Use of sequential leaching, mineralogy, morphology and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments--a case study: Brahmani and Nandira Rivers, India

The particle size distribution, geochemical composition and sequential leaching of metals (Fe, Mn, Ni, Cu, Co, Cr, Pb, Zn and Cd) are carried out in core sediments (<88 microm) from the Brahmani and Nandira Rivers, India. To confirm the contamination of downstream sediments by fly ash, mineralogical and morphological characterizations were carried out. High environmental risk of Co, Pb and Ni is due to their higher availability in exchangeable fraction. The metals like Zn, Cu and Mn represent an appreciable portion in the carbonate phase. Metals such as Zn, Pb, Cd, Co and Ni are associated with reducible phase may be due to adsorption. The organic bound Cu, Zn, and Pb seem to be second dominant fraction among non-lithogenous in Nandira sediments. Factor analysis data reveals that textural parameters, Fe-Mn oxy/hydroxides, organic precipitation and coal fly ash disposals, are individually responsible for the enrichment of heavy metals. The relationships among the stations are highlighted by cluster analysis to identify the contamination levels.     

Stabilization of a chlorine-rich fly ash by colloidal silica solution

Fly ash from municipal solid waste incinerators (MSWI) consists of various substances, including a lot of heavy metals. In cases where fly ash contains a lot of chlorides, it is very difficult to apply general treatment methods because chlorides could hinder hydration in cementation and cause great loss in vitrification. In this study, we report a promising method for the treatment of fly ash containing a high concentration of chlorides. A colloidal silica solution was induced to stabilize the fly ash. The fly ash used in this research has a chlorine level over 35 wt.% as well as containing heavy metals, such as Pb (1120 ppm) and Zn (5430 ppm). The samples were prepared at a temperature of 600-800 degrees C for 2h after mixing with the fly ash and a 4 wt.% colloidal silica solution. The effect of the colloidal silica was evaluated by the leaching test, Toxicity Characteristic Leaching Procedure (TCLP). The solidified products with fly ash and colloidal silica at temperatures of more than 700 degrees C had an excellent resistance, with Pb(2+) <0.02 ppm, Zn(2+) <0.52 ppm, and Cd(2+), Cr(2+), Cu(2+), Mn(2+) <0.01 ppm, and it could be influenced by the phases containing Ca and Si formed above 600 degrees C and reduction of a chemically weak phase.     

Thermal treatment of the fly ash from municipal solid waste incinerator with rotary kiln

Reuse of the fly ash from the municipal solid waste incinerator (MSWI) is a policy of Taiwan EPA. However, the fly ash is often classified as a hazardous waste and cannot be reused directly because the concentrations of heavy metals exceed the TCLP regulations. The main objective of this study is to investigate the continuous sintering behavior of fly ash with a rotary kiln and seek a solution to reduce the concentrations of heavy metal to an acceptable value. The partitions of the heavy metals in the process are also considered. The results of TCLP showed that among the metals of Cr, Cd, Cu and Pb, only the concentrations of Pb in raw fly ash exceeded the regulation. At sintering temperatures of 700, 800 and 900 degrees C, the concentration of Pb decreased in sintering products, however, the concentration of Pb still exceeded the limitation at 700 and 800 degrees C. Additionally, the water-washing was used to pre-treat the fly ash before sintering process. The washing treatment effectively reduced the leaching concentrations of Pb to agree the regulations. Therefore, water-washing followed by a sintering treatment is an available process for detoxifying the fly ash of MSWI.     

Trace elements partitioning during co-firing biomass with lignite in a pilot-scale fluidized bed combustor

This study describes the partitioning of 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and 9 major and minor elements (Al, Ca, Fe, K, Mg, Na, S, Si, Ti) during co-firing of olive residue, hazelnut shell and cotton residue with high sulfur and ash content lignite in 0.3 MW(t) Middle East Technical University (METU) Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) test rig with limestone addition. Concentrations of trace elements in coal, biomass, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission and mass spectroscopy (ICP-OES and ICP-MS). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Tl, V and Zn) are recovered in fly ash when firing lignite only. Co-firing lignite with biomass enhances partitioning of these elements to fly ash. Co-firing also shifts the partitioning of Cd, P, Sb and Sn from bottom to fly ash.     

