Polychlorinated dibenzo-p-dioxin and dibenzofuran concentrations in serum samples of workers at intermittently burning municipal waste incinerators in Japan

Objectives: To find whether or not incinerator workers employed at intermittently burning municipal incineration plants are exposed to high concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs).

Methods: 20 Workers employed at three municipal waste incineration plants (incinerator workers) and 20 controls were studied. The previous job, dietary, smoking, and body weight and height were obtained from a questionnaire survey. Concentrations of PCDDs and PCDFs were measured in serum samples of the workers and the deposited dust of the plants. The influence of occupational exposure on concentrations of PCDDs and PCDFs in serum samples was examined by multiple regression analysis.

Results: Dust analysis showed that dominant constituents were octachlorodibenzo-p-dioxin (OCDD) and 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) among the PCDDs, and 1,2,3,4,6,7,8-heptachlorodibenzofuran (HpCDF) and octachlorodibenzofuran (OCDF) among the PCDFs. The toxicity equivalents (TEQs) of summed PCDDs and PCDFs in the deposited dust were 0.91, 33, and 11 ng TEQ/g, respectively, for plants I, II, and III. The means of TEQ in serum samples of summed PCDDs and PCDFs in the incinerator workers and controls were 22.8 and 16.4 pg TEQ/g lipid for area I, 29.4 and 19.3 pg TEQ/g lipid for area II, and 22.8 and 24.9 pg TEQ/g lipid for area III, which were almost the same as for the general population of Japan. No significant differences in the TEQ of PCDDs and TEQ of PCDDs and PCDDs were found between the incinerator workers and the controls. However, the TEQ of PCDFs was significantly higher among the incinerator workers in areas I and II, and the 1,2,3,4,6,7,8-HpCDF concentration was also significantly higher for all three areas. When the occupational exposure index for each constituent of PCDDs and PCDFs was defined as the product of the duration of employment at the incineration plant and the concentration of the constituent in the deposited dust, multiple regression analysis showed that the concentrations of HxCDF, HpCDF, and TEQ of PCDFs in serum samples increased with the occupational exposure index. The multiple regression analysis also suggested that significant factors affecting the concentrations in serum samples were area for HxCDD, age for TCDD, PeCDD, PeCDF, TEQ of PCDDs, TEQ of PCDFs, and TEQ of summed PCDDs and PCDFs, and BMI for HxCDD, HpCDD, and OCDD.

Conclusion: This study showed that incinerator workers employed at intermittently burning incineration plants were not necessarily exposed to high concentrations of PCDDs and PCDFs. However, the increases in the concentrations in serum of HxCDF, HpCDF and TEQ of PCDFs with the occupational exposure index suggest that the incinerator workers had inhaled dust containing PCDDs and PCDFs during their work.

     

Polychlorinated dibenzo-p-dioxin and dibenzofuran concentrations in serum samples of workers at an infectious waste incineration plant in Japan

In 1998-2000, concentrations of summed polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in the exhaust gas of an infectious waste incineration plant were 17-510 ng toxic equivalents (TEQ)/m(3), which reached levels above the Japanese legal limit value of 80 ng TEQ/m(3). The incinerator ceased operation in November 2000. This study was aimed at determining whether the incinerator workers were exposed to high levels of PCDDs and PCDFs. Blood samples of five workers were collected at 1 month and 16 months after the end of the occupational dioxin exposure. For comparison, blood samples were also collected from control subjects. Ash remaining in the incinerator and dust deposited around the conveyer and incinerator areas were collected; TEQ values were 44 and 10 ng TEQ/g, respectively. A month after the end of occupational dioxin exposure, mean TEQ for the workers was 49.1 pg TEQ/g lipid, which was 2.7 times as high as that for the controls. At 16 months, the mean TEQ for the workers decreased to 29.4 pg TEQ/g lipid, which was 1.6 times that for the controls. Ratios of serum level of each congener of PCDDs and PCDFs between 1 and 16 months after exposure were 0.44 to 0.69. This study showed that the serum dioxin levels for the infectious waste incinerator workers were higher than the controls, and the serum dioxin level decreased after the end of the occupational dioxin exposure.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran concentrations in the serum samples of workers at continuously burning municipal waste incinerators in Japan

