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 metal mobility and potential availability in animal manure: using a sequential extraction procedure

In this study, dairy cow manure, goat manure, and chicken manure were collected from three farms and analyzed to find out the concentration of Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn. The concentration and potential of mobility and availability of heavy metals were studied in the animal manure samples. BCR Sequential extraction procedure was used to determine the binding forms of the metals. In this study, pseudo total concentrations of Mn and Zn were found out to be predominant in all the types of animal manure samples. According to the results, it was traced that Cr, Cu, and Ni were observed to be at the second highest level while Cd, Co, and Pb were seen at the lowest level in all the manure samples. When extractable amounts of heavy metals are taken into consideration, it is seen that the amount of the mobile fractions of heavy metals except for Cr and Ni are higher in comparison with that of immobile fraction in all the animal manure samples. It was also viewed that Mn, Cd, and Zn are more available in dairy cow manure and chicken manure whereas Cd, Co, and Mn are more available in goat manure.     

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.     

Effect of sintering temperature on the properties and leaching of incinerator bottom ash.

The fine particle size fraction of municipal solid waste incinerator bottom ash is often problematic because reuse applications for this material are limited. In these experiments incinerator bottom ash with a particle size of less than 8 mm was processed using conventional ceramic production techniques involving wet milling, drying, compacting and sintering. The effect of sintering temperature on the sintered density, microstructure, acid neutralization capacity (ANC) and the release of metal ions as a function of leachate pH are reported. Sintering at 1080 degrees C produced samples with maximum density. This material contained diopside (CaMgSi2O6), clinoenstatite (Mg2Si2O6) and wollastonite (CaSiO3) as the major crystalline phases. The acid neutralization capacity of sintered samples is significantly lower than milled bottom ash, and further reduces as the sintering temperature increases. This is associated with reduced leaching of Ca from sintered ash samples under all leachate pH conditions. Heavy metals present in the incinerator bottom ash included Cr, Cu, Ni, Zn, Cd and Pb. Sintering under optimum conditions reduced the leachable fraction of these metals under aggressive acid conditions (leachate pH 3) by factors ranging from 90% for Ni to greater than 99% for Cr, Cd, Zn and Pb.     

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.     

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.     

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.     

Characterization of trace elements in chicken and duck litter ash

For safe and sustainable management of poultry litter, it is important to evaluate and understand the chemical forms and concentrations of their constituent trace elements during treatment for disposal. This experiment was carried out to compare changes in metal (Cu, Mn, Zn, Pb and Ni) fractions in chicken and duck litter after incineration at temperatures ranging from 200 to 900 degrees C. The metals were stepwise fractionated into exchangeable, adsorbed, organically bound, carbonate precipitated and residual forms by extracting with 0.5M KNO3, de-ionized water, 0.5M NaOH, 0.05M Na2 EDTA and 4M HNO3, respectively. The content of total metal and other elements (i.e., Ca, Mg and K) were was also determined. Results showed an increasing trend in the total concentrations of metals with increasing temperature with higher amounts in chicken litter ash (CLA) than duck litter ash (DLA). Higher temperatures significantly reduced the levels of H2O-soluble Mn, Zn and Ni and enhanced those of Cu and Pb. The metal fractions extracted by EDTA and HNO3 increased directly with increasing temperature while the fraction extracted with KNO3 and NaOH decreased with ashing. For Cu, Mn, Pb and Ni, the amount extracted varied in the order EDTA>HNO3>NaOH>KNO3>H2O, but the absolute amounts differed between CLA and DLA. Peak concentrations of the total metals were achieved at the highest burning temperature. The amount of H2O soluble Ca and Mg decreased and K increased in both CLA and DLA with temperature. Total and exchangeable forms of cations increased with increasing temperature. Total Ca was highest in DLA, whereas total Mg and K were higher in CLA. This study indicated that incinerating poultry litter before soil application may have mixed effects on the vulnerable metal fractions by increasing or decreasing some fractions, depending on poultry type.     

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.     

Concentrations of heavy metals in fly ash from a coal-fired power plant with respect to the new Finnish limit values

In Finland, the new limit values for heavy metals in fertilizers used in agriculture and in forestry came into force in March 2007, and for materials used as earth construction agents, in June 2006. From the utilization point of view, it was notable that the total heavy metal concentrations (Cd, Cu, Pb, Cr, Mo, Zn, As, Ni, Ba, and Hg) in fly ash from a coal-fired power plant were lower than those limit values. The concentrations of the easily soluble elements Ca, Mg, Na, P, and Zn in the fly ash were between 3.5 and 35 times higher than those found in the coarse mineral soils of Finland. Fly ash is a potential agent for soil remediation and for improving soil fertility. If inorganic materials and by-products are utilized in earthworks, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix. Therefore, a five-stage sequential extraction procedure was used to evaluate the extractability of different elements in fly ash into the following fractions: (1) the water-soluble fraction, (2) the exchangeable fraction (CH₃COOH), (3) the easily reduced fraction (NH₂OH-HCl), (4) the oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) the residual fraction (HF + HNO₃ + HCl).     

