A pilot and field investigation on mobility of PCDDs/PCDFs in landfill site with municipal solid waste incineration residue

A field investigation by boring was carried out in a landfill site primarily with municipal solid waste incineration residue. From the collected core samples, vertical profiles of homologous content of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in the landfill layer were traced and the behavior of PCDDs/PCDFs was examined. In addition, a pilot-scale study was conducted on the PCDDs/PCDFs leached from incineration fly ash and the treated one using large landfill simulation columns (lysimeters) and the leaching behavior of PCDDs/PCDFs was examined. As a result, it was found that the coexistence of dissolved coloring constituents (DCCs), which might be composed of constituents like dissolved humic matters having strong affinity for hydrophobic organic pollutants, could enhance the leachability of PCDDs/PCDFs, thus contributing to the vertical movement and leaching behavior of PCDDs/PCDFs in the landfill layers of the incineration residue. Moreover, it is highly probable that DCCs derive from the unburned carbon in the bottom ash mixed and buried with the fly ash containing a high content of PCDDs/PCDFs.     

Dechlorination and destruction of PCDDs/PCDFs in fly ashes from municipal solid waste incinerators by low temperature thermal treatment

Dechlorination and destruction characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/PCDFs) in fly ashes from commercial-scale municipal solid waste incinerators by low temperature thermal treatment using a laboratory-scale heating system were investigated. Experiments were carried out in reducing atmosphere at temperatures of 300 degrees C, 450 degrees C and 600 degrees C respectively, for the treatment time of 1h and 3h. Concentrations of PCDDs/PCDFs in raw fly ashes ranged from 35.5 to 107.3 microg kg(-1) (1.5-3.4 microg TEQ kg(-1)) and treated fly ashes ranged from 0.34 to 45.3 microg kg(-1) (0.012-1.63 microg TEQ kg(-1)). Concentrations of PCDDs/PCDFs in fly ashes treated at the different temperatures and times were observed to decrease with increase of treatment temperature and time by dechlorination or destruction. The distribution of octa- and hepta-chlorinated congeners were decreased and tetra-, penta- and hexa-chlorinated congeners were increased at 300 degrees C and 450 degrees C, but the distribution of octa- and hepta-chlorinated congeners were increased and tetra-, penta- and hexa-chlorinated congeners were again decreased at 600 degrees C. Total destruction efficiencies of PCDDs/PCDFs in fly ashes showed above 95% at the treatment temperature of 450 degrees C for 3h. However, removal efficiency of each congener in fly ashes varied, especially, 2,3,7,8-TeCDD and 1,2,3,7,8-PeCDD in fly ash A increased. And the dechlorination and destruction characteristics of PCDDs/PCDFs in fly ash A and B was different due to difference in contents of Ca-compounds and metal oxides such as CuO and PbO in fly ashes.     

Alumina as a model support in the formation and dechlorination of polychlorinated dibenzo-p-dioxins and dibenzofurans

Alumina was studied as a model matrix for formation and dechlorination reactions of PCDDs and PCDFs. Only small differences in PCDD and PCDF formation were found between de-novo synthesis on alumina and on fly ash. The amounts of PCDDs and PCDFs formed on acidic alumina were much larger than on neutral and alkaline alumina. OCDD and OCDF were rapidly dechlorinated on basic alumina.     

Mechanochemical degradation of chlorinated contaminants in fly ash with a calcium-based degradation reagent

This report presents our results in a low-temperature mechanochemical hydrodechlorination process applied to fly ash coming from a municipal waste incinerator in order to efficiently remove all traces of PCDDs, PCDFs and PCBs. We found that the most suitable degradation agent is a mixture of metallic calcium and calcium oxide. A sample of fly ash presenting a TEQ of 5200 pg g⁻¹ was completely detoxified (no traces of PCDDs, PCDFs and PCBs detected) after ball-milling at 400 rpm over night.     

The effect of metal catalysts on the formation of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran precursors

The catalytic effects of copper and iron compounds were examined for their behavior in promoting formation of chlorine (Cl₂), the major chlorinating agent of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), in an environment simulating that of municipal waste fly ash. Formation of Cl₂ occurred as a result of a metal-catalyzed reaction of HCl with O₂. Catalytic activity was greatest at a temperature of approximately 400 °C, supporting a theory of de novo synthesis of PCDDs and PCDFs on fly ash particles downstream of waste combustion.     

