Salinity, organic content, micronutrients and heavy metals in pig slurries from South-eastern Spain

The increase in commercial pig production is an opportunity to reuse animal manures in arid and semiarid soils as a source of nutrients and organic matter. However, there are components in pig slurry that are potentially dangerous for the environment. In this study, pig slurries of 36 pig farms in South-eastern Spain were evaluated for salt content (electrical conductivity, chloride and sodium), organic load (BOD5 and COD), micronutrients (Fe, Cu, Mn and Zn), and heavy metals (Cd, Co, Cr, Ni and Pb). Except for electrical conductivity, Cu and Zn, components in pig slurries did not vary considerably between animal production stages, indicating similar management of diverse animal types. Assuming an application rate based on the maximum input of nitrogen from animal manure (210 kg total N/ha/yr), the estimates for soil annual load of Cl and Na, 415 kg/ha, could be a significant salinisation risk. Cu and Zn seemed to be the metals that could be accumulated most in soils where application of pig slurries is common (4 and 15 kg/ha/yr, respectively). The estimated heavy metal (Cd, Co, Cr, Ni and Pb) input to soils would be 260 g/ha/yr, with a relative contribution of Cr>Ni>Pb>Co>Cd.     

Fixation and partitioning of heavy metals in slag after incineration of sewage sludge

Fixation of heavy metals in the slag produced during incineration of sewage sludge will reduce emission of the metals to the atmosphere and make the incineration process more environmentally friendly. The effects of incineration conditions (incineration temperature 500-1100°C, furnace residence time 0-60min, mass fraction of water in the sludge 0-75%) on the fixation rates and species partitioning of Cd, Pb, Cr, Cu, Zn, Mn and Ni in slag were investigated. When the incineration temperature was increased from 500 to 1100°C, the fixation rate of Cd decreased from 87% to 49%, while the fixation rates of Cu and Mn were stable. The maximum fixation rates for Pb and Zn and for Ni and Cr were reached at 900 and 1100°C, respectively. The fixation rates of Cu, Ni, Cd, Cr and Zn decreased as the residence time increased. With a 20min residence time, the fixation rates of Pb and Mn were low. The maximum fixation rates of Ni, Mn, Zn, Cu and Cr were achieved when the mass fraction of water in the sludge was 55%. The fixation rate of Cd decreased as the water mass fraction increased, while the fixation rate of Pb increased. Partitioning analysis of the metals contained in the slag showed that increasing the incineration temperature and residence time promoted complete oxidation of the metals. This reduced the non-residual fractions of the metals, which would lower the bioavailability of the metals. The mass fraction of water in the sludge had little effect on the partitioning of the metals. Correlation analysis indicated that the fixation rates of heavy metals in the sludge and the forms of heavy metals in the incinerator slag could be controlled by optimization of the incineration conditions. These results show how the bioavailability of the metals can be reduced for environmentally friendly disposal of the incinerator slag.     

添加CaO对燃煤重金属元素富集效果的影响

选取CaO作为吸附剂,探究了不同燃烧温度下添加CaO对重金属元素在燃煤灰渣中富集效果的影响规律。实验结果表明:添加CaO对重金属元素Cr未起到富集作用,而对Mn,Ni,Cu,Zn,As,Cd,Pb 7种重金属元素的富集效果显著;随燃烧温度的升高,CaO对各赋存形态的Mn,Ni,Cu,Zn,As的富集效果先变好而后变差,对各赋存形态的Cd和Pb的富集效果越来越好;CaO添加比(预处理后的CaO颗粒与预处理后的原煤的质量比)越大,CaO对Mn,Ni,Cu,Zn,As,Cd,Pb的富集效果越好,燃烧温度为850℃时的最佳CaO添加比为4%。     

Chemical properties of heavy metals in typical hospital waste incinerator ashes in China

