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1.
PCDD and PCDF were found in urban air particulates from St. Louis and Washington, D.C., and in sediments from the Great Lakes and Siskiwit Lake, Isle Royale. The similarity between the PCDD and PCDF found in air particulates and sediment samples and the presence of PCDD and PCDF in sediment from Siskiwit Lake (a location which can receive only atmospheric inputs) suggest that these compounds are emitted to the atmosphere from combustion sources. The historical input of PCDD and PCDF to dated sediment cores shows a strong increase since 1940, and this suggests that the incineration of chlorinated organic compounds is an important source of PCDD and PCDF to the environment.  相似文献   

2.
On-line detectable indicator parameters in the flue gas of municipal solid waste incinerators (MSWI) such as chlorinated benzenes (PCBz) are well known surrogate compounds for gas-phase PCDD/PCDF concentration. In the here presented work derivation of indicators is broadened to the detection of fly and boiler ash fractions with increased PCDD/PCDF content. Subsequently these fractions could be subject to further treatment such as recirculation in the combustion chamber to destroy their PCDD/PCDF and other organic pollutants' content. Aim of this work was to detect suitable on-line detectable indicator parameters in the gas phase, which are well correlated to PCDD/PCDF concentration in the solid residues. For this, solid residues and gas-phase samples were taken at three MSWI plants in Bavaria. Analysis of the ash content from different plants yielded a broad variation range of PCDD/PCDF concentrations especially after disturbed combustion conditions. Even during normal operation conditions significantly increased PCDD/PCDF concentrations may occur after unanticipated disturbances. Statistical evaluation of gas phase and ash measurements was carried out by means of principal component analysis, uni- and multivariate correlation analysis. Surprisingly, well known indicators for gas-phase PCDD/PCDF concentration such as polychlorinated benzenes and phenols proved to be insufficiently correlated to PCDD/PCDF content of the solid residues. Moreover, no single parameter alone was found appropriate to describe the PCDD/PCDF content of fly and boiler ashes. On the other hand, multivariate fitting of three or four parameters yielded convenient correlation coefficients of at least r=0.8 for every investigated case. Thereby, comprehension of plant operation parameters such as temperatures and air flow alongside concentrations of inorganic compounds in the gas phase (HCl, CO, SO2, NOx) gave the best results. However, the suitable set of parameters suited best for estimation of PCDD/PCDF concentration in solid residues has to be derived anew for each individual plant and type of ash.  相似文献   

3.
Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m3 sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m3) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.  相似文献   

4.
Leclerc D  Duo WL  Vessey M 《Chemosphere》2006,63(4):676-689
This paper discusses the effects of combustion conditions on PCDD/PCDF emissions from pulp and paper power boilers burning salt-laden wood waste. We found no correlation between PCDD/PCDF emissions and carbon monoxide emissions. A good correlation was, however, observed between PCDD/PCDF emissions and the concentration of stack polynuclear aromatic hydrocarbons (PAHs) in the absence of TDF addition. Thus, poor combustion conditions responsible for the formation of products of incomplete combustion (PICs), such as PAHs and PCDD/PCDF precursors, increase PCDD/PCDF emissions. PAH concentrations increased with higher boiler load and/or low oxygen concentrations at the boiler exit, probably because of lower available residence times and insufficient excess air. Our findings are consistent with the current understanding that high ash carbon content generally favours heterogeneous reactions leading to either de novo synthesis of PCDD/PCDFs or their direct formation from precursors. We also found that, in grate-fired boilers, a linear increase in the grate/lower furnace temperature produces an exponential decrease in PCDD/PCDF emissions. Although the extent of this effect appears to be mill-specific, particularly at low temperatures, the results indicate that increasing the combustion temperature may decrease PCDD/PCDF emissions. It must be noted, however, that there are other variables, such as elevated ESP and stack temperatures, a high hog salt content, the presence of large amounts of PICs and a high Cl/S ratio, which contribute to higher PCDD/PCDFs emissions. Therefore, higher combustion temperatures, by themselves, will not necessarily result in low PCDD/PCDFs emissions.  相似文献   

