中国部分城市污泥中矿质元素形态与生物可利用性研究

近年来随着城市污水处理厂数目迅速增加,低成本、高效率的污泥农用受到越来越多的关注。研究从北到南的五家污水处理厂消化污泥中矿质元素的含量和形态分布,为污泥资源化的合理利用提供科学参考。结果表明：消化污泥总体呈高有机质、高氮磷、低K、高矿质元素营养的相似性,但其理化性质如阳离子交换容量(CEC)、pH等差异较大,对矿质元素的形态分布与生物可利用性有明显的影响。同种元素在不同污泥中含量的差异较大,相差数倍,甚至十倍以上。污泥中不同元素含量明显不同,Fe的浓度最高,次之是Mg、Zn、B的浓度最低。连续提取研究表明,污泥pH对污泥中矿质元素的形态分布有明显影响,酸性污泥(厦门污水处理厂)中各矿质元素酸溶／交换态百分率明显高于其他污泥。Cu主要分布在氧化态;Zn的三态分布百分率均在10％以上;Mg、Mn的酸溶／交换态含量较高;Fe主要分布在残渣态;B氧化态和还原态的百分率较高。建议在全国范围内进行一次污水处理厂污泥品质调查,为污泥合理农用提供科学依据。     

Cu,Cr and As distribution in soils adjacent to pressure-treated decks,fences and poles

Chromated copper arsenate (CCA)-treated wood has been widely used in the Southeastern United States to protect wood products from microbial and fungal decay. The aims of this study were to (1). determine the distribution of arsenic (As), chromium (Cr), and copper (Cu), in soils surrounding CCA-treated wood structures such as decks, fences and poles; and (2). evaluate the impacts of these structures on As, Cr and Cu loading of the soils. Profile and lateral soil samples were collected under CCA-treated decks and adjacent to poles and fences. The results showed elevation of As, Cr and Cu concentrations close to and under the structures, with mean As concentrations as high as 23 mg x kg(-1) close to utility poles compared with less than 3 mg x kg (-1) at distances of about 1.5 m away. Concentrations of As, Cr, and Cu decreased with depth in areas close to CCA-treated poles. However, these results were only apparent in relatively new structures. A combination of weathering and leaching with time may have reduced the impact in older poles. Increased concentrations of As, Cu and Cr were also observed close to CCA-treated decks and fences, with age showing a similar impact. These results are helpful for CCA-treated wood product users to determine the safe use of these structures.     

Elemental analysis of ash residue from combustion of CCA treated wood waste before and after electrodialytic extraction

Element distribution in a combined fly ash and bottom ash from combustion of copper chromate arsenate (CCA) treated wood waste was investigated by scanning electron microscopy (SEM/EDX) before and after electrodialytic extraction. The untreated ash contained various particles, including pieces of incompletely combusted wood rich in Cr and Ca, and irregular particles rich in Si, Al and K. Cr was also found incorporated in silica-based matrix particles. As was associated with Ca in porous (char) particles, indicating that Ca-arsenates had been formed during combustion. Cu was associated with Cr in the incompletely combusted wood pieces and was also found in almost pure form in a surface layer of some matrix particles - indicating surface condensation of volatile Cu species. In treated ash, Ca and As were no longer found together, indicating that Ca-arsenates had been dissolved due to the electrodialytic treatment. Instead particles rich in Ca and S were now found, indicating precipitation of Ca-sulphates due to addition of sulphuric acid in connection with the electrodialytic treatment. Cu and Cr were still found associated with incompletely combusted wood particles and incorporated in matrix particles. Chemical analyses of untreated and treated ash confirmed that most As, but only smaller amounts of Cu and Cr was removed due to the electrodialytic extraction. Overall metal contents in the original ash residue were: 1.4 g As, 2.76 g Cu and 2.48 g Cr, after electrodialytic extraction these amounts were reduced by 86% for As, 15% for Cu and 33% for Cr.     