Incineration has become the main mechanism for hospital waste (HW) disposal in China after the outbreak of Severe Acute Respiratory Syndrome (SARS) in 2003. However, little information is available on the chemical properties of the resulting ashes. In the present study, 22HW ash samples, including 14 samples of bottom ash and eight samples of fly ash, were collected from four typical HW incineration plants located across China. Chemical analysis indicated that the HW ashes contained large amounts of metal salts of Al, Ca, Fe, K, Mg, Na with a concentration range of 1.8-315gkg(-1). Furthermore, the ashes contained high concentrations of heavy metals such as Ag, As, Ba, Bi, Cd, Cr, Cu, Mn, Ni, Pb, Ti, Sb, Sn, Sr, Zn with a vast range of 1.1-121,411mgkg(-1), with higher concentrations found in the fly ash samples. Sequential extraction results showed that Ba, Cr, Ni and Sn are present in the residual fraction, while Cd existed in the exchangeable and carbonate fractions. As, Mn, Zn existed in the Fe-Mn oxide fraction, Pb was present in the Fe-Mn oxide and residual fractions, and Cu was present in the organic matter fraction. Furthermore, toxicity characteristic leaching procedure (TCLP) results indicated that leached amounts of Cd, Cu and Pb from almost all fly ash samples exceeded the USEPA regulated levels. A comparison between the HW ashes and municipal solid waste (MSW) ash showed that both HW bottom ash and fly ash contained higher concentrations of Ag, As, Bi, Cd, Cr, Cu, Pb, Ti, and Zn. This research provides critical information for appropriate HW incineration ash management plans.     

Heavy metals in source-separated compost and digestates

The production of compost and digestate from source-separated organic residues is well established in Europe. However, these products may be a source of pollutants when applied to soils. In order to assess this issue, composts, solid and liquid digestates from Switzerland were analyzed for heavy metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) addressing factors which may influence the concentration levels: the treatment process, the composition, origin, particle size and impurity content of input materials, the season of input materials collection or the degree of organic matter degradation.Composts (n = 81) showed mean contents being at 60% or less of the legal threshold values. Solid digestates (n = 20) had 20–50% lower values for Cd, Co, Pb and Zn but similar values for Cr, Cu and Ni. Liquid digestates (n = 5) exhibited mean concentrations which were approximately twice the values measured in compost for most elements. Statistical analyses did not reveal clear relationships between influencing factors and heavy metal contents. This suggests that the contamination was rather driven by factors not addressed in the present study.According to mass balance calculations related to Switzerland, the annual loads to agricultural soils resulting from the application of compost and digestates ranged between 2% (Cd) and 22% (Pb) of total heavy metal loads. At regional scale, composts and digestates are therefore minor sources of pollution compared to manure (Co, Cu, Ni, Zn), mineral fertilizer (Cd, Cr) and aerial deposition (Pb). However, for individual fields, fertilization with compost or digestates results in higher heavy metal loads than application of equivalent nutrient inputs through manure or mineral fertilizer.     

气化炉渣的重金属浸出特性及化学形态分析

分别采用硫酸硝酸法、水平振荡法和醋酸缓冲溶液法制取气化炉渣的浸出液，考察了不同提取方式对浸出液中重金属质量浓度的影响。采用改进BCR连续提取法对气化炉渣中的重金属Cr，Zn，Cu，Pb，Ni，As，Cd的化学形态进行了分析。实验结果表明：煤气化工艺中的气化炉渣属第Ⅰ类一般工业固体废物;在3种提取方式中，醋酸缓冲溶液法的重金属浸出种类最多，且浸出量最大;Cd和Cr对环境具有较高的潜在危害性，Cu次之，Zn，Pb，Ni，As主要以残渣态形式存在，对环境的直接危害性较低。     

Fractionation of heavy metals in sludge from anaerobic wastewater stabilization ponds in southern Spain

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 necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, a sequential extraction scheme according to the Standard, Measurements and Testing Programme of the European Commission was applied to sludge samples collected from ten anaerobic wastewater stabilization ponds (WSPs) located in southern Spain. Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, 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 the metal concentrations exceeded maximum permitted levels. Overall, heavy metals were mainly associated with the two less-available fractions (34% oxidizable metal and 55% residual metal). Only Mn and Zn showed the highest share of the available (exchangeable and reducible) fractions (25-48%).     

