An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

螯合剂对小麦幼苗吸收金属以及土壤金属形态的效应

本文通过盆栽试验研究三种螯合剂(EDTA、[S,S]-EDDS、DTPA)对小麦幼苗吸收土壤中重金属及其它微量元素的效应,并且通过改进的BCR连续提取法分析了种植后土壤样品中金属元素的形态。结果表明:EDTA、DTPA的添加导致小麦幼苗地上部分生物量以及叶片叶绿素a含量显著下降。螯合剂的存在明显增加了Pb和Mn在幼苗根部和茎叶的富集,并增加其由根部向茎叶的传输,但对Fe和Ni的作用比较小。小麦幼苗收获时,除Zn之外,其它元素酸溶/可交换态金属含量与对照组相比均有非常显著的增加,而各元素的可还原态由于EDTA等螯合剂的添加而有明显下降。添加螯合剂的情况下,富集量与酸溶/可交换态含量之间的相关系数大大提高,且各处理组茎叶富集量与酸溶/可交换态之间呈显著(P0.05)或极显著相关(P0.01)。因此,三种螯合剂的添加主要影响的是生物可利用形态以及潜在的生物可利用形态,并且可能导致可还原态以及可氧化态向酸溶/可交换态转变,增加金属的生物可利用性,从而也增加潜在生态风险。     

The effect of application time of mobilising agents on growth and phytoextraction of lead by Brassica napus from a calcareous mine soil

Phytoremediation of heavy metal contaminated sites is often limited by the low-bioavailability of the contaminants. Complexing agents can help to improve this technique by enhancing heavy metal solubility. Pot experiments were conducted to determine the best time for the application of ethylene diamine tetraacetic acid (EDTA) and sheep manure extract (SME) for phytoremediation of a contaminated soil by Brassica napus. The plant was grown on a mine calcareous soil treated with increasing concentrations of EDTA or SME 30 and 10?days before sowing (T1 and T2) and 10 and 30?days after sowing (T3 and T4). Soil available Pb and lead concentrations in plant organs of Brassica napus increased with EDTA concentration. The EDTA application before seed germination significantly reduced rapeseed seedling emergence and dry weight. However, the actual amount of phytoextracted Pb by rapeseed did not decrease significantly, due to severe growth depression, at high EDTA concentrations when it had applied at a suitable time (T4). SME application after sowing increased plant dry weight and Pb concentration in the soil solution and enhanced the accumulated metal concentrations in shoots and roots. Comparing the effect of EDTA and SME on Pb phytoextraction, the study showed that SME is not more effective than EDTA. The efficiency of EDTA on Pb phytoextraction by Brassica napus depends on the time of application. The most efficient treatment for Pb phytoextraction by rapeseed was application of 2?g EDTA/kg soil at T4.     

Remobilization of selected metal ions from Nile sediment (Egypt) according to sequential extraction and metal–EDTA complex

River sediments are basic components of our environment, providing nutrients for living organisms and serving as sinks for deleterious chemical species. The metal contents may be remobilized and released back into waters with changes in environmental conditions, thus affecting living organisms and human activities. This paper aims to determine the effect of a synthetic anthropogenic chelating agent (EDTA) as industrial discharges on the remobilization of several metals (Cu, Zn, Cd, and Pb) in River Nile sediments (at Aswan and Mansoura cities) under different concentrations and pH values, and to investigate the influence of metal–EDTA complexes on this remobilization. For these purposes, sequential extraction and experiments on the effect of pH and metal EDTA complex were carried out on the two representative sediment samples south and north of the River Nile in Egypt. The results of sequential extraction show that most of metal contents present in the residual form (Cu, 11.36–72.34%; Pb, 29.64–66.67%; and Zn, 43.76–50.09% at Aswan and Mansoura, respectively). Non-residual fractions which may be available for the remobilization by EDTA represented anthropogenic (industrial, agriculture, and domestic discharges) and lithiopogenic (metals bound to Fe and Mn oxides) sources. A clear increase was detected for Cu and Zn remobilization from the increase in EDTA concentrations, in contrast, Cd independent of the EDTA concentration and slight influence on Pb content. The remobilization of metals as a function of pH exhibited. The metals were greatly remobilized under the complexing action of EDTA, showing that some of these elements were adsorbed on the sediments. The remobilization rate of metals was dependent upon the added metal–EDTA complex (with the exchange rate being in the order Ca–EDTA>Zn–EDTA>Cd–EDTA>Cu–EDTA>Pb–EDTA), due to the stability constant of the metal–EDTA complex. The results of these experiments showed that heavy metals are greatly remobilized under the complexing action of EDTA when it is present in excess, so all precautions should be taken to prevent any wastewater containing EDTA or any chelating agents discharging directly or indirectly via the River Nile stream because most EDTA remains in the aquatic phase. The ability of this portion to remobilize metals from sediments should be taken into account.     

