Heavy metal speciation in the composting process

Composting is one of the more efficient and environment friendly methods of solid waste disposal and has many advantages when compared with landfill disposal on which the UK and Ireland are currently heavily dependent. Composting is a very complicated process involving intensive microbial activity and the detailed mechanisms of the process have yet to be fully understood. Metal speciation information can provide an insight into the metal-microbial interaction and would help in the evaluation of the quality of compost. This would facilitate the exploitation of composts in remediation of heavy metal contaminated land. In this work a systematic approach to metal speciation in compost has been taken by applying the three-step method for operationally defined metal speciation of soils and sediments, developed by the European Commission's Standards, Measurement and Testing Programme to monitor the change in metal speciation with time (up to 106 days) for four different waste composting processes. The results have shown that in general metals become less available for the first extraction step as the composting process proceeds. This implies that composting tends to redistribute the metals from more labile forms to more fixed forms which may explain why the application of composts could be useful for with heavy metal contaminated land. There are exceptions to this trend and in some cases, certain metals appear to behave differently depending on the source of the compost.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

Study on the law of heavy metal leaching in municipal solid waste landfill

Comparative leaching experiments were carried out using leaching medium with different pH to municipal solid waste in the landfill columns in order to investigate the mobility of heavy metals. The leachate pH and oxidation–reduction potential were measured by oxidation–reduction potential analyzer; the contents of heavy metals were measured by inductively coupled plasma mass spectrometry. It is very different in leaching concentrations of heavy metals; the dynamic leaching of heavy metals decreased with the rise of the leaching amount on the whole. Acid leaching medium had definite influence on the leaching of heavy metals in the early landfill, but it had the obvious inhibition effect on the leaching in the middle and late period of landfill; the neutral and alkaline leaching medium are more beneficial to the leaching of heavy metals. Due to the influence of the environment of landfill, the differences of the results in cumulative leaching amount, leaching rate, and leaching intensity of heavy metals are very big. The calculation results of the release rates of heavy metals prove that the orders of the release rates are not identical under different leaching conditions. Acid rain made heavy metals migrate from municipal solid waste to soil and detain in soil more easily; approached neutral and alkaline leaching mediums are more beneficial to leaching of heavy metals in the municipal solid waste and soil with leachate. The field verification of experimental data showed that the law of heavy metal leaching in municipal solid waste revealed by the experiment has a good consistency with the data obtained by municipal solid waste landfill.     

Speciation and assessment of heavy metals in surface sediments of Jinjiang River tidal reach, southeast of China

The concentration and speciation of heavy metals (Cr, Ni, Cu, Zn, Cd, Pb) in surface sediments (??≤ 63 μm) of Jinjiang River tidal reach are determined to evaluate the metal behavior. A modified BCR three-step sequential extraction procedure is carried out, and the residual fraction is undertaken by microwave-assisted acid digestion. The index of geo-accumulation indicates that Cd appeared highest among all these heavy metals in surface sediments, Cr, Cu, Zn lower, and Ni, Pb the least. The percentage of Zn, Cd is comparatively higher in the acid soluble fraction, Pb and Cu higher in the reductive fraction, indicating larger potential danger to the environment. So it is essential for developing the future remediation plans and pollution control strategies.     

Determination and speciation of heavy metals in sediments of the Juru River,Penang, Malaysia

The Juru River flows through largely urbanized areas and is grossly polluted by domestic wastes and discharges from pig farms. Other than carrying highly polluting organic materials, these wastes are also contaminated with heavy metals. To ascertain the extent of heavy metal pollution in the river, total and non-residual concentrations of Cu, Pb, Zn, Mn and Fe in sediment samples collected along the river were determined. The results indicate that both the total and non-residual metal concentrations in sediments can successfully be used to identify heavy metal pollution sources. The speciation of Zn, Mn and Fe in the sediment samples were investigated using a sequential leaching technique which identifies the elements among six operationally defined host fractions: (1) exchangeable, (2) carbonate and surface-associated, (3) easily reducible, (4) moderately reducible, (5) bound to organic matter and sulphides and (6) residual. The results indicate that Zn is mainly associated with the reducible fractions. Zn and Fe found in the moderately reducible fraction are significantly correlated, indicating that iron oxides is the preferred host phase by Zn.     

