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1.
ABSTRACT

Emissions of polychlorinated dibenzo-p-dioxins and poly-chlorinated 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 alk-ene precursors coupled with flue gas cleaning parameters. Three data sets from pilot-scale incineration experiments were examined for correlations between C2 chlorinated alk-enes 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.  相似文献   

2.
This study shows the catalyzing effects of iron and copper on the formation of chlorinated compounds such as chlorobenzenes (ClBzs), chlorophenols (CIPhs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Both total concentrations and congener distributions have been studied. The parameters and conditions varied during the combustion tests were the complete and incomplete combustion and the metal and chlorine addition. The incomplete combustion promoted the formation of organic chlorinated compounds in flue gas particles. Highly chlorinated congeners of PCDD/F were dominant in the flue gas particles, whereas the importance of lower chlorinated congener were increased in the gas phase. In the complete combustion conditions the concentrations of PCDD/Fs increased when the degree of chlorination were high, nevertheless the concentrations of tetra and penta PCDD/Fs were higher in the gas phase than the concentrations in the fly ash particles. Organic chlorine promoted the formation of chlorinated compounds more effectively than inorganic chlorine, which instead promoted the formation of PCDD/Fs in the gas phase, especially with copper catalyst. Different concentration levels of chlorinated compounds were observed in the gas phase and in particles when the chlorine source and combustion conditions were varied from incomplete to optimum conditions. Both copper and iron seem to have a catalytic effect on PCDD/F formation.  相似文献   

3.
Particle-bound polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) were monitored at two sites in northern Greece for an eight-month period in 1999. PCDD/F concentrations were close to the lower end of reported values worldwide. Excepting a few cases, the PCDD/Fs homologue profile was stable. The gaseous PCDD/F fractions calculated were found to account for a small percentage of the total concentrations (<2% for OCDD/Fs and HpCDD/Fs, while 30-35% for TCDFs). Particle-bound PCBs were also found at low concentrations which, however, were higher at the urban site. Calculations of the dry deposition of particulate PCDD/ Fs and PCBs gave mean values of 0.52 and 0.59 pg I-TEQ/m2/day of PCDD/Fs, while 242 and 74 pg/m2/day of sigmaPCBs for the urban and the semirural areas respectively. An anticorrelation of PCDD/F concentrations with ambient temperature was derived particularly for the lower chlorinated congeners. A weak association with winds of western and southern origin was also observed. Factor analysis and literature source profiles were employed to identify possible emission sources. It was appeared that the PCDD/F compositional pattern of TSP is influenced by mixed sources the most prominent being uncontrolled fires and car exhausts.  相似文献   

4.
The stack gases of a municipal solid waste incinerator (MSWI), and ambient air were sampled in four locations around the plant for the analysis of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs). The sampling area was close to an industrial area near Trieste, in north-east Italy. The purpose of the study was to estimate the impact of the MSWI emissions and to distinguish the contribution of these emissions from other potential emission sources in the industrial area.PCDD/F atmospheric concentrations were similar to those generally detected in urban–rural areas with one location about 2–3 times more contaminated than the others. Since the most contaminated location was inside the industrial area but upwind of the MSWI, principal component analysis (PCA) was used to establish whether other sources were the cause. This analysis clearly showed that a local steel plant’s emission was the main source of PCDDs/Fs in ambient air. This study highlights the usefulness of multivariate data analysis such as PCA to identify, among different potential emission sources, the one really responsible for the contamination.  相似文献   

