中国五个典型城市污水厂污泥中重金属的形态分布研究

Metal content and bioavailability are often the limiting factors for application of sewage sludge in agricultural fields. Sewage sludge samples were collected from five typical urban wastewater treatment plants in China to investigate their contents and distribution of various chemical fractions of Cu, Zn, Ni, Cr, Pb and Mo by using the BCR （Community Bureau of Reference） sequential extraction procedure. The sludges contained considerable amounts of organic matter （31.8%- 48.0%）, total N （16.3-26.4 g kg^-1） and total P （15.1-23.9 g kg^-1）, indicating high potential agricultural benefits of their practical applications. However, total Zn and Ni contents in the sludge exceeded the values permitted in China＇s control standards for pollutants in sludges from agricultural use （GB 4284-1984）. The residual fraction was the predominant fraction for Mo, Ni and Cr, the oxidizable fraction was the primary fraction for Cu and Pb, and the exchangeable and reducible fractions were principal for Zn. The distribution of different chemical fractions among the sludge samples refiected differences in their physicochemical properties, especially pH. The sludge pH was negatively correlated with the percentages of reducible fraction of Cu and exchangeable fraction of Zn. The sludges from these plants might not be suitable for agricultural applications due to their high contents of Zn, Ni and Cr, as well as high potential of mobility and bioavailability of Zn.     

污泥和水溶性重金属盐的植物有效性比较研究

采用盆栽方法研究了污泥中重金属的植物有效性,并与等量重金属盐进行了比较。结果表明,施用污泥50 g/kg土和100 g/kg土能明显增加番茄和玉米苗期地上部Zn、Cu、As的含量,对Cr、Ni、Pb含量影响不大。施用污泥可以降低玉米苗期地上部Cd的含量。施用污泥与施用等量水溶性重金属盐比较,污泥重金属有效性低于水溶性重金属盐的有效性。在土壤污泥施用量为50 g/kg时,污泥重金属在番茄苗期的Zn、Cu有效系数分别为80.9%和54.8%;玉米苗期Zn、Cu的有效系数分别为53.4%和70.3%;污泥用量为100 g/kg土时,污泥重金属在玉米苗期的Zn、As有效系数分别为74.5%和64.4%。     

Heavy metals in mine soils amended with sewage sludge

In order to reclaim a clay quarry, a topsoil material was mixed with gravelly spoil at different ratios and with various rates of sewage sludge. The influence of three spoil/topsoil ratios (1:1, 2:1 and 3:1) and three sludge rates (40, 80 and 120 t ha⁻¹) on chemical properties of the resulting material was investigated, with emphasis on heavy metal (Fe, Cu, Mn, Ni and Zn) contents. The mixtures topsoil/spoil/sludge were water saturated and incubated for 15 or 30 days in a chamber under controlled conditions. The incubated samples were analysed for pH, total carbon and nitrogen, and total, available, exchangeable and soluble heavy metals. The addition of spoil to the topsoil increased the volume of material available, by utilizing an inert material unsuitable by itself to grow plants. The addition of sewage sludge repaired the disadvantages of the spoil, increasing the pH and the organic matter contents. The total heavy metal contents in the mixtures followed the sequence Fe>>Mn>>Zn, Cu>Ni. All except Cu were within the ranges allowed for agricultural lands. The available heavy metals constituted a small fraction of total contents and decrease with time due to complexation and immobilization processes. The exchangeable and soluble fractions were almost negligible; only small amounts of Mn, Zn and Cu were detected. Therefore, the risk of contamination by heavy metals is insignificant in the conditions investigated. Copyright © 1999 John Wiley & Sons, Ltd.     

