Evaluation of PCDD/Fs patterns emitted from incinerator via direct ambient sampling and indirect serum levels assessment of Taiwanese

The aim of this study was to evaluate the PCDD/Fs patterns in ambient air based on data information emitted from incinerator generated from ambient air measurements and those in serum. Four circular zones, namely A, B, C, and D, were identified based on simulated ambient annual average PCDD/Fs concentrations, from a selected municipal waste incinerator. Sixteen ambient samples were taken from the 4 circular zones across 4-seasons. Eighty-nine volunteers were recruited according to the demographic distribution within each zone. PCDD/Fs profiles were documented both for air and serum samples collected. Comparing to the congener patterns from ambient air and serum samples, we found that OCDD, OCDF, 1,2,3,4,6,7,8-HpCDD, and 1,2,3,4,6,7,8-HpCDF were the predominant groups among 17 congeners from both the ambient air and serum sample. And, factor analysis showed the distribution patterns of PCDD/Fs from ambient air and serum samples are almost identical across different zones, except for congener patterns of serum samples from residents in zone C. In addition, the average PCDD/Fs level significantly reduced for about 10 folds than those of the other three seasons when the incinerator was shut down in one of sampling periods. We might conclude that ambient air exposure was the most important contributor to PCDD/Fs levels in ambient air but not the single in serum. Therefore, another or more powerful source, such as occupational exposure, dietary intake or the consumption of local food, should be further investigated at the same time.     

Depletion of selected polychlorinated biphenyl, dibenzodioxin, and dibenzofuran congeners in farmed rainbow trout (Oncorhynchus mykiss): a hint for safer fish farming

Farmed fish can be exposed to persistent organic contaminants--such as polychlorinated biphenyls (PCBs), dibenzodioxins (PCDDs), and dibenzofurans (PCDFs)--via feed, this eventually resulting in accumulation levels of health concern. To study the correlation between feed contamination, chemical accumulation in fish muscle (fillet), and chemical depletion, an all-vegetal base (or blank) feed was prepared and fortified with a commercial PCB mixture (Aroclor 1254) and six PCDD and PCDF congeners (namely, 2,3,7,8-T(4)CDD, 2,3,7,8-T(4)CDF, 1,2,3,7,8-P(5)CDD, 1,2,3,7,8-P(5)CDF, O(8)CDD, and O(8)CDF) to reproduce realistic low, medium, and high contamination levels. After a 1-month exposure, trout (Oncorhynchus mykiss) were fed with the blank feed and sacrificed every 0.5 months over a 3-month period from exposure end; fillet specimens were sampled at each time. In all groups, the average fish weight increased linearly through the observation period. The chemical diminishing patterns observed were due to the combined effect of clearance and growth dilution: for 10 PCB and four PCDD and PCDF congeners, patterns were described with an empirical one-compartment (fish muscle) model. The canonical pseudo-first-order kinetic equation used was also modified into the form C=[C(0)exp(-k(C)t)] (m(W)t+1)(-1) to distinguish between the contributions to depletion from clearance, exp(-k(C)t), and growth dilution, (m(W)t+1)(-1). Most mean clearance half-life (HL(C)) estimates appear to be greater than 4 months, in a number of cases reaching magnitudes well over 10 months or even negative, thus clearly indicating a non-negligible contribution from a second compartment. Based on means and their 95% confidence intervals, the depletion HL(D) estimates of the 14 selected congeners seem to be comprised between 1.2-3.4 and 1.0-5.0 months, respectively: these values, accounting for both clearance and growth dilution, provide an indication of the relevance of a blank feed as a management option to reduce the overall PCB, PCDD, and PCDF content in farmed trout. Due to a lack of bioaccumulation, O(8)CDD and O(8)CDF yielded no results for evaluation, whereas for many PCB congeners results were insufficient for empirical modelling.     