5.
There is no previous report from Turkey on chemically determined polychlorinated dibenzo-para-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) in human tissues expressed as World Health Organization (WHO) toxic equivalents (TEQs). The objective of this study was to determine the occurrence of PCDDs/Fs, and dioxin-like PCBs in the general adult Turkish population. For this reason we measured adipose tissue concentrations of PCDDs/Fs and dioxin-like PCBs in 23 Turkish men living in Ankara,Turkey in 2004. PCDD/F concentrations ranged between 3.2 and 19.7 pg WHO-TEQ/g fat (5.34 and 42.7 WHO-TEQ/g fat, respectively, including dioxin-like PCBs). The mean concentrations of WHO(PCDD/F)-TEQ and WHO(PCB)-TEQ were 9.2 and 6.67 pg/g on a lipid basis , respectively. Samples were analyzed for PCDD/F and twelve dioxin-like PCB congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). This study is very important since it is the first report on PCDDs/Fs and dioxin-like PCB contamination in human adipose tissue from Turkey.  相似文献   

6.
Recently, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in soil and herbage samples collected in the vicinity of a municipal solid waste incinerator (MSWI) from Tarragona (Catalonia, Spain). Since these concentrations could be increased by the presence of other emission sources of PCDD/Fs in the same area in which the MSWI is placed, the main goal of the present study was to determine the PCDD/F congener profiles in the soil and vegetation samples collected in 1996 and again in 1997 near to the facility and to compare with those from samples collected in a close area outside of direct emissions of the plant. From an accurate inspection of the PCDD/F congener profiles, it was concluded that PCDD/F emissions from the MSWI here examined are neither the only nor the main responsible for the presence of PCDD/Fs in the samples of environmental matrices collected in the area under direct influence of the plant.  相似文献   

7.
Emission of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) by municipal solid waste incinerators (MSWI) is an issue of great concern. In 1997, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an MSWI from Tarragona (Catalonia, Spain). As a result, PCDD/F emissions were significantly reduced. The aim of this study was to determine the current levels of PCDD/Fs in soil and vegetation samples collected near the facility and to compare these levels with those obtained in previous surveys (1996 and 1997). In the period 1997-1999, PCDD/F concentrations in vegetation samples were significantly decreased (60%). By contrast, the levels of PCDD/Fs in soil samples increased slightly (14%, P > 0.05) during the same period. An exhaustive analysis of the present data indicates that other emission sources of PCDD/Fs have also a notable environmental impact on the area under direct influence of the MSWI.  相似文献   

8.
Sawmill workers in British Columbia (B.C.), Canada, have been exposed to chlorophenate fungicides which are known to be contaminated with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Due to concern about the potential of these workers to have significant body burdens of PCDD/Fs, and the absence of measurements in these worker, a single-compartment pharmacokinetic model was developed to estimate the concentration of PCDD/Fs in the fat tissue of the sawmill workers. Data from a large cohort of B.C. sawmill workers and literature-based data on chlorophenate exposures and PCDD/F concentrations in chlorophenates were used in Monte Carlo simulations to predict a PCDD/F body burden distribution. The median concentrations of HxCDF and HpCDF predicted using the model for the B.C. sawmill worker population exceeded the range measured in unexposed populations. PeCDF and OCDF concentrations exceeded the range measured in unexposed populations at the 70th percentile of the model-predicted distribution, and PeCDD at the 90th percentile. The primary limitation of the model was the scarcity of input data about actual dermal and inhalation exposures to chlorophenates.  相似文献   