Initial organic matter transformation of soil amended with composted sewage sludge

 An incubation experiment with composted sewage sludge (CSS) just added to the soil was conducted to determine its initial effects on C decomposition, N nitrification and the transformation of organic matter. CSS was mixed with a sandy loam soil from uncultivated ochric epipedon of a Typic Haploxeralf at rates of 0, 40 and 80 t ha^–1 (dry weight). The data obtained showed that with regard to the unamended soil, both the 40 and the 80 t ha^–1 treatments produced the same result in decreasing respiratory activity, but the addition of increasing amounts of CSS progressively delayed C decomposition. The nitrification index (NI), defined as the relation between nitrate-N and nitrate-N + ammonium-N, increased in correlation with the C mineralization coefficient. Total organic matter decreased after incubation whereas the humic substances increased in relation to the total C mineralized. Received: 28 October 1999     

Behavior of heavy metals from sewage sludge in a Chernozem of the dry belt in Saxony‐Anhalt/Germany

In a small‐plot trial different doses of sewage sludge (equivalent 82‐330 tons of dry matter per hectare) were incorporated in 0—25 cm depth (1982—1985). The aim of the investigations was to study the fate of the heavy metals Zn, Cd, Cu, Ni, Pb, and Cr, to determine their concentration in different soil fractions using a sequential extraction method and to ascertain their uptake by Zea mays L. plants. Eleven years after the last application the metals supplied with the sludge had moved as far as 50 cm in depth. The concentrations of Zn, Cd, Cu, Ni, and Cr in the saturation extract of the sampled soil layers were closely correlated with the concentrations of dissolved organic carbon (DOC). This result suggests that the heavy metal displacement was partly connected with the DOC movement in the soil. Considerable amounts of Zn and Cd coming from sewage sludge were found in the mobile fractions of the soil. Cu, Ni, and Pb were located especially in organic particles, and Cr was obviously bound by Fe‐oxides. Nine years after the last application the binding species of heavy metals were still different compared with those in the untreated soil. The whole withdrawal of heavy metals by plants yielded <1 % of the applied amounts. In the case of Zn the uptake from the sludge amended soil decreased during the experimental period. No similar tendency was observed for the other elements. In any case their annual variations of uptake exceeded the effect of sludge application.     

重庆市城市污泥中的重金属及其农用环境容量

城市污泥农用的环境风险取决于城市污泥中的污染物含量及土壤理化性质。该文分析了重庆市10个城市污水处理厂污泥中的Cu,Zn,Pb和Cd含量及形态,根据土壤环境容量及氮肥施用量计算了重庆主要旱地土壤的最大施用量和年施用量。结果表明,重庆市城市污泥中的Zn、Cu、Pb和Cd含量分别为362.12～725.32mg/kg,69.84～170.22mg/kg,21.25～107.24mg/kg和1.26～4.25mg/kg。污泥中不稳定态Zn、Cu、Pb和Cd的比例分别为42.89%～44.74%,2.69%～9.45%,0.95%～12.06%和61.05%～79.91%。根据土壤重金属的静态容量,计算出重庆主要旱地土壤紫色土和黄壤城市污泥的一次性最高施用量分别为384.62t/hm2和98.90t/hm2。根据土壤重金属动态容量,以15、20、50为年限,计算出的城市污泥的年施用量,紫色土为66.10,60.91和55.71t/(hm2·a),黄壤为30.32,28.99和27.53t/(hm2·a)。根据作物的需氮量计算城市污泥的年施用量为3.04～6.40t/(hm2·a),该施用量低于根据土壤环境的动态容量计算的施用量,按此用量施用城市污泥更安全。     

Pig manure digestate-derived biochar for soil management and crop cultivation in heavy metals contaminated soil

