Dioxin like compounds from municipal waste incinerator emissions: assessment of the presence of polychlorinated naphthalenes

Polychloronaphthalenes (PCN) were identified and quantified in emission samples collected from five different municipal waste incinerators (MWI). Polychlorodibenzo-p-dioxins (PCDD) and polychlorodibenzofurans (PCDF) were also determined to find a possible relationship between these classes of organochlorinated compounds. The analyses of PCDD/PCDF and PCN were carried out by high resolution gas chromatography coupled with high resolution mass spectrometry using a positive electron ionization source and operating in the selected ion monitoring analyzer mode (HRGC-HRMS/EI(+)-SIM). The total levels of PCN varied from 1.08 up to 21.36 ng/Nm3 (mono- to octachlorinated) and 0.33 to 5.72 ng/Nm3 (tetra- to octachlorinated), whereas the levels of PCDD/PCDF ranged between 1.14 and 276.26 ng/Nm3 (0.01 and 5 ng I-TEQ/Nm3), depending on the type of the MWI. These findings do not corroborate a PCN and PCDD/PCDF correlation.     

Dioxin mass balance in a municipal waste incinerator

A dioxin mass balance in an Spanish municipal waste incinerator (MWI) is presented. Input and output inventories from two sampling collection episodes including the analysis of PCDD/PCDF in urban solid waste (USW), stack gas emissions, fly ash and slag are reported. In one collection the levels of USW were around 8 pg I-TEQ/g and non-thermal destruction was observed overall. In the other collection the levels of USW were higher (around 64 pg I-TEQ/g) and the dioxin balance revealed a thermal destruction. Analysis of the different waste materials (textile, organic, plastic, wood and paper) was performed separately and the textile samples presented the highest levels.     

Dioxin emissions from waste incinerators

Mechanisms that have been proposed to account for the emission of PCDD/PCDF from municipal waste incinerators were evaluated in the light of extensive experimental data obtained from the Quebec City municipal solid waste incinerator by Environment Canada. It was found that PCDD/PCDF emissions were closely related to the quantity of material entrained by the combustion gases.     

Dioxin exposure and public health in Chapaevsk, Russia

One of the largest environmental polluters in Chapaevsk (Samara Region, Russia) is the Middle Volga chemical plant. From 1967 to 1987, it produced hexachlorocyclohexane (lindane) and its derivatives. Currently, it produces crop protection chemicals (liquid chlorine acids, methyl chloroform, vinyl chloride, and some other chemicals). Dioxins were detected in air (0.116 pg/m3), in soil (8.9-298 ng/kg), in the town's drinking water (28.4-74.1 pg/liter), and in the cow's milk (the content of 2,3,7,8-TCDD was 17.32 pg TEQ/g fat). The mean content of dioxins in seven pooled samples of human milk (40 individual trials) was 42.26 pg TEQ/g fat, in four female workers' blood samples -412.4 pg TEQ/g fat, in six residents blood samples (those who lived 1-3 km from the chemical plant) -75.2 pg TEQ/g fat, in four residents' blood samples (5-8 km from the plant) -24.5 pg TEQ/g fat. To assess cancer risk and reproductive health status, official medical statistical information was used. In general, the male cancer mortality observed rate in Chapaevsk is higher than expected. The SMR is higher for lung cancer 3.1(C.I. 2.6-3.8), urinary organs 2.6(C.I. 1.7-3.6). Chapaevsk women have a higher risk overall due to breast cancer 2.1(C.I. 1.6-2.7) and cervix cancer 1.8(C.I. 1.0-3.1). The incidence rates were higher for lung cancer in males and for female breast cancer in all age groups compared to Russia and Samara Region in 1998. Significant disruptions in reproductive function were detected. The mean frequency of spontaneous abortions in the last seven years was statistically higher 24.4% in Chapaevsk (compared to other of the towns region). The average rate of premature labor was 45.7 per 1000 women in Chapaevsk that is significantly higher than in most Samara Region towns. The frequency of newborns with low birth weight was 7.4%. In Russia and in most of the Samara Region towns, this rate is lower (6.2-5.1%) but not statistically different. For the determination of congenital morphogenetic conditions (CMGC), 369 children born between 1990 and 1995 were examined. The average number of CMGC per child was significantly higher, 4.5 for boys and 4.4 for girls. The first results indicated serious disruptions associated with high dioxin levels in human milk and blood in Chapaevsk. We suggest that Chapaevsk is an incredibly interesting site for further environmental-epidemiological research to assess the impact of dioxins on human health.     