SEM/EDS and XRD characterization of raw and washed MSWI fly ash sintered at different temperatures

The disposal of fly ash generated during municipal solid waste incineration (MSWI) may pose a significant risk to the environment due to the possible leaching of hazardous pollutants, such as toxic metals. Sintering technology attracted more attention than the vitrification process because of its low energy needed. Generally, a preliminary washing treatment of raw fly ash with water was necessary for this sintering technology. This study investigated the composition and morphology of raw fly ash (RFA) and washed fly ash (WFA) at different sintering temperatures, and examined the newly formed minerals during sintering. Toxicity characteristic leaching procedure (TCLP) tests were carried out to investigate the effect of the washing treatment and sintering process on the leaching performance of heavy metals in fly ash. Results showed that, with an increase of sintering temperature more complex aluminosilicates were formed; the incorporation of Mg, Fe and Pb into the aluminosilicates occurred during the sintering process at higher temperatures (800 and 900 degrees C). The washing treatment reduced the leachable concentration of Cd, Pb and Ni, but increased that of Cr. A CaCrO(4) compound was considered as a potential soluble species.     

生物质与生活垃圾共气化过程重金属的迁移转化规律

为了研究流化床生物质气化协同处置生活垃圾衍生燃料过程中重金属的迁移转化规律,在湖北某循环流化床气化炉耦合燃煤发电厂进行掺烧试验。研究表明重金属主要赋存于飞灰和炉渣中。空白工况下86.2%的Cr赋存于飞灰中,13.3%于炉渣中;75.5%的Pb在飞灰中,23.8%在炉渣中;79.5%的As迁移至飞灰中,11.7%在炉渣中。RDF工况下75.8%的Cr迁移至飞灰,20.7%迁移至炉渣;44.6%的Pb存在于飞灰中,52%存在于炉渣。协同处置后,重金属在飞灰和炉渣中的分配比例明显发生了变化,飞灰中重金属含量减少12.5%~31.3%,炉渣中重金属增加7.33%~20.1%,气化气的引入改变了炉内重金属的分配情况。协同处置可以有效处理生活垃圾,对固废中的热量进行资源化利用,且出炉物料中重金属含量均低于我国现行标准限值。     

Stabilization/solidification of a municipal solid waste incineration residue using fly ash-based geopolymers

The stabilization/solidification (S/S) of a municipal solid waste incineration (MSWI) fly ash containing hazardous metals such as Pb, Cd, Cr, Zn or Ba by means of geopolymerization technology is described in this paper. Different reagents such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, kaolin, metakaolin and ground blast furnace slag have been used. Mixtures of MSWI waste with these kinds of geopolymeric materials and class F coal fly ash used as silica and alumina source have been processed to study the potential of geopolymers as waste immobilizing agents. To this end, the effects of curing conditions and composition have been tested. S/S solids are submitted to compressive strength and leaching tests to assess the results obtained and to evaluate the efficiency of the treatment. Compressive strength values in the range 1-9 MPa were easily obtained at 7 and 28 days. Concentrations of the metals leached from S/S products were strongly pH dependent, showing that the leachate pH was the most important variable for the immobilization of metals. Comparison of fly ash-based geopolymer systems with classical Portland cement stabilization methods has also been accomplished.     