Management of heavy metal-contaminated soil under drought and other harsh hydrological conditions is critical for protecting soil ecosystem services. In this study, we examined the effect of pig manure digestate-derived biochar as a soil amendment (15 t ha⁻¹) with N fertilizer (180 kg ha⁻¹) on soil and plant heavy metal levels and nutrient availability under various moisture regimes (optimal moisture ~15%, drought condition ≤5%, and flooded condition ≥35% wt.). It was observed that biochar applications significantly decreased heavy metals in the spring wheat plants, lowering Cr by 90%, Ni by 50%, Cd by 9% and Pb by 34% compared to non-biochar (control) treatments. However, the pig digestate-derived biochar increased heavy metals in soil under all moisture regimes, increasing soil Cr by 21%, Ni by 43%, Cu by 55%, Zn by 70%, and Pb by 12%. The availability of macroelements also increased with the biochar applications under the optimum moisture regimes in both soil and plants, increasing Mg²⁺ by 11%, P by 4%, K⁺ by 50%, and Ca²⁺ by 56% in the soil, and Mg²⁺ by 13%, P by 69%, K⁺ by 29, and Ca²⁺ by 39% in plants. Biochar addition also improved chlorophyll fluorescence (CF) levels in the crop for the entire season (12^th to 62^nd day) and the aboveground crop biomass and dry matter contents both increased. Consequently, the use of pig manure digestate-derived biochar with N fertilizer under normal moisture conditions was able to reduce heavy metal availability to plants and thus could be used in contaminated soils to maintain better crop growth and development.     

用固定剂减少污泥中重金属污染土壤的研究

该研究将加有重金属固定剂的污泥装入废弃塑料容器制成施肥器,利用人工淋水或自然降水,使污泥中的养分从施肥器中流入土壤,而重金属被固定在污泥中,减少重金属土壤污染,再收集处理残渣,防止二次污染。通过淋滤试验和种植油麦菜、蕹菜的盆栽试验得出以下结论：硫酸钾作为固定剂和污泥混合,不仅肥效好,作物产量高,而且污泥重金属被水淋出量少,植物体内重金属的含量低。该文为污泥合理农用提供了新方法,同时充分利用了废弃塑料容器等废弃物,成本低而收效显著。     

污泥与秸秆掺烧过程及污泥灰中重金属含量分析

焚烧是处理污泥的一种有效方式,但处理过程中会产生重金属等污染物,若对焚烧后的污泥灰进行填埋等处理会污染土壤,因此降低污泥灰中重金属含量是亟待解决的问题.基于此,在一台实验室规模的管式炉中,研究了350～650℃下污泥与玉米秸秆的掺烧反应.主要目的是探究不同温度及秸秆掺混比对燃烧灰中8种重金属(Zn、Mn、Pb、Sb、A...     

改良剂原位修复重金属污染土壤研究进展

改良剂原位修复重金属污染土壤因其成本低廉、易于实施,已经得到广泛应用。然而,改良剂对土壤重金属的修复仍然存在着一定的局限性和潜在风险。无机和有机改良剂的修复效果不仅与重金属离子的种类有关,而且还受作物、土壤类型及环境因子的制约。本文就目前常用改良剂的修复效果,存在的问题,改良剂原位修复重金属污染土壤的作用机制以及国内外研究进展作简要综述,并对此方面研究的未来趋势提出展望。     

污泥农用对土壤和作物重金属累积及作物产量的影响

以3 a定位试验为基础,比较3种不同处理的污泥肥料（消化污泥、污泥堆肥及污泥复混肥）农田施用下土壤养分、土壤和作物籽粒中Mn、Cu、Zn、Pb、Cd 5种重金属的积累以及作物产量的变化情况,以阐明污泥农用对土壤及作物的影响。研究表明,3种污泥肥料提高了土壤中氮素和有机质的含量;与空白和普通化肥处理相比,3种污泥肥料增加了土壤中Mn和Cu的含量,而对土壤交换态重金属含量没有显著影响;3种污泥处理均增加了小麦籽粒中Zn的含量;相对普通化肥处理,3种污泥肥料处理对小麦和玉米产量均无显著影响。合理施用污泥肥料可以有效地提高作物产量;污泥肥料施用对土壤重金属有一定累积效应,但短期施用对土壤比较安全。     