9.
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.  相似文献   

10.
The atmospheric fate of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was simulated for the year 2000 in North America using a SMOKE/CMAQ-based chemical transport model that was modified for this purpose. The 1999 USEPA emission inventories of PCDD/Fs and criteria pollutants were used. The 1995 Canadian emission inventory of criteria pollutants and the 1995 Canadian area source emissions for PCDD/Fs were used with the 2000 Canadian point source emissions. Modifications to CMAQ involved coupling it with dual organic matter (OM) absorption and black carbon (BC) adsorption models to calculate PCDD/F gas–particle partitioning. The model satisfactorily reproduced the particle bound fractions at all rural sites for which there were measured data and across the whole domain, the modeled vs. measured differences in particle bound fractions were less than 20% for nearly all congeners. The model predicted ambient air PCDD/F concentrations were also consistent with measurements. Simulated deposition fluxes were within 58% of direct measurements. PCDD/F atmospheric depositions to each of the Great Lakes were estimated for the year 2000. The results indicate that approximately 76% of the total deposition of PCDD/Fs to the Great Lakes (in W-TEQ, or toxic equivalent units as defined by the World Health Organization) is attributed to PCDD/Fs absorbed into OM in aerosol. For all of the lakes, more than 92% of all deposition is particle phase wet deposition and only 5–8% is particle phase dry deposition. Wet deposition from the gas phase is negligible. Of the 17 toxic PCDD/F congeners, the Cl4–5DD/F compounds contribute approximately 70% to the total atmospheric deposition to the Great Lakes. The seasonal changes in the PCDD/F deposition flux track variations in ambient temperature.  相似文献   

11.
Despite their environmental importance, there are still relatively few historical studies of the environmental occurrence of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), especially in middle Europe. Trends in PCBs and PCDD/Fs were, therefore, assessed in lake sediments of the Grosser Arbersee over the past 130 years (1860-1990). Ballschmiter-PCB concentrations (congeners # 28, 52, 101, 138, 153, 180) increased between 1946 and 1972 from 4.2 to 32.0 microg kg(-1) dry wt, but have since decreased to 25.6 microg kg(-1) dry wt. High chlorinated PCB congeners reached their maxima earlier (1968-1972) than low chlorinated congeners (1985-1991). These trends were consistent with patterns expected from the production and use of PCBs and their precursors. PCDD/F concentrations increased between 1950 from 0.6 microg kg(-1) dry wt to 2.3 microg kg(-1) dry wt in 1977, falling to 1.7 microg kg(-1) dry wt by 1993. PCDF concentrations exceeded those of PCDD until 1968, but afterwards PCDDs (especially OCDD) were predominant. These patterns suggest that domestic heating and waste combustion were the most likely sources, but pollution from local industries, such as metal smelting and glass production, might also have been involved. The data provide a valuable case study from central Europe which confirms the overall declining trends of PCB and PCDD/F contamination shown elsewhere.  相似文献   

12.
《Chemosphere》2012,86(11):1719-1724
Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) were analyzed in samples of the emissions from a secondary aluminum smelter (ALS) and soil samples around the plant. The purpose was to estimate the impact of the emissions on the surrounding environment.PCDD/F soil concentrations were higher in the proximity of the plant, exceeding the limit adopted in Italy in soils for green areas and residential uses and the upper limit of several reference concentrations. The most contaminated sites were less than 500 m from the plant and the dioxin concentration with the distance from the ALS.Principal component analysis (PCA) showed that emissions from the ALS were the source of PCDD/F contamination in the soils closest to the plant. Multivariate data analyses such as PCA are therefore useful to identify sources of emission causing contamination.  相似文献   

13.
Kim KS  Hong KH  Ko YH  Yoon KD  Kim MG 《Chemosphere》2003,53(6):601-607
Emission characteristics of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in diesel engine were studied with variable load rate of the diesel engine with the emission test cycles, US D-13 mode. The load rate is changed from 25% to 50% and 75% at constant speed of 2400 rpm. PCDD/Fs concentration and phase distribution of PCDD/Fs with the isokinetic sampling of exhaust gas is obtained in this study. The average PCDD/Fs concentrations per unit of exhaust gas with 25%, 50% and 75% load rate are 14.5, 6.9 and 6.4 pg-TEQ/N m3, respectively. In all diesel engine runs, PCDFs are more prevalent than PCDDs. As a load rate is increased, the ratio of PCDDs is gradually decreased. The amount of high-chlorinated PCDDs emitted in diesel engine is larger than that of low-chlorinated PCDDs. The significant emission form of PCDD/Fs produced from diesel engines exhaust is a gas phase.  相似文献   