Assessment of single extraction methods for the prediction of bioavailability of metals to Brassica juncea L. Czern. (var. Vaibhav) grown on tannery waste contaminated soil

Various single extractant (DTPA, EDTA, NH(4)NO(3), CaCl(2), and NaNO(3)) was used to evaluate the bioavailability of heavy metals from tannery wastewater contaminated soil and translocation of metals to the plant of Brassica juncea L. Czern. (var. Vaibhav). The extraction capacity of the metals was found in the order: EDTA>DTPA>NH(4)NO(3)>CaCl(2)>NaNO(3). Cluster analysis between different extractants showed close relationship between DTPA, CaCl(2), NH(4)NO(3) except EDTA and NaNO(3), which showed dispersed relationship. Principal components analysis (PCA) applied to metals extracted with EDTA showed different grouping of metals (i) Na, Co, Pb, Ni and (ii) K, Mn, Zn, Cr, in the loading plot which showed similar availability from contaminated soil. PCA applied on metals accumulation data in the plants also exhibited different grouping of variables (i) Cu, Co, Ni, Cd and (ii) Mn, Zn, Pb, Fe showed almost similar accumulation pattern in the plants. The data displayed positive loading for Mn and negative loading for Cr with PC(2). Cd and Zn have shown high loadings in PC(1) and PC(2), respectively. The translocation of most of the tested metals (Pb, Mn, Cd, Ni, Fe) in the shoot of the plant was found better except Cr, Cu, Co and K. The correlation analysis between different extractable metals and metal accumulation in the shoot of the plant showed significant positive correlation with Pb and Cr. Overall, extraction capacity and cluster analysis augmented that EDTA was found suitable extractant for tannery wastewater contaminated soil to B. juncea.     

Evaluation of the emission characteristics of trace metals from coal and fuel oil fired power plants and their fate during combustion

Coal as well as fuel oil combustion generates emissions of potentially toxic trace pollutants including organic and inorganic chemical compounds besides major pollutants. A study on As, Cd, Co, Cr, Cu, Hg, Fe, Mn, Ni, Pb, Se, and Zn emissions from a 220 MW coal-fired power plant equipped with a electrostatic precipitators (ESPs) and 6 MW oil fired-power plant was carried out, using stack monitoring kit, Envirotech APM 620, which is similar to EPA Method 29. Simultaneous sampling of coal, fuel oil, oil waste, bottom ash, fly ash, flue gases, and particles associated with the gas phase has been performed. This sampling method was used for trace metal sampling. The content of all these metals in coal, oil, oil waste, bottom ash, fly ash have been determined by XRF, whereas their contents in the flue gases, and particles associated with the gas phase has been analyzed with ICP-AES. The mass balances obtained for trace elements were satisfactory in case of fuel oil based power plant, whereas in case of coal fired power plant, the mass balance for all the trace elements were below 50% except for the As, Se, and Hg. The enrichment factors for all trace metals was <1 in both cases. The above sampling method is moderately adequate method for trace element sampling in coal as well as oil fired power plants except for Hg. The results indicate that trace metals emissions were higher in coal-based power plant than the fuel oil-fired power plant.     

Electrodialytic removal of heavy metals from different fly ashes. Influence of heavy metal speciation in the ashes

Electrodialytic remediation, an electrochemically assisted extraction method, has recently been suggested as a potential method for removal of heavy metals from fly ashes. In this work, electrodialytic remediation of three different fly ashes, i.e. two municipal solid waste incinerator (MSWI) fly ashes and one wood combustion fly ash was studied in lab scale, and the results were discussed in relation to the expected heavy metal speciation in the ashes. The pH-dependent desorption characteristics for Cr differed between the two MSWI ashes but were similar for Cd, Pb, Zn and Cu. Thus, it was expected that the speciation of Cd, Pb, Zn and Cu was similar in the two ashes. However, in succeeding electrodialytic remediation experiments significant differences in removal efficiencies were observed, especially for Pb and Zn. In analogous electrodialytic remediation experiments, 8% Pb and 73% Zn was removed from one of the MSWI ashes, but only 2.5% Pb and 24% Zn from the other. These differences are probably due to variations in pH and heavy metal speciation between the different ashes. Cd, the sole heavy metal of environmental concern in the wood ash, was found more tightly bonded in this ash than in the two MSWI ashes. Approximately 70% Cd was removed from both types of ashes during 3 weeks of electrodialytic remediation, although the total concentration was a factor of 10 lower in the wood ash. It was suggested that complex Cd-silicates are likely phases in the wood ash whereas more soluble, condensed phases are dominating in the MSWI ashes.     