Levels of PCDD/FS in ambient air and soil in the vicinity of a municipal solid waste incinerator in Hsinchu

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in twenty-one ambient air samples, eight soil samples and two stack gas samples, collected near or in a municipal solid waste incinerator (MSWI) in Hsinchu, Taiwan. A systematic decrease of PCDD/Fs in the ambient air from the northeastern area was observed. PCDD/Fs levels measured in the ambient air range from 0.058 to 0.127 pg-TEQ/m3. Higher PCDD/Fs levels in the ambient air were found during winter. In addition, PCDD/Fs levels measured in the soil range from 0.524 to 5.02 pg-TEQ/g d.m. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) did not provide sufficient evidence that the environmental PCDD/Fs contamination was caused by emissions from the Hsinchu MSWI. An unknown PCDD/Fs source was proposed using congener profile analysis and supported by both PCA and HCA.     

Congener profiles of PCBs and PCDD/Fs in Yucheng victims fifteen years after exposure to toxic rice-bran oils and their implications for epidemiologic studies

In 1978-1979, a mass poisoning occurred in central Taiwan from rice-bran oil contaminated by heat-degraded PCBs was later called the Yucheng (oil disease in Chinese). Only a few studies have so far investigated the levels of specific polychlorinated biphenyl (PCB) or polychlorinated dibenzodioxin/furan (PCDD/F) congeners in the Yucheng victims. This study aimed to investigate the serum residual levels of thirty-three PCBs and seventeen 2,3,7,8-substituted PCDD/F congeners in the Yucheng victims 15 years after the exposure. Forty-one blood samples were collected from individual Yucheng victims in 1994-1995. The mean levels of total 33 PCBs and 17 PCDD/Fs were 2468 ng/g lipid (13.3 ng/g sample) and 6550 pg/g lipid (30.9 pg/g sample) respectively. The higher levels were found in PCBs #99, #138, #153, #156, #170, #179, and #180 among 33 PCB congeners, while 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, and OCDD had the higher concentrations among 17 PCDD/F congeners. The total TEQ was contributed in decreasing order by 10 PCDFs (44%), three non-ortho-PCBs (24%), six mono-ortho-PCBs (20%), and seven PCDDs (12%). The mean total PCB levels and TEQ value of the 17 PCDD/Fs in the Yucheng victims 15 years after the toxic exposure were still 9 and 46 times higher than those in the general population in Taiwan. Principle component analysis (PCA) indicated that seven PCB congeners, PCBs #99, #138, #153, #156, #170, #179, and #180, accounted for 73% of the total variances in PCBs. On the other hand, six PCDD/F congeners, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDF, and OCDD, accounted for 97% of the total variances in PCDD/Fs. In addition, PCA revealed that at least three characteristic patterns of congener profiles for PCBs were observed among the Yucheng victims. Similar trend was also observed for PCDD/Fs. These patterns may reflect distinctive exposure scenarios and/or different metabolizing capabilities among the Yucheng victims. We suggest that these patterns, in contrast to total PCB and PCDD/F levels, may be valuable for the future epidemiologic studies when linking exposure with specific health effect.     

Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride and other polymers in the presence of HCl

PVDC and three non-chlorinated polymers (PP, PET, and PA) were incinerated at 700-850 degrees C in a laboratory-scale quartz tubular furnace in the presence of HCl (ca. 500 ppm congruent with 0.8 mg/l), and the gas-phase formation of PCDD/Fs, their putative precursors and their homologue profiles were investigated. The addition of HCl had little or no apparent effect on the level of PCDD/Fs formation during PVDC combustion, and their homologue profiles were quite different from those of the three non-chlorinated polymers. With PVDC, O8CDD and particularly O8CDF were by far most prevalent, apparently as a result of the selective formation of the precursors. With each of the three non-chlorinated polymers, combustion at 800 degrees C or higher in the presence of HCl resulted in PCDD/Fs formation at levels equaling or exceeding those observed with PVDC. In trials made with one of them (PP) under the same conditions but using a large polymer sample (100 mg vs 20 mg in all other trials), the level of PCDD/Fs formation was far higher than with the smaller polymer samples, and thus demonstrated the importance of appropriate combustion conditions for polymer incineration.     