Dioxin and dioxin-like PCB exposure of non-breastfed Dutch infants

The exposure of humans to PCDD/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) and dioxin-like PCBs (dl-PCBs, i.e. polychlorinated non-ortho and mono-ortho biphenyls) occurs predominantly via the intake of food. Young children have a relatively high intake of these substances, due to their high food consumption per kilogram body weight. As the exposure of non-breastfed infants to these compounds has not been assessed before in The Netherlands, we studied the dietary intake of 17 PCDD/Fs and 11 dioxin-like PCBs in 188 Dutch non-breastfed infants between 4 and 13 months. The food intake of the infants was assessed by a 2-d food record. From these data PCDD/F and dioxin-like PCB intake was calculated using PCDD/F and dioxin-like PCB concentrations of food products sampled in 1998/1999 in The Netherlands. The long-term PCDD/F and dioxin-like PCB exposure of the infants was calculated using the statistical exposure model (STEM). For infants of 5 months the chronic exposure to PCDD/F and dioxin-like PCB was 1.1pg WHO-TEQ (toxic equivalents) per kilogram body weight (bw) per day (95th percentile: 1.7pg WHO-TEQ/kg bwxd), which mainly originated from infant formula and vegetables and increased to 2.3pg WHO-TEQ/kg bwxd (95th percentile 3.7pg WHO-TEQ/kg bwxd) for infants just over 1 year old eating the same food as their parents. The percentage of formula-fed infants with an exposure exceeding the TDI of 2pg WHO-TEQ/kg bwxd was 5% at 5 months, 49% at 9 months and 64% at 12 months.     

Dioxins,furans and polycyclic aromatic hydrocarbons emissions from a hospital and cemetery waste incinerator

An experimental campaign was carried out on a hospital and cemetery waste incineration plant in order to assess the emissions of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polycyclic aromatic hydrocarbons (PAHs). Raw gases were sampled in the afterburning chamber, using a specifically designed device, after the heat recovery section and at the stack. Samples of slags from the combustion chamber and fly ashes from the bag filter were also collected and analyzed. PCDD/Fs and PAHs concentrations in exhaust gas after the heat exchanger (200–350 °C) decreased in comparison with the values detected in the afterburning chamber. Pollutant mass balance regarding the heat exchanger did not confirm literature findings about the de novo synthesis of PCDD/Fs in the heat exchange process. In spite of a consistent reduction of PCDD/Fs in the flue gas treatment system (from 77% up to 98%), the limit of 0.1 ng ITEQ Nm⁻³ at the stack was not accomplished. PCDD/Fs emission factors for air spanned from 2.3 up to 44 μg ITEQ t⁻¹ of burned waste, whereas those through solid residues (mainly fly ashes) were in the range 41–3700 μg ITEQ t⁻¹. Tests run with cemetery wastes generally showed lower PCDD/F emission factors than those with hospital wastes. PAH total emission factors (91–414 μg kg⁻¹ of burned waste) were in the range of values reported for incineration of municipal and industrial wastes. In spite of the observed release from the scrubber, carcinogenic PAHs concentrations at the stack (0.018–0.5 μg Nm⁻³) were below the Italian limit of 10 μg Nm⁻³.     