Leaching Characteristics of Heavy Metals and As from Two Urban Roadside Soils

The leaching tests, including the Toxicity Characteristic Leaching Procedure (TCLP), EDTA extraction and BCR sequential extractions before and after EDTA treatments, were performed on two specific soils to elucidate heavy metal-associated mineral fractions and general leachability. The TCLP illustrated the low leachability of heavy metals in soils from two sites. EDTA is a strong chelator and therefore had higher extraction efficiency compared to that of TCLP. The lower extraction percentages by EDTA for As and Sb were found compared to the other heavy metals derived from anthropogenic sources. Sequential extractions showed that the importance of acid-extractable, organically-bound and Fe–Mn oxide fractions was identified for anthropogenic heavy metals with the exception of As and Ni while the importance of residual fraction was identified for endogenous metals. Changes in sequential fractions of heavy metals after leaching with EDTA are very complex and it is difficult to generalize on which fraction was more mobile than the others. These combined results are helpful in elucidating the association of heavy metals to soil fractions and the mobility characteristics of heavy metals under certain environmental conditions.     

Availability and Assessment of Fixing Additives for The in Situ Remediation of Heavy Metal Contaminated Soils: A Review

The use of low-cost and environmental safety amendments for the in situ immobilization of heavy metals has been investigated as a promising method for contaminated soil remediation. Natural materials and waste products from certain industries with high captive capacity of heavy metals can be obtained and employed. Reduction of extractable metal concentration and phytotoxicity could be evaluated and demonstrated by the feasibility of various amendments in fixing remediation. In this review, an extensive list of references has been compiled to provide a summary of information on a wide range of potentially amendment resources, including organic, inorganic and combined organic-inorganic materials. The assessment based on the economic efficiency and environmental risks brought forth the potential application values and future development directions of this method on solving the soil contamination.     

Petroleum contaminated soil in Oman: Evaluation of bioremediation treatment and potential for reuse in hot asphalt mix concrete

This paper presents a study that aims at evaluating the leaching characteristics of petroleum contaminated soils as well as their application in hot mix asphalt concrete. Soil samples are environmentally characterized in terms of their total heavy metals and hydrocarbon compounds and leachability. The total petroleum hydrocarbon (TPH) present in the PCS before and after treatment was determined to be 6.8% and 5.3% by dry weight, indicating a reduction of 1% in the TPH of PCS due to the current treatment employed. Results of the total heavy metal analysis on soils indicate that the concentrations of heavy metals are lower when extraction of the soil samples is carried out using hexane in comparison to TCE. The results show that the clean soils present in the vicinity of contaminated sites contain heavy metals in the following decreasing order: nickel (Ni), followed by chromium (Cr), zinc (Zn), copper (Cu), lead (Pb), and vanadium (V). The current treatment practice employed for remediation of the contaminated soil reduces the concentrations of nickel and chromium, but increases the concentrations of all remaining heavy metals.     

Effect of methods of preparation on distribution of heavy metals in different size fractions of municipal solid waste composts

The present study compares the distribution and nature of heavy metals in composts from 12 cities of India, prepared from different types of processed urban solid wastes, namely mixed wastes (MWC), partially segregated wastes (PSWC), and segregated bio-wastes (BWC). Compost samples were physically fractionated by wet sieving, followed by extraction of heavy metals by dilute HCl and NaOH. Bigger particles (>0.5 mm) constituted the major fraction in all three types of composts and had a relatively lower concentration of organic matter and heavy metals, the effect being more pronounced in MWC and PSWC in which a significant portion of the heavy metals was distributed in finer size fractions. Cd, Ni, Pb, and Zn were extracted to a greater extent by acid than by alkali, the difference being greater in MWC, which contained a higher amount of mineral matter. In contrast, Cu and Cr were extracted to a greater extent by dilute alkali, particularly from BWC containing a higher amount of organic matter. Water-soluble heavy metals were generally related to the water-soluble C or total C content as well as to pH, rather than to their total contents. This study concludes that wet sieving with dilute acid can effectively reduce heavy metal load in MWC and PSWC.     