PCDD/Fs levels in indoor environments and blood of workers of three municipal waste incinerators in Taiwan

This study monitored ambient air concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in three municipal waste incineration plants. Blood PCDD/Fs levels of 133 workers randomly selected from these plants were also measured. The associations between workers' blood PCDD/Fs concentrations and occupational exposures to PCDD/Fs were assessed. Means of air PCDD/Fs levels ranged from 0.08 to 3.01 pg/m3 in international toxic equivalents (I-TEQ). The geometric means of blood PCDD/Fs concentrations were 14.6, 15.8, 19.1 pg/g lipid in World Health Organization (WHO) TEQ, respectively, for workers from three plants. Air levels of total I-TEQ and all congeners, except 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TeCDD) and 1,2,3,4,7,8,9-heptachlorinated dibenzofuran (HpCDF), were significantly higher in plant B. However, blood concentrations of 2,3,7,8-TeCDD, 1,2,3,7,8-PeCDD, 2,3,7,8-TeCDF, 1,2,3,7,8-PeCDF and 1,2,3,4,7,8,9-HpCDF were significantly elevated in plant C workers. Although job contents, duration of employment and time spent in certain location were significantly different among incineration plants, they were not significantly associated with blood concentrations of any congener. Furthermore, results of the multiple regression analysis that assessed important occupational factors simultaneously and adjusted for potential confounders, showed significant associations between four congeners and incineration plant or job contents. However, the results were limited by small R-squares of the regression models. In conclusion, blood concentrations of several PCDD/Fs congeners were significantly different among three incineration plants. The differences were not explained by the discrepancy in job contents, duration of employment, and time activity in these plants.     

Melting and incineration plants of municipal waste. Chemical and biochemical diagnosis of thermal processing samples (emission,residues)

Control of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in emissions and thermal residues from incinerators has been a cause of public concern for more than one decade. Recently, several studies showed that other persistent organic pollutants (POPs) such as coplanar polychlorinated biphenyls (co-PCBs) also have dioxin-like activity and are released from incinerators. Therefore, the present study was aimed at making a risk assessment about dioxin-like activity in extracts of thermal waste residues (e.g. combustion gas; fly ash, slag) from incineration and melting processes in Germany and Japan. For this purpose, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), coplanar polychlorinated biphenyls (co-PCBs), polychlorinated naphthalenes (PCNs) and polyaromatic hydrocarbons (PAHs) were analyzed by chemical analysis. Additionally, 2, 3, 7, 8-TCDD equivalents (EROD-TEQs) were determined by in vitro Micro-EROD bioassay using rat H4IIE hepatoma cells. EROD-TEQs could be correlated to I-TEQ values (from PCDD/Fs/co-PCBs) analyzed by chemical analysis resulting in a maximal sixfold higher estimate. Our study indicates minor influences of co-PCBs, PAHs and PCNs to the sum of dioxin-like toxicity in the extracts of thermal waste residues as determined here. Furthermore, we showed that the levels of dioxins and co-PCBs contained in slag from melting processes and bottom ashes from incineration processes were lower by 1-2 orders of magnitude than that in fly ash.     

Gas-particle partitioning of PCDD/Fs in Nagoya urban air, Japan

Polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) in the atmosphere were sampled by a high-volume filter/sorbent air sampler at an urban (Nagoya, Japan) site from May 2000 to January 2001 under the average ambient temperatures ranging from 1 degrees C to 33 degrees C. The gas and particle phase concentrations of PCDD/Fs were measured and then the field gas-particle partitioning data were used to assess the Junge-Pankow adsorption model and the K(OA) absorption model. For both PCDDs and PCDFs, passable agreement was obtained between the measured and predicted particulate-band fraction (phi) values by the Junge-Pankow model, but the model tends to overpredict phi for all individual Cl4-8DD/F congeners, especially for the lower chlorinated congeners. On the other hand, good agreement was obtained between the measured and predicted log K(p) values by the K(OA) model for both PCDDs and PCDFs. However, the K(OA) absorption model did not fit the field data at low ambient temperature below 5 degrees C. The disagreement at low ambient temperatures was estimated to arise from the gas adsorption artifacts during the sampling. From the validation by the field measurement data in Nagoya urban air, it is found that the K(OA) absorption model is capable of predicting more accurately gas-particle partitioning of PCDD/Fs than the Junge-Pankow adsorption model.     