OBJECTIVES—To find whether concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in serum increased in workers at municipal incinerators that burn continuously.
METHODS—30 Workers employed at three municipal waste incineration plants (incinerator workers) and 30 control workers were studied. The incinerator workers had worn dust masks or airline masks during the periodic repair work inside the incinerators. Previous job, dietary habit, smoking habit, distance from residence to the incineration plant, and body weight and height were obtained from a questionnaire survey. Concentrations of PCDDs/PCDFs were measured in the serum of the workers and the dust deposited in the plants. The influence of various factors on serum concentrations of PCDDs/PCDFs was examined by multiple regression analysis.
RESULTS—Dust analysis showed the greatest amount of octachlorodibenzo-p-dioxin (OCDD), followed by 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD), 1,2,3,4,6,7,8-heptachlorodibenzofuran (HpCDF), and octachlorodibenzofuran (OCDF). The toxicity equivalents (TEQs) of PCDDs and PCDFs in the deposited dust were 4.8, 1.0, and 6.4 ng TEQs/g, respectively, for plants A, B, and C. The mean serum TEQs of PCDDs and PCDFs in the incinerator workers and control workers were 19.2 and 22.9 pg TEQs/g lipid, respectively, for area A, 28.8 and 24.5 pg TEQs/g lipid for area B, and 23.4 and 23.6 pg TEQs/g lipid for area C. No significant differences were found between the incinerator workers and the controls for TEQs of PCDDs and PCDFs separately, and TEQs of PCDDs and PCDFs together. However, the serum 1,2,3,4,6,7,8-HpCDF concentration was significantly higher in the incinerator workers than in the controls for all the three areas. When the exposure index to 1,2,3,4,6,7,8-HpCDF is defined as the product of the concentration of 1,2,3,4,6,7,8-HpCDF in the deposited dust and duration of employment, the concentration of 1,2,3,4,6,7,8-HpCDF in serum increased as the exposure index increased. Multivariate analysis suggested that the serum concentration of HpCDF increased with duration of employment at the incineration plants and OCDF increased with employment of 21 years. The other significant variables (p<0.01 or p<0.001) were area for hexachlorodibenzo-p-dioxin (HxCDD) and tetrachlorodibenzofuran (TCDF), Brinkman index for HpCDD, and body mass index (BMI) for tetrachlorodibenzo-p-dioxin (TCDD), HpCDD, and TEQs of PCDDs.
CONCLUSION—The serum TEQs of PCDDs and PCDFs was not significantly higher among the incinerator workers, but the serum concentration of 1,2,3,4,6,7,8-HpCDF was. This suggests that the incinerator workers had inhaled dust containing PCDDs and PCDFs while working in plants equipped with incinerators that burn continuously.


Keywords: serum dioxins; municipal waste incinerators; continuous burning; heptachlorodibenzofuran     

Isomer pattern and elimination of dioxins in workers exposed at a municipal waste incineration plant

The aim of this study was to clarify patterns of serum concentrations of dioxins in the employees of a waste incineration plant and to estimate elimination rates and half-lives of serum dioxin isomers, and the maximum serum concentrations of dioxin isomers at the time of plant shutdown. Sixteen subjects participating 3 times or more in annual health examinations during an 8-yr period from 2000 to 2007 were recruited for this study. Serum concentrations of dioxins expressed as TEQ/g lipid decreased gradually after plant shutdown with the highest decrease observed in polychlorinated dibenzofurans (PCDFs) followed by polychlorinated deibenzo-p-dioxins (PCDDs) and then coplanar PCBs. The serum toxic equivalency (TEQ) concentrations of PCDF and PCDD congeners in the employees were higher than those in the general population survey by the Ministry of the Environment, Japan, whereas the serum concentrations of coplanar PCBs were similar to those in the general population. The estimated half-lives and elimination rates of PCDDs and PCDFs in the highly exposed workers increased compared with the moderately exposed workers. The estimated geometric mean serum concentrations of PCDDs, PCDFs and total dioxins at the time of plant shutdown were 35, 53 and 107 pg TEQ/g lipid, respectively.     

Health survey on workers and residents near the municipal waste and industrial waste incinerators in Korea

Hazardous substances, such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) also have been detected in Municipal Solid Waste (MSW) and industrial waste incinerators in Korea. In this study, we estimated the exposure status of these hazardous substances and their heath effects in workers and residents near the MSW incinerators and residents near the industrial waste incinerators. We interviewed 13 workers and 16 residents from the area around the two MSW incinerators, and further 10 residents from the area around one industrial waste incinerator, which is suspected to emit higher hazardous substances. During the interview we collected information including sociodemographic information, personal habits, work history, detailed gynecologic and other medical history. Blood samples from 45 subjects were also collected for analysis of PCDDs and PCDFs, which were analyzed by HRGC-HRMS (High Resolution Gas Chromatography-High Resolution Mass Spectrometer). In addition to a questionnaire survey, urinary concentrations of 8-hydroxydeoxyguanosine (8-OH-dG) and malondialdehyde (MDA) were measured as oxidative injury biomarkers. Urinary concentrations of 8-OH-dG were determined by in vitro ELISA (JAICA, Fukuroi, Japan). MDA were determined by HPLC using adduct with TBA (thiobarbituric acid). The PCDD/F concentrations in residents from the area around industrial waste incinerator were higher than those in workers and residents from the area around MSW incinerator. The average toxic equivalency (TEQ) concentrations of PCDD/Fs in residents from the area around industrial waste incinerator were 53.4 pg I-TEQs/g lipid. The average TEQ concentrations of PCDD/Fs in workers and residents near MSW incinerator were 12.2 pg I-TEQs/g lipid. Estimated daily intake (EDI) of each person was calculated, and the EDI of all workers and residents near MSW incinerator were within the tolerable daily intake range. But for only 30% of 10 people near the industrial waste incinerator were the EDI within the tolerable daily intake range (1-4 pg I-TEQ/kg bw/day) suggested by WHO (1997). The oxidative stress of residents near the industrial waste incinerator was higher than that in workers and residents from the area around MSW incinerator. This oxidative stress may have been caused by hazardous substances, such as PCDD/Fs emitted by incinerators. The residents from the area around industrial waste incinerator were exposed to hazardous substances such as PCDD/ Fs. Proper protection strategies against these hazardous chemicals are needed.     