Serial batch leaching procedure for characterization of coal fly ash

Although many leaching methods have been used for various purposes by research groups, industries, and regulators, there is still a need for a simple but comprehensive approach to leaching coal utilization by-products and other granular materials in order to estimate potential release of heavy metals when these materials are exposed to natural fluids. A serial batch characterization method has been developed at the National Energy Technology Laboratory that can be completed in 2–3 days to serve as a screening tool. The procedure provides an estimate of cumulative metals release under varying pH conditions, and leaching the sample at increasing liquid/solid ratios can indicate the rate at which this process will occur. This method was applied to eight fly ashes, adapted to the acidic or alkaline nature of the ash. The leachates were analyzed for 30 elements. The test was run in quadruplicate, and the relative standard deviation (RSD) was used as a measure of method reproducibility. RSD values are between 0.02 and 0.70, with the majority of the RSD values less than 0.3. The serial batch leaching procedure was developed as a simple, relatively quick, yet comprehensive method of estimating the risk of heavy metal release from fly ash when it is exposed to natural fluids, such as acid rain or groundwater. Tests on a random selection of coal fly ashes have shown it to be a reasonably precise method for estimating the availability and long-term release of cations from fly ash.     

Secondary mobilisation of heavy metals in overbank sediments

Heavy metal mobility was studied in overbank sediments of the Grote Beek river in Central Belgium. The geochemical signature of heavy metals in fine-scale sampled overbank sediments was compared with data on heavy metal emission into the river. The influence of acidification, organic and inorganic complexation on heavy metal mobility in overbank sediments was studied by single and sequential extractions and leaching tests. As confirmed by these tests, the elevated CaCl(2) content of the river water significantly enhanced the mobilisation of especially Cd, while Zn was mobilised to a lesser extent. The mobilisation of As on the other hand decreased in the presence of elevated CaCl(2) concentrations. Based on the results of single extractions, two highly contaminated zones with a different Cd mobility were observed in one of the overbank profiles. A detailed investigation of Cd leaching behaviour in the zone of Fe-accumulation during pH(stat) leaching tests, suggested that it was related to the association of Cd with Fe-oxides, while adsorption was the dominant binding form of Cd in the clay-rich part of the overbank sediment profile.     

Heavy Metal Availability in Soil Amended with Composted Urban Solid Wastes

A study was performed to evaluate the pH and the availability of Zn, Cu, Mn, Pb, and Ni in soil amended with increasing doses of composted solid wastes, collected in Rio de Janeiro, Rio de Janeiro State and in Coimbra, Minas Gerais State, Brazil. The influence of the time elapsed between compost application to the soil and the sampling of the plant growth substrate (soil + compost) for pH and metal availability analyses was also examined. The availability of heavy metals in the soil, in the compost and in the substrate was evaluated using DTPA solution for metal extraction. The increase of the compost doses added to the soil resulted in the increase of the pH in the substrate. The addition of the compost from the bigger city, Rio de Janeiro, resulted in higher increase in soil pH and available Zn, Cu, Pb, and Ni levels as compared to the addition of the compost from the smaller city, Coimbra. Increasing the time elapsed between the compost application to the soil and the sampling of the mixture resulted in higher available Zn, Cu, Mn, and Pb levels. The addition of the compost from Rio de Janeiro resulted in substrate metal concentrations in the order Zn > Pb > Ni > Cu > Mn and for the Coimbra compost the metal concentrations in the substrate was Zn > Pb > Cu > Ni > Mn. The higher values of pH and available metals obtained for the bigger city were attributed to the greatest metal contamination of its compost.     