Effect of red mud addition on the fractionation and bio-accessibility of Pb,Zn and As in combined contaminated soil

Using soil incubation experiments, the effect of red mud addition on the fractionation and bioaccessibility of Pb, Zn and As in combined contaminated soil was studied. The results showed that red mud addition could significantly decrease the concentration of HOAc-extractable Pb and Zn in soil. Compared with the control, 5% red mud addition could significantly reduce the concentrations of HOAc-extractable Pb and Zn in soil after 1, 2 and 3 months of incubation [62.5, 65.3 and 73.5% decrease (Pb), 56.7, 65.8 and 67.4% decrease (Zn)]. Whereas adding red mud could remarkably increase the concentrations of specific absorbed As and residual As in soil. The result of a simple bioavailability extraction test (SBET) indicated that all treatments with red mud addition markedly reduced the concentration of bioaccessible Zn but increased the concentration of bioaccessible As in soil, while having little effect on the concentration of bioaccessible Pb in soil. After 3 months incubation, all treatments including 1, 2 and 5% red mud addition reduced the concentration of bioaccessible Zn by 53.1–56.7% compared with the control, but increased the concentration of bioaccessible As by 1.81–6.25 times. The results suggested that red mud is an additive with potential for the remediation soil contaminated soil by combinations of heavy metals, although it should be added based on the different heavy metals in the soil. Combined use of red mud and hyperaccumulators to remediate heavy metal contaminated soil needs further study.     

重金属Cd污染土壤毒性的发光菌法评价

应用明亮发光杆菌 Ｔ３ 对重金属污染土壤的毒性评价方法进行探索;进行了土壤平衡、土壤浸提实验及土壤中人为添加 Ｃｄ 对明亮发光杆菌 Ｔ３ 的效应实验;确定了土壤最佳平衡时间、土壤浸提剂、土壤最佳浸提时间及草甸棕壤中 Ｃｄ 对明亮发光杆菌 Ｔ３ 的毒性响应水平．实验结果表明：在土壤浸出液的提取过程中,土壤最佳平衡时间为１ ｄ ,最佳浸提液为０ ．１ ｍｏｌ／ Ｌ 盐酸,最佳浸提时间为２ ｈ ;草甸棕壤中 Ｔ３ 菌的发光强度与投加的 Ｃｄ浓度呈显著负相关（ Ｐ＜ ０ ．０１） ,ρ（ Ｃｄ） 对 Ｔ３ 菌的 Ｅ Ｃ５０ 值为２６ ．２ ｍｇ／ｋｇ ．     

Heavy metal bioavailability and chelate mobilization efficiency in an assisted phytoextraction process

The heavy metal bioavailable fraction of a soil is a core parameter to verify the potential risks of contaminant exposure to organisms or plants. The purpose of the present work is to identify the bioavailable metal fraction in soils treated with chelates. This fraction was evaluated directly by analyzing metal concentrations in soil solution and indirectly using sequential extraction procedures. The metal bioavailable fraction was compared with metal accumulated in plant leaves, grown in both untreated and chelate-treated reactors. In order to verify the effect of the readily and slowly biodegradable chelates [S,S]-ethylenediaminedisuccinic acid (EDDS), methylglycine diacetic acid (MGDA), and ethylenediaminetetraacetic acid (EDTA) on metal speciation in soils, a simulation of chelate treatment was made and metal concentrations in different soil compartments before and after the simulation were compared. Lead concentration in the soil solution was positively correlated with metal concentration in the test plants. The soluble fraction showed the best correlation with metal concentration in soil solution. The simulation of the chelate treatment demonstrated that EDTA and EDDS were able to extract part of the organic- and sulfide-bound fraction, which are less available to plants.     