5.
Polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDF) were overall measured and compared in ambient air, water, soils, and sediments along the upper reaches of the Haihe River of North China, so as to evaluate their concentrations, profiles, and to understand the processes of gas–particle partitioning and air–water/soil exchange. The following results were obtained: (1) The average concentrations (toxic equivalents, TEQs) of 2,3,7,8-PCDD/PCDF in air, water, sediment, and soil samples were 4,855 fg/m3, 9.5 pg/L, 99.2 pg/g dry weight (dw), and 56.4 pg/g (203 fg TEQ/m3, 0.46 pg TEQ/L, 2.2 pg TEQ/g dw, and 1.3 pg TEQ/g, respectively), respectively. (2) Although OCDF, 1,2,3,4,6,7,8-HpCDF, OCDD, and 1,2,3,4,6,7,8-HpCDD were the dominant congeners among four environmental sinks, obvious discrepancies of these congener and homologue patterns of PCDD/PCDF were observed still. (3) Significant linear correlations for PCDD/PCDF were observed between the gas–particle partition coefficient (K p) and the subcooled liquid vapor pressure (P L 0) and octanol–air partition coefficient (K oa). (4) Fugacity fraction values of air–water exchange indicated that most of PCDD/PCDF homologues were dominated by net volatilization from water into air. The low-chlorinated PCDD/PCDF (tetra- to hexa-) presented a strong net volatilization from the soil into air, while high-chlorinated PCDD/PCDF (hepta- to octa-) were mainly close to equilibrium for air–soil exchange.  相似文献   

6.
Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in fourteen ambient air samples collected in twelve cities of five provinces and one large municipality in China. The PCDD/F concentrations varied from 2.6 to 120 pg m−3 (or from 0.04 to 1.93 pg I-TEQ m−3). Generally, TCDF was the dominant homologue group and as a rule the homologue concentration of PCDF decreased with rising chlorine substitution number of PCDF. In all cases 2,3,4,7,8-PeCDF was the most important contributor to the I-TEQ value, accounting for 35–57% of the total I-TEQ value. Higher PCDD/F levels in ambient air were found during winter. The highest PCDD/F levels were found in Chengdu, Sichuan Province. In general, the PCDD/F levels in this study were in the same range as in other studies in China.  相似文献   

7.
This report presents results of emission measurements of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) in the flue gas of seven oil, nine gas, and two wood firing systems under laboratory conditions. The burn rate of the combustion was in the range of the rated useful heat output. Two additional test series varied the amount of combustion air and thus the heat output. The PCDD/PCDF emissions for oil- and gas-fired boilers are in the range of 0.0020-0.0142 ng I-TEQ/m3 (referring to 3% O2 in the dry flue gas). No correlation between the combustion technique and the PCDD/PCDF emissions could be established. In the tests with the wood-fired furnaces PCDD/PCDF concentrations in the flue gas ranging from 0.014 to 0.076 ng I-TEQ/m3 (referring to 13% O2 in the dry flue gas) were found. A significant correlation between the firing rate of the heating insert and the measured PCDD/PCDF concentrations was found. On examination of three typical 2,3,7,8-CDD/CDF congener profiles, a comparable pattern could be observed with natural gas and light fuel oil. The congener distribution for wood combustion is considerably different.  相似文献   

8.
PCDD/PCDF were determined in solid samples from wood combustion. The samples included grate ashes, bottom ashes, furnace ashes as well as fly and cyclone ashes. The solid waste samples were classified into bottom and fly ash from native wood and bottom and fly ash from waste wood. For each of the four classes concentration distribution patterns from individual congeners, the sums of PCDD/PCDF and the international toxicity equivalents (I-TEQ) values are given. The I-TEQ levels of fly ash from waste wood burning can be approximately up to two thousand times higher than the values from fly ashes of natural wood. The I-TEQ levels in bottom ashes from waste wood combustion systems are as low as the corresponding ashes from the combustion of native wood. Grate ash samples from waste wood combustion systems with low carbon burnout show high levels of PCDD/PCDF.  相似文献   

9.
In laboratory-scale combustion of polyvinylidene chloride (PVDC) with a quartz tubular furnace designed and fabricated to provide the desired combustion temperature and mixing state of combustion gas with air, it was found that at 800 degrees C or higher the level of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans [corrected] (PCDDs/PCDFs) resulting from PVDC combustion was no higher than that from heating air alone, and thus far below the levels which resulted from PVDC combustion at 750 degrees C or lower. The results provide the first laboratory confirmation of the relation between PVDC incineration temperature and PCDD/PCDF formation, and of the primary importance of high temperature, turbulence for mixing between air and combustion gas, and sufficient residence time, as governing factors for the minimization of PCDD/PCDF formation in municipal solid waste incinerators.  相似文献   

10.
H.Y. Tong  F.W. Karasek 《Chemosphere》1986,15(9-12):1219-1224
Flyash samples were collected from the electrostatic precipitators of seven municipal refuse incinerators of four different countries. Analytical results of PCDD and PCDF in these samples shows a very similar iosmer distribution pattern for all PCDD/PCDF although concentrations of PCDD and PCDF vary. These results imply that PCDD/PCDF were formed through the same mechanism in those incinerators regardless of garbage composition or incinerator design.  相似文献   