Evaluation of pressure treated wood impact on landfill waste decomposition using a methane yield assay

Research was conducted to investigate the potential impact of CCA-treated wood and other arsenic-free Cu-based preservative-treated wood on microorganisms, involved in the anaerobic decomposition of waste in landfills. Wood preservatives used included alkaline copper quat (ACQ), copper citrate (CC), copper boron azole (CBA), copper dimethyldithiocarbamate (CDDC), and chromated copper arsenate (CCA). The biochemical methane potential (BMP) assay was used to estimate the possible impacts. The methane yields of mixtures of preservative-treated wood or untreated wood with cellulose (group 1) and these wood samples only (group 2) were determined. An analysis of variance (ANOVA) test found that there were no significant differences among methane yields results in either group 1 or group 2, at the 0.05 level of significance. The results indicate that under the conditions tested, none of the treated wood products evaluated were toxic to the methane-producing organisms. At the end of the assays, test bottle contents were analyzed for Cu, Cr, and As. When the fraction of each metal in the solution (relative to original metal in the wood, leachability %) was examined, As was present at the great extent. The leachability of As was in the range from 15.1% to 21.7% while relatively low leachability (1.7-7.6%) of Cu was observed.     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.     

Chemical fractionation and heavy metal accumulation in the plant of Sesamum indicum (L.) var. T55 grown on soil amended with tannery sludge: Selection of single extractants

A pot experiment was carried out to study the single and sequential extractions of metals in different tannery sludge amendment and the potential of the plant of Sesamum indicum L. var. T55 (sesame) for the removal of metals from tannery waste contaminated site. The metal extraction efficiency obtained with each extractants was slightly different and follow the order; EDTA>DTPA>NH(4)NO(3)>NaNO(3)>CaCl(2). The correlation analysis between extractable metals in the different amendments of sludge and metal accumulation in the plant (lower and upper parts) showed better correlation for most of the tested metals with EDTA extraction. In this study, a sequential extraction technique was applied on different amendments of tannery sludge. The results showed that Mn, Zn, Cr and Cd were mostly associated with Fe-Mn oxide fraction in most of the amendments, K and Ni was found in residual (RES) fraction, Fe and Cu was bound with organic matter (OM) and RES fractions and Na was associated with carbonate (CAR) fraction. The metal accumulation after 60 d of growth of the plant was found in the order of K>Na>Fe>Zn>Cr>Mn>Cu>Pb>Ni>Cd and its translocation was found less in upper part. The accumulation of toxic metals (Cr, Ni and Cd) in the plants was found to increase with increase in sludge ratio, in contrast, the accumulation of Pb decreased. In view of growth parameters and metal accumulation in the plant, it was observed that lower amendments (25%) of tannery sludge were found suitable for the phytoremediation of most of the studied metals.     

Heavy metal extractable forms in sludge from wastewater treatment plants

The analysis of heavy metals is a very important task to assess the potential environmental and health risk associated with the sludge coming from wastewater treatment plants (WWTPs). However, it is widely accepted that the determination of total elements does not give an accurate estimation of the potential environmental impact. So, it is necessary to apply sequential extraction techniques to obtain a suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the BCR's guidelines was applied to sludge samples collected from each sludge treatment step of five municipal activated sludge plants. Al. Cd, Co, Cu, Cr, Fe, Mn, Hg, Mo, Ni, Pb, Ti and Zn were determined in the sludge extracts by inductively coupled plasma atomic emission spectrometry. In relation to current international legislation for the use of sludge for agricultural purposes none of metal concentrations exceeded maximum permitted levels. In most of the metal elements under considerations, results showed a clear rise along the sludge treatment in the proportion of two less-available fractions (oxidizable metal and residual metal).     

Geochemical partitioning of Co, Cr, Fe, Sc and Zn in polluted and non-polluted marine sediments

The partitioning of Co, Cr, Fe, Sc and Zn into three fractions (reducible by acidified hydroxylamine hydrochloride, oxidizable by acidified hydrogen peroxide, and the residual after the previous extractions) of Saronikos Gulf surface sediments was determined by using a sequential extraction technique. The metal concentrations were determined by Instrumental Neutron Activation Analysis. With the exception of Sc, the metal content in the reducible and oxidizable fractions increases in the polluted sediments near the Athens Sewage Outfall (ASO) and a Fertilizer Plant (FP). In the non-polluted sediments, the residual fraction is the most important carrier for all metals examined. Oxidizable Cr and Zn correlate well with the organic carbon content of the sediments, but the reducible fraction (mainly Fe/Mn hydroxides) is the most important sink for Co, Cr, Fe and Zn in the polluted sediments near the ASO. The pyrite-rich wastes from the FP are influencing the geochemical partitioning of the metals examined in the sediments in front of the FP and, partially, in the sediments near the ASO.     