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

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

Precipitation scavenging of particle-bound contaminants – A case study of PCDD/Fs

Precipitation scavenging of particles is a major mechanism for atmospheric deposition of organic contaminants, but there have been few field studies. We studied precipitation scavenging of PCDD/Fs with the aim of deepening understanding of environmental variables influencing this process. Bulk deposition of PCDD/Fs and their concentrations in ambient air measured at a background site in Sweden were used to calculate precipitation scavenging ratios. Contrary to expectations, increasing scavenging ratios with decreasing degree of chlorination of the PCDD/F congeners were observed when the particle-associated PCDD/F concentrations in air were used for the calculation. This was attributed to differences in temperature and thereby in the gas – particle partitioning of the PCDD/Fs between ground level and clouds where much of the particle scavenging occurs. When the particle-associated PCDD/F concentrations were recalculated for a 10–20 °C lower temperature, the scavenging ratios of the different PCDD/F congeners were similar. Hence differences between ground level and in-cloud temperature should be considered when calculating scavenging ratios from field observations and when modeling this process. The scavenging ratios averaged ～200 000, with lower values when the particle-associated PCDD/F concentration in air was lower. The soot concentration in air was a good predictor of bulk deposition of PCDD/Fs.     

Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

Sampling and analysis of ambient dioxins in northern Taiwan

In this study, ambient air samples were taken concurrently in the vicinity area of a large-scale municipal waste incinerator (MWI) and the background area for measuring polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) concentrations from November 1999 through July 2000 in northern Taiwan. The results obtained from eighteen ambient air samples indicate that the mean PCDD/F concentration of seventeen 2,3,7,8-substituted congeners in wintertime (188–348 fg-I-TEQ/m³) is significantly higher than that measured in summertime (56–166 fg-I-TEQ/m³). In addition, the seasonal PCDD/F concentrations are compared with the ambient air quality data including CO, NO₂, PM₁₀ and TSP sampled from Taipei area to gain better insights. It indicates that the variation of ambient air PCDD/F concentrations is closely correlated with that of PM₁₀ concentrations. Besides, the results indicate that the I-TEQ concentration of ambient air in sampling site B (directly downwind of the MWI) is of the highest while the sampling site A (upwind of MWI) is of the lowest among all sampling sites. This implies that existing MWI can be a significant emitter of PCDD/Fs in this area. Furthermore, the patterns of the PCDD/F congener distribution at all sampling sites (including the background site in Taoyuan) are quite similar. OCDD concentration is of the highest among seventeen PCDD/F congeners investigated and accounts for about 35% of the total concentration. As for the I-TEQ concentrations, 2,3,4,7,8-PeCDF is the most significant contributor, generally being responsible for 30–45% of the total I-TEQ values depending on the sampling sites and seasons.     

Formation behavior of PCDD/Fs in PVC pyrolysis with copper oxide

Formation and decomposition behaviors of PCDD/Fs during pyrolysis of polyvinyl chloride (PVC) with CuO have been investigated. These reactions proceed simultaneously, and the rate of decomposition exceeds that of formation with further retention. More 2,3,7,8-TCDD is formed when the dechlorination of PCDD/Fs proceeds significantly. Homologue profile patterns of PCDD/Fs show that the fractions of O8CDD and H6CDFs are relatively larger within PCDDs and PCDFs, respectively. Extremely large amounts of PCDD/Fs are obtained with the long retention time at 200 degrees C. The formation of PCDD/Fs decreases drastically with increase in the molar ratio of CuO/PVC. The acceptability of thermodynamic calculations on the formation of PCDD/Fs is also investigated. The thermodynamic calculated tendency of the effect of oxygen on the formation of PCDD/Fs agrees well with the experimental results, although absolute values of the amount of PCDD/Fs are much different.     