PCB levels and congener patterns from Korean municipal waste incinerator stack emissions

Congener specific polychlorinated biphenyl (PCB) data from the stack gas of nine Korean municipal waste incinerators was used to determine characteristic congener patterns of emitted PCBs. Principal component analysis revealed three classes of incinerators according to their pattern of PCB congener emissions: those resembling the background sampling material; those producing large quantities of a few tetra-chlorinated congeners; those producing large proportions of mono (MO-) and non-ortho (NO-) congeners relative to di-ortho (DO-) levels. Also, correlations between individual PCB congeners and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) were discovered for several NO-PCBs and tetra and penta chlorinated PCDFs. Full PCB congener data is presented along with operating conditions for each incinerator.     

Control of mercury emissions from a municipal solid waste incinerator in Japan

The control of Hg emissions from a municipal solid waste incinerator (MSWI) is very important, because more than 78% of municipal solid waste (MSW) is incinerated. The Hg content of coal used in utility boilers is relatively low in Japan. In this study, recent trends in the Hg content of MSW in Japan and activated carbon (AC) injection as a control technology of Hg emission from an MSWI are discussed. The effect of AC injection on Hg removal from flue gas in an MSWI was investigated by pilot-scale experiments using a bag filter (BF). The injection of AC increases the Hg reduction ratio by 20-30% compared with cases without AC injection. The Hg reduction ratio increases as the flue gas temperature decreases. The Hg reduction ratio is closely related to the inlet Hg concentration and was expressed with a Langmuir-type adsorption isotherm.     

Memory effect on the dioxin emissions from municipal waste incinerator in Taiwan

Evaluation of the dioxin removal efficiency of the air pollution control device (APCD) at an existing municipal waste incinerator (MWI) located in Taiwan is conducted via stack sampling and analysis. The MWI investigated is equipped with cyclones, dry lime scrubbing systems and fabric filters as APCDs. Results indicate that the patterns of dioxin isomers at APCDs' inlet and stack are similar. During the first year of carbon injection, the concentrations of emitted dioxin decreased greatly. The dioxin removal efficiency increased from 26.9% to 96.6% after injecting 115 kg/day activated carbon (AC). At the second year, the dioxin removal efficiency reaches 98.7% after injecting the same rate of AC continuously. The lower efficiency achieved with activated carbon injection (ACI) during the first year can be attributed to the memory effect, i.e. the dioxin or precursor desorbs slowly to the flue gas and increases the dioxin concentration at stack, resulting in a lower dioxin removal efficiency than expected.     

Levels and characteristic homologue patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans in various incinerator emissions and in air collected near an incinerator

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were monitored in stack gas and fly ash of various Korean incinerators and in air samples collected near the facilities. Concentrations of PCDD/Fs in emissions were investigated, and characteristic PCDD/F homologue patterns were classified using statistical analyses. The PCDD/F emission levels in stack gas and fly ash samples from small incinerators (SIs) were higher than those from municipal solid waste incinerators (MSWIs). The PCDD/F concentrations ranged between 0.38 and 1.16 pg I-TEQ/m3 (21.2-75.2 pg/m3) in ambient air samples. The lower-chlorinated furans were the dominant components in most of the stack gas and fly ash samples from SIs, although this was not the case for fly ash from MSWIs. This homologue pattern is consistent with other studies reporting a high fraction of lower-chlorinated furans in most environmental samples affected by incinerator emissions, and it can be used as an indicator to assess the impact of such facilities on the surrounding environment.     

Dioxin emissions after installation of a polishing wet scrubber in a hazardous waste incineration facility

Dioxin levels measured after wet scrubbing systems have been found to be higher than levels measured before the scrubber. It is believed that there is an adsorption of PCDD/Fs on plastic materials in the scrubber. The PCDD/F levels after a polishing wet scrubber were followed continuously for 18 months using long-time sampling equipment at a hazardous waste incineration facility in Sweden. Each sampling period lasted two weeks. It was found that the levels during and shortly after start-up periods were elevated. The decline was very slowly, which supports a memory effect in the scrubber. Further, a multivariate model showed that the relation between different homologues changed over time, which is in agreement with a desorption model, taking into account the vapour pressures for different congeners.     