An investigation on the potential of metal recovery from the municipal waste incinerator in Taiwan

This study aimed to identify distribution of metals and to estimate the amount of these metals that can be potentially recovered from incineration residues. First, the partitioning behavior of Cr, Cu, Fe, Cd, Al, Zn, and Pb in bottom ash and fly ash was investigated in one large municipal waste incinerator in Taiwan. In addition, the material flow analysis (MFA) method was used to estimate the material flux of metals within incinerator plant, and to calculate the amount of metal recovery. According to the findings of this study, six metals (Fe, Al, Cu, Zn, Cr, and Pb) concentrated in bottom ash mostly, while Cd existed primarily in fly ash. The weight percentages of Fe (4.49%), Al (5.24%), Cu (1.29%), Zn (2.21%), and Pb (0.58%) in incinerator ash are high, and even higher than the compositions of natural minerals. Finally, the amount of Cr, Cu, Fe, Cd, Al, Zn and Pb that can be potentially recovered from incineration residues will reach 2.69 x 10(2), 1.46 x 10(4), 4.91 x 10(4), 6.92 x 10(1), 5.10 x 10(4), 1.85 x 10(4) and 4.66 x 10(3) ton/yr, respectively.     

Sewage sludge ash to phosphorus fertiliser: variables influencing heavy metal removal during thermochemical treatment

The aim of this study was to improve the removal of heavy metals from sewage sludge ash by a thermochemical process. The resulting detoxified ash was intended for use as a raw material rich in phosphorus (P) for inorganic fertiliser production. The thermochemical treatment was performed in a rotary kiln where the evaporation of relevant heavy metals was enhanced by additives. The four variables investigated for process optimisation were treatment temperature, type of additive (KCl, MgCl(2)) and its amount, as well as type of reactor (directly or indirectly heated rotary kiln). The removal rates of Cd, Cr, Cu, Ni, Pb, Zn and of Ca, P and Cl were investigated. The best overall removal efficiency for Cd, Cu, Pb and Zn could be found for the indirectly heated system. The type of additive was critical, since MgCl(2) favours Zn- over Cu-removal, while KCl acts conversely. The use of MgCl(2) caused less particle abrasion from the pellets in the kiln than KCl. In the case of the additive KCl, liquid KCl - temporarily formed in the pellets - acted as a barrier to heavy metal evaporation as long as treatment temperatures were not sufficiently high to enhance its reaction or evaporation.     

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.     

Heavy metals in domestic refuse and their distribution in incinerator residues

The principal heavy metal loads to municipal solid waste incinerators are determined from analyses of bottom ash, fly ash and gaseous effluents. Upper values in g per Mg refuse are: Cl, 8000; F, 200; S, 5000; Zn, 2000; Pb, 1200; Cu, 600; Cr, 250; Ni, 80; Cd, 15; Hg, 5; As, 4. More than half of the Cl, Cd, Hg and As pass into the flue gas and are either captured in the fly ash or emitted in the stack gas.     

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.     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

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%).     

Chemical sequential extraction of heavy metals and sulphur in bottom ash and in fly ash from a pulp and paper mill complex

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.     

Urban Metal Flows – A Case Study of Stockholm. Review and Conclusions

Metals have rapidly accumulated in the anthroposphere, especiallyin urban areas, indicating possible environmental and resource problems. Here, Stockholm City was chosen for a case study of urban metal flows, i.e. metal inflow to, metals in the stock of,and metal outflow from the anthroposphere to the biosphere. Themetal stock of Stockholm is large and still growing. The large amounts of metals in the solid waste fraction totally dominatethe outflow from the city. For major parts of the stock, the emissions from goods in use are negligible. There are, however,goods applications corresponding to significant emissions: e.g. the traffic sector (Cu, Zn, Cr, Ni, Pb), the tapwater system (Cu), roofs/fronts or other metal surfaces (Cu, Zn). Today's known metal flows from the anthroposphere of Stockholm to the biosphere and sewage sludge are quantitatively dominated by Zn(34 ton y^-1) and Cu (14 ton y^-1). Historical and present emissions have resulted in high metal concentrations insediments (especially Cd, Hg and Pb, but also Cu and Zn), groundwater (Cu, Hg) and in soils (Hg, Cu, Pb). At present theannual median concentrations are below the Swedish limits for metals in sewage sludge, even if the safety margins aresmall for Cd, Hg and to some extent Cu. The flows of Cu and Zn to Stockholm soils are high with a significant accumulationindicating an environmental impact in a longer time perspective.High levels of metals in surface sediments in the waterenvironments reflects an ongoing input where these metals aretransported from known (Cu, Zn) and or partly unknown (Cd, Hg, Pb) sources. In future urban areas, monitoring of metal flows must be performed both in the anthroposphere and the biospherein order to have a pro active approach to urban environmentalproblems and to get prompt answers to measures taken.     

Heavy metal and nutrient changes during vermicomposting animal manure spiked with mushroom residues

A pilot-scale trial of four months was conducted to investigate the responses of heavy metal and nutrient to composting animal manure spiked with mushroom residues with and without earthworms. Results showed that earthworm activities accelerated organic matter mineralization (e.g. reduction in C/N ratio, increase in total concentrations of N, P, K) and humification (e.g. increase in humic acid concentration, humification ratio and humification index). Despite composting increased total heavy metal (i.e. As, Pb, Cu, Zn) concentrations irrespective of earthworm, the availability of heavy metals extracted by DTPA significantly (P < 0.05) decreased particularly in treatments with earthworms introduced. The shift from available to unavailable fractions of heavy metals was either due to earthworm bioaccumulation, as indicated by total heavy metal concentrations being higher in earthworm tissues, or due to the formation of stable metal-humus complexes as indicated by the promotion of humification. Our results suggest that vermicomposting process could magnify the nutrient quality but relieve the heavy metals risk of agricultural organic wastes.