赤泥中重金属元素的浸出性与结合形态

采用等离子体质谱仪分析了拜耳法赤泥(BRM)和烧结法赤泥(SRM)中Cr,Ni,Cu,Zn,As,Cd,Cs,Pb等8种重金属元素的含量。采用逐级提取的方法分析了BRM和SRM中8种重金属元素的浸出情况和形态分布差异。实验结果表明:SRM中水溶态As的质量浓度达到17.3μg/L,BRM和SRM中可交换态Cr的质量浓度均在2 300μg/L以上,对水环境可能存在潜在危害;两种赤泥中不同形态重金属的浸出率有较大差异,SRM中Ni和BRM中Zn的总浸出率分别在60%和50%以上。     

Metals in Sediments from the Stockholm Region: Geographical Pollution Patterns and Time Trends

The city of Stockholm is intersected and surrounded by water.Freshwater flows eastward and mixes with slightly brackish water in central Stockholm to finally reach the Baltic Sea. Inorder to estimate the magnitude and geographical impact of Stockholm as a source of metals to the aquatic environments, sediments from 117 stations in the Stockholm region have beenanalysed for metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn).This paper reports on the geographical pollution pattern and onthe time trends in metal pollution in Stockholm during the 20th century. Stockholm is a strong source of Cd, Cu, Hg,Pb and Zn whereas the Cr concentrations are moderately perturbed.In contrast, the concentrations of As, Co, and Ni are in generalclose to preindustrial levels. The concentrations of Cd, Cu, Hg,Pb and Zn are highest in central Stockholm and eastwards (i.e., in the water flow direction). Sediments upstream of Stockholm andin lakes that are not hydrologically connected to central Stockholm show a significantly lower impact. This may be indicative of metals emitted in Stockholm mainly being transported by the water route. Of Cd, Hg, Pb, and Zn, Cd showsthe most pronounced decline in accumulation rates over the lasttwo decades.     

Evaluation of heavy metal content in digestate from batch anaerobic co-digestion of sunflower hulls and poultry manure

In this experimental study, the biogas digestate from mesophilic batch anaerobic co-digestion of poultry manure and an agricultural residue, sunflower hulls, was characterized, particularly in terms of heavy metal content, in order to evaluate whether the biogas digestate was suitable for land applications. Ni, Zn, Cu, Pb, Cr, Cd, and Hg were detected in the biogas digestate in each trial, however, their concentrations were always lower than the limit values stated in Turkish regulations. The main source of heavy metals in the biogas digestate seemed to be the poultry manure, not the agricultural residue. The commercial feedstuffs that are frequently supplemented with various essential elements to promote optimum nutrient supply and optimum growth rates may have contributed to heavy metals presence in the biogas digestate. The results indicated that the biogas digestate from anaerobic co-digestion of manure and agricultural residue could be utilized as fertilizer in agricultural applications.     

Acidic bioleaching of heavy metals from sewage sludge

The overall objective of this study was to evaluate the use of controlled bio-acidification prior to land application as a decontamination process to remove heavy metals from sludge. The sulfur-oxidizing bacteria were naturally available in the sludge samples and were activated by providing sulfur and aeration at 28°C–30°C. Activation resulted in bio-acidification to pH 2 within 5–11 days. Successive inoculation of fresh sludges with 5% acidified samples reduced the acidification time to 2–3 days in most samples. Bio-acidification resulted in dissolving significant quantities of heavy metals from all sludge types tested. The maximum solubilization results were: 86%–97% for Ni; 48%–98% for Pb; 26%–71% for Cr; 18%–91% for Zn; 16%–90% for Cu; 7%–60% for Cd. Limited metal solubilization results were observed in the various control samples that accompanied the bio-acidified samples. The leaching results in the control samples were limited to 2%–19% for Ni, 0%–7% for Pb, 0%–5% for Cr, 0.3%–4% for Zn, 0.2%–4% for Cu and 0%–3% for Cd. The results confirmed that Ni and Pb were the easiest metals to dissolve from the various sludge types. On the other hand, the lowest solubilization results were observed for Cu and Cd, and moderate solubilization results were achieved for Cr. The bio-acidification process resulted in moderate gains in terms of improving the suitability of tested sludges for land application. Received: April 19, 1999 / Accepted: November 4, 1999     

