that contaminated soils pose to the environment properly a greater understanding of how soil biota influence the mobility of metal(loid)s in soils is required. Lumbricus terrestris L. were incubated in three soils contaminated with As, Cu, Pb and Zn. The concentration and speciation of metal(loid)s in pore waters and the mobility and partitioning in casts were compared with earthworm-free soil. Generally the concentrations of water extractable metal(loid)s in earthworm casts were greater than in earthworm-free soil. The impact of the earthworms on concentration and speciation in pore waters was soil and metal specific and could be explained either by earthworm induced changes in soil pH or soluble organic carbon. The mobilisation of metal(loid)s in the environment by earthworm activity may allow for leaching or uptake into biota.     

Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd, Cu, Pb, and Zn

The effectiveness of phosphate treatment for Cd, Cu, Pb, and Zn immobilization in mine waste soils was examined using batch conditions. Application of synthetic hydroxyapatite (HA) and natural phosphate rock (FAP) effectively reduced the heavy metal water solubility generally by about 84-99%. The results showed that HA was slightly superior to FAP for immobilizing heavy metals. The possible mechanisms for heavy metal immobilization in the soil involve both surface complexation of the metal ions on the phosphate grains and partial dissolution of the phosphate amendments and precipitation of heavy metal-containing phosphates. HA and FAP could significantly reduce Cd, Cu, Pb, and Zn availability in terms of water solubility in contaminated soils while minimizing soil acidification and potential risk of eutrophication associated with the application of highly soluble phosphate sources.     

Influence of ozonation on extractability of Pb and Zn from contaminated soils

The effect of soil ozonation on Pb and Zn extraction with EDTA, bioavailability (Ruby's Physiologically Based Extraction Test, PBET) and mobility (Toxicity Characteristic Leaching Procedure, TCLP) of Pb was studied on contaminated soils taken from 7 different locations in the Mezica Valley, Slovenia. EDTA extraction (40 mmol kg(-1)) removed from 27.4+/-1.5% to 64.8+/-1.5% of Pb, and from 1.9+/-0.2% to 22.4+/-2.0% of Zn from tested soils, and significantly reduced soil Pb bioavailability (PBET) and mobility (TCLP). Pretreatment of tested soils with ozone before EDTA extraction enhanced EDTA extractability of Pb for 11.0 to 28.9%, but had no effect on the extractability of Zn. In most of the soils, ozonation had no statistically significant effect on bioavailability and mobility of Pb, residual after EDTA extraction. Using linear regression analysis we found a significant increase (p<0.01) in EDTA extractability of Pb after soil ozonation in soils with a higher initial Pb content. EDTA extractability of Pb after soil ozonation was also significantly higher for soils with a lower Pb extractability when treated with EDTA alone. We found no correlation between soil organic matter content and the percentage of the Pb fraction bound to soil organic matter (where from 25.6+/-1.3% to 73.2+/-0.6% of Pb reside in tested soils) and Pb extractability with EDTA after soil ozonation.     

Leaching behaviour of Cd, Cu, Pb and Zn in surface soils derived from dredged sediments

Leaching of heavy metals from land-disposed dredged sediment spoils is a potential environmental hazard. The leaching behavior of Cd, Cu, Pb and Zn in surface soils sampled from abandoned dredged sediment disposal sites was assessed. Using simple mass-balance calculations, the significance of the leaching test results with respect to metal migration into underlying clean soil was appraised. The potential leachability, defined as the amounts released at constant pH 4, decreased in the order (% of total contents): Zn (58%) approximately equal to Cd (49%)>Cu (5%) approximately equal to Pb (2%). The kinetics of metal release were determined in a cascade shaking test using de-mineralized water acidified to pH 4 (HNO(3)). Metal concentrations in the leachates were low and metal migration was, assuming uniform convective flow, predicted to be of no environmental concern. It is emphasized that any long-term prediction of metal migration is uncertain.     

Bio-immobilization of Cu and Zn in recirculated bioreactor landfill

Purpose  

To protect the environmental quality of soil, groundwater, and surface water near the landfill site, it is necessary to make an accurate assessment of the heavy metal mobility. This study aims to present the bio-immobilization behavior of heavy metals in landfill and provide some reference suggestion for the manipulation of heavy metal pollution control after closure.     

Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract--I. Leaching in soil columns

Application of poultry litter to cropland may increase metal mobility, because the soluble organic ligands in poultry litter can form water-soluble complexes with metals. In this study, one uncontaminated soil and two metal-contaminated soils were sampled. A portion of the uncontaminated soil was amended with Zn, Pb, and Cd at rates of 400, 200, and 8 mg kg(-1), respectively. Packed soil columns were leached with H2O, EDTA, CaCl2, and poultry litter extract (PLE) solutions separately. No leaching of Zn, Cd, and Pb with the PLE was found in the uncontaminated soil. The retention of PLE-borne Zn indicated the potential for Zn accumulation in the soil. A large portion of the metals was leached from the metal-amended soil, and EDTA solubilized more Zn, Cd, and Pb than CaCl2 and PLE. In the metal-contaminated soils, the leaching of Zn and Cd with PLE was consistently larger than that for CaCl2, indicating that these metals were mobilized by organic ligands. The PLE did not mobilize Pb in these soils. The utilization of poultry litter in metal-contaminated soils might accelerate the movement of Zn and Cd in soil profiles.     

Cu accumulation in the earthworm Dendrobaena veneta in a heavy metal (Cu, Pb, Zn) contaminated site compared to Cu accumulation in laboratory experiments

Earthworms (Dendrobaena veneta) were exposed to heavy metal contaminated soil from a field site under both laboratory and field conditions. In the laboratory study, D. veneta were analysed for Cu after 2 weeks' exposure. The tissue Cu concentration (Cu(W)) increased proportionally with the total extractable soil Cu content (Cu(T)) in soils that contained less than 150 mg Cu kg(-1). In D. veneta exposed to soils containing more than Cu(T) = 150 mg kg(-1), however, we observed no further increase in Cu(W). In a 64-m(2) field plot at a contaminated site, 81 soil samples were taken and analysed for Cu, Pb, Zn and pH. In June 1994, 1000 D. veneta were homogeneously distributed in the plot and sampled after 1, 2 and 5 weeks to analyse for Cu. Additionally, 2000 D. veneta were introduced in September 1994 and sampled after 1, 2 and 4 weeks. At locations where earthworms were removed, the soil Cu content was estimated by disjunctive kriging. Cu concentration factors (ratio of Cu(W) to Cu(T)) in the field experiment were in excellent agreement with those of the laboratory experiment. This indicates that, with a sufficiently high sampling density, it may be feasible to predict earthworm Cu accumulation in the field using a concentration factor determined in the laboratory.     

Mobility of Zn, Cd and Pb in soils as affected by poultry litter extract--II. Redistribution among soil fractions

The application of poultry litter to metal-contaminated soils may influence metal leaching and distribution of metals among soil fractions. Soil columns (one uncontaminated control, one metal-amended, and two metal-contaminated soils) were leached with H2O, CaCl2, EDTA, and poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for water soluble (WS), exchangeable (EXC), organic matter (OM), Mn oxide (MNO), amorphous Fe oxide (AFEO), crystalline Fe oxide (CFEO) and residual (RES) fractions. The OM fraction showed high retention for Zn from the PLE. The EDTA redistributed Zn, Cd and Pb from the EXC, OM and MNO fractions to the WS fraction. The PLE usually solubilized more Zn and Cd from the EXC fraction than CaCl2. Neither PLE nor CaCl2 mobilized Pb. The application of poultry litter on metal-contaminated soils might cause Zn and Cd redistribution from the EXC to the WS fraction and enhance metal mobility.     

Tillage management to mitigate herbicide loss in runoff under simulated rainfall conditions

Conservation tillage mitigates soil loss in cropland because plant residues help protect the soil, but effects on pesticide movement in surface runoff are not as straightforward. Effects of soil disturbance on surface runoff loss of chlorimuron and alachlor were evaluated utilizing runoff trays. Soil in the trays was either disturbed (tilled) and kept bare or was not tilled, and existing decomposed plant residue was left on the surface. Rainfall (25mm, 20min) was simulated 1d after alachlor (2.8kg ha(-1)) or chlorimuron (54g ha(-1)) application, and runoff was collected. Runoff fractions were analyzed for herbicide and sediment. Total alachlor loss from bare plots was greater than that in no-tillage plots (4.5% vs. 2.3%, respectively). More than one-third of total alachlor lost from bare plots occurred in the first l of runoff, while no-tillage plots had less runoff volume with a more even distribution of alachlor concentration in the runoff during the rainfall simulation and subsequent runoff period. In contrast, more chlorimuron was lost from no-tillage plots than bare plots (12% vs. 1.5%) even though total runoff volume was lower in the no-tillage plots (10.6mm vs. 13.6mm). This was attributed to dense coverage with partially decomposed plant residue in no-tillage plots (1652kg ha(-1)) that intercepted chlorimuron. It was likely that chlorimuron, a polar compound, was more easily washed off surface plant residues and transported in runoff.     