壳聚糖辅助下玉米修复铅污染土壤能力的研究

为了研究壳聚糖辅助下玉米(ZeamaysL.)对铅污染土壤的修复能力,采用L9(34)正交试验进行研究,考虑了4因素3水平,4因素为土壤铅含量、壳聚糖含量、壳聚糖溶液pH值以及加入壳聚糖后的提取时间.研究结果表明,加入壳聚糖会造成玉米生长停滞,甚至死苗,原因在于壳聚糖属于天然高分子有机物,会造成土壤板结,阻碍植物吸收水分,同时壳聚糖将土壤中的大量重金属溶出,造成玉米重金属中毒.加入壳聚糖后,玉米对铅的吸收较对照结果有很大提高,壳聚糖能够促进铅元素从土壤向植物体内转移,但壳聚糖促进铅元素从玉米地下部分向地上部分转移的能力较弱;综合壳聚糖的促进效果,在土壤铅含量为1.8g·kg-1,壳聚糖含量为5mmol·kg-1(土),壳聚糖溶液pH值为4.5,提取时间为7天的条件下,有利于促进铅在玉米地上部分的吸收.     

Application of portable X-ray fluorescence (pXRF) for heavy metal analysis of soils in crop fields near abandoned mine sites

To get representative soil samples, a sampling method was verified for crop fields in the vicinity of abandoned mine sites. Application of appropriate sampling or analytical methods is very important as it affects the costs, time, and accuracy of the refined investigation of soil contamination. Two-time sampling for each crop field was conducted to verify the reproducibility of a zigzag method for soil sampling. The soil analysis using a portable X-ray fluorescence (pXRF) device was conducted to measure concentrations of metal species in soils, and its results were compared to the extracted concentrations by the Korean Standard Test (KST) for soils. As a result, the determination coefficient (R ²) of linear regression analysis for data obtained by ex situ precise measurement or in situ field screening using pXRF was closely related with the ratio of the extracted concentration by KST to interference-free detection limits (IFDL) of pXRF (designated as KST/IFDL). As the specific metal species had a higher ratio of KST/IFDL, its R ² was even higher in the field screening tests. However, the slopes of linear regression analysis for most metal species extracted by aqua-regia were close to 1.0 so that extracted concentrations by aqua-regia were similar to the analytical values obtained by pXRF, whereas extraction using a weak acid (0.1 M HCl) had different slopes for soils contaminated with different ranges of concentrations of metal species. Especially Zn showed not only high ratios of KST/IFDL because of aqua regia extraction, but also high determination coefficients. Because of its simple, rapid, and accurate capacities for metal analysis, the pXRF analysis showed high applicability in ex situ precise measurements or in situ field screening of metal analysis. In terms of applicability for regulation, especially in situ pXRF field screening with the zigzag method could be effectively applied to achieve an economical survey by determining hot spots or non-contaminated areas if aqua-regia was applied as the extracting agent in the KST for soils.     

微胶囊EDTA对2种土壤中铅释放的影响

选用不同铅污染程度及pH值的土壤,采用连续批浸提实验和土柱淋溶实验,比较研究微胶囊EDTA（Cap-EDTA）和未微胶囊化EDTA（Ncap-EDTA）对不同土壤溶液中pH值和铅离子浓度动态变化影响,以及土壤渗滤液中铅离子淋失特征。结果表明：施加2种不同形式的EDTA,可极显著地增加土壤溶液中铅离子浓度,Cap-EDTA能控制土壤溶液中铅浓度的突增幅度,且使土壤溶液中的铅持续保持在适度浓度的时间更长。同一种土壤不同处理间土壤pH值的变化趋势基本一致,无显著差异。施用2种不同形式EDTA可极显著地增加土壤渗滤液中铅离子含量,土壤铅累积淋失量呈对数曲线上升,但施用Cap-EDTA处理能显著降低土壤中铅的初始淋失量和淋失总量。在相同浓度及形式的EDTA下,高铅浓度和高pH值的土壤铅更易活化和淋失。因此,在进行污染土壤植物修复的EDTA调控时,采用微胶囊化EDTA,能降低其带来的污染地下水风险。     