Investigation of potentially toxic heavy metals in different organic wastes used to fertilize market garden crops

The benefits of using organic waste as fertilizer and soil amendment should be assessed together with the environmental impacts due to the possible presence of heavy metals (HMs). This study involved analysing major element and HM contents in raw and size-fractionated organic wastes (17 sewage sludges and composts) from developed and developing countries. The overall HM concentration pattern showed an asymmetric distribution due to the presence of some wastes with extremely high concentrations. HM concentrations were correlated with the size of cities or farms where the wastes had been produced, and HM were differentiated with respect to their origins (geogenic: Cr–Ni; anthropogenic agricultural and urban: Cu–Zn; anthropogenic urban: Cd–Pb). Size fractionation highlighted Cd, Cu, Zn and Pb accumulation in fine size fractions, while Cr and Ni were accumulated in the coarsest. HM associations with major elements revealed inorganic (Al, Fe, etc.) bearing phases for Cr and Ni, and sulfur or phosphorus species for Cd, Cu Pb and Zn.     

Effect of nine years of animal waste deposition on profile distribution of heavy metals in Abeokuta,south-western Nigeria and its implication for environmental quality

Uncontrolled deposition of waste from animal farms is a common practice in south-western Nigeria, and the presence of heavy metals in soil constitutes environmental and health hazards by polluting the soil, ground water, adjoining streams and rivers. The study investigated the profile distribution of Mn, Pb, Cd, Zn, Fe, Cu, Ni and Cr in some tropical Alfisols in south-western Nigeria after nine years disposal of animal wastes. The amount of these metals in the soil horizons was high enough to cause health and phytotoxic risks. All the metals except Zn and Cr increased down the profile, while Mn, Pb, Cd, Fe, Cu and Ni accumulated at 80–120 cm depth. The increment of these metals at this depth over the top soil were 26%, 143%, 72%, 47%, 328% for Mn, Pb, Cd, Cu and Ni, respectively. It thus, shows their mobility and the possibility of polluting ground water. The Mn content at the poultry and cattle waste sites increased by 127% and 25%, respectively over the control, while that of cattle and swine dump site for Cd content were 9.82 and 15.63 mg kg^?1, respectively. Lead content also increased by 8.52 and 5.25 mg kg^?1, respectively.There was the accumulation of Zn and Cu at the swine dump site while the cattle dump site had the highest amounts of nickel and chromium. The least amount of Fe was recorded at the swine waste dump site. The reduction in organic matter with depths together with the reduced pH might have favored the mobility of the metals. The ranking of pollution among the sites was poultry > swine > cattle > sheep and could be due to the type of ration fed, the vaccination programmes, sanitation programmes and other management practices.     

Sequential extraction of metals from mixed and digested sludge from aerobic WWTPs sited in the south of Spain

The content of heavy metals is the major limitation to the application of sewage sludge in soil. However, assessment of the pollution by total metal determination does not reveal the true environmental impact. It is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, sequential extraction of metals from sludge before and after aerobic digestion was applied to sludge from five WWTPs in southern Spain to obtain information about the influence of the digestion treatment in the concentration of the metals. The percentage of each metal as residual, oxidizable, reducible and exchangeable form was calculated. For this purpose, sludge samples were collected from two different points of the plants, namely, sludge from the mixture (primary and secondary sludge) tank (mixed sludge, MS) and the digested-dewatered sludge (final sludge, FS). Heavy metals, Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn, were extracted following the sequential extraction scheme proposed by the Standards, Measurements and Testing Programme of the European Commission and determined by inductively-coupled plasma atomic emission spectrometry. The total concentration of heavy metals in the measured sludge samples did not exceed the limits set out by European legislation and were mainly associated with the two less-available fractions (27-28% as oxidizable metal and 44-50% as residual metal). However, metals as Co (64% in MS and 52% in FS samples), Mn (82% in MS and 79% in FS), Ni (32% in MS and 26% in FS) and Zn (79% in MS and 62% in FS) were present at important percentages as available forms. In addition, results showed a clear increase of the concentration of metals after sludge treatment in the proportion of two less-available fractions (oxidizable and residual metal).     