Remediation of contaminated agricultural soils near a former Pb/Zn smelter in Austria: batch, pot and field experiments

Metal contaminated crops from contaminated soils are possible hazards for the food chain. The aim of this study was to find practical and cost-effective measures to reduce metal uptake in crops grown on metal contaminated soils near a former metal smelter in Austria. Metal-inefficient cultivars of crop plants commonly grown in the area were investigated in combination with in-situ soil amendments. A laboratory batch experiment using 15 potential amendments was used to select 5 amendments to treat contaminated soil in a pot study using two Barley (Hordeum vulgare L.) cultivars that differed in their ability to accumulate cadmium. Results from this experiment identified 3 of these amendments for use in a field trial. In the pot experiment a reduction in ammonium nitrate extractable Cd (<41%) and Pb (<49%) compared to the controls was measured, with a concurrent reduction of uptake into barley grain (Cd<62%, Pb<68%). In the field extractable fractions of Cd, Pb, and Zn were reduced by up to 96%, 99%, and 99%, respectively in amended soils.     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

模拟酸雨对磷酸二氢钾钝化污染土壤Cu、Cd、Pb和P释放的影响

以磷酸二氢钾(PDP)钝化后的重金属污染土壤为研究对象,通过室内土柱淋溶实验,考察在pH为3.5、4.5和5.6的模拟酸雨作用下土壤Cu、Cd、Pb和P的释放特征。结果表明:PDP处理较对照处理显著增加了淋出液中pH、电导率(EC)和总有机碳(TOC)含量,但不同pH模拟酸雨对对照和PDP处理淋出液pH、EC和TOC含量影响较小。对照处理中,正磷酸盐含量维持在较低水平(0.02~0.13 mg·L-1);PDP处理下,正磷酸盐含量在1~3 L和4~12 L分别是《地表水环境质量标准》(GB 3838-2002)五类水标准(总磷含量0.4 mg·L-1)的55.1~819倍和9.46~46.6倍,对地表水表现出较大的富营养化风险。PDP处理较对照处理显著降低了淋溶初期淋出液中的Cu、Cd和Pb含量,但是随模拟酸雨pH降低,对照和PDP处理的土壤淋出液中Cu、Pb含量均未表现出显著差异。因此,PDP处理能够显著钝化污染土壤中的Cu、Cd和Pb,但需关注酸雨淋溶下过量磷释放对地表水富营养化的潜在风险。     

超声强化淋洗修复Pb、Cd、Cu复合污染土壤

针对传统淋洗法修复土壤中重金属效率较低的问题,研究了超声强化淋洗技术以提高重金属去除率。以铅（Pb）、镉（Cd）、铜（Cu）为目标污染物,在0.05 mol·L-1柠檬酸、0.05 mol·L-1EDTA和0.05 mol·L-1皂角苷作为淋洗剂条件下,使用传统振荡、超声强化以及超声波加振荡3种不同的作用方式,对Pb、Cd、Cu的去除率进行比较,并对3种不同淋洗方式后Pb、Cd、Cu的形态变化进行了探讨。结果表明,当使用柠檬酸和皂角苷作为淋洗剂进行振荡淋洗时,重金属洗脱效果不理想。超声对于强化柠檬酸洗脱效果并不明显,而对于强化皂角苷洗脱重金属效果明显,平均去除率提高了120.47%。当淋洗剂为EDTA时,土壤样品在传统振荡2 h作用下,对Pb、Cd、Cu的去除率依次为50.33%、76.65%和47.35%,而在超声波30 min条件下对Pb、Cd、Cu的去除率依次为82.19%、83.31%和53.89%,平均去除率高出28.60%,可显著提高重金属去除率,缩短淋洗时间。但超声波30 min加传统振荡2 h相较于单纯超声强化效果提升不明显。通过对比3种淋洗方式后土壤中的Pb、Cd、Cu形态发现,酸可提取态的重金属在超声强化作用后有明显降低,同时超声强化对于铁锰氧化物结合态、有机物结合态和残渣态也具有较好的去除能力。因此,超声强化在化学淋洗中的应用具有一定的可行性,是一种简单、极快速去除污染场地中重金属Pb、Cd、Cu的增效手段。     

