Effects of injected activated carbon and solidification treatment on the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans from air pollution control residues of municipal waste incineration

To assess the effectiveness of the injected activated carbon, cement, and sulfur-containing chelating agent in controlling polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) release from the surface of air pollution control (APC) residues, this study examined the leachability of PCDD/Fs from APC residues generated by municipal solid waste incinerators. Results showed that PCDD/Fs were stably retained in the APC residues when the samples were leached with acetic acid solution. Highly chlorinated PCDD/F homologues (i.e., hepta- and octa-CDDs and CDFs) were relatively easy to leach. The leaching percentages of PCDD/Fs from raw APC residue samples containing activated carbon were smaller than those from samples without activated carbon, especially when n-hexane was used as the leachant. These results indicate that the flue gas injected activated carbon not only controls PCDD/F emissions, but also suppresses the leachability of PCDD/Fs from the APC residues. Solidification/stabilization (S/S) processes with 30wt% cement and 5wt% sulfur-containing agent can additionally decrease the leachability of PCDD/Fs with humic acid. Using n-hexane as the leachant, S/S processes increased the leachability of PCDD/Fs. Various low chlorinated PCDD/F congeners were moreover leached out of the APC residue samples, markedly increasing the leachate toxicity. The enhancement of leachability and toxicity owing to S/S processes may negatively impact the environment when APC residues are exposed to nonpolar organic solvents.     

EFFECT OF SOIL STERILIZATION BY MERCURIC CHLORIDE ON HERBICIDE SORPTION BY SOIL

Microbial inhibitors such as mercuric chloride are frequently used to sterilize soil or soil–water slurries in experimental studies on the fate of xenobiotics in the environment. This study examined the influence of mercuric chloride additions to soil–water slurries on the sorptive behaviour of a phenoxy herbicide (2,4-D) in soil. The results demonstrated that mercuric chloride strongly decreased the capacity of the soil to retain herbicides, and that the interference of mercuric chloride with herbicide sorption increased with increasing soil organic carbon contents. Because of the competitive sorption between mercuric chloride and the phenoxy herbicide, we conclude that mercuric chloride may not be a good soil sterilization procedure for use in xenobiotic fate studies.     

Stabilization of APC residues from waste incineration with ferrous sulfate on a semi-industrial scale

A stabilization method for air pollution control (APC) residues from municipal solid waste incineration (MSWI) involving mixing of the residue with water and FeSO4 has been demonstrated on a semi-industrial scale on three types of APC residues: a semidry (SD) APC residue, a fly ash (FA), and an FA mixed with sludge (FAS) from a wet flue gas cleaning system. The process was performed in batches of 165-175 kg residue. It generates a wastewater that is highly saline but has a low content of heavy metals such as Cd, Cr, and Pb. The stabilized and raw residues have been subject to a range of leaching tests: the batch leaching test, the pH-static leaching test, the availability test, and the column test. These tests showed that the stabilized residues have remarkably improved leaching properties, especially with respect to Pb but also with respect to Cd, Cu, and Zn. The release of Pb was reduced by a factor of 250-36,000.     

Stabilization of APC Residues from Waste Incineration with Ferrous Sulfate on a Semi-Industrial Scale

Abstract

A stabilization method for air pollution control (APC) residues from municipal solid waste incineration (MSWI) involving mixing of the residue with water and FeSO₄ has been demonstrated on a semi-industrial scale on three types of APC residues: a semidry (SD) APC residue, a fly ash (FA), and an FA mixed with sludge (FAS) from a wet flue gas cleaning system. The process was performed in batches of 165-175 kg residue. It generates a wastewater that is highly saline but has a low content of heavy metals such as Cd, Cr, and Pb. The stabilized and raw residues have been subject to a range of leaching tests: the batch leaching test, the pH-static leaching test, the availability test, and the column test. These tests showed that the stabilized residues have remarkably improved leaching properties, especially with respect to Pb but also with respect to Cd, Cu, and Zn. The release of Pb was reduced by a factor of 250-36,000.     