焦化废水处理过程外排污泥中重金属形态特征及其潜在环境风险

焦化废水处理过程所排放污泥中重金属的含量及化学形态是否构成环境风险将直接影响污泥处置方法的选择,为此,实验采用BCR顺序提取法分析了焦化废水处理站外排污泥中重金属(Cd、Hg、Pb、Cr、As、Ni、Zn、Cu和Mn)的形态特征,并采用地累积指数(Igeo)和潜在生态危害指数(RI)评价了重金属对土壤的潜在环境风险。研究结果表明:除Ni主要以可氧化态存在外,焦化废水外排污泥中其他几种重金属元素主要存在于残渣态,重金属元素的含量低于《城镇污水处理厂污染物排放标准(GB18918—2002)》中的控制限值;与城市污泥相比,焦化废水外排污泥具有低Pb、Cr、Zn、Cu含量,而高Cd、Hg、Mn含量的特点;基于Igeo和RI的评价结果,Cd和Hg是外排污泥中具有一定环境风险的元素,需要考虑其下游去向。焦化废水处理外排污泥中主要存在残渣态重金属成分,不表现为很高的环境风险,其处置应重点考虑其中有机污染物特别是POPs。     

Speciation of heavy metals in estuarine sediments in the northeast of Brazil

An analytical procedure involving a three-step sequential extraction was used to determine the chemical association of heavy metals (Zn, Cr, Mn and Fe) with the major phases (exchangable, reducible and oxidizable) in samples from a fishpond of estuarine sediments. The pond is located in the Capibaribe River estuary, within the boundaries of the city of Recife, in the State of Pernambuco in the northeast of Brazil. The total metal content was determined as well. All metals were extracted from the residual fraction at a percentage greater than 50%.     

Evaluating landfill disposal of chromated copper arsenate (CCA) treated wood and potential effects on groundwater: evidence from Florida

Chromated copper arsenate (CCA) treated wood has been used for more than 50 years. Recent attention has been focused on appropriate disposal of CCA-treated wood when its service life ends. Groups in the US and Europe concerned with the possibility of arsenic migration to groundwater from disposed CCA-treated wood have proposed that consumers be required to dispose of the wood as a hazardous waste, in the most protective of landfills. We examined available data for evidence of arsenic migration from unlined construction and demolition (C&D) debris landfills in Florida, where CCA-treated wood is disposed. Florida was chosen because soil, groundwater, landfill design, weather, and levels of CCA-treated wood use make the state a uniquely sensitive indicator for observing arsenic migration from CCA-treated wood disposal sites, should it occur. We developed and quality-checked a CCA-treated wood disposal model to estimate the amount of wood and associated arsenic disposed. By 2000, an estimated 13 million kg of arsenic in CCA-treated wood was disposed in Florida; however, groundwater monitoring data do not indicate that arsenic is migrating from unlined C&D landfills. Our results provide evidence that highly stringent regulation of CCA-treated wood disposal, such as treatment as a hazardous waste, is unnecessary.     

Availability and bio-accessibility of metals in the clay fraction of urban soils of Sevilla

The availability of Cd, Cr, Cu, Ni, Mn, Pb and Zn present in the finest size particles of urban soils is studied by comparing the concentrations in the clay fraction with those extracted from the whole soil by either single-extraction or sequential extraction method. Many metals are preferentially present in the finest particles as compared to coarser fractions. This is true for most metals studied, except Mn and, perhaps, Cd. Those metals present in the clay fraction are often in easily bio-accessible forms, especially Cu, Pb and Zn. The results suggest that bio-accessible forms of these three metals are distributed among the three sequential fractions, and even the fraction considered as ‘residual’ is also bio-accessible to a significant extent. The statistical analysis shows some distinctions among metals that are compared to the ‘urban’, ‘natural’, or intermediate behaviour of the various metals as proposed earlier in the literature.     