Modeling the atmospheric transport and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans in North America

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 Cl_4–5DD/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.     

A study of polychlorinated dibenzo-p-dioxins and dibenzofurans in the atmosphere of Hong Kong

A total of 27 ambient air samples of were collected from six locations in Hong kong during the period of January-August, 2000 and analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). In all sampling locations, higher concentrations of PCDDs/PCDFs, ranging from 0.03 to 0.43 pg I-TEQ/m3 were measured in winter months (January and March) than in the summer months (July and August) of concentrations at 0.018-0.025 pg I-TEQ/m3. These concentrations are similar to annual ranges reported earlier for two Hong Kong urban sites and other urban cities in Asia. Europe, and the United States. Despite significant seasonal variations in ambient air concentrations of PCDD/Fs (expressed in I-TEQ) were observed, the congener profiles of all the samples in this study period were similar, with OCDD, 1,2,3,4,6,7,8-HpCDD, OCDF and 1,2,3,4,6,7,8-HpCDF being the predominant species. However, the homologue profiles for the samples collected at the six locations of this study were found to display significantly different spatial and seasonal trends.     

Influence of a municipal solid waste incinerator on ambient air and soil PCDD/Fs levels

To examine the influence of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) emissions from a municipal solid waste incinerator (MSWI) on the environment, we measured the levels of PCDD/Fs in ambient air and soil samples collected near a MSWI in Bucheon, Korea. The PCDD/Fs concentrations in the ambient air samples ranged from 0.22 to 1.16 pg I-TEQm(-3) (13.39-75.16 pg m(-3)), with an average of 0.66 pg I-TEQ m(-3) (35.62 pg m(-3)). The soil samples contained between 1.25 and 74.98 pg I-TEQ g(-1) (38.15-3,303.33 pg g(-1)), with an average of 19.06 pg I-TEQ g(-1) (1,077.11 pg g(-1)). These levels were higher than those previously reported by other investigators in a number of surveys. The furan homologues predominated in the air samples and some soil samples, and the soil PCDD/Fs levels decreased with increasing distance from the MSWI. Comparison of the homologue patterns and a multivariate statistical analysis showed that PCDD/Fs emission from the MSWI directly affected the pattern of PCDD/Fs in air, while the PCDD/Fs patterns in soil differed according to the location relative to the MSWI, roads, and construction sites. These results collectively indicate that the MSWI was the major PCDD/Fs emission source in this area, but that unidentified combustion sources and vehicles might influence the environment to some extent.     

Dioxins in adipose tissue of women in Southern Spain

Seventeen polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were quantified in adipose tissue samples of non-occupationally exposed women living in Southern Spain. Geometric mean levels of sum of congeners and WHO(PCDD/F)-TEQ(2005) were 410 and 17.9pgg(-1) fat, respectively. Among PCDDs, octachlorodibenzo-p-dioxin (OCDD) showed the highest concentration with a mean value of 265pgg(-1) fat, followed by 1,2,3,6,7,8-HxCDD (49.3pgg(-1) fat) and 1,2,3,4,6,7,8-HpCDD (45.2pgg(-1) fat). These three congeners were responsible for around 90% of the sum of all PCDD/F congeners in adipose tissue. The geometric mean 2,3,7,8-TCDD value was 1.87pgg(-1) fat. 2,3,4,7,8-PeCDF (8.43pgg(-1) fat) showed the highest concentration among the PCDFs, followed by 1,2,3,4,7,8-HxCDF (4.17pgg(-1) fat) and 1,2,3,6,7,8-HxCDF (3.28pgg(-1) fat), and these three congeners were responsible for 4% of the sum of all studied PCDD/F congeners in adipose tissue and 76% of the sum of ten PCDFs. 1,2,3,7,8,9-HxCDF was the only congener not quantified in any sample, while 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF and 2,3,7,8-TCDF were found in 5, 16, 16 and 19 samples, respectively. All other congeners were quantifiable in all 20 samples. Congeners contributing most to the WHO(PCDD/F)-TEQ(2005) were 1,2,3,7,8-PeCDD (31.6%), 1,2,3,6,7,8-HxCDD (28.3%) and 2,3,4,7,8-PeCDF (14.6%). The body burden of log-transformed WHO(PCDD/F)-TEQ(2005) levels increased with age (B=0.02; 95% CI=0.01, 0.03; p=0.02). Although these adipose tissue PCDD/F levels are similar to previously published findings in Spain and other European countries, further research is needed to determine trends in the exposure of women to these chemical residues.     

