Sequential extraction analysis of heavy metals in sediments of variable composition using nitrilotriacetic acid to counteract resorption

Artificial sediments were made that contained variable amounts (up to 20% by weight) of feldspar, calcite, Fe-oxide or organic matter. Analysis of samples spiked with Pb and Zn in the presence and absence of nitrilotriacetic acid (NTA) showed that 400 mg l(-1) of chelating agent greatly reduced or eliminated sorption in each case. Further study showed that this NTA concentration did not cause significant mineral dissolution. Resorption during sequential extraction analysis of artificial sediments is indicated by the fact that with NTA, levels of metals are higher in the first step and lower during subsequent steps, compared with levels obtained without NTA. However, the addition of 400 mg l(-1) of NTA to each extracting solution in the sequence appears to be effective for counteracting resorption in feldspathic, calcareous, ferruginous and carbonaceous sediments.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

螯合剂与水泥协同稳定垃圾焚烧飞灰中的重金属

开展了水泥和螯合剂协同处置全烧垃圾循环流化床炉飞灰的研究,并对经济性进行了分析.实验结果表明,当水泥添加比例为30%时,重金属的浸出毒性均低于生活垃圾填埋污染物控制标准的规定.有机硫螯合剂TMT(三巯基均三嗪三钠盐类)对Cu、Pb、Cd的稳定效果最好,有机硫螯合剂DTCR(二硫代氨基甲酸盐衍生物)以Cu、Pb最佳,同等有效添加量时TMT的稳定效果优于DTCR,完全达标时二者所需的添加量分别为2%和3%.水泥和螯合剂协同处置时,满足生活垃圾填埋标准的水泥和螯合剂之间的用量关系并非为线性.螯合剂在实现减容化的同时,存在成本提高的问题,以DTCR为例,在兼顾经济性和增容性时水泥用量可以控制在20%,稳定剂为1.75%.     

新型DTC类络合重金属捕集剂的合成及其在废水处理中的应用

为了更有效地去除废水中络合态重金属离子且不添加任何絮凝剂, 合成了一种新型的重金属捕集剂聚-二硫代氨基甲酸铵（PADTC）, 并采用傅里叶红外光谱, 核磁共振, 元素分析和凝胶渗透色谱推测产物结构。考察反应时间, pH对重捕剂去除效果的影响, 结果表明：在pH=6、反应时间为20 min时, Cu2+、Ni2+和Zn2+的最大吸附能力分别为246、234和227 mg·g-1;同时还探讨了不同络合剂的吸附影响, 其去除顺序为TA > CA > EDTA。在实际废水处理中, PADTC取得了良好的处理效果。通过FT-IR、SEM-EDS和XPS表征证实了PADTC对络合重金属的抓捕机理。使用PADTC从废水中去除重金属可能具有良好的工业发展前景。     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.     

Effects of chelates (EDTA,EDDS, NTA) on phytoavailability of heavy metals (As,Cd, Cu,Pb, Zn) using ryegrass (Lolium multiflorum Lam.)

Environmental Science and Pollution Research - This paper summarises a study of the application of the synthetic chelate ethylenediaminetetraacetic acid (EDTA), and the natural chelates...     

有机螯合剂与磷酸盐联合稳定垃圾焚烧飞灰中重金属的作用机理

为探讨二硫代氨基甲酸型有机螯合剂(FACAR)和重过磷酸钙(TSP)对垃圾焚烧飞灰中重金属Pb、Cd、Ni的稳定作用机制,对稳定前后的飞灰采用BCR连续提取法、X射线衍射(XRD)分析以及扫描电镜-能谱(SEM-EDS)联用等分析方法进行了表征。结果表明：投加质量分数5%的FACAR能有效稳定飞灰中Pb、Cd和Ni,其浸出浓度低于《生活垃圾填埋场污染控制标准》(GB 16889-2008)规定的浸出浓度限值;采用3% FACAR和3% TSP复配药剂处理,可使飞灰达到GB 16889-2008进场要求;经复合药剂稳定处理后的飞灰颗粒表面孔隙度明显降低,飞灰中Pb、Cd和Ni的形态均由不稳定态向稳定态转化。该复合稳定剂的稳定机制主要为螯合、共沉淀和吸附联合作用机制,其中,有机螯合剂中含硫官能团是影响重金属稳定的主要因素,且重金属具有优先与含硫官能团结合的特性。     

高效重金属捕集剂TDTC对络合铜的去除性能

传统化学沉淀法存在对酸性及低浓度的络合态重金属去除率低的问题,为解决此问题,以三乙烯四胺、二硫化碳为原料合成了重金属捕集剂N,N-双(二硫代羧基)三乙烯四胺(TDTC),并采用红外光谱等分析方法对其结构和主要官能团进行了表征.以酒石酸铜、柠檬酸铜和EDTA铜3种络合铜为去除对象,研究了TDTC对络合铜的去除性能及去除机...     