西南某省14种尾矿重金属浸出量及总量分析

研究中国西南某省不同类型尾矿的重金属浸出量及总量,为尾矿的污染防范、环境管理和综合利用提供参考和建议。采集了14种类型共164个有代表性尾矿进行浸出毒性试验,并分析其中79个典型尾矿样品的9种重金属含量,以评估其污染风险和综合利用价值。结果表明,有5种类型共7个样品出现浸出毒性超标,分别为铅锌矿、镍矿、银矿、铁矿、锰矿,总体超标率为4.3%。超标元素分别为砷、镉、锌、铅、铜、镍等6种元素,最大超标倍数分别为砷18.3倍、锌4.8倍、镉3.0倍、铅0.56倍、铜0.32倍、镍0.16倍;尾矿含有较多重金属,其中砷、锌、铅、铜含量较高,最高分别达到11.75%、2.60%、1.01%、0.29%,不同类型尾矿其重金属含量各有不同,铅锌矿尾矿的重金属总量最高。总体上,该省绝大多数尾矿为普通固废,少部分为危险废物,砷、镉、锌、铅、铜、镍等6种元素存在污染风险,其中砷元素是最主要污染物;尾矿由于重金属含量较高而有一定的综合利用价值。     

土壤重金属污染的工程危害及修复方法

分析了重金属污染对地基土和地下结构物的危害,比较了电动修复、土壤冲刷、原位土壤淋洗、化学固化修复土壤的优缺点,重点介绍固化/稳定化技术在修复重金属污染土壤中的应用。     

Speciation of selected heavy metals geochemistry in surface sediments from Tirumalairajan river estuary, east coast of India

Surface sediment samples from the Tirumalairajan river estuary were studied for grain size pattern, organic matter, and heavy metals (Fe, Mn, Zn, and Pb) using the sequential and bulk metal extraction methods to evaluate metal behavior. Ten surface sediment samples were collected during the monsoon and summer seasons of the year 2009. The observed orders of concentrations of heavy metals in the sediments were as follows: Fe?>?Mn?>?Zn?>?Pb. The results obtained from sequential extraction showed that, among the metals studied, a larger portion of the metals were associated with the residual phase, although they are available in other fractions. The low concentration of metals available in bioavailable phases indicated that the sediments of Tirumalairajan river estuary were relatively unpolluted. Correlation analysis was also carried out to understand the associations of metals in different phases with sand, silt, clay, and organic matter. To understand the risk of heavy metals to sediment-dwelling organisms, the data were compared with risk assessment code and sediment quality values using the screening quick reference table. The main source of metals to the estuary is from the irrigation field and its associated activities in the study area.     

Speciation of Trace Metals in Coastal Sediments of El-Mex Bay South Mediterranean Sea–West of Alexandria (Egypt)

Sediments of El-Mex Bay estuary on the southern Mediterranean Sea have been analyzed for trace metals after sediment fractionation by sequential leaching. A sequential extraction procedure was applied to identify forms of Mn, Cu, Cd, Cr, Zn and Fe. The five steps of the sequential extraction procedure partitioned metals into: CH₃COONH₄ extractable (F1); NaOAC carbonate extractable (F2); NH₂OH.HCl/CH₃COOH reducible extractable (F3); H₂O₂–HNO₃ organic extractable (F4) and NHO₃/HClO₄/HF acid soluble residue (F5). Extracted concentrations of trace metals analyzed after all five steps, were found to be (μg/g) for Mn: 1930.2, Cu: 165.3, Cd: 60.9, Cr: 386.3, Zn: 2351.3 and Fe: 10895. Most of elements were found in reducible fraction except Fe found in acid soluble residue, characterizing stable compounds in sediments. Labile (non-residual) fractions of trace elements (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis was used to understand and visualize the associations between the labile fractions of trace metals and certain forms, since Fe-and Mn-oxides play an important role in trace metals sorption within aquatic systems, especially within El-Mex Bay sediments that characterized by varying metal bioavailability.     

Metal Pollution Assessment of Surface Sediments Along a New Gas Pipeline in the Niger Delta (Nigeria)