14.
Ryu JY 《Chemosphere》2008,71(6):1100-1109
Formation of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and chlorinated phenols on CuCl(2) from unsubstituted phenol and three monochlorophenols was studied in a flow reactor over a temperature range of 100-425 degrees C. Heated nitrogen gas streams containing 8.0% oxygen were used as carrier gas. The 0.00024mol of unsubstituted phenol and 0.00039mol of each monochlorophenol were passed through a 1g and 1cm SiO(2) particle containing 0.5% (Cu by mass) CuCl(2). Chlorination preferentially occurred on ortho-(2, 6) and para-(4) positions. Chlorination increased up to 200 degrees C, and thereafter decreased as temperature increased. Chlorination of phenols plays an important role in the formation of the more chlorinated PCDD/Fs. Chlorinated benzenes are formed possibly from both chlorination of benzene and chlorodehydroxylation of phenols. Chlorinated phenols with ortho chlorine formed PCDD products, and major PCDD products were produced via loss of one chlorine. For PCDF formation, at least one unchlorinated ortho carbon was required.  相似文献   

15.
Liu W  Zheng M  Wang D  Xing Y  Zhao X  Ma X  Qian Y 《Chemosphere》2004,57(10):1317-1323
The occurrence and distribution of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in a typical process of production of 1,4-dichlorobenzene (p-DCB) were investigated systematically in this study. P5CDFs and H6CDFs were the main congeners of PCDD/Fs, while only low levels of other PCDD/Fs were detected in the samples. The concentrations of PCBs were up to 4614 ng/g in the semi-manufactured products, and 1797 ng/g in the product p-DCB. It was also found that high chlorinated PCB congeners increased with the further chlorination. The levels of PCDD/Fs decreased obviously in the purification process, while PCBs could not be removed effectively. Polychlorophenols and other important dioxin precursors (1,4-dichloro-2-phenoxybenzene and 2-phenyl-2',5,5'-trichlorophenol) were also analyzed. Polychlorophenols which ortho- and para-positions of the hydroxyl were substituted by chlorine were the main congeners. In addition, a possible pathway of the formation of PCDD/Fs and PCBs in the production of p-DCB was presented. The results of this article suggest that re-estimation on the risk of using p-DCB products, especially the products for daily use such as mothballs, is expected.  相似文献   

16.
The contaminated air with burning plastic floor and electronic scrap was monitored with semipermeable membrane devices (SPMDs) and fresh unpolluted spruce needles at the same time for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). It was found that there were more polychlorinated dibenzofurans (PCDFs) than polychlorinated dibenzo-p-dioxins (PCDDs) collected from contaminated air. The total amounts of PCBs were much higher than that of PCDD/Fs, but the contribution of them to the WHO-TEQ was less than that of PCDD/Fs. Triolein-containing SPMDs can absorb much more PCDD/Fs and PCBs than spruce needles when they were exposed in contaminated air simultaneously. The logarithm of the concentrations of PCDD/Fs and PCBs in SPMDs and in spruce needles at the same sampling time exhibited a significant linear correlation, the correlation coefficients were larger than 0.86 for PCDD/Fs and 0.92 for PCBs. SPMDs and spruce needles are effective passive air sampler for PCDD/Fs and PCBs. SPMDs and spruce needles can complement each other in passive air sampling.  相似文献   