Sequential extraction of heavy metals in river sediments of an abandoned pyrite mining area: pollution detection and affinity series

In this paper heavy metal pollution at an abandoned Italian pyrite mine has been investigated by comparing total concentrations and speciation of heavy metals (Fe, Cu, Mn, Zn, Pb and As) in a red mud sample and a river sediment. Acid digestions show that all the investigated heavy metals present larger concentrations in the sediment than in the tailing. A modified Tessier's procedure has been used to discriminate heavy metal bound to organic fraction from those originally present in the mineral sulphide matrix and to detect a possible trend of metal mobilisation from red mud to river sediment. Sequential extractions on bulk and size fractionated samples denote that sediment samples present larger percent concentrations of the investigated heavy metals in the first extractive steps (I-IV) especially in lower dimension size fractionated samples suggesting that heavy metals in the sediment are significantly bound by superficial adsorption mechanisms.     

Removal of heavy metals and arsenic from contaminated soils using bioremediation and chelant extraction techniques

A combined chemical and biological treatment scheme was evaluated in this study aiming at obtaining the simultaneous removal of metalloid arsenic and cationic heavy metals from contaminated soils. The treatment involved the use of the iron reducing microorganism Desulfuromonas palmitatis, whose activity was combined with the chelating strength of EDTA. Taking into consideration that soil iron oxides are the main scavengers of As, treatment with iron reducing microorganisms aimed at inducing the reductive dissolution of soil oxides and thus obtaining the release of the retained As. The main objective of using EDTA was the removal of metal contaminants, such as Pb and Zn, through the formation of soluble metal chelates. Experimental results however indicated that EDTA was also indispensable for the biological reduction of Fe(III) oxides. The bacterial activity was found to have a pronounced positive effect on the removal of arsenic, which increased from the value of 35% obtained during the pure chemical treatment up to 90% in the presence of D. palmitatis. In the case of Pb, the major part, i.e. approximately 85%, was removed from soil with purely chemical mechanisms, whereas the biological activity slightly improved the extraction, increasing the final removal up to 90%. Co-treatment had negative effect only for Zn, whose removal was reduced from 80% under abiotic condition to approximately 50% in the presence of bacteria.     

基于响应面法的重金属螯合剂前体物合成条件优化研究

以小分子的乙二胺与环氧氯丙烷为原料,以黏度为考察对象,对高分子重金属螯合剂的前体物合成条件进行优化。采用单因素实验确定黏度的主要影响因素,然后采用响应面法对制备条件进行优化。结果表明:(1)拟合的模型回归项显著而失拟项不显著,拟合性良好。(2)最佳制备条件为环氧氯丙烷和乙二胺摩尔比1.1、反应温度82.8℃、反应时间9.2h、NaOH和乙二胺摩尔比1.2。(3)产物傅立叶红外光谱表明,特征官能团的存在证明了前体物的生成。(4)利用前体物进一步合成了螯合剂,该螯合剂的Pb去除和稳定效果明显优于市售螯合剂。     

Fractionation of heavy metals in liquefied chromated copper arsenate 9-treated wood sludge using a modified BCR-sequential extraction procedure

Chromated copper arsenate (CCA)-treated wood was liquefied with polyethylene glycol/glycerin and sulfuric acid. After liquefaction, most CCA metals (98% As, 92% Cr, and 83% Cu) were removed from liquefied CCA-treated wood by precipitation with calcium hydroxide. The original CCA-treated wood and liquefied CCA-treated wood sludge were fractionated by a modified Community Bureau of Reference (BCR) sequential extraction procedure. The purpose of the BCR-sequential extraction used in this study was to examine the availability of CCA metals in treated wood for reuse. Both As and Cr had a slightly higher concentration in the sludge sample than in original CCA-treated wood. The sequential extraction showed that As and Cr were principally existed in an oxidizable fraction (As, 67%; Cr, 88%) in original CCA-treated wood. Only 1% of both As and Cr were extracted by hot nitric acid with the last extraction step. The distribution of As and Cr changed markedly in liquefied CCA-treated wood sludge.The amount of As in the exchangeable/acid extractable fraction increased from 16% to 85% while the amount of Cr increased from 3% to 54%. Only about 3% of As was present in the oxidizable fraction. However, there was still about 34% of Cr in the same fraction. Based on these results from sequential extraction procedures, it can be concluded that the accessibilities of CCA metals increase markedly by the liquefaction–precipitation process.     