11.
Ogura I  Masunaga S  Nakanishi J 《Chemosphere》2001,44(6):1473-1487
The atmospheric bulk (dry and wet) deposition of dioxins was investigated at four locations (Tokyo, Yokohama, Tsukuba, and Tanzawa) in the Kanto region (in Japan) over one year using a stainless-steel pot. Annual average polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/PCDF) deposition fluxes were estimated to be from 450 to 1300 ng/m2/yr, and the annual average TEQ fluxes from 5.7 to 17 ng-TEQ/m2/yr at the four locations. The PCDD/PCDF deposition flux was higher in winter than in summer. The deposition flux could be related to ambient temperature, particularly for less chlorinated PCDDs/PCDFs, while the deposition flux is not necessarily related to the amount of precipitation. The PCDD/PCDF deposition flux increased as the particle deposition flux increased, for the winter samples. Based on the ratio of the PCDD/PCDF deposition fluxes to the particle deposition fluxes, the contribution of the reentrainment of soil particles to the TEQ of PCDD/PCDF deposition was considered to be negligible in this region. Based on the air concentrations monitored near our deposition sampling points by the municipalities, the ratio of the annual deposition flux to the annual average air concentration was roughly estimated to be 0.082 cm/s. The range of deposition flux in the Kanto region was estimated to be from 1.5 to 31 (median: 9.8) ng-TEQ/m2/yr based on the range of air concentration data measured by the municipalities. The total annual deposition flux in the entire Kanto region was estimated to range from 50 to 900 g-TEQ/yr (median 320 g-TEQ/yr). This estimated flux was of the same order as the sum of estimated emissions from municipal solid waste incinerators and industrial waste incinerators in the Kanto region. The contributions of dioxin-like PCBs in Yokohama, Tsukuba, and Tanzawa depositions were less than 10% of the total TEQ; however, in Tokyo it was almost equal to or more than 50%.  相似文献   

12.
Ryu JY  Choi KC  Mulholland JA 《Chemosphere》2006,65(9):1526-1536
Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.  相似文献   

13.
In Germany, there is a lack of consistent and comparable data for the time dependent behaviour and spatial distribution of dioxin-like and indicator PCB in ambient air, deposition and plants. The aim of this study was to improve the data on PCDD/PCDF, dioxin-like PCB and non dioxin-like PCB in spruce and pine shoots from different locations and years by retrospective monitoring. The survey was conducted with archived samples of one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) from the German environmental specimen bank. Two sets of samples from locations in urbanized areas in western and eastern Germany (Warndt and Duebener Heide Mitte, respectively) were investigated as time series. Additionally, spruce shoots from seven different rural locations sampled in the years 2000-2004 were analyzed in order to get an overview about the spatial distribution of PCB and PCDD/PCDF. The analytical results of the samples from the two urbanized areas clearly show that the atmospheric contamination with PCDD and PCDF has declined by about 75% between 1985 and 1997 at Warndt and about 40% between 1991 and 1997 at Duebener Heide. However, concentrations stayed virtually constant at both locations from 1997 to 2004 at a level of about 1 ng WHO-TEQ/kg dry matter (d.m.). Similarly, the investigation of spruce shoots from rural locations from 2000 to 2004 did not reveal a temporal trend at any site. PCDD/PCDF levels were between 0.1 and 1.0 ng WHO-TEQ/kg d.m. At the urbanized location Warndt the six indicator PCB as well as the 12 dioxin-like PCB according to WHO revealed a significant decline by more than 75% between 1985 and 1999. Thereafter, PCB levels stayed virtually constant. At the location Duebener Heide an overall decrease of PCB concentrations in pine shoots of about 60% was detected between 1991 and 2004. Spruce shoots from all locations showed a relevant contribution of dioxin-like PCB to the total WHO toxicity equivalent (PCDD/PCDF+PCB). In most samples, the contribution of dioxin-like PCB was between 21% and 41%. The TEQ contribution of PCB in the samples from three rural sites was higher and similar to the TEQ value of PCDD/PCDF. The investigated pine shoots from the urbanized site Duebener Heide showed a 15-28% contribution of dioxin-like PCB to total TEQ and thus lower than in spruce shoots from different locations. In all samples except one PCB 126 contributed to more than 80% to the PCB-TEQ.  相似文献   

