Active capping technology—New approaches for in situ remediation of contaminated sediments

This study evaluated pilot‐scale active caps composed of apatite, organoclay, biopolymers, and sand for the remediation of metal‐contaminated sediments. The active caps were constructed in Steel Creek, at the Savannah River Site near Aiken, South Carolina. Monitoring was conducted for 12 months. Effectiveness of the caps was based on an evaluation of contaminant bioavailability, resistance to erosion, and impacts on benthic organisms. Active caps lowered metal bioavailability in the sediment during the one‐year test period. Biopolymers reduced sediment suspension during cap construction, increased the pool of carbon, and lowered the release of metals. This field validation showed that active caps can effectively treat contaminants by changing their speciation, and that caps can be constructed to include more than one type of amendment to achieve multiple goals. © 2012 Wiley Periodicals, Inc.     

Metal releases from a municipal solid waste incineration air pollution control residue mixed with compost

The influence of 10 wt.% mature compost was tested on the heavy metal leachate emissions from a calcium-rich municipal solid waste incineration air pollution control residue (MSWI APC). Apart from elongated columns (500 and 1250 mm), an otherwise norm compliant European percolation test setup was used. More than 99% of the metals Al, As, Cd, Cr, Cu, Fe and Ni were left in the APC residue after leaching to a liquid-to-solid ratio (L/S) of 10. Apparent short-term effects of elevated leachate DOC concentrations on heavy metal releases were not detected. Zn and Pb leachate concentrations were one order of magnitude lower for L/S 5 and 10 from the pure APC residue column, which suggests a possible long-term effect of compost on the release of these elements. Prolonging the contact time between the pore water and the material resulted in elevated leachate concentrations at L/S 0.1 to L/S 1 by a factor of 2. Only Cr and Pb concentrations were at their maxima in the first leachates at L/S 0.1. Equilibrium speciation modelling with the PHREEQC code suggested portlandite (Ca(OH)2) to control Ca solubility and pH.     

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.     

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.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Sequestration of metals in active cap materials: A laboratory and numerical evaluation

Active capping involves the use of capping materials that react with sediment contaminants to reduce their toxicity or bioavailability. Although several amendments have been proposed for use in active capping systems, little is known about their long‐term ability to sequester metals. Recent research has shown that the active amendment apatite has potential application for metals‐contaminated sediments. The focus of this study was to evaluate the effectiveness of apatite in the sequestration of metal contaminants through the use of short‐term laboratory column studies in conjunction with predictive, numerical modeling. A breakthrough column study was conducted using North Carolina apatite as the active amendment. Under saturated conditions, a spike solution containing elemental As, Cd, Co, Se, Pb, Zn, and a nonreactive tracer was injected into the column. A sand column was tested under similar conditions as a control. Effluent water samples were periodically collected from each column for chemical analysis. Relative to the nonreactive tracer, the breakthrough of each metal was substantially delayed by the apatite. Furthermore, breakthrough of each metal was substantially delayed by the apatite compared to the sand column. Finally, a simple 1‐D, numerical model was created to qualitatively predict the long‐term performance of apatite based on the findings from the column study. The results of the modeling showed that apatite could delay the breakthrough of some metals for hundreds of years under typical groundwater flow velocities. © 2012 Wiley Periodicals, Inc.     

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.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

Heavy metal content of combustible municipal solid waste in Denmark.

Data on the heavy metal composition of outlets from Danish incinerators was used to estimate the concentration of Zn, Cu, Pb, Cr, Ni, Cd, As and Hg in combustible waste (wet as received) at 14 Danish incinerators, representing about 80% of the waste incinerated in Denmark. Zn (1020 mg kg(-1)), Cu (620 mg kg(-1)) and Pb (370 mg kg(-1)) showed the highest concentration, whereas Hg (0.6 mg kg(-1)) showed the lowest concentration. The variation among the incinerators was in most cases within a factor of two to three, except for Cr that in two cases showed unexplained high concentrations. The fact that the data represent many incinerators and, in several cases, observations from a period of 4 to 5 years provides a good statistical basis for evaluating the content of heavy metals in combustible Danish waste. Such data may be used for identifying incinerators receiving waste with high concentrations of heavy metals suggesting the introduction of source control, or, if repeated in time, the data must also be used for monitoring the impacts of national regulation controlling heavy metals. It is recommended that future investigations consider the use of sample digestion methods that ensure complete digestion in order to use the data for determining the total heavy metal content of waste.     