Remediation of a soil contaminated with heavy metals by immobilizing compounds

The labile fraction of heavy metals (HM) in soils is the most important for toxicity for plants and microorganisms. Thus, it is crucial to reduce this fraction in contaminated soils to decrease the negative effect of HM. In a greenhouse experiment, the effects of several additives on the labile fractions of Zn, Cd, Cu, Ni, and Pb were investigated in a soil contaminated during long‐term sewage‐sludge application. The accumulation of HM was studied in the aboveground biomass of wheat (Triticum aestivum L.). The additives used were the clay minerals Na‐bentonite, Ca‐bentonite, and zeolite; the Fe oxides hematite and goethite; the phosphate fertilizers superphosphate and Novaphos. Wheat was planted three times during 5 months, allowed to grow for 7 w, and harvested. Dry matter and HM content of shoots were determined after each harvest. Soil samples were taken after the first and third harvest, and the NH₄NO₃‐extractable HM contents were determined. After the addition of 2% Na‐bentonite as well as 2% Ca‐bentonite, a strong reduction of the labile HM soil fraction and shoot HM concentration was observed. At the end of the experiment, the labile fraction was reduced due to the addition of Na‐bentonite and Ca‐bentonite by 24% and 31% for Zn, by 37% and 36% for Cd, by 41% and 43% for Cu, by 54% and 61% for Ni, and by 48% and 41% for Pb, respectively. Furthermore, the shoot HM concentrations with the exception of Zn were reduced below the phytotoxicity range. Accordingly, the shoot dry‐matter production was significantly increased. The addition of phosphate fertilizers (notably Novaphos) strongly reduced the bioavailability of Pb for wheat plants. By addition of 0.05% Novaphos, the labile fraction and the shoot concentration of Pb were lowered by 39% and 64%, respectively. However, the addition of Fe oxides and zeolite resulted only in a small reduction in HM bioavailability to wheat plants. Among the studied additives, Na‐bentonite and Ca‐bentonite have the most promising potential to reduce the bioavailability for the studied HM.     

生物淋滤去除农用污泥中重金属的效果及工艺

污水处理厂污泥中的重金属含量高是污泥农用的主要障碍。该文针对天津污水处理厂污泥含铜量高的特性,分别以硫酸亚铁和硫粉作为培养基进行生物淋滤对比试验,前者对铜的去除率远远高于后者。以硫酸亚铁作为培养基,研究了投配比、接种污泥量、pH值和温度对污泥中重金属去除效果的影响。结果表明,在硫酸亚铁投配比为10 g/L、污泥接种量为20%、温度为28℃、淋滤时间为4 d时,污泥中重金属Cu、Pb、Cr、Ni、Zn和Cd的去除率分别为89%、38%、61%、76%、72%和57%,其相应残余量分别为116、62.5、98、22、174、1.1 mg/kg。在7～28℃范围内,温度越高,氧化亚铁硫杆菌活性越高,生物淋滤时间越短;28℃和35℃下氧化亚铁硫杆菌活性基本相同。以硫酸亚铁为培养基淋滤处理后污泥中重金属的含量可满足《农用污泥中污染物控制标准》(GB4284-1984)。     

水稻子实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属(Cd、Cr、Pb、Cu、Zn)全量、各形态含量及相应点位种植的水稻子实重金属含量的基础上,通过统计分析、空间插值及线性回归方程的模拟,研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征,以及水稻子实对重金属各形态的累积差异及其影响因素。结果表明,成都平原水稻土重金属污染较轻,除Cd外,均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低,Cd主要以铁锰氧化态存在,Cr、Cu、Zn、Pb主要以残渣态存在。水稻子实对5种重金属的累积效应顺序为:Cd>Zn>Cu>Pb>Cr。与水稻重金属累积关系密切的重金属活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)主要有:Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量;Zn各活性形态对水稻子实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响;活性态Cr与pH、有机质、CEC和容重密切相关;活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系;Cu的活性主要受粘粒、有机质含量的影响;Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来,对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重,而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