14.
Paddy soils and sediments from the Yoneshirogawa, Omonogawa, and Koyoshigawa River Basins in Akita were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The levels and compositions in those samples including soils from non-agricultural areas (non-agricultural soils) were investigated using isomer-specific analysis to determine characteristic sources. The PCDD/PCDF compositions in the samples were compared with respect to possible sources. The PCDD/PCDF concentrations in paddy soils were much higher than those in the non-agricultural soils and much higher than those found in other parts of Japan. Although PCDD/PCDFs were ubiquitous in sediments from river sources to mouths of the respective river basins, those concentrations were much lower than those from paddy soils and non-agricultural soils, and from other parts of Japan. Comparison of PCDD/PCDF homologues and isomer compositions for samples indicated that compositions of paddy soils and sediments, except for those from river sources, had similar characteristics to PCDD/PCDFs originating from impurities in herbicides, 2,4,6-trichlorophenyl 4-nitrophenyl ether (CNP) and pentachlorophenol (PCP), and that compositions of river-source sediments and non-agricultural soils resembled those of atmospheric depositions. Results of statistical analyses suggest that PCDD/PCDF contamination of paddy soils and sediments is attributable mainly to three sources: CNP, PCP, and atmospheric deposition. Results of this study also demonstrate that CNP and PCP are not only important contaminants of local areas of Japan, but that they exist throughout Akita, in northern Japan. We therefore conclude that PCDD/PCDF pollution caused by those compounds has a widespread influence on paddy soils and river sediments in Japan.  相似文献   

15.
Weber R  Sakurai T  Ueno S  Nishino J 《Chemosphere》2002,49(2):127-134
The correlation of PCDD/PCDF levels with the CO emissions in a full-scale municipal waste incinerator was assessed during a four-week measurement effort. PCDD/PCDF concentrations in fly ashes-containing more than 99% of the total PCDD/PCDF burden of the fluidized bed incinerator (FBI)-were measured and compared with the emitted CO concentrations. The CO concentration during the sampling time showed no significant correlation to the PCDD/ PCDF amount in fly ash (R2 = 0.078). However, a comparison of the time integrated CO concentration several hours before sampling lead to a correlation with the PCDD/PCDF burden. Maximum correlation was found for the time integrated CO values of 3 and 4 h before sampling (R2 = 0.467 and R2 = 0.457 respectively). This indicates a memory effect in the high temperature cooling section of several hours. Possible mechanisms leading to the memory effect are discussed. The correlation of PCDD/PCDF with CO concentration demonstrate that the combustion conditions play an important role for PCDD/PCDF formation in FBIs. However the variability in the correlation of CO to PCDD/PCDF levels show that other factors have a significant influence on PCDD/PCDF formation.  相似文献   

16.
Abad E  Caixach J  Rivera J 《Chemosphere》1999,38(1):109-120
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.  相似文献   

17.
The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing–Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing–Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R?=?0.474, P?<?0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.  相似文献   

18.
Polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were found in annually laminated sediments from Lakes Zurich, Baldegg, and Lugano in Switzerland. Octachlorodibenzo-p-diox in (OCDD) predominated, averaging approximately 1.3 ppb. The congener distribution indicated that combustion was the source of PCDD and PCDF in these sediments. In these dated sediment cores, we found that PCDD and PCDF were absent from the sediments before about 1945, but increased thereafter.  相似文献   

19.
Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and non-ortho substituted biphenyls (PCB, CB) were determined in 6 polar bear milk samples from Svalbard (Norway). For these compounds, no data for polar bears have been reported before from this region. Most of the PCDD/PCDF congeners were found at detectable levels. Concentrations expressed as 2,3,7,8-TCDD equivalents (Nordic model) were in the order of 1–3 pg/g−1 fat (0.2–1.6 pg ml−1 milk) which is comparable with ringed and harp seal blubber from the same region. On whole milk basis, concentrations were similar to those found in human milk. An estimation of the daily uptake via milk showed that the intake is lower for polar bears compared to humans. As in human milk, relatively high levels of OCDD were found in some polar bear milk samples. The PCDD/PCDF congener pattern in the milk was different to that found in polar bear fat from the Canadian Arctic. Non-ortho substituted PCB levels in polar bear milk were similar to those found in polar bear fat from the Canadian North. However, CB 77 or 169 dominated in the milk while CB 126 was the most abundant congener in fat. PCDD/PCDF levels expressed as 2,3,7,8-TE were highly correlated with the fat content of the milk. No correlation between CB and PCDD/PCDF concentrations was found. Some data indicate that PCDD/PCDF concentrations in polar bear milk decrease with increasing time after delivery.  相似文献   

20.
Experimental data on PCDD and PCDF emissions in raw gases from municipal solid waste combustion in a pilot plant were processed by Response Surface models to gain information on process parameter values which minimize both the total PCDD/PCDF concentrations and those of a selected congener group.  相似文献   

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