Removal of PCDDs/DFs and dl-PCBs in MWI fly ash by heating under vacuum

Temperature dependence of PCDD/DF and dioxin-like polychlorinated biphenyl (dl-PCB) concentrations in fly ash from a municipal waste incinerator (MWI) heated under vacuum has been investigated as a function of sample temperature ranging from T(s)=425 to 800 K to find out if PCDDs/DFs in fly ash evaporate and are trapped in a liquid nitrogen-cooled trap. The results show that more than 99.98% of PCDDs/DFs in TEQ is removed from fly ash by vacuum heat treatment at T(s)>650 K for 4 h. Almost no PCDDs/DFs were detected in the liquid nitrogen-cooled trap. Homologue distributions indicate that dechlorination/hydrogenation (DCH) reactions proceed in fly ash at T(s)>450 K. Arrhenius rate parameters for the DCH reactions have been determined for each homologue assuming that only DCH reactions occur. The fly ash heated under vacuum at 650 or 800 K was reheated at 573 K (300 degrees C) in a stream of dry or humid air to see how much PCDDs/DFs and dl-PCBs are regenerated. We have found that (1) PCDDs/DFs are regenerated in both 650 K and 800 K treated fly ash, whereas dl-PCBs are regenerated in 650 K treated fly ash, (2) formation of PCDFs predominates over that of PCDDs or dl-PCBs, and (3) less chlorinated homologues are abundant for PCDDs/DFs and dl-PCBs.     

Polychlorinated dibenzothiophenes in Japanese environmental samples and their photodegradability and dioxin-like endocrine-disruption potential

Polychlorinated dibenzothiophenes (PCDTs) in sediment, soil, and fly ash samples collected in Japan were analyzed and their dioxin-like endocrine-disruption potential and photodegradability investigated. PCDTs were detected in all three types of sample, although the concentrations were lower than those of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). An Ah-immunoassay confirmed that 2,3,7,8-TeCDT, 1,2,3,7,8-PeCDT, 1,2,3,7,8,9-HxCDT, and 1,2,3,4,7,8,9-HpCDT had Ah receptor-binding activities, which means that these PCDTs have the potential to cause dioxin-like endocrine-disruption. Photodegradation of PCDTs by UV irradiation was accompanied by dechlorination. The photodegradation rates of 2,3,7,8-TeCDT and OCDT were lower than the rates for the corresponding PCDF isomers (2,3,7,8-TeCDF and OCDF), which indicates that PCDTs are more stable than PCDFs to photodegradation.     

Bioavailability of 2,3,7,8-tetrachlorodibenzo-p-dioxin from municipal incinerator fly ash to freshwater fish

The bioavailability of 2,3,7,8-TCDD from municipal incinerator fly ash to freshwater fish was determined. It was observed that carp exposed to fly ash containing all 22 TCDD isomers, or the solvent extract of the fly ash, retain only 2,3,7,8-TCDD. Exposures with fly ash appears to follow a dose response relationship for bioconcentration, however, the bioavailability of 2,3,7,8-TCDD was not directly related to the level of 2,3,7,8-TCDD in fly ash for two fly ash samples studied.     

Concentrations and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans in aquatic tissues, and ambient air from South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), including 2378-substituted isomers were present in samples of shellfish and fish, and ambient air collected from Masan Bay, and Masan City, South Korea. Total concentrations of PCDDs/DFs in mussel and clam were 750 pg g(-1), lipid weight (lw), and 3418 pg g(-1), lw, respectively. Total concentrations of PCDDs/DFs in mullet, gizzard and flounder were 52, 82, and 122 pg g(-1), lw, respectively. Shellfish tissues contained a greater number of PCDD/DF isomers, contributing greater total concentrations of PCDDs/DFs compared to fish collected from the same locations. The predominance of 2378-substituted PCDDs/DFs in fish is represented in greater total concentrations of 2378-TeCDD equivalents (TEQs), whereas there was very limited occurrence of 2378-substituted isomers in shellfish. TEQ concentrations in samples of mussel and clam were 0.97 and 12 pg g(-1), lw, respectively. Total TEQs in mullet, gizzard and flounder were 12, 22 and 18 pg g(-1), lw, respectively. In fish 2378-substituted PCDDs accounted for 100% of the total concentrations of PCDDs, and 2378-substituted PCDFs accounted from 59% to 73% of the total PCDFs. The 2378-substituted isomers accounted for only 3% of the total PCDDs/DFs in shellfish. Ambient air collected from two sites contained a wide range of isomers of tetra- through heptachlorinated PCDDs/DFs. Even though the total concentration of PCDDs/DFs in ambient air (12.8 pgm(-3)) collected from an industrial area was 2-fold greater than that in air samples (6.3 pgm(-3)) collected from an urban/rural area, total TEQs (0.07 and 0.08 pgm(-3)) there was no statistical difference between the two samples.     

Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan

In this study, fly ash samples were collected from three municipal waste incinerators (MWI) in Taiwan. These MWIs investigated are equipped with different air pollution control devices (APCDs). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for all three MWIs. Concentrations of higher-chlorinated congeners of PCDDs and PCDFs were remarkably higher than those of lower-chlorinated congeners. In the case of MSW-A, the PCDD/PCDF ratios of ashes were found in the decreasing order for cyclone, boiler and baghouse. The PCDD/PCDF ratios in various types of fly ash of MWI-B was boiler-A < boiler-B < ESP < boiler-C. As for MSW-C, no obvious trend has been observed for PCDD/PCDF ratio. However, the ratio in boiler ash was higher than that in baghouse ash of MWI-A. The dioxin contents in fly ash would increase as the fly ash passed through APCD zones. In other words, the environmental conditions of APCD may actually cause the increase of the dioxin contents in fly ash. The trend for dioxin contents in fly ash collected from three MSW incinerators investigated was MSW-C < MSW-A < MSW-B.     

Vehicle dependent bioavailability of polychlorinated dibenzo-p-dioxins (PCDDs) and -dibenzofurans (PCDFs) in the rat

PCDDs and PCDFs were administered as fly ash (500 mg) or fly ash extract to male Wistar rats. The extract was administered orally and intravenously by using arachidis oil and miglyol 812 as oily vehicles. Liver retentions were determined after 48 hours as a degree of bioavailability. In all experiments only the 2,3,7,8-substituted congeners, with the exception of 2,3,4,6,7-PnCDF, were detected in the liver. The dose was 10 to 40 ng for each congener. The lowest bioavailability was found in the experiments with crude or hydrochloric acid pretreated fly ash. Liver retentions were comparable for both experiments with fly ash (0.4 – 3.8%) and were approximately 10 times higher in the oral experiments with oily vehicles. Miglyol 812 produced slightly lower liver retentions compared with arachidis oil. Intravenous dosage with miglyol 812 resulted in liver retentions twice as high as oral administration with this vehicle.     

Emissions of Chlorinated Organics from Two Municipal Incinerators in Ontario

In this paper the results of sampling for trace chlorinated organics at two municipal refuse incinerators in Ontario are presented. The information may be of Interest to individuals concerned with the assessment of PCDD/PCDF (polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran) emissions from incineration of refuse and their impact on the energyfrom- waste program. PCDDs, PCDFs, PCBs (polychlorinated biphenyls), CBs (chlorobenzenes) and CPs (chlorophenols) were quantified in all process streams including refuse, ash and stack emissions. Manual sorting of refuse and collection of ash samples were carried out simultaneously with three 24-hour continuous stack sampling tests at each plant. The results suggested that the total output of PCDDs and PCDFs varied proportionately with their input at both incinerators. However, the input of PCDDs/PCDFs could not account for their total output. The chemistry of PCDDs/PCDFs in the input and output streams were different in that only heptachlorinated and octachlorinated species were present in significant quantities in the refuse while lower chlorinated species were predominant in stack emissions and ash streams. There was no correspondence between the Input of PCBs/CBs/CPs and the output of PCDDs/PCDFs. The output of PCDDs/PCDFs, however, varied Inversely with the total output of PCBs/CBs/CPs, suggesting that the latter compounds could have been partially responsible for the formation of PCDDs and PCDFs. The PCDF emissions were also affected by combustion conditions; they were higher in magnitude and consisted of predominantly tetrachlorinated and pentachlorinated species at the plant where the combustion temperatures were lower.     