缓释微胶囊EDTA强化玉米提取土壤中铅铜的效应研究

将EDTA转化成具有缓释性能的微胶囊EDTA（Cap-EDTA）作为螯合剂,采用大宝山矿区周边重金属复合污染农田土壤进行重金属连续批浸提及盆栽试验,比较研究Cap-EDTA和未微胶囊化EDTA（Ncap-EDTA）对土壤铅铜活化的动态变化及其对玉米吸收提取铅铜的影响。结果表明：Cap-EDTA处理土壤溶液中初始增溶的铅铜质量分数显著低于Ncap-EDTA处理,且使土壤溶液中的铅铜质量分数长时间持续保持在适度范围内。添加Cap-EDTA的处理显著提高玉米吸收提取铅铜的效率,如实施3 mmol·kg-1的Cap-EDTA使玉米地上部Pb的积累高达1.26 mg·pot-1,是对照处理的1.9倍,是等量Ncap-EDTA处理的1.4倍。因此,在进行污染土壤植物修复的EDTA调控时,采用微胶囊化EDTA,能降低因直接实施EDTA而带来的污染地下水风险,且显著提高玉米修复效率。     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

应用脂肪酸甲酯淋洗去除土壤中多环芳烃

针对煤气厂土壤等高浓度多环芳烃污染土壤修复困难的现实,采用易生物降解的新型淋洗剂脂肪酸甲酯淋洗修复高浓度多环芳烃污染的土壤,同时进行了以甲醇、植物油(大豆油)作为淋洗剂的淋洗实验,比较不同淋洗剂的淋洗效果.结果证明脂肪酸甲酯对人工模拟污染土壤中蒽、荧蒽、芘、苯并(a)芘的去除率可以达到80%—95%,对煤气厂土壤中多环芳烃的去除效果也非常明显,总多环芳烃的去除率达到41%.脂肪酸甲酯的淋洗效果要优于其它两种淋洗剂.     

Response of roselle (Hibiscus sabdariffa) to heavy metals contamination in soils with different organic fertilisations

The response of green roselle (Hibiscus sabdariffa) to Cu/Pb contamination and manure application in soil was investigated using pot experiments. Subsamples of a mineral soil were treated with increasing doses (0–500 mg kg^?1) of Cu/Pb only and/or amended (at 10% w/w) with poultry or swine manure. Roselle plants were grown, monitored for changes in growth rate and post-harvest aboveground dry biomass and tissue Cu/Pb concentrations were determined. The plants were typically greenish with linear growth profiles at all metal doses, indicating some level of tolerance. Dry biomass yields decreased as metal dose increased. Poultry manure enhanced roselle biomass yields better than swine manure. Tissue Cu/Pb concentrations increased linearly as metal doses increased in unamended soils; whereas nonlinear responses were observed in manure-amended soils. Soil-to-plant transfer factors, T _f (%) indicated that Cu (13≤T _f (% )≤60) was more phytoavailable to roselle than Pb (11≤T _f (% )≤20). Tissue metal concentrations were modelled from soil pH, organic matter, plant available and pseudototal metal; but the models appeared more reliable with plant available metal as a covariate than with pseudototal metal content. These observations may become useful whenever phytoextraction is the remedial option for soils moderately contaminated by toxic metals.     

Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Stabilization of metal processing plant sludge via sequential application of phytoremediation and pyrolysis

The aim of this study is to evaluate the metal removal ability of three different plants from metal processing sludge containing Pb, Cd, and Zn. Therefore, phytoremediation and pyrolysis were sequentially applied. In the phytoremediation applications, sunflower (Helianthus annuus), corn (Zea mays), and rape (Brassica napus) seeds were sown in sludge/soil mixtures at four different levels (25/75, 50/50, 75/25, 100/0). The chelating agent, ethylenediaminetetraacetic acid, was added to the mixtures for plant uptake during phytoremediation. At the phytoremediation stage, it was noted that rape was the most effective plant for the mixture of 75/25 sludge/soil, with metal removal efficiencies ranging between 80%–90%. At the pyrolysis stage, after harvesting, contaminated plants grown in a 75/25 sludge/soil mixture were pyrolyzed at 500 °C, with a heating rate of 35 °C/min. The results show that 60%–90% of the initial metal content was held by the solid product. In addition to this, it can be concluded that pyrolysis stabilizes metals into a solid product and that this solid product can be safely landfilled as inert waste since its toxicity leaching value is lower than the limit values.     