底泥生长基质中重金属的迁移特征及生物有效性

河道底泥中重金属含量较高,重金属的迁移性及生物有效性是限制疏浚底泥土地施用或用作废弃场地修复基质资源化利用途径的主要因素。以沈阳细河待疏浚底泥为材料,通过盆栽实验的方法研究了河道底泥与碱性粉煤灰、炉渣和锯木屑配比基质中重金属在紫花苜蓿体内累积、迁移及生物有效性的变化。结果发现,配比底泥基质上紫花苜蓿生物量、株高及株径均好于纯底泥处理,其中底泥、粉煤灰、炉渣、锯木屑以2：0．5：0．5：0．5配比的s2处理中紫花苜蓿生物量是纯底泥处理的11．7倍。与底泥对照相比,配比底泥基质上植株体内重金属含量极显著降低,而且地上部重金属含量显著低于根部含量;底泥基质中紫花苜蓿地上部和根部对Cd、Cu、Pb、Zn的富集系数（BCF）显著低于底泥处理,但转移系数（TF）无显著变化,富集系数（BCF）和转移系数（TF）均小于1．0。紫花苜蓿种植后底泥基质中重金属含量显著低于农用污泥重金属控制标准,除Cd含量略高外,Cu、Pb和Zn含量低于土壤环境质量三级标准。这些结果表明,城市重污染河道底泥经过合理处置后,重金属浓度、活性及生物有效性降低,在其土地施用或废弃地修复中可以用作一些耐性植物的生长基质。     

Mobility of polychlorinated aromatic compounds in soils contaminated with wood-preserving oil

Greater understanding of the mobility of polychlorinated aromatic compounds in soils is needed to investigate contamination and design suitable remediation strategies for sites contaminated with wood-preserving oil. The objectives of this study were (1) to develop a suitable aqueous batch extraction method for soil containing wood-preservative residues; (2) to determine partition coefficients for the primary contaminants [pentachlorophenol (PCP), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFS)] in oil, soil, and aqueous phases; and (3) to evaluate the potential soil migration of the primary contaminants. In a three-phase oil-soil-water mixture, PCP, PCDDs, and PCDFs were partitioned to the greatest extent in the oil phase. These results suggest that the migration of contaminants can occur in a saturated subsurface soil zone containing an oil phase at a wood-preserving site. In the absence of a free oil phase, PCDDs and PCDFs were highly partitioned onto soil and were considered non-leachable in the aqueous phase. However, PCP was considered highly leachable from contaminated soil containing only an aqueous liquid phase. Results from this study indicate that removal of any free oil phase present in subsurface soil should have highest priority during the cleanup of contaminated wood-preserving sites.     

柠檬酸浸出土壤中铜、锌的优化设计

以某工业废弃地土壤为供试材料,采用批次实验方法,研究了柠檬酸对重金属Cu、Zn的浸出效果。并在单因素实验基础上,探讨不同pH值、柠檬酸浓度、固液比和浸提时间等对浸出效果的影响,进而对实验条件进行正交优化组合,确定优化工艺参数为：pH值为3.2,柠檬酸浓度为0.4 mol/L,壤土固液比为1/10,土壤中Cu、Zn接近平衡的时间分别为1 h和1.5 h。结果表明,在此条件下,对这2种金属来说,Cu较Zn易释放,Cu、Zn的最大浸出率分别为74.8%和65.3%。柠檬酸浸提前后,土壤中有机质含量下降范围为0.61%~3.16%。单从土壤有机质含量来看,柠檬酸对土壤质量影响较小,具有较好的应用前景。     

Airborne Pb,Cd, Zn and Cu concentration by particle size near a Pb smelter

A study of airborne Pb, Cd, Zn and Cu was conducted on 2 farms: a test farm exposed to a lead smelter and associated sources of lead contamination in the New Lead Belt of southeast Missouri, and a control farm outside the lead production area. An Andersen eight-stage impactor sampler was used on both farms to collect air samples during winter, spring and summer seasons. The trace element concentrations were measured by atomic absorption spectrophotometry. The concentrations of all four elements were higher on the test farm than on the control farm in all of the three seasons. Approximately 66% of the Pb. 88% of the Cd. 73% of the Zn and 54% of the Cu was composed of particles smaller than 4.7 μm the upper practical limit of respirable size.