Concentration changes of PCDDs, PCDFs, and dioxin-like PCBs in human breast milk samples as shown by a follow-up survey

Breast milk is known to discharge dioxins from the human body. However, to date, no direct comparison has been made of the concentrations of dioxin analogues in breast milk obtained from identical population after successive deliveries. We present here follow-up survey results of PCDDs, PCDFs, and dioxin-like PCBs concentrations in human breast milk samples from 35 women living in Tokyo from whom samples had been obtained and analyzed to determine the corresponding concentrations in the past. The average concentrations of total PCDDs, PCDFs, dioxin-like PCBs were 8.5, 5.5, 11 TEQ pg/g fat for the first samples and 5.4, 4.0, 6.6 TEQ pg/g fat for the second samples, respectively. The degrees of reduction of total PCDDs and total dioxin-like PCBs were higher than that of total PCDFs because 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3',4,4',5-PeCB (#126), which were the predominant congeners among PCDDs, PCDFs, and dioxin-like PCBs, respectively, had different degrees of reduction. Moreover we observed a significant increase of the concentrations of PCDDs, PCDFs, and dioxin-like PCBs in samples from three women in this follow-up survey, and the patterns of increased isomers differed among the three samples. It was conjectured that the increase of the concentrations was due mainly to dietary intake between deliveries. It is important for pregnant women to have a balanced diet to mitigate the exposure of infants to these chemicals.     

PCDDs, PCDFs, and PCBs concentrations in breast milk from two areas in Korea: body burden of mothers and implications for feeding infants

We determined breast milk concentration of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in 24 mothers living in Korea, and assessed the maternal body burden based on PCDDs/PCDFs and PCBs concentrations in breast milk and an infant intake rate through breast-feeding based on their concentration in breast milk. PCDDs/PCDFs and PCBs levels in breast milk from primipara mothers were found to be higher than those from multipara mothers. For total PCDDs/PCDFs TEQ level, 2,3,4,7,8-PeCDD was the predominant congener, and the proportion of 2,3,7,8-TCDD was less than 3% of total PCDDs/PCDFs TEQ level. For PCBs TEQ level, PCB-126 was the predominant congener. Maternal body burden levels of PCDDs/PCDFs and PCBs based on their concentrations in breast milk were 268-622 TEQ ng. The daily dioxin intakes of mothers were predicted to be 0.78-2.18 TEQ pg/kg/day for PCDDs/PCDFs and 0.34-0.66 TEQ pg/kg/ day for PCBs. For the first year, the body burden of an infant was predicted to be 212 TEQ ng and the daily intake of an infant was predicted to be 85 TEQ pg/kg/day, assuming the mean dioxin-related compounds concentration (27.54 TEQ pg/g fat).     

Formation of dioxin analogs by open-air incineration of waste wood and by fire of buildings and houses concerning Hanshin Great Earthquake in Japan

Ash samples were collected from site of open-air incineration and fire concerning Hanshin Great Earthquake which occurred in western Japan in the early morning of 17 January 1995. The average concentrations of total sum of PCDDs, PCDFs and Co-PCBs in ash collected from wood scrap of broken building fire site, house fire site, shoe-making factory fire site and electric appliances store fire site were 541, 442, 859 and 22,800 pgTEQ/g, respectively. Particularly, PCDFs among dioxin analogs generated remarkably at sites with a high TEQ. In addition, 79,000 t of ash was totally produced at five open-air incineration sites, and consequently the formation amount of PCDDs, PCDFs and Co-PCBs was estimated to be 70.7 gTEQ on the basis of these analytical data.     

PCDDs, PCDFs and dioxin-like PCBs in food of animal origin (Slovakia)

The levels of 17 toxic polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and 12 non-ortho and mono-ortho polychlorinated biphenyls (PCBs) in 73 foodstuff samples of animal origin collected from shops and small farms in selected districts of Slovak Republic are presented in this paper. The concentrations expressed as WHO-TEQ in analysed samples ranged for PCDDs/PCDFs from 0.25 pg/g fat in pork to 75 pg/g fat in cod liver. The TEQ concentrations of non-ortho PCBs were between 0.007 and 181 pg/g fat and mono-ortho PCBs between 0.0083 and 66.5 pg/g fat. The mean concentrations in freshwater fish and imported species of marine fish were 0.089 pg TEQ/g fresh weight for PCDDs/PCDFs, 0.17 pg TEQ/g fresh weight for non-ortho PCBs and 0.034 pg TEQ/g fresh weight for mono-ortho PCBs. The mean total concentration of PCDDs/PCDFs and dioxin-like PCBs in samples of infant milk formula imported from EU countries was 0.98 pg TEQ/g fat.     