Metal fractionation in soil profiles at automobile mechanic waste dumps.

Soil profiles at five automobile mechanic waste dumps in Port-Harcourt, Nigeria were investigated to assess the spatial distribution, chemical speciation, and likely mobility of Cd, Cu, Pb, Zn, Cr and Ni in the soil as a function of the soil properties. A sequential fractionation protocol was used that generated six different fractions into which soil metal could partition. Cadmium was associated with non-residual fractions at surface horizons, but at lower depths it was in the residual fractions. Copper and Cr partitioned into organic and residual fractions, while Pb was associated with an Fe-Mn oxide fraction and the residual fractions. Zinc in surface horizons partitioned into an Fe-Mn oxide fraction and a fraction that captured carbonate-bound species, but in subsurface horizons, it was mainly in the residual fractions. Ni was predominantly found in the residual fractions. Mobility factors were calculated, and their values tended to decrease with increasing profile depth, indicating that these metals are relatively mobile in the surface horizons compared the subsurface except for chromium in the 15-30 cm depths. The mobility factors for the heavy metals follow the order: Cd > Zn > Pb > Cu > Cr > Ni. The results suggest that there is serious contamination hazard with Cd, Pb, and Zn in the soil profiles.     

Nutrients and heavy metals distribution in thermally treated pig manure.

Ash from pig manure treated by combustion and thermal gasification was characterized and compared in terms of nutrient, i.e., potassium (K), phosphorus (P) and heavy metal, i.e., cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) contents. Total nutrient and metal concentrations were measured using energy dispersive X-ray fluorescence analysis. Acid (HNO3, H2SO4) and water-extractable concentrations were also measured both in non-classified ash and in selected ash particle size fractions using flame atomic absorption spectrometry and colorimetric spectrometry. Results indicate that ash from gasified manure contained more water-extractable K in comparison with combusted manure whereas the opposite was the case with respect to P. Heavy metals Ni, Cr and Cd were present in higher concentrations in the fine particle size fractions (< 30 microm of particle diameter), whereas K, P, Zn and Cu exhibited higher concentrations in the coarser particle size fractions (> 30 microm).     

Characterization of a thermal power plant air heater washing waste: a case study from Iran.

In Iran most of the electricity is generated by thermal power plants. As a result of fuel oil burning in winter time, the air heaters of the boilers have to be washed and cleaned frequently. The wastewater originating from air heater washing is then treated in an effluent treatment plant by chemical precipitation followed by dewatering of the sludge produced. The resulting waste is classified as specific industrial waste that should be characterized in detail under the Waste Management Act of Iran. The quantity of this waste produced in the studied power plant is about 20 tonnes year(-1). In the present investigation, the first to be carried out in Iran, seven composite samples of dewatered sludge from air heater washing wastewater treatment were subjected to investigation of the physical properties, chemical composition and leaching properties. The most likely pollutants that were of concern in this study were heavy and other hazardous metals (Cd, Co, Cr, Mn, Ni, Pb, Zn and V). The results revealed that mean pH, wet and dry density and moisture content of the waste were 6.31, 1532 kg m(-30, 1879 kg m(-3) and 15.35%, respectively. Magnetite, SiO2, P2O5, CaO, Al2O3 and MgO were the main constituents of the waste with a weight percentage order of 68.88, 5.91, 3.39, 2.64, 2.59 and 1.76%, respectively. The toxicity characteristic leaching procedure test results for some heavy and other hazardous metals showed that mean elemental concentrations of Cd, Co, Cr, Mn, Ni, Pb, V and Zn in leachate were 0.06, 1.55, 5.49, 36.32, 209.10, 0.58, 314.06 and 24.84 mg L(-1), respectively. According to the Waste Management Act of Iran this waste should be classified as hazardous and should be disposed of in accordance with hazardous waste disposal regulations.     