Evaluation of Risk from Using Poultry Litter to Remediate and Reuse Contaminated Estuarine Sediments

The availability of heavy metals in contaminated sediment evaluated for beneficial reuse, before and after chemical amendment, was evaluated using poultry manure as the amendment. The dredged sediment was only slightly contaminated with heavy metals. Availability tests on the amended sediment showed an increase in heavy metals, most likely because of poultry feed amendments passed to the manure. There would be difficulty finding one chemical amendment to reduce the availability of a number of heavy metals because the metals exhibit different chemical properties. © 2001 John Wiley & Sons, Inc.     

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.     

Changes in Extractability of Cr and Pb in a Polycontaminated Soil After Bioaugmentation With Microbial Producers of Biosurfactants, Organic Acids and Siderophores

Partly because of the low bioavailability of metals, the soil cleaning-up using phytoremediation is usually time-consuming. In order to enhance the amount of metals at the plant's disposal, the soil bioaugmentation coupled together with phytoextraction is an emerging technology. In this preliminary work, two agricultural soils which mainly differed in their Cr, Hg and Pb contents (LC, low-contaminated soil; HC, high-contaminated soil) were bioaugmented in laboratory conditions by either bacterial (Bacillus subtilis, Pseudomonas aeruginosa, Pseudomonas fluorescens or Ralstonia metallidurans) or fungal inocula (Aspergillus niger or Penicillium simplicissimum) and incubated during three weeks. The LC soil pots bioaugmented with A. niger and P. aeruginosa contained higher concentrations of Cr (0.08 and 0.25 mg.kg⁻¹ dw soil) and Pb (0.25 and 0.3 mg.kg⁻¹ dw soil) in the exchangeable fraction F1 (extraction with MgCl₂) by comparison with the non-bioaugmented soil where neither Cr nor Pb was detected. Conversely, immobilization of Cr and Pb in the soil were observed with the other microorganisms. The soil bioaugmentation not only modified the metal speciation for the most easily extractable fractions but also modified the distribution of metals in the other fractions, to a lesser extent nevertheless. The difference in microbial concentrations between the bioaugmented or not HC soils reached up to 1.8 log units. Thus the microorganisms that we chose for the soil bioaugmentation were competitive towards the indigenous microflora. The PCA analysis showed close positive relationships between the microorganisms which potentially produced siderophores in the soil and the amount of Cr and Pb in the fraction F1.     

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.     

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%。     

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.     

脱硫用电石渣的重金属浸出特性及其对环境的影响

针对电厂用脱硫剂电石渣,分析了其基本组成及重金属浸出特性,为电厂脱硫设施的参数设计和环境影响评价提供依据和参考。研究结果表明,脱硫用电石渣主要成分为Ca（OH）2,含量在40%～50%之间;在8种重金属的含量中,只有Cd的含量超出土壤质量三级标准的要求,基本不会对土壤造成污染。浸出毒性试验表明,电石渣及其脱硫产物属于非危险废物,其各种重金属的浸出浓度主要受其本身重金属含量和最终pH的影响,这种影响在Pb、Cu和Cd上表现得较为突出,酸性环境下更有利于他们的浸出;碱性环境下有利于Pb和Ni的浸出。     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

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.     

Assessment of biotechnological strategies for the valorization of metal bearing wastes

The present work deals with the application of biotechnology for the mobilization of metals from different solid wastes: end of life industrial catalysts, heavy metal contaminated marine sediments and fluorescent powders coming from a cathode ray tube glass recycling process. Performed experiments were aimed at assessing the performance of acidophilic chemoautotrophic Fe/S-oxidizing bacteria for such different solid matrices, also focusing on the effect of solid concentration and of different substrata. The achieved results have evidenced that metal solubilization seems to be strongly influenced by the metal speciation and partitioning in the solid matrix. No biological effect was observed for Ni, Zn, As, Cr mobilization from marine sediments (34%, 44%, 15%, 10% yields, respectively) due to metal partitioning. On the other hand, for spent refinery catalysts (Ni, V, Mo extractions of 83%, 90% and 40%, respectively) and fluorescent powders (Zn and Y extraction of 55% and 70%, respectively), the improvement in metal extraction observed in the presence of a microbial activity confirms the key role of Fe/S oxidizing bacteria and ferrous iron. A negative effect of solid concentration was in general observed on bioleaching performances, due to the toxicity of dissolved metals and/or to the solid organic component.