一种多DTC基团重金属螯合剂的合成及处理含铜废水性能

合成了一种新的二硫代氨基甲酸盐类重金属螯合剂CDTC,并对其处理游离铜离子、EDTA络合铜和柠檬酸络合铜废水的性能进行了研究.实验结果表明:CDTC能直接去除已络合的铜,对不同形态的Cu2+去除率均达99%以上,处理后的废水中Cu2+剩余浓度达到我国<污水综合排放标准>(GB 8978-1996)一级标准;在废水pH=...     

An ultrasonic assisted extraction method to release heavy metals from untreated sewage sludge samples

A rapid ultrasound accelerated sequential extraction procedure has been used to develop sequential extraction proposed by BCR protocol (the community Bureau of Reference now the European Union "Measurement and Testing Programme"). The effects of the ultrasonic treatment on the extraction of Cu, Cd, Cr, Pb, Ni and Zn from untreated sewage sludge collected from industrial site of Hyderabad city (Pakistan) were compared with those obtained from conventional sequentional extraction procedure of modified BCR protocol. In BCR method, each extraction steps takes 10h, where as with the use of compromise sonication conditions in ultrasonic bath, steps 1-3 of the sequential extraction (excluding the hydrogen peroxide digestion in step 3, which was not performed with sonication) could be completed in 30, 30 and 30 min, respectively. Extractable Cd, Cr, Pb and Ni contents were obtained by both comparable methodologies were measured by electrothermal atomic absorption spectrometry (ETAAS), while for Cu and Zn Flame atomic absorption spectrometry (FAAS) was used. The validations of both methods were compared by the analysis of certified reference material of soil amended with sewage sludge (BCR 483). According to statistical evaluation of the results, the proposed accelerated extraction method is valid alternative to conventional shaking with much shorter extraction time with p value <0.05. The overall metal recoveries in steps 1-3 (excluding residual step) were 95-100% of those obtained with the conventional BCR protocol, except for Cu extracted (91.6%) as related to indicative values of Cu in BCR 483 obtained in 1-3 steps. The results of the partitioning study of untreated industrial waste water sewage sludge, indicate that more easily mobilized forms (acid exchangeable) were predominant for Cd and Zn, in contrast, the largest amount of Pb and Cr was associated with the iron/manganese oxide and organic matter/sulphide fractions.     

Phenotypic plasticity in Scenedesmus incrassatulus (Chlorophyceae) in response to heavy metals stress

The microalgae genus Scenedesmus is commonly found in freshwater bodies, wastewater facilities and water polluted with heavy metals. Phenotypic plasticity in Scenedesmus has been documented in response to a wide variety of conditions; however, heavy metals have not been comprehensively documented as phenotypic plasticity inducers. In this study, we report the phenotypic plasticity of Scenedesmus incrassatulus (a non-spiny, four-cell coenobium forming species) in response to EC₅₀ value of copper, cadmium and hexavalent chromium. S. incrassatulus was grown in batch cultures in the presence of each metal. Chlorophyll-a content, cell size, parameters derived from the schematic energy-flux model for photosystem II, and morphotype expressions were recorded. Divalent cation metals induced unicellular forms, and hexavalent chromium produced out-of-shape coenobia corresponding to various stages of autospore formation. The changes induced by divalent metals were interpreted as phenotypic plasticity, because they were always associated to population doublings and were reversible when toxicant pressure was removed (only for Cu). Copper was the best inductor of unicellular forms and also affected significantly all the photosynthetic parameters measured. The developed morphotypes could confer ecological advantages to S. incrassatulus in metal stressed environments.     

EDTA-enhanced extraction of heavy metals from a coarse grained simulated soil by the CEHIXM process

The effect of ethylenediaminetetraacetic acid (EDTA) in extracting heavy metal contaminants, namely Pb, Cd, Zn, and Mn, from soils with organometallic complexes, was explored using the coupled electric-hydraulic gradient assisted by ion exchange medium (CEHIXM) decontamination process. The experiments were conducted with a constant electric voltage of 50 DC V and a constant hydraulic flow rate of 4 cm3/min. The results obtained from the experiments demonstrated that EDTA was effective in extracting Pb, Cd, Zn, and Mn from soils in which acidic pH did not produce significant dissolution. Metal removal as high as 99% was achieved with 0.05 M EDTA solution within 200 hr.     