Characterization of Municipal Solid Waste Incineration Residues From Facilities with Different Air Pollution Control Systems

Abstract

Municipal Solid Waste incinerator residues produced in two types of facilities were exhaustively characterized: granulometry, mineralogy, chemical composition, leaching behavior, and elemental distribution as a function of particle size. Air Pollution Control (APC) residues coming from a semi-dry scrubber have shown higher solubility than fly ashes originating in an Electrostatic Precipitator (ESP), as well as higher contents in volatile metals (Cd, Hg). Different metal speciation and distribution as a function of particle size have been found in fly ashes (ESP residues) and APC residues. In APC residues, heavy metals (with the exception of Hg) show a parabolic distribution with maxima in the smallest and largest particles, following the same profile as soluble salts. Metal distribution for APC residues exhibits that metals generally are not associated with silicate aluminate matrix. Results show the effect of adding lime to APC residues in metal speciation and distribution.     

Effect of soil sterilization by mercuric chloride on herbicide sorption by soil

Microbial inhibitors such as mercuric chloride are frequently used to sterilize soil or soil-water slurries in experimental studies on the fate of xenobiotics in the environment. This study examined the influence of mercuric chloride additions to soil-water slurries on the sorptive behaviour of a phenoxy herbicide (2,4-D) in soil. The results demonstrated that mercuric chloride strongly decreased the capacity of the soil to retain herbicides, and that the interference of mercuric chloride with herbicide sorption increased with increasing soil organic carbon contents. Because of the competitive sorption between mercuric chloride and the phenoxy herbicide, we conclude that mercuric chloride may not be a good soil sterilization procedure for use in xenobiotic fate studies.     

Evaluation of the leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans in raw and solidified air pollution control residues from municipal waste incinerators

Leachability of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues with selected solvents, including acetic acid, simulated acid rain, humic acid, linear alkylbenzene sulfonate (LAS) and n-hexane was investigated. High-chlorinated PCDD/F congeners were observed in all leachates of raw APC residue samples, with the largest total leaching concentration (61.60 ngm(-3); 0.30 ngI-TEQm(-3)) from treatment with humic acid. Low-chlorinated congeners were mainly leached with LAS and n-hexane. Solidification and stabilization (S/S) processes with cement and sulfur-containing chelating agent decreased the leachability of PCDD/Fs by up to 98% with humic acid and LAS as solvents. However, S/S processes enhanced the leachability of both high- and low-chlorinated PCDD/F congeners with n-hexane as the solvent, which largely increased the toxic equivalent quantity of leachates. These results suggest that conventional S/S processes may effectively restrain the release of PCDD/Fs when APC residues are leached with rain water or natural organic compounds (e.g., humic acid), but may have a deteriorated effect when APC residues are leached with nonpolar organic solvents (e.g., n-hexane) coexisting in the landfill sites.     

Investigation of acute toxicity of cadmium chloride (CdCl2 . H2O) metal salt and behavioral changes it causes on water frog (Rana ridibunda Pallas, 1771)

The 96-h LC(50) value of cadmium chloride (CdCl(2).H(2)O), a metal salt widely used in industry, was determined in the water frog (Rana ridibunda Pallas, 1771). The experiments were conducted in two series and a total of 140 frogs were used to determine acute toxicity. In addition, behavioral changes in the water frog were determined for each cadmium chloride concentration. Data obtained from the cadmium chloride investigation were evaluated by using the probit analysis statistical method and the 96 h LC(50) value for water frog was estimated to be 51.2 mg/l.     

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans from raw and solidified waste incineration residues

Quasi-dynamic leaching characteristics of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from raw and solidified air pollution control (APC) residues were examined via a nine-time multiple leaching test. The effect of injected activated carbon in the APC residues on the PCDD/F leachability was also evaluated. When humic acid solution was used as a leachant, the leaching concentrations of PCDD/Fs fluctuated between the first and the fifth leaching, followed by a gradual increase and then suddenly reached maximum values at the leaching sequences around seventh and eighth. This significant enhancement in PCDD/F leachability was mainly due to an increase in the release of highly chlorinated PCDD/Fs. Leaching of PCDD/Fs with n-hexane was, in contrast, primarily caused by the partitioning of hydrophobic PCDD/Fs between the APC residue surface and the liquid phase of n-hexane. Consequently, the largest leaching concentrations for n-hexane tests achieved at the first leaching, followed by a decrease and reached plateaus. Solidification/stabilization (S/S) decreased the PCDD/F leachability up to the fifth leaching by the use of humic acid solution. However, S/S increased the PCDD/F leaching concentrations and rates with n-hexane. The activated carbon in APC residues significantly inhibited the release of PCDD/F with n-hexane. The inhibiting effect provided by activated carbon was, however, less significant by the use of humic acid solution.     