水稻籽实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属（Cd、Cr、Pb、Cu、Zn）全量、各形态含量及相应点位种植的水稻籽实重金属含量的基础上，通过统计分析、空间插值及线性回归方程的模拟，研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征，以及水稻籽实对重金属各形态的累积差异及其影响因素。结果表明，成都平原水稻土重金属污染较轻，除Cd外，均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低，Cd主要以铁锰氧化态存在，Cr、Cu、Zn、Pb主要以残渣态存在。水稻籽实对5种重金属的累积效应顺序为：Cd＞Zn＞Cu＞Pb＞Cr。与水稻重金属累积关系密切的重金属活性形态（可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态）主要有：Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量；Zn各活性形态对水稻籽实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响；活性态Cr与pH、有机质、CEC和容重密切相关；活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系；Cu的活性主要受粘粒、有机质含量的影响；Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来，对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重，而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

Growth and Heavy-Metal Uptake by Lettuce Grown in Soils Applied with Sewage Sludge Compost

A pot experiment was conducted to investigate the effect of sewage sludge compost (SSC) alone and applied with chemical fertilizer on growth and heavy-metal accumulations in lettuce grown on two soils, a Xanthi-Udic Ferralosol and a Typic Purpli-Udic Cambosol. The treatments included control; nitrogen–phosphorus–potassium (NPK) fertilizer; sewage sludge compost applied at the rates of 27.54 (SSC), 82.62 (3SSC), 165.24 (6SSC) t hm^–2; and coapplication treatment (1/2 SSC + 1/2 NPK), where the N, P, and K inputs from NPK fertilizer, SSC, and coapplication treatments were normalized to the local recommend rates. The SSC application increased the biomass; copper, zinc, and lead contents in lettuce; and soil total and diethylenetriaminepentaacetic acid (DTPA)–extractable metals. However, SSC alone at the recommended rate caused less plant biomass than NPK fertilizer alone. Coapplication treatment obtained greater or similar biomass to NPK fertilizer alone and did not increase heavy-metal accumulation in soils and plants. The results demonstrated that SSC should be applied to soils with chemical fertilizers.     

Bioremediation of the soil contaminated with petroleum oil products using sewage sludge

ABSTRACT

The remediation technologies of soils contaminated with petroleum products are developed in two main directions: the first one encompasses searching for new effective bioagents and the other one explores the ways to activate those microorganisms present in the soil that are capable of degrading oil. The objective of this research was to determine if it is possible to increase the effectiveness of biodegradation of petroleum products by using chemical additives. The soil was supplemented with additives: CuSO4, MnSO4, KMnO4, H2O2, 5% and 10% chemical industry plants sludge, 5% and 10% Stock Company ‘Klaipedos vanduo’ (SC‘KV’) municipal wastewater treatment plants sludge. The data suggest that all the additives statistically significantly stimulated the degradation of diesel fuel (F = 12.01; p = .001) and black oil (F = 9.93; p = .001) compared with the control. It was determined that diesel fuel was degraded the fastest in samples with KMnO4, where efficiency of degradation was 90%, and 88% efficency in samples with 10% chemical industry plants sludge. Black oil was degraded the best in samples, where KMnO4 was added: efficiency of degradation was up to 63%. In the samples with 10% of sewage sludge from chemical industry plant degradation efficiency was 62%.     