Freshwater Ulva (Chlorophyta) as a bioaccumulator of selected heavy metals (Cd, Ni and Pb) and alkaline earth metals (Ca and Mg)

We analyzed the ability of freshwater taxa of the genus Ulva (Ulvaceae, Chlorophyta) to serve as bioindicators of metal in lakes and rivers. Changes in heavy metal (Ni, Cd and Pb) and alkaline earth metal (Ca and Mg) concentrations in freshwater Ulva thalli were investigated during the period from June to August 2010. The study was conducted in two ecosystems in Western Poland, the Malta lake (10 sites) and the Nielba river (six sites). Three components were collected for each sample, including water, sediment and Ulva thalli. The average concentrations of metals in the water sample and in the macroalgae decreased in the following order: Ca > Mg > Ni > Pb > Cd. The sediment revealed a slightly altered order: Ca > Mg > Pb > Ni > Cd. Ca and Mg were found at the highest concentrations in thalli due to the presence of carbonate on its surface. Among the examined heavy metals in thalli, Ni was in the highest concentration, and Cd found in the lowest concentration. There were statistically significant correlations between the levels of metals in macroalgae, water and sediment. Freshwater populations of Ulva exhibited a greater efficiency to bioaccumulate nickel as compared to species derived from marine ecosystems.     

半焦吸附养殖废水中的重金属

采用生物质半焦作为吸附剂处理养殖废水中的重金属,并对半焦吸附重金属的吸附容量及吸附效率进行了分析和评估。实验结果表明,生物质半焦对养殖废水中Cu、Zn、Pb和Cd 4种重金属具有较好的吸附效果,吸附容量分别为22.4、19.03、17.30和16.94 mg/g,且吸附率均达到70%以上,氮磷的影响吸附不超过30%。重金属离子在半焦表面上的吸附过程符合Langmuir等温吸附模型,且主要为单分子层表面吸附。由此生物质半焦作为廉价高效的吸附剂处理养殖废水中重金属技术上可行,为养殖废水中重金属吸附研究及生物质半焦资源化利用提供新途径。     

Leaching of heavy metals from contaminated soils using EDTA

Ethylenediaminetetraacetic acid (EDTA) extraction of Zn, Cd, Cu and Pb from four contaminated soils was studied using batch and column leaching experiments. In the batch experiment, the heavy metals extracted were virtually all as 1:1 metal-EDTA complexes. The ratios of Zn, Cd, Cu and Pb of the extracted were similar to those in the soils, suggesting that EDTA extracted the four heavy metals with similar efficiency. In contrast, different elution patterns were obtained for Zn, Cd, Cu and Pb in the column leaching experiment using 0.01 M EDTA. Cu was either the most mobile or among the most mobile of the four heavy metals, and its peak concentration corresponded with the arrival of full strength EDTA in the leachate. The mobility of Zn and Cd was usually slightly lower than that of Cu. Pb was the least mobile, and its elution increased after the peaks of Cu and Zn. Sequential fractionations of leached and un-leached soils showed that heavy metals in various operationally defined fractions contributed to the removal by EDTA. Considerable mobilisation of Fe occurred in two of the four soils during EDTA leaching. Decreases in the Fe and Mn oxide fraction of heavy metals after EDTA leaching occurred in both soils, as well as in a third soil that showed little Fe mobilisation. The results suggest that the lability of metals in soil, the kinetics of metal desorption/dissolution and the mode of EDTA addition were the main factors controlling the behaviour of metal leaching with EDTA.     

环境丝状真菌对3种重金属的耐受性能比较与解析

考察11种丝状真菌在3种重金属(Cr(Ⅵ)、Pb~(2+)、Cd~(2+))胁迫条件下的生长情况,测定重金属对供试菌株的最小抑制浓度(MIC),探讨供试菌株对重金属的耐受性。结果表明,重金属对供试菌株生长的抑制作用随重金属浓度升高而增大,高浓度重金属胁迫条件会改变供试菌株的培养性状。在14d的观察期内,Mucor sp.(菌株号Mu-tea1)对Cr(Ⅵ)表现出较好耐受性,MIC为220mg/L,在此条件下菌落直径为3.1cm,与其他菌株相比有显著性差异(p0.05)。对Cd~(2+)有较好耐受性的菌株有Neofusicoccum sp.(菌株号Nf1172)和Penicilliumsp.(菌株号Pe-soil2),MIC均为18mmol/L,在此条件下菌落直径分别为2.3、2.7cm,与其他菌株相比均有显著性差异(p0.05)。对Pb~(2+)耐受性最好的菌株为Pe-soil2,MIC为18mmol/L,在此条件下菌落直径为4.3cm,与其他菌株相比有显著性差异(p0.05)。研究结果可为下一步利用优势菌株修复环境中重金属污染提供科学依据和研发材料。