The calcination process in a system for washing, calcinating, and converting treated municipal solid waste incinerator fly ash into raw material for the cement industry

Calcination is the second step in a washing-calcination-conversion system in which treated municipal solid waste incinerator fly ash and bottom ash can be reused as raw material in the cement industry and can decompose or stabilize hazardous compounds, reduce residue amounts, and alter residue characteristics. In this research, only fly ash is discussed. Chloride reduction is important if treated fly ash is to be reused in cement; however, the relationship between washed fly ash properties and chloride reduction by calcination is not well understood. This study used washed residues of three types of fly ash-raw fly ash (RFA) from the boiler or economizer of an incineration system, fly ash collected in a bag filter injected with calcium hydroxide (Ca(OH)2) for acid removal (CaFA), and fly ash collected in a bag filter injected with sodium bicarbonate (NaHCO3) for acid removal (NaFA)-in calcination experiments with varying temperature (400-1100 degrees C) and atmosphere (100% nitrogen [N2] at 25 mL/min or 10% oxygen [O2] [90% N2] at fluxes of 25, 50, and 75 mL/min). From the perspective of chloride reduction, heating to 1000 degrees C with 1-hr heating time, 1-hr holding time, and an atmosphere of 10% O2/90% N2 was most suitable for calcination. Under these conditions, chloride levels were reduced by 91, 52, and 96% in washed residues of RFA, CaFA, and NaFA, respectively. Among the washed residues, the weight of the washed residue of NaFA decreased the most.     

Fluidized-bed-combustion ash for the solidification and stabilization of a metal-hydroxide sludge

Fluidized-bed-combustion (FBC) ash is a by-product from a developing technology for coal-fired power plants that will economically reduce air emissions to meet requirements of the Clean Air Act. FBC ash has physical and chemical properties similar to Portland cement, but only has moderate success as a pozzolan in concrete applications due to low compressive strengths. However, FBC ash has proven effective for use as a binder for the solidification and stabilization (S/S) of metal-bearing sludges. Physical and chemical characterization procedures were used to analyze FBC ash and a metal-bearing sludge obtained from a hazardous waste treatment facility to develop 12 different S/S mix designs. The mix designs consist of four binder designs to evaluate sludge-to-binder ratios of approximately 0, 0.5, and 1. Portland cement is used as a control binder to compare unconfined compressive strengths and Toxicity Characteristic Leaching Procedure (TCLP) analyses from different ratios of the FBC ash streams: fly ash, char, and spent bed material (SBM). Compressive strengths ranging from 84 lbs per square inch (psi) to 298 psi were obtained from various mix designs containing different sludge-to-ash ratios cured for 28 days. All the mix designs passed the TCLP. Recoveries from leaching for each metal were less than 5% for most mix designs. Results of unconfined compressive strengths, TCLP, and percent recovery calculations indicate that the mix design containing approximately a 1:1 ratio of fly ash to char-and-sludge is the best mix design for the S/S of the metal-bearing sludge.     

An automated overlying water-renewal system for sediment toxicity studies

An automated water-renewal toxicity test system is described for exposing benthic invertebrates to whole sediments. The system will intermittently deliver laboratory or on-site water for overlying water replacement in sediment exposures. A range of cycle rates can be used to produce different volume additions of overlying water per day to exposure chambers. The system can be used with six different treatments and eight replicates per treatment producing 48 exposure chambers. Three formulated sediments with variable organic carbon (1.5%, 7.5%) and sand (14%, 63%) content were prepared to test the system exposing amphipods, Hyalella azteca and midges, Chironomus tentans in 10 day whole sediment tests. Intermittent water flow was used with a 90 min cycle time to create two volume additions of laboratory water per 24 h in exposure chambers (180 ml sediment, 320 ml water). Overlying water quality conditions, and survival and growth of both species were consistent and within acceptable limits for the testing requirements of the U.S. EPA guidelines for sediments with freshwater invertebrates.     