Emissions behavior and distribution of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from cement kilns in China

The production of cement in China is accompanied by various emissions, such as fine particulate matter, heavy metals, nitrogen oxides, sulfur oxides, carbon dioxide…. Moreover, cement kiln presents a potential health risk to its surroundings, linking to emissions of persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), in brief dioxins. Flue gas samples were collected from five typical cement kilns during twelve runs and were used to evaluate the levels and distribution of PCDD/Fs in the emissions from cement kilns. The PCDD/Fs concentrations (136 congeners) and I-TEQ values ranged from 2.3 to >40 ng/m³ and 9.3?～?90.8?×?10^?3 ng I-TEQ/m³, respectively, which were lower than the emission standard in China (0.1 ng I-TEQ/m³). In weight units, the dominant congeners were OCDD, 1,2,3,4,6,7,8-HpCDF, and OCDF; 2,3,4,7,8-PeCDF is the largest contributor (36–66 %) to the total I-TEQ value of twelve runs. HxCDF and TCDF were the first two most abundant homologue groups (12–85 and 4–52 %), and the homologue concentration decreased with rising chlorine number for PCDDs. In addition, there was no marked difference in homologue profiles when solid wastes (refuse-derived fuel and municipal solid waste) and hazardous wastes (DDT and POPs) were combusted as supplemental fuels. The use of various supplemental fuels had no obvious effect on the fingerprint of PCDD/F homologues. Moreover, there was no significant difference in levels of PCDD/Fs emission due to the diversity of production capacity, which were consistent with reported previously. Air pollution control device had effect on the homologue profiles, and cement system with electrostatic precipitators (ESP) had more fractions of octachloro congeners to the total.     

Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers

The concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) were determined in air samples collected at four sampling sites located in two zones of Barcelona (Spain): near a municipal solid waste incinerator (MSWI) and a combined cycle power plant (3 sites), and at a background/control site. Samples were collected using high-volume active samplers. Moreover, 4 PUF passive samplers were deployed at the same sampling points during three months. For PCDD/Fs, total WHO-TEQ values were 27.3 and 10.9 fg WHO-TEQm(-3) at the urban/industrial and the background sites, respectively. The sum of 7 PCB congeners and the Sigma PCN levels were also higher at the industrial site than at the background site. In order to compare active and passive sampling, the accumulated amounts of PCDD/Fs, PCBs and PCNs in the four passive air samplers, as well as the total toxic equivalents in each sampling site were also determined. To assess the use of PUF passive samplers as a complementary tool for PCDD/F, PCB and PCN monitoring, sampling rates were calculated in accordance with the theory of passive air samplers. PUF disks allowed establishing differences among zones for the POP levels, showing that they can be a suitable method to determine POP concentrations in air in areas with various potential emission sources. Although both particle and gas phase were sorbed by the PUFs, data of gas phase congeners are more reproducible.     

Concentrations,atmospheric partitioning,and air–water/soil surface exchange of polychlorinated dibenzo-p-dioxin and dibenzofuran along the upper reaches of the Haihe River basin,North China

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.