Embryonic abnormalities and organochlorine contamination in double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes in 1988

Persistent organochlorine contaminants including polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were determined in eggs with normal and deformed embryos collected in 1988 from different colonies during an epizootiological survey of double-crested cormorants (Phalacrocorax auritus) and Caspian terns (Hydroprogne caspia) from the upper Great Lakes. PCBs and p,p'-DDE were found in the highest concentrations in eggs of both species. The residue pattern of PCB isomers and chlordane compounds suggested that double-crested cormorants have greater metabolic capacity to degrade contaminants than Caspian terns. According to the toxicity evaluation using the 2,3,7,8-TCDD equivalents (TEQs) approach, non-ortho coplanar PCBs contributed much more toxicity than PCDDs and PCDFs. Total TEQ of dioxin-like compounds was likely associated with occurrence of live-deformed embryos in double-crested cormorants eggs. The toxic effects of these contaminants were also estimated in Caspian tern eggs, where elevated levels of coplanar PCBs, PCDDs and PCDFs were observed in concordance with increased rate of anomalies in eggs during a breeding season in the Great Lakes.     

Standardization and application of an E.L.S.-bioassay for PCDDs and PCDFs

An early life stage bioassay (E.L.S.-bioassay) for the determination of polychlorinated dibenzo-p-dioxins and dibenzofurans in complex matrices has been developed. The bioassay is based upon mortality, resulting from a typical toxicopathological syndrome in rainbow trout eleutheroembryos. Its reliability is demonstrated by the application to incinerator fly ash. It is concluded, that the E.L.S.-bioassay is a simple, useful and relatively inexpensive method to determine the amount of PCDDs and PCDFs in potentially contaminated environmental samples.     

Correlation of polychlorinated naphthalenes with polychlorinated dibenzofurans formed from waste incineration

Isomer composition of polychlorinated naphthalenes (PCNs) was measured for municipal waste incinerator fly ash samples and for emission samples produced from soot and copper-deposit experiments conducted at the United States Environmental Protection Agency (US-EPA). Two types of PCN isomer patterns were identified. One pattern contained specific PCN isomers in which chlorine atoms are substituted as if the peri(alpha-) position were dechlorinated from the higher chlorinated PCNs one by one. In another pattern, the isomers had a tendency for the chlorine atoms to assume successive positions on the naphthalene ring, which may be caused by specifically oriented chlorination. Some of these isomers increased, together with several polychlorinated dibenzofuran (PCDF) and a few polychlorinated dibenzo-p-dioxin (PCDD) isomers. The ratios between some specific PCN, PCDF, and PCDD isomers measured for the fly ash samples agree with those obtained from the soot and copper-deposit experiments. The observations suggest that these isomers were formed possibly from de novo synthesis utilizing the carbon structure contained in soot under the catalytic effect of a copper compound. Typical isomers for PCNs and PCDFs produced from incineration emissions were identified.     

Dechlorination/hydrogenation and destruction reactions of PCDDs in OCDD-added fly ash heated under vacuum

Octachlorodibenzo-p-dioxin (OCDD)-added, pretreated fly ash was heated under vacuum at sample temperatures ranging from T(s)=450 to 650 K. The fly ash and liquid nitrogen-cooled trap samples were analyzed for DD/DF through OCDD/DF. The total amounts of DD through OCDD decrease with increasing T(s), which indicates that dechlorination/hydrogenation (DCH) reactions are not the only reaction channels. Reduction of toxic equivalent (TEQ) for PCDDs by more than 99% was achieved in the fly ash by the vacuum heat treatment at T(s)=650 K for 4 h. The total amount of PCDDs and DD detected in the liquid nitrogen-cooled trap relative to that of added OCDD was about 17%, i.e., PCDDs and DD which were adsorbed to the fly ash surfaces can evaporate into the gaseous phase. The difference between the evaporation behavior of PCDDs in the present and the previous studies is discussed in the light of their states of existence.