Goods in the Anthroposphere as a Metal Emission Source A Case Study of Stockholm,Sweden

The aim of this study was to quantify the diffuse emissionsduring use of metal containing goods in the capital of Sweden,Stockholm. The following metals were studied: Cadmium (Cd), Chromium (Cr), Copper (Cu), Lead (Pb), Mercury (Hg), Nickel (Ni) and Zinc (Zn).A major part of the metals are found in a protected environmentwhere degrading processes like corrosion are most limited. However, during the lifetime of some goods the metal release to the environment is significant. The quantitatively most dominant emissions were found for Cu and Zn. The tap water system and roofs/fronts (Cu) represent goods with large exposedareas but with relatively small release rates per unit. In contrast, brake linings, aerial lines and electrical grounding (Cu) and tyres, brake linings and chemicals (Zn) are allgoods with high release rates but mostly limited exposed stocks.High yearly emissions are also found for Pb, ammunition andsinkers dominate the calculated emissions totally. For Cr and Ni, stainless steel represent the major part of the stocks, butcorrosion was estimated to give only a minor contribution to the emissions. Potential emission sources, i.e. stabilisers,pigments and plated goods dominate the exposed Cd stock. Theseemissions were not quantified due to lack of data. Hg is currently phased out, but one major source of emission, i.e. the use of amalgam, will be continuously significant for several decades. The importance of the traffic sector is obvious. The emissionsfrom brake linings (Cu, Zn and Pb), tyres (Zn, Pb, Cr and Ni)and asphalt wear (Cu, Zn, Cr, Ni and Pb) are all of large importance for the total emission from respectively metal.     

硫酸锰渣污染土壤中重金属的形态分布及生物活性

测定了硫酸锰渣污染土壤中Cu,Zn,Cd,Pb,Mn的总量和各形态含量.结果表明重金属总量远超过环境背景值和土壤环境二级标准.重金属各形态分布特征:Cu,有机态>残渣态>铁锰氧化态>碳酸盐态>可交换态;Zn,残渣态>铁锰氧化态>有机态>碳酸盐态>可交换态;Cd,铁锰氧化态>可交换态>碳酸盐态>残渣态>有机态;Pb,铁锰氧化态>残渣态>有机态>碳酸盐态>可交换态;Mn,铁锰氧化态>残渣态>可交换态>有机态>碳酸盐态.重金属的生物可利用性系数和迁移系数均为Cd>Mn>Pb>Cu>Zn.     

万山汞矿区土壤重金属污染特征及来源解析

以万山汞矿区土壤为研究对象,采用电感耦合等离子体质谱仪和原子荧光光谱仪测定土壤中的重金属含量,分别运用内梅罗综合污染指数（NPI）法和潜在生态风险指数（RI）法评价土壤重金属污染和潜在生态风险,并应用相关性分析、主成分分析和聚类分析对土壤重金属来源进行分析。结果表明：土壤Hg、Cd、As、Pb、Cu、Ni和Zn出现不同程度累积,分别达贵州省背景值的263.61、2.31、1.28、2.11、1.70、1.01和3.52倍;土壤重金属平均NPI为188.00,属于严重污染水平,Hg是主要污染因子;土壤重金属平均RI为10 655.70,属于极强潜在生态风险水平,Hg是主要潜在生态风险因子;土壤中Cu、Ni、Cr主要源于自然活动,As、Pb、Zn主要源于燃煤和交通运输污染,Cd主要源于农业污染,Hg主要源于汞冶炼污染。