Influence of ageing of residues on the availability of herbicides for leaching

Losses by leaching of chlorotoluron, isoproturon and triasulfuron from small intact columns of a structured clay loam and an unstructured sandy loam soil were measured in five separate field experiments. In general, losses of all three herbicides were greater from the clay loam than from the sandy loam soil and the order between herbicides was always triasulfuron > isoproturon > chlorotoluron. Differences between experiments were also consistent for every soil/herbicide combination. There was no relationship between total loss and either total rainfall or cumulative leachate volume. When weighting factors were applied to the rainfall data to make early rainfall more important than later rainfall, there were significant positive relationships between cumulative weighted rainfall and total losses. Also, there were significant negative correlations between total losses and the delay to accumulation of 25 mm rainfall (equivalent to one pore volume of available water) in the different experiments. In laboratory incubations, there was a more rapid decline in aqueous (0.01 M calcium chloride) extractable residues than in total solvent extractable residues indicating increasing sorption with residence time. However, the rate of change in water extractable residues could not completely explain the decrease in leachability with ageing of residues in the field. Short-term sorption studies with aggregates of the two soils indicated slower sorption by those of the clay loam than by those of the sandy loam suggesting that diffusion into and out of aggregates may affect availability for leaching in the more structured soil. Small scale leaching studies with aggregates of the soils also demonstrated reductions in availability for leaching as residence time in soil was increased, which could not be explained by degradation. These results therefore indicate that time-dependent sorption processes are important in controlling pesticide movement in soils, although the data do not give a mechanistic explanation of the changes in leaching with ageing of residues.     

Organo-chlorine pesticide (DDT and HCH) residues in the Taihu Lake Region and its movement in soil-water system I. Field survey of DDT and HCH residues in ecosystem of the region

The use of organo-chlorine (DDT and HCH) has been banned in China for 20 years. A field survey was carried out during 1999-2000 in the Taihu Lake Region. Organo-chlorine pesticide (OCP) residues in soil, water, fish and sediment samples were investigated. DDT was detected in 5 out of 10 samples with concentration ranging from 0.3 to 5.3 microg/kg in the surface (0-15 cm) layer, 6 out of 10 with 0.5 to 4.0 microg/kg in the subsoil layer (16-30 cm), and 4 of 10 with 0 to 2.7 microg/ kg in the deep soil layer (31-50 cm). Results for HCH residues in soil samples were similar to those of DDT. These results indicate that OCP residues in 0-50 cm profile had been leached out or degraded to safe level. In river water DDT was detected in 10 out of 13 samples ranging from 0.2 to 9.3 microg/l, with an average of 1.0 microg/l. While HCH was detected in 12 out of 13 samples ranging from 0.02 to 36.1 microg/l, with an average 5.6 microg/l. DDT residues in sediment ranged from 0.1 to 8.8 microg/kg, while HCH ranged from 0.3 to 66.5 microg/kg. DDT residues in fish body ranged from 3.7 to 23.5 microg/kg and HCH ranged from 3.7 to 132 microg/kg. These results demonstrate an accumulation through food chain (from soil-water-sediment-microbes-crop-fish-... etc.), also that HCH residues are generally more persistent than DDT residues. However, all these data are well below than the state warning standard limit.     

Bound residues: environmental solution or future problem?

The paper examines the issue of bound residues from the viewpoint of the risk assessment procedures employed for environmental protection. It considers, on one hand, the evidence that such residues are so tightly bound to soil organic matter as to be essentially unavailable; and on the other, the perspective that we should not be loading up the environment with compounds whose future behaviour and release we cannot predict. Existing knowledge of the mechanisms by which residues bind to soil organic matter suggests that release will be closely dependent on soil organic matter breakdown. Simple models of organic matter turnover suggest that the release following single applications of individual compounds will be very slow; but the significance of releases following repeated application over many years of a number of compounds needs to be investigated further. Applying environmental risk assessment techniques is complicated by the difficulty in identifying parent molecules and potential metabolites in the bound residue fraction. The paper concludes that for single additions of individual compounds, bound residues probably do represent an environmental solution. But the long-term significance of bound residues formed from multiple additions of a number of compounds is less clear. The paper recommends that future work should emphasise the biological significance of such residues and their release.     

Partial dissolution of ACQ-treated wood in lithium chloride/N-methyl-2-pyrrolidinone: separation of copper from potential lignocellulosic feedstocks

A cellulose solvent system based on lithium chloride (LiCl) in N-methyl-2-pyrrolidinone (NMP) was used to assess the merits of partial dissolutions of coarsely ground wood samples. Alkaline Copper Quaternary (ACQ)-treated pine wood was of particular interest for treatment given the potential to generate a copper-rich stream apart from solid and/or liquid lignocellulosic feedstocks. Treatment with NMP alone gave yields of soluble materials that were higher than typical extractives contents thereby suggesting a limited degree of wood dissolution. Inclusion of LiCl, which disrupts hydrogen bonding, gave lower wood residue recoveries (i.e., higher dissolution) with higher LiCl concentration. Lower wood residue recoveries coincided with lower Klason lignin and hemicellulose-derived sugar contents in the wood residues. After treatment with 8% LiCl in NMP, subsequent filtration afforded 34% of the ACQ-treated sapwood as a wood residue retaining only 2% of the original copper. Pouring the filtrate over an excess of water resulted in the recovery of 30% of the solids and 50% of the copper together as a copper-enriched lignocellulosic precipitate. Results demonstrate a solvent system showing potential as a means to separate heavy metals from preservative-treated wood and to recover lignocellulosic feedstocks that may be suitable for use in a biorefinery.     