Potential use of treated wastewater and sludge in the agricultural sector of the Gaza Strip

Twelve elements (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed in 120 composite samples of influent and effluent wastewater; the results revealed that domestic wastewater influent contains considerable amounts of heavy metals and the partially functional treatment plants of Gaza are able to remove 40–70% of most metals during the treatment process. Heavy metals in 31 industrial wastewater effluents are within the ranges of international standards. All industries of Gaza are light; although they have no treatment facilities, their effluents are being discharged to municipal sewerage system and the existing treatment plants are capable of absorbing the industrial effluents with no significant impact on treatment bioprocesses.Thirty parameters were determined in 35 sludge samples: P, AOX, C, S, CaCO₃, Mg, Ca, Na, K, Li, Cu, Zn, Ni, Pb, Mn, Fe, Cr, Co, Cd, As, Hg, Ti, Se, Br, Rb, Th, Sr, Y, U, and Zr. Although there are no treatment facilities for sludge within the treatment plants, the results indicated that sludge in general is clean of heavy metals. Only Zinc and AOX showed anomalous concentrations; more than 85% of sludge samples showed that averages of zinc and AOX are 2,000 mg/kg and 550 mg Cl/kg, respectively, which exceed the standards of all industrial countries for sludge to be used in land application.     

The partitioning of heavy metals in incineration of sludges and waste in a bubbling fluidized bed 2. Interpretation of results with a conceptual model

This work addresses the behavior, fate and/or partitioning of six targeted (Cd, Pb, Cr, Cu, Zn and Ni) heavy metals (HMs) in the incineration of sludges and waste in a bubbling fluidized bed (BFB) of 15 cm i.d. and 5.2m high followed by a filter chamber operated at 750-760 degrees C with a commercial ceramic filter. This paper presents three different things: (1) an in depth review of the published work relating to the problem of partitioning of the HMs in BFBs, (2) some more experimental incineration tests regarding the influence of the temperature of the bed of the BFB and the effect of the chlorine content in the feedstock on the partitioning of the HMs, and (3) the modelling of the partitioning of the HMs in the exit flows: bottom ash, coarse fly ashes, fine fly ash and vapour phase. The partitioning of the HMs is governed by fluid dynamic principles together with the kinetics of the diffusion of the HMs inside the ash particles and the kinetics of the reactions between the HMs and the components of the matrix of the ash. Some thermodynamic predictions do not fit the results from the BFB incinerator well enough because equilibria are not reached in at least three exit ash flows: coarse fly ash, fine fly ash and submicron particles. The residence time of these ash particles in these type of incinerators is very short and most of the HMs have no time to diffuse out of the ash particle. Finally, an examination was made on how in the ceramic hot filter the partition coefficients for the HMs increased, mainly for Cd and Pb, when the Cl-content in the feedstock was increased.     

Utilization of MSWI fly ash for stabilization/solidification of industrial waste sludge

This work investigated the potential for utilization of MSWI incineration fly ash as solidification binder to treat heavy metals-bearing industrial waste sludge. In the study, Municipal Solid Waste Incineration (MSWI) fly ash was used along with ordinary Portland cement to immobilize three different types of industrial sludge while MSWI incineration fly ash was stabilized at the same time. The results showed that the matrixes with heavy metals-bearing sludge and MSWI fly ash have a strong fixing capacity for heavy metals: Zn, Pb, Cu, Ni and Mn. Specimens with only 5-15% cement content was observed to be sufficient to achieve the target compressive strength of 0.3 MPa required for landfill disposal. An optimum mix comprising 45% fly ash, 5% cement and 50% of the industrial sludge could provide the required solidification and stabilization. Addition of MSWI can improve the strength of matrix. Meanwhile, the main hydration products of new S/S matrix are ettringite AFt, Friedel's salt and C-S-H. These hydration products play an important role in the fixing of heavy metals. The co-disposal of MSWI fly ash with heavy metals-bearing sludge can minimize the enlargement of the landfill volume and stabilize the heavy metals effectively.     