17.
This study investigates the emissions of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) from four electric arc furnaces (EAFs) and eight secondary aluminum smelters (secondary ALSs) in Taiwan. The mean PCDD/F International-Toxicity Equivalents (I-TEQ) concentrations in the stack gases of these EAFs and secondary ALSs are 0.28 ng I-TEQ/Nm3 (relative standard deviation [RSD]= 100%) and 3.3 ng I-TEQ/Nm3 (RSD = 260%), respectively. The high RSDs, especially for those obtained from secondary ALSs, could be caused by the intrinsic differences in their involved feeding materials, furnace operating conditions, and air pollution control devices. The mean I-TEQ emission factor of PCDD/Fs for EAFs (1.8 microg I-TEQ/tonne-feedstock) is lower than that for secondary ALSs (37 microg I-TEQ/tonne-feedstock). This result might be because the involved furnace temperatures for secondary ALSs (650-750 degrees C) are lower than those for EAFs (1600-1700 degrees C), resulting in the deterioration of the combustion condition, leading to the formation of PCDD/Fs during the industrial process. This study found that the total PCDD/F emissions from EAFs (20 g I-TEQ/yr) and secondary ALSs (18 g I-TEQ/yr) are approximately 27, 53, and approximately 24, 49 times higher than those from municipal solid waste incinerators (MSWIs; 0.74 g I-TEQ/yr) and medical waste incinerators (MWIs; 0.37 g I-TEQ/yr), respectively; while those are 44 and 40% of total PCDD/F emission from sinter plants (45 g I-TEQ/ yr), respectively. Considering a more stringent emission limit has been applied to waste incinerators (0.1 ng I-TEQ/Nm3) in Taiwan lately, the results suggest that the control of the emissions from metallurgical processes has become the most important issue for reducing the total PCDD/F emission from industrial sectors to the ambient environment.  相似文献   

18.
Nine samples of butter from producers in various states of Australia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). Detectable concentrations of 2,3,7,8-chlorine substituted PCDD/Fs were found in all samples. The mean PCDD/F concentration expressed as 2,3,7,8-TCDD equivalents (TEQs) was 0.19 pg TEQ g-1 fat. The highest concentration (0.46 pg TEQ g-1 fat) was observable in a sample from Victoria which is the most densely populated state. Overall the results indicate that PCDD/F concentrations in dairy products from Australia are low in comparison to the levels in dairy products of industrialized countries on the Northern Hemisphere. As expected, this study provides evidence that the environmental and consequently the human body burden of PCDD/Fs to be relatively low in Australia.  相似文献   

19.
A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.  相似文献   

20.
A study was conducted to observe the changes in polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) levels and congener profiles in the flue gas of a hazardous waste incinerator during two start-up periods. Flue gas samplings were performed simultaneously through Air Pollution Control Devices (APCDs) (including boiler outlet, electrostatic precipitator (ESP) outlet, wet scrubbers (WS) outlet, and activated carbon (AC) filter outlet) in different combustion temperatures during a planned cold (long) start-up and an unplanned warm (short) start-up. The results showed that PCDD/F concentrations could be elevated during the start-up periods up to levels 3–4 times higher than those observed in the normal operation. Especially lower combustion temperatures in the short start-ups may cause high PCDD/F concentrations in the raw flue gas. Assessment of combustion temperatures and Furans/Dioxins values indicated that surface-catalyzed de novo synthesis was the dominant pathway in the formation of PCDD/Fs in the combustion units. PCDD/F removal efficiencies of Air Pollution Control Devices suggested that formation by de novo synthesis existed in ESP also when in operation, leading to increase of gaseous phase PCDD/Fs in ESP. Particle-bound PCDD/Fs were removed mainly by ESP and WS, while gaseous phase PCDD/Fs were removed by WS, and more efficiently by AC filter.

Implications: This paper evaluates PCDD/F emissions and removal performances of APCDs (ESP, wet scrubbers, and activated carbon) during two start-up periods in an incinerator. The main implications are the following: (1) start-up periods increase PCDD/F emissions up to 2–3 times in the incinerator; (2) low combustion temperatures in start-ups cause high PCDD/F emissions in raw gas; (3) formation of PCDD/Fs by de novo synthesis occurs in ESP; (4) AC is efficient in removing gaseous PCDD/Fs, but may increase particle-bound ones; and (5) scrubbers remove both gaseous and particle-bound PCDD/Fs efficiently.  相似文献   

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