Chromium, nickel, copper, zinc and cadmium were determined in sediments of the Niger Delta (Nigeria) in order to discriminate between natural metal sources and anthropogenic ones. Surface sediments were collected at seven sites along a new gas pipeline near Port Harcourt, between the New Calabar River and the Bonny River towards Bonny town. Chemical characterisation is obtained by hydrofluoric–nitric acid digestion procedure, providing the ‘total’ (‘residual’) metal contents. Information about the anthropogenic metal fraction was obtained by cold diluted hydrochloric acid extraction procedure. This ‘labile’ acid soluble fraction of metals, perhaps due to relatively recent inputs in the sediments, constitutes the fraction more likely to be available to marine organisms, and furnishes a first evaluation of the possible toxicity of sediments of this sensitive ecosystem. Zinc appears to be the most available of all the heavy metals: its ‘labile’ fraction attains 40–50% of the ‘total’ zinc in sediment. Sites near Port Harcourt city are the most contaminated. All the examined metals are one order of magnitude below the respective values proposed as a limit for toxicity and are comparable with those observed by other authors in similar Niger Delta areas. Some anomalous data found near Port Harcourt city suggest that zinc and cadmium are the metals that require further monitoring. Their anthropogenic source could be derived from urban and industrial sewage.     

Continuous-flow fractionation of trace metals in environmental solids using rotating coiled columns. Some kinetic aspects and applicability of three-step BCR leaching schemes

The applicability of the three-step BCR leaching scheme to the continuous-flow fractionation of trace metals (TM) using rotating coiled columns (RCC) has been investigated taking soil and sediment reference samples (SRM-2710, CRM-601, BCR-701) as examples. A particulate sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents, used according to the original and optimised BCR protocols, were continuously pumped through. The whole procedure required 3-4 h instead of at least 50 h needed for the traditional sequential extraction. It has been shown that in comparison with batch sequential extraction procedures (SEP), the recoveries of Cd, Zn, Cu, and Pb at the first stage (most mobile and potentially dangerous acid soluble forms) are somewhat higher, if a dynamic extraction in RCC is used. Nevertheless, the distribution patterns for TM in the first two leachable fractions (acid soluble and reducible forms) are similar in most cases. Since no heating is used in RCC, the recoveries of TM at the third stage (when hydrogen peroxide is applied to oxidize the organic matter) may be incomplete and matrix-dependent. The effect of eluent volume and flow rate on the recovery of TM in different forms has been investigated. It has been shown that the kinetics of heavy metal leaching vary significantly with samples. Hence, investigating the elution profiles can provide additional important information for risk assessment of TM mobilization.     

Effects of selected soil properties on phytoremediation applicability for heavy-metal-contaminated soils in the Apulia region, Southern Italy

Phytoremediation is a well-known promising alternative to conventional approaches used for the remediation of diffused and moderated contaminated soils. The evaluation of the accumulation, availability, and interactions of heavy metals in soil is a priority objective for the possible use of phytoremediation techniques such as phytoextraction and phytostabilization. The soils used in this work were collected from a number of sites inside a protected area in the Apulia region (Southern Italy), which were contaminated by various heavy metals originated from the disposal of wastes of different sources of origin. Soils examined contained Cd, Cr, Cu, Ni, Pb, and Zn in amounts exceeding the critical limits imposed by EU and Italian laws. However, the alkaline conditions, high organic matter content, and silty to silty loamy texture of soils examined would suggest a reduced availability of heavy metals to plants. Due to the high total content but the low available fraction of heavy metals analyzed, especially Cr, phytoextraction appears not to be a promising remediation approach in the sites examined, whereas phytostabilization appears to be the best technique for metal decontamination in the studied areas.     

北方某水库表层沉积物重金属的赋存形态及其环境影响因子分析

为了解北方某水库重金属污染状况,采用BCR连续提取法对该水库表层沉积物中Cu、Pb、Zn、Cd的赋存形态进行了分析,对其含量及空间分布进行了研究,结合重金属总量讨论了各元素的潜在环境风险。结果表明,该水库表层沉积物中Cu、Pb、Zn、Cd的平均质量比分别为65.20 mg/kg、36.69 mg/kg、137.5 mg/kg、2.38 mg/kg,与该地区土壤元素背景值、该地区水系沉积物平均值及全国水系沉积物平均值相比,4种重金属元素均有一定程度的累积,其中Cd累积最为严重。形态分析结果表明,Cd主要以醋酸可提取态及可还原态存在,具有很高的环境风险;Pb主要以极高比例的可还原态存在,潜在风险较高;Zn和Cu存在较大比例的酸可提取态及可还原态,也具有一定程度的潜在风险。各元素生物有效性即可提取态含量排序为:Cd>Cu>Pb>Zn。