Behaviour of metals under the conditions of roasting MSW incinerator fly ash with chlorinating agents.

A total elemental analysis was performed on a municipal solid waste (MSW) fly ash sample, before and after it was treated at 1000 degrees C, to reveal the metal distribution between the volatile matter and the ash residue. Metals such as Pb, Zn, Cd, and to a lesser degree, Cr, Mn and Ni, were volatilized. Addition of chlorinating agents generally increased the volatility of certain elements. More acid resistant compounds were formed in the ash residue after the heat treatment using CaCl2 as a chlorinating agent. The efficiencies of volatilization of the metals, using Cl2 as a chlorinating agent, were generally higher compared with using CaCl2. However, CaCl2 was found to be a more selective chlorinating agent for volatilizing the heavy metals of concern, i.e., Pb, Cd, Zn and Cu. The efficiencies of volatilization of the recovered metals were approximately proportional to their standard free-energy changes (delta G(o) for the corresponding chlorination reactions.     

Chromium behavior during thermal treatment of MSW fly ash.

Energy-from-waste incineration has been promoted as an environmentally responsible method for handling non-recyclable waste from households. Despite the benefits of energy production, elimination of organic residues and reduction of volume of waste to be landfilled, there is concern about fly ash disposal. Fly ash from an incinerator contains toxic species such as Pb, Zn, Cd and Cr which may leach into soil and ground water if landfilled.Thermal treatment of the fly ash from municipal solid waste has been tested and proposed as a treatment option for removal of metal species such as Pb, Cd and Zn, via thermal re-volatilization. However, Cr is an element that remains in the residue of the heat treated fly ash and appears to become more soluble. This Cr solubilization is of concern if it exceeds the regulatory limit for hazardous waste. Hence, this unexpected behavior of Cr was investigated. The initial work involved microscopic characterization of Cr in untreated and thermally-treated MSW fly ash. This was followed by determining leaching characteristics using standard protocol leaching tests and characterization leaching methods (sequential extraction). Finally, a mechanism explaining the increased solubilization was proposed and tested by reactions of synthetic chemicals.     

Partitioning behavior of trace elements during pilot-scale fluidized bed combustion of high ash content lignite

This study describes the partitioning of 20 trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and eight major and minor elements (Al, Ca, Fe, K, Mg, Na, Si, Ti) during the combustion of high ash content lignite. The experiments were carried out in the 0.3 MW(t) Middle East Technical University (METU) atmospheric bubbling fluidized bed combustor (ABFBC) test rig with and without limestone addition. Inert bed material utilized in the experiments was bed ash obtained previously from the combustion of the same lignite without limestone addition in the same test rig. Concentrations of trace elements in coal, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Cr, Hg, Li, Mo, Ni, Sn, V, Zn) are recovered in fly ash. Limestone addition shifts the partitioning of Ba, Cr, Mo, Ni, Sn, V, Zn from bottom ash to fly ash.     

Electrodialytic removal of heavy metals from municipal solid waste incineration fly ash using ammonium citrate as assisting agent

Electrodialytic remediation, an electrochemically assisted separation method, has previously shown potential for removal of heavy metals from municipal solid waste incineration (MSWI) fly ashes. In this work electrodialytic remediation of MSWI fly ash using ammonium citrate as assisting agent was studied, and the results were compared with traditional batch extraction experiments. The application of electric current was found to increase the heavy metal release significantly compared to batch extraction experiments at comparable conditions (same liquid-to-solid ratio, same assisting agent, and same extraction time). Up to 86% Cd, 20% Pb, 62% Zn, 81% Cu and 44% Cr was removed from 75 g of MSWI fly ash in electrodialytic remediation experiments using ammonium citrate as assisting agent. The time range for the experiments varied between 5 and 70 days.     