Interrelation of Cd‐lon concentrations and the growth and activities of microorganisms in two growth media†

Partitioning of native or anthropogenic heavy metals in solid and solution phases of soil is a result of network of several physico‐chemical reactions. The attainment of equilibrium between two phases is also regulated by biochemical processes. For practical purposes, the bioavailability of metal present in soil is predominantly regulated by the soil solution phase which is in dynamic equilibrium with the solid phase. The results of a model laboratory and greenhouse growth experiments have been used to investigate the effect of Cd‐ion concentrations (either in soil solution or in nutrient solution) on the growth and activities of microorganisms. The soil solution has been simulated by preparing a suspension of soil with 0.1 M NaNO₃ (1: 2.5) equilibrated for two hours. Important conclusions are as follows:

Increase in Cd‐ion concentration in soil solution or in nutrient solution induces corresponding adverse effect on the growth and activities of microorganisms. Thus, it seems that Cd‐ion concentration is a more sensitive indicator for assessing the effect of metal pollution upon the growth and activities of soil microorganisms in comparison to total Cd contents.

During active microbial growth phase, a large part of the organically bound Cd was released in the soil solution which is largely bioavailable. This process is termed as mobilisation. There was momentary increase of Cd‐ion concentration in soil solution which intoxicated the growing organisms. After this stage, the Cd ions from the solution phase were removed by the newly formed solid phase (nonviable biomass) and were transformed in non‐available form. This process is termed as immobilisation.

The consequences and importance of these results for practical agriculture and in deciding the limits or guidelines on the maximum tolerable metal load in soils are discussed.     

非离子表面活性剂淋洗萘污染土壤的修复研究

采用土柱实验研究了非离子表面活性剂对焦化厂萘污染砂土的淋洗效果,同时研究了超声预处理对非离子表面活性剂土壤淋洗的增强效果及粉土和粘土对非离子表面活性剂土壤淋洗的不利影响.研究表明,1)1g·L-1的TritonX-100、AEO-9和Tween80对同一萘浓度(192.4mg·kg-1)的土壤洗脱效率分别为73.0%、81.5%和59.0%,2g·L-1的表面活性剂的洗脱效率要高于1g·L-1的洗脱率,分别为96.5%、95.1%和88.2%.2)对土壤进行短时超声处理(80Hz)促进了洗脱率的提高,超声10min的淋洗效果要高于超声5min的淋洗效果;土壤分别经5min和10min超声处理后,2g·L-1浓度的TritonX-100对萘的洗脱率从94%分别提高到98.8%和99.6%,洗脱时间从255min分别减少到172min和160min.3)砂土中含有粉土和粘土对洗脱效果有不利影响,且粘土的影响要更严重,当萘污染的砂土混入5%的粘土时,2g·L-1浓度的TritonX-100对萘的洗脱率从94.7%下降至73.8%,洗脱时间从255min增加至605min,而混入20%的粉土洗脱率仅下降到88.4%,洗脱时间增加至512min.     

不同来源重金属污染的土壤对水稻的影响

采用人工污染土壤、尾矿砂、污泥等不同载体的污染源来模拟土壤污染 ,研究其对水稻生长、吸收养分和吸收重金属的影响。结果表明 ,不同污染载体对水稻生长的影响不同 ,其影响的大小顺序为人工污染土壤 >尾矿砂 >污泥 >尾矿砂 +污泥。不同污染载体对水稻吸收重金属的影响亦不同 ,以纯化学试剂的形式添加到土壤中的重金属最易被提取出来 ,植物从中吸收的Cu、Zn、Pb、Cd最多 ,而从以污泥为污染载体的土壤中吸收的Zn、Pb、Cd最少。研究表明 ,用添加纯化学试剂的方法来模拟污染土壤对生态与环境的影响是可行的 ,确定土壤负载容量是安全的 ,因为在实验条件下它对供试植物的影响最明显     

Radioactive Isotopes of Strontium,Caesium and Plutonium in Sediments of the Northern Adriatic Sea

Changes in nitrification rates of an acid grassland soil with and without air drying have been monitored over 9 days, after first flushing native nitrate from the soils with deionised water. The results confirmed that full re-establishment of nitrification after air drying takes several days, supporting the hypothesis that any immediate first flush of nitrate from air-dried soils originates from cell lysis or flushing of ‘stored’ nitrate. Ammonium spiking confirmed that nitrification was not ammonium substrate limited. It was also found that ammonium accumulates in the soil during the drying process, providing a substrate pool once the population of nitrifiers has re-established. Over the first week of incubation, nitrate immobilisation was less conspicuous in the soil that had been rewetted after air drying compared with the incubated field moist soil.