Protozoan bioassays of soil amended with sewage sludge and heavy metals,using the common soil ciliate Colpoda steinii

The common soil protozoan Colpoda steinii was used to study the toxicity of sulphate solutions of Ni, Cd, Cu, and Zn. The growth of C. steinii was reduced by 50% in the presence of 0.10, 0.22, 0.25, and 0.85 mg litre^-1 of Ni, Cd, Cu and Zn, respectively, during 24 h of incubation at 25°C, as calculated from a regression analysis of probit-transformed data. The same growth assay was used to assess the toxicity of soil solution extracted by centrifugation from soil samples of field plots of a grass/clover ley on a sandy loam treated with sewage sludge spiked with additional Cd, Cu, Cr, Ni, Pb, or Zn at concentrations either equivalent to or twice the limits for heavy metals recommended in recent EC guidelines (Commission of European Communities directive 86/278/EEC). The toxicity of these soil solutions varied with the season of the year. None of the soil solutions extracted in winter (February 1991) inhibited the growth of C. steinii. In summer (July 1991), the growth was reduced in solutions extracted from plots that were amended with sludge plus additional Zn or Ni at twice the maxima recommended by the EC. The changes in toxicity to C. steinii of the soil solutions between February and July were positively correlated with increases in heavy metal concentrations of Zn and Ni between winter and summer. These preliminary results suggest that regular protozoan bioassays may be used to monitor the biological availability of heavy metals in soils, especially when combined with other microbial assays and with chemical analyses of soil solutions.     

玉米秸秆与污泥混合热解对生物碳特性及重金属的影响

利用热解装置开展不同质量比例玉米秸秆(0,25%,50%和75%)与污泥混合热解实验,分别得到4种生物炭(SCB0,SCB25,SCB50和SCB75),研究了生物炭性质、重金属(Cu,Zn,Pb,Ni,Cr,Mn和As)含量、BCR形态和TCLP浸出毒性特征,并开展潜在生态风险评估。结果表明,随着玉米秸秆添加比例的增加,生物炭产率、灰分、H/C和N/C比显著降低,p H值显著增大,生物炭芳香化程度明显提高。添加玉米秸秆与污泥混合热解可以促进重金属向更稳定的形态(F4态)转化。4种生物碳中重金属浸出均未超出GB5085.3-2007浸出毒性鉴别标准规定的限值,生态风险均明显降低至轻微风险水平,在玉米秸秆添加量为50%时达到最低风险水平,该研究为污泥与玉米秸秆资源化和无害化利用提供了理论依据。     

Leaching of heavy metals and nutrients from calcareous sandy‐loam soil receiving municipal solid sewage sludge

Leaching column experiments were conducted to determine the degree of mobility of heavy metals (HMs) and nutrients after the addition of municipal solid sewage sludge (MSS) in a sandy‐loam soil. Treatments were (1) soil application of low metal content MSS, (2) soil application of metal‐enriched municipal solid sewage sludge (EMSS), and (3) control. The MSS application represented a dose of 200 Mg dry weight (dw) ha^–1. Soil columns were incubated at room temperature for 15 d and were irrigated daily with distilled water to make a total of 557 mm. Leachates were collected and analyzed for HMs and nutrients. The Ni and Pb added to soil via MSS and EMSS were found to be leached through the 20 cm columns of calcareous sandy soil although Ni and Pb concentrations in the percolate were small relative to the total amounts of metals applied. Losses of K⁺ from the EMSS, MSS, and control were 92.5, 82.0, and 52.5 kg ha^–1, respectively. Losses of Mg²⁺ were in the range from 104.4 (control treatment) to 295.2 kg ha^–1 (EMSS), while the loss of Ca²⁺ was in the range from 265.0 (control treatment) to 568.2 kg ha^–1 (EMSS). The results showed that the amounts of P leached from EMSS (3.02 kg ha^–1) and MSS (2.97 kg^–1 ha^–1) were significantly larger than those from the control treatment (1.54 kg ha^–1). The geochemical code Visual MINTEQ was used to calculate saturation indices. Leaching of P in different treatments was controlled by rate‐limited dissolution of hydroxyapatite, β‐tri‐Ca phosphate, and octa‐Ca phosphate. The results indicate that application of MSS to a sandy soil, at the loading rate used in this study, may pose a risk in terms of groundwater contamination with Ni, Pb, and the studied nutrients.