Prediction of dioxin/furan incinerator emissions using low-molecular-weight volatile products of incomplete combustion

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from incinerators and other stationary combustion sources are of environmental concern because of the toxicity of certain PCDD/F congeners. Measurement of trace levels of PCDDs/Fs in combustor emissions is not a trivial matter. Development of one or more simple, easy-to-measure, reliable indicators of stack PCDD/F concentrations not only would enable incinerator operators to economically optimize system performance with respect to PCDD/F emissions, but could also provide a potential technique for demonstrating compliance status on a more frequent basis. This paper focuses on one approach to empirically estimate PCDD/F emissions using easy-to-measure volatile organic C2 chlorinated alkene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C2 chlorinated alkenes and PCDDs/Fs. Each data set contained one or more C2 chloroalkenes that were able to account for a statistically significant fraction of the variance in PCDD/F emissions. Variations in the vinyl chloride concentrations were able to account for the variations in the PCDD/F concentrations strongly in two of the three data sets and weakly in one of the data sets.     

Tetrachloroethylene emissions and exposure in dry cleaning

Tetrachloroethylene (PCE) emissions and the exposure of workers in six commercial and three industrial dry-cleaning establishments that use dry-to-dry machines were determined. The personal samples and area samples [8-hr time-weighted average (TWA) and short-term exposure] were collected with charcoal tubes and passive monitors. The temporal variation of PCE concentration in the workplace air was monitored using a Fourier transform infrared analyzer (FTIR). The PCE emission rates were determined by multiplying the average PCE concentration in the room and the total airflow rate in the room. The PCE emissions were related to the cleaning rate in units of kg/hr. The operators' mean TWA exposure in commercial shops and industrial establishments was 28 (4.1 ppm) and 32 mg/m3 (4.6 ppm), and the pressers' exposure was 3.4 (0.5 ppm) and 7.7 mg/m3 (1.1 ppm), respectively. The customer service personnel had the lowest TWA exposure with a mean value of 0.8 mg/m3 (0.1 ppm). The highest peak concentration (2300 mg/m3; 334 ppm) was observed during cleaning of the lint and button trap, during which operation respirators were used. The PCE emission rates ranged from 4 to 118 g/hr corresponding to emission factors (mass of solvent evaporated per mass of cleaned cloths) of 0.3-3.6 g/kg. The workers' exposure to PCE was below the occupational limit values in the United States [according to the American Conference of Governmental Industrial Hygienists (ACGIH)] and in Finland. The outdoor PCE emissions were clearly below the limit values given in the European Union volatile organic compound (VOC) directive requirements.     

Cadmium exposure from the cement dust emissions: a field study in a rural residence

The cement dust is one of the causes of pollution in the environment. In the present study, the cadmium concentrations of soil and plant specimens taken from a rural area exposed to cement factory emissions were determined and also the blood concentrations and sensitivity conditions in humans residing in this rural area were investigated. The 108 soil (36 for control) and plant specimens were collected from eight different directions of the cement plant located in Cukurhisar town in Eski?ehir city. Blood samples of the individuals residing in this area were taken from 258 subjects (258 for control) following a physical examination, and patch tests were also applied. The results show that the cadmium concentrations of the soil and plant specimens taken from different places in different directions of the factory were higher than in the control areas. The physical examination of subjects did not reveal results different from those of the control group except for the diagnosis of contact dermatitis. The analysis of venous blood samples showed that cadmium concentrations were found to be within the reference values given for both groups, but higher in the subjects (p<0.001). According to the results of patch tests, sensitivity to cadmium was found to be more frequent for the subject group than the control group (p<0.05). Those results show that, although clinical tools revealed no toxic effects for the subject, except contact dermatitis, the cement plant increases cadmium pollution on the surrounding environment.     