Incineration of doped sludges in fluidized bed. Fate and partitioning of six targeted heavy metals. I. Pilot plant used and results

Incineration of sewage sludge doped with several heavy metals was studied at small pilot plant scale in a bubbling fluidized bed of 15 cm i.d. and 5.2 m height. Some ceramic and metallic filters were tested at a relatively high temperature (600–700°C) to check their usefulness for partitioning of heavy metals in the flue gas. The work was focused on the fate of six selected heavy metals (Cr, Cd, Ni, Zn, Cu, Pb). In this process, there were four exit flows or discharges for these metals: bottom ash, coarse fly ash, cake filter or fine fly ash and flue exit gas. The distribution or partitioning of each heavy metal (HM) among these four exit flows was studied. Only cadmium and sometimes lead showed any difference between the different HMs considered. All other HMs seems to have the same fate, distribution or partitioning. Such distribution is governed or ruled by the fluid dynamics in the incinerator, cyclone and ceramic filter. Most of the HMs do not have enough residence time in this incinerator type to diffuse out of the ash particle and so remain in the particle. The amount of each HM in each exit flow in this process is governed by fluid dynamics and kinetics and not at all by thermodynamics.     

Typical pollutants in bottom ashes from a typical medical waste incinerator

Incineration of medical waste (MW) is an important alternative way for disposal of this type of hazardous waste, especially in China because of the outbreak of severe acute respiratory syndromes (SARs) in 2003. Thus, far, fly ash has received much attention but less attention has been paid to bottom ash. In this study, bottom ash samples were collected from a typical MW incinerator, and typical pollutants including heavy metals and polycyclic aromatic hydrocarbons (PAHs) in the ash were examined. X-ray fluorescence spectroscopy results indicated that CaO, SiO₂ and Al₂O₃ were the main components of the bottom ash. Inductively coupled plasma-optical emission spectroscopy showed that the ash contained large amounts of heavy metals, including Zn, Ti, Ba, Cu, Pb, Mn, Cr, Ni and Sn. Most of the heavy metals (e.g., Ba, Cr, Ni, and Sn) presented in the residual fraction; whereas Mn, Pb and Zn presented in Fe–Mn oxides fraction, and Cu in organic-matter fraction. Toxicity characteristic leaching procedure tests indicated that the leached amounts of heavy metals were well below the limits. The sum of 16 US EPA priority PAHs (ΣPAHs) varied from 10.30 to 38.14 mg kg^?1, and the total amounts of carcinogenic PAHs ranged between 4.09 and 16.95 mg kg^?1, exceeding the limits regulated by several countries. This research provides basic information for the evaluation of the environmental risk of MW incinerator bottom ash.     

Effects of water-washing pretreatment on bioleaching of heavy metals from municipal solid waste incinerator fly ash

Previous studies demonstrated that the bioleaching of municipal solid waste incinerator fly ash by Aspergillus niger was an efficient "green technology" for heavy metals removal, however, it demanded a long operational period. In this study, water-washing was used as a fly ash pretreatment before the bioleaching process (one-step and two-step). This pretreatment extracted 50.6% of K, 41.1% of Na, 5.2% of Ca and 1% of Cr from the fly ash. Due to the dissolution of alkali chlorides which hold particles together, fly ash particles were smashed into smaller granules by the hydraulic flushing action caused by vibration. After the pretreatment, the lag phase and bioleaching period were reduced by 45 and 30%, respectively, in one-step bioleaching of 1% (w/v) fly ash. Meanwhile, the metals extraction yield both in one-step and two-step bioleaching was increased markedly, e.g. in two-step bioleaching, 96% Cd, 91% Mn, 73% Pb, 68% Zn, 35% Cr and 30% Fe was extracted from 1% water-washed fly ash, respectively. The reduction of the bioleaching period and improvement of metals extraction yield will likely allow the practical application of the bioleaching technology for heavy metals removal from fly ash.