The use of a sequential leaching procedure for heavy metal fractionation in green liquor dregs from a causticizing process at a pulp mill

A five-stage sequential leaching procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V, Ba and Ti) in green liquor dregs into the following fractions: (1) water-soluble fraction (H2O), (2) exchangeable fraction (CH3COOH), (3) easily reduced fraction (HONH3Cl), (4) oxidizable fraction (H2O2 + CH3COONH4), and (5) residual fraction (HF + HNO3 + HCl). The green liquor dregs were derived from a causticizing process at a pulp mill at Kemi, Northern Finland. According to the leaching studies, the leachability of heavy metals in the water-soluble fraction varied between 0.5 and 2 mg kg(-1) expressed on a dry weight (d.w.) basis, indicating relatively low bioavailability of the metals. However, the concentration of Mn (2065 mg kg(-1); d.w.) showed a strong and of Zn (17.6 mg kg(-1); d.w.), Ni (39.7 mg kg(-1); d.w.) and Ba (32.0 mg kg(-1); d.w.) slightly tendency to be extracted in the exchangeable fraction. In addition, Zn, Mn, Ni, Co, V and Ba showed clear leachability in the easily reduced fraction, as well as Cd, Cu, Cr, Zn, Mn, As and Ba in the oxidizable fraction. For Cd, Cu, Cr, Zn, Mn, Ni, Co, Ba and Ti, the sum of leachable heavy metal concentrations in fractions 1-5 agreed relatively well with the "total" heavy metal concentrations. Recoveries of the sum of fractions 1-5 were 84-56% of those obtained by the US EPA method 3052 (i.e. concentrations obtained after microwave oven digestion with a mixture of HF and HNO3).     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Effects of compost and phosphate on plant arsenic accumulation from soils near pressure-treated wood

Leaching of arsenic (As) from chromated copper arsenate (CCA)-treated wood may elevate soil arsenic levels. Thus, an environmental concern arises regarding accumulation of As in vegetables grown in these soils. In this study, a greenhouse experiment was conducted to evaluate As accumulation by vegetables from the soils adjacent to the CCA-treated utility poles and fences and examine the effects of soil amendments on plant As accumulation. Carrot (Daucus carota L.) and lettuce (Lactuca sativa L.) were grown for ten weeks in the soil with or without compost and phosphate amendments. As expected, elevated As concentrations were observed in the pole soil (43 mg kg(-1)) and in the fence soil (27 mg kg(-1)), resulting in enhanced As accumulation of 44 mg kg(-1) in carrot and 32 mg kg(-1) in lettuce. Addition of phosphate to soils increased As accumulation by 4.56-9.3 times for carrot and 2.45-10.1 for lettuce due to increased soil water-soluble As via replacement of arsenate by phosphate in soil. However, biosolid compost application significantly reduced plant As uptake by 79-86%, relative to the untreated soils. This suppression is possibly because of As adsorbed by biosolid organic mater, which reduced As phytoavailability. Fractionation analysis showed that biosolid decreased As in soil water-soluble, exchangeable, and carbonate fraction by 45%, whereas phosphate increased it up to 2.61 times, compared to the untreated soils. Our results indicate that growing vegetables in soils near CCA-treated wood may pose a risk of As exposure for humans. Compost amendment can reduce such a risk by reducing As accumulation by vegetables and can be an important strategy for remediating CCA-contaminated soils. Caution should be taken for phosphate application since it enhances As accumulation.     

Evolution of heavy metal speciation during the aerobic composting process of sewage sludge

The contents of heavy metals and their bioavailability to the soil-plant system were the major limitation to the application of sewage sludge compost in soil. This study was conducted to determine the evolution of heavy metal speciation in the course of an aerobic composting, and investigate the influence of changes of composting process parameters including pH, temperature and organic matter (OM) content on distribution of heavy metal speciation in composted sludge. The sequential extraction procedure developed by Tessier et al. was used in sludge compost to determine the heavy metal speciation. Results showed that, during composting, (1) the contents of the residue fraction for Pb, Zn and Cd were decreased but those for Ni and Cr were increased; the Cu residue fraction was almost constant; (2) the contents of the total mobile fractions (including fractions 1-4) for Zn and Pb were significantly increased, but the increase of those for Cu and Ni were not so remarkable; (3) there were significant degrees of correlation between heavy metal fractions and changes of some selected parameters (for example, pH, composting temperature, and OM content). Only the content of the total mobile fractions for Cu could be predictable from its total content. For the prediction of the total mobile fractions of Zn, Ni, Cd and Cr, the R(2) value was significantly increased by the inclusion of other variables such as pH, temperature and OM content.     