Dioxin analysis in stack emissions, slags and the wash water circuit during high-temperature incineration of chlorine-containing industrial wastes; Part 2

PCB's and polychlorobenzene sumps have been incinerated in a high-temperature installation. The working conditions, wastes, sampling methods and analysis of the stack emissions, slag and wash water are described. No 2,3,7,8-TCDD and only ppt-traces of some PCDD congeners were detected in the stack emission. The performance criteria of the incinerator and the more important sampling procedures are discussed.     

An environmental fate, exposure and risk assessment of ethylene oxide from diffuse emissions

Ethylene oxide (EO) is mainly used as a chemical intermediate and as a fumigant and sterilizing agent. Through its manufacturing and intended uses, EO may be released into the environment. Therefore, an assessment of the environmental significance of those potential emissions was conducted. Data were collected describing pertinent physical properties, degradation and other loss mechanisms that control the fate of EO in the environment. Available aquatic and terrestrial ecotoxicity data were assembled and used as the basis of calculating critical toxicity values to characterize hazard. Environmental compartment concentrations of EO were calculated using Level III fugacity-based modeling. Six scenarios were developed to account for different climatic conditions in various portions of the US. Finally, potential regional-scale risks to aquatic and terrestrial wildlife were determined. In the conceptual model that was developed in this assessment, EO diffuses into air, partitions between environmental compartments, is transported out of the different compartments via advection, and undergoes abiotic and biological degradation within each compartment. All known emissions within the continental USA were assumed to enter a modeled region roughly the size of the State of Ohio. Organisms (receptors) were assumed to dwell in both terrestrial and aquatic compartments. Receptors were assumed to include small mammals, soil invertebrates, water column (pelagic) organisms, and sediment benthos. The goal of this assessment was to characterize any potential adverse risks to terrestrial and aquatic wildlife populations. Hazard Quotients (HQ) were calculated by dividing predicted concentrations of EO in air, water, sediment, and soil by their critical toxicity values. Maximum calculated HQ values in air were 1.52x10(-7), in water were 1.17x10(-5), in sediment were 2.25x10(-4), and in soil were 1.37x10(-5). The results of this assessment suggest that EO as currently manufactured and used does not pose adverse risks to aquatic or terrestrial wildlife. In all cases, the HQ values were much less than the maximum desired HQ value of 1.0 (4,400-6,600,000 times), indicating that the potential for diffuse emissions of EO to pose adverse environmental risks is quite low.     

Dietary exposure to PCDD/PCDFs by individuals living near a hazardous waste incinerator in Catalonia, Spain: temporal trend

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were measured in foodstuffs randomly acquired in July 2006 in various locations of Tarragona County (Catalonia, Spain), which are near a hazardous waste incinerator (HWI). A total of 35 composite samples, belonging to various food groups (vegetables, pulses, cereals, fruits, fish and seafood, meat and meat products, eggs, milk, dairy products, and oils and fats) were analyzed by HRGC/HRMS. The dietary intake of PCDD/PCDFs was subsequently determined and compared with a previous survey performed in 2002. For calculations, recent data on consumption of the selected food items were used. Total dietary intake of PCDD/PCDFs for the general population of Tarragona County was estimated to be 27.81 pg WHO-TEQ/day, value notably lower than that found in the 2002 study, 63.80 pg WHO-TEQ/day. Fish and seafood (28%), oils and fats (22%), eggs (17%), and dairy products (11%) were the most important contributors to this intake, while pulses (1%), milk (2%), vegetables (3%) and fruits (3%) showed the lowest contribution to total WHO-TEQ. The current PCDD/PCDF intake is also considerably lower than the intake estimated in 1998 for the population of the same geographical area, 210.1 pg I-TEQ/day, when a baseline study was carried out during the construction of the HWI. The present intake is also compared with the dietary intakes of PCDD/PCDFs recently (2006-2007) reported for a number of regions and countries.