Development of IC-ELISA for detection of organophosphorus pesticides in water

Diethyl (carboxymethyl) phosphonate (DECP) was used as the hapten to develop an indirect competitive enzyme-linked immunosorbent assay (IC-ELISA) for detecting organophosphorus pesticides (OPs). Conjugator of DECP with bovin serum albumin (BSA) was used as the immunogen for producing the polyclonal antibodies (PcAbs). Three antisera were obtained after the immune procedure. Characterization studies of the PcAbs indicated that the titer of antiserum-1 was highest in 3 antisera, and antiserum-1 had high affinity and specificity to the parathion, dichlorvos and pirimiphos. The IC-ELISA showed an IC50 of 0.428 micro g/mL with a detection limit of 0.0125 micro g/mL to parathion. The assay also indicated that the IC50 values of pirimiphos and dichlorvos were 0.331 micro g/mL and 1.25 micro g/mL respectively, and the detection limits of pirimiphos and dichlorvos were 0.0116 micro g/mL and 0.048 micro g/mL respectively. Recoveries of parathion, pirimiphos and dichlorvos spiked into water samples ranged from 90% to 160%. The results indicated that the ELISA could be a convenient and supplemental analytical tool for monitoring OPs residues in environmental water samples.     

Investigation of acute toxicity and the effect of cadmium chloride (CdCl2 . H2O) metal salt on behavior of the guppy (Poecilia reticulata)

In this study 96-h LC50 value of cadmium chloride (CdCl2 . H2O), a metal salt widely used in industry, was determined for the guppy (Poecilia reticulata, Pallas, 1859). The experiments were planned in four series of a total of 440 guppies employing the static test method of acute toxicity. 10 fish were placed in each replicate of each dose. The experiments were performed as four replicates, and behavioral changes in the guppy were determined for each cadmium chloride metal salt concentration. The data obtained were statistically evaluated by the use of EPA computer program based on Finney's Probit Analysis Method and a 96-h LC50 value for P. reticulata was found to be 30.4 mg/l in a static bioassay test system. This value was estimated to be 30.6 mg/l with Behrens-Karber's method. The two methods were in good agreement. 95% lower and upper confidence limits for the LC50 were 29.3 and 31.7 mg/l, respectively. The water temperature was kept between 21 and 23 degrees C. The behavioral changes observed in fish were, swimming in imbalanced manner, capsizing, attaching to the surface, difficulty in breathing and gathering around the ventilation filter.     

Development of ELISA technique for the analysis of atrazine residues in water

A highly sensitive enzyme immunoassay is described for the detection of atrazine residues in water. Atrazine derivative was conjugated to Bovine Serum Albumin (BSA) to obtain an immunizing antigen and to Horseradish Peroxidase enzyme (POD) to obtain a marker for immunoassay. The formation of these conjugations was confirmed by UV spectroscopy as well as by gel-electrophoresis. Polyclonal antibodies were raised in rabbits by immunization with an atrazine-BSA conjugate containing 29 atrazine residues per BSA molecule. An ELISA on microtitration plates was optimized with peroxidase-atrazine conjugate. The middle of the test (50% B/Bo) was found to be at 90 ng/l, which is well below the maximum concentration permitted by the EC guidelines for drinking water. Detection limits for atrazine of about 1 ng/l could be reached. The assay did not require concentration or cleanup steps for drinking or ground water samples. Validation experiments showed good accuracy and precision. No cross-reactivities were shown by other s-triazines like terbutryn, ametryn, terbuthylazine, des-isopropylatrazine, and de-ethylatrazine except hydroxyatrazine. The latter was present at very low levels that can be calibrated/standardized before analysis or it may be considered as leftover residues of atrazine. Based on these results, it is suggested that this test can be applied to obtain fairly accurate results for atrazine concentration in water samples from different sources.     

Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.