电镀污泥回收重金属的新工艺

合理、经济地处理混合电镀污泥,回收其中有价值的金属具有重要意义。以不同的酸作为浸出剂对电镀污泥中的金属进行了浸出效果实验。结果表明,在相同条件下,各酸的浸出效果顺序为:硫酸>盐酸>王水>硝酸;液体水与固体电镀污泥比为3,干污泥为5 g,硫酸加入量为15 mL,时间1 h条件下,混合电镀污泥中金属铜锌的浸出率最大,达到97.38%。分别采用铁和铁锰合金还原剂常温还原低熔点重金属离子铜、锌,浸出液中99%以上含量的铜、锌沉淀,使低熔点重金属与黑色金属铁、锰、铬有效分离。低熔点混合重金属可以用来做铜合金添加剂使用,最后沉淀的混合黑色金属氢氧化物处理后可以用来做炼钢合金添加剂使用。     

Increased PCDD/F formation in the bottom ash from fires of CCA-treated wood

Bottom ash that was the result of the combustion of chromated copper arsenate (CCA) treated wood under controlled fire conditions showed an increase of several orders of magnitude in the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), compared to that of untreated timber. Wood that has been pressure treated with CCA contains copper (II), which is known to catalyse the so-called de novo formation of PCDD/Fs. Comparable levels of PCDD/Fs would be expected in residual ash from burning CCA-treated wood in backyard fires, stoves and wood heaters, as a consequence of similar combustion conditions.     

Remediation of Cr(VI) from chromium slag by biocementation

Here we demonstrate a calcifying ureolytic bacterium Bacillus sp. CS8 for the bioremediation of chromate (Cr(VI)) from chromium slag based on microbially induced calcite precipitation (MICP). A consolidated structure like bricks was prepared from chromium slags using bacterial cells, and five stage Cr(VI) sequential extraction was carried out to know their distribution pattern. Cr(VI) mobility was found to significantly be decreased in the exchangeable fraction of Cr slag and subsequently, the Cr(VI) concentration was markedly increased in carbonated fraction after bioremediation. It was found that such Cr slag bricks developed high compressive strength with low permeability. Further, leaching behavior of Cr(VI) in the Cr slag was studied by column tests and remarkable decrease in Cr(VI) concentration was noticed after bioremediation. Cr slags from columns were characterized by SEM–EDS confirming MICP process in bioremediation. The incorporation of Cr(VI) into the calcite surface forms a strong complex that leads to obstruction in Cr(VI) release into the environment. As China is facing chromium slag accidents at the regular time intervals, the technology discussed in the present study promises to provide effective and economical treatment of such sites across the country, however, it can be used globally.     

还原焙烧电镀污泥中的金属形态和浸出性

分别以煤粉和稻杆为还原剂对电镀污泥进行还原焙烧，并通过酸浸回收焙烧渣中的金属。研究了焙烧温度、焙烧时间和还原剂投加量对目标金属Cu浸出率的影响以及主要杂质金属的浸出性，并采用BCR逐级提取法分析了焙烧前后污泥中的金属形态分布。结果表明，当在电镀污泥中投加30％的煤粉在600℃下焙烧1h后Cu的浸出率达到97．78％，当投加50％的稻杆时浸出率为89．47％，而氧化焙烧后浸出率仅为37．71％；并且还原焙烧渣中多数杂质金属的浸出率较低，从而可以实现Cu与杂质金属的初步分离。氧化焙烧容易导致金属从易浸出的非残渣态向难浸出的残渣态转化，而还原焙烧则能抑制这种转化过程，金属形态是决定其浸出性的重要因素。