Evaluation of serum dioxin congeners among residents near continuously burning municipal solid waste incinerators in Korea

The objective of this study was to evaluate the congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in Korean serum samples as biological markers. Serum samples from 103 participants were analyzed. Participants consisted of 28 workers in municipal solid waste incinerators (MSWIs), and 21 men and 54 women who had lived for at least 3 years prior to 2002 in areas within 300 m of incinerators in large Korean cities. Serum samples were analyzed for 17 PCDD/PCDFs congeners by high resolution gas chromatography-high resolution mass spectrometry. Geometric mean (GM) PCDD/PCDF levels in the serum samples were 3.14, 8.04, 6.12 and 6.60 pg TEQ/g lipid for workers, male residents, female residents and the sum of male and female residents, respectively. The GM PCDD/PCDF level in the serum of workers was not significantly different from the values for residents near MSWIs. In the 75 participants who resided near MSWIs, the congeners that most contributed to the total TEQ were 1,2,3,6,7,8-hexachlorodibenzofuran (1,6-HxCDF), 2,3,4,7,8-pentachlorodibenzofuran (4-PeCDF), 1,2,3,4,6,7,8-heptachlorodibenzofuran (1,4,6-HpCDF), 1,2,3,7,8,9-hexachlorodibenzofuran (1,9-HxCDF), 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (1,4-HxCDD), 1,2,3,6,7,8-hexachlorodibenzo-p-dioxin (1,6-HxCDD). In the workers, the congeners that made the greatest contribution were 1,6-HxCDD, 4-PeCDF, 1,2,3,4,6,7,8-heptachlorodibenzop-dioxin (HpCDD), and 1,6-HxCDF. In conclusion, the serum TEQ levels for PCDD/PCDFs in the incinerator workers and residents near the MSWIs in Korea were lower than those reported for other countries. Comparison of the PCDD/PCDF levels of workers at MSWIs and nearby residents revealed no significant enhancement of PCDD/PCDF exposure in workers. PCDD/PCDF intake from animal origin was assumed to be lower than that of Europeans. Further studies of Korean foods are needed to clarify the exposure route for PCDD/PCDFs in the Korean population.     

Dioxin concentrations in the blood of workers at municipal waste incinerators.

OBJECTIVES--Increased concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) in pooled blood samples from workers at municipal waste incinerators have been reported. This study was undertaken to confirm these results in individual blood samples from potentially exposed and unexposed workers at municipal waste incinerators compared with matched unexposed controls and compared with concentrations in the slag and fly ash from the municipal waste incinerators. METHODS--Concentrations of PCDDs and PCDFs were determined in the blood of 10 workers from an old municipal waste incinerator without adequate pollution controls, 11 workers from a newer incinerator with modern pollution controls, and 25 controls from the general population group matched for age (+/- 10 years), sex, and race, and in the slag and fly ash from the older incinerator. RESULTS--Significant increases of certain PCDDs and PCDFs were found in the blood of the workers from the older incinerator compared with the controls as follows: octaCDD (1051 (438) v 637 (344), P < 0.001), hexaCDF (52.3 (28.7) v 30.2 (18.2), P < 0.01), heptaCDF (43.9 (30.4) v 22.7 (12.4), P < 0.001), total PCDDs (1262 (484) v 825 (454), P < 0.001), total PCDFs (133.0 (68.1) v 93.7 (36.7), P < 0.05), and total PCDD/Fs (1395 (537) v 918 (437), P < 0.001). The workers from the older incinerator with the greatest exposure were found to have the most significant increases of the blood PCDDs and PCDFs, and the pattern of increased PCDD and PCDF congeners in the blood corresponded to the pattern in the incinerator slag and ash. No significant differences were found between the blood concentrations of the workers at the newer incinerator and the controls. CONCLUSION--Occupational exposure to slag and fly ash from municipal waste incinerators may increase the blood concentrations of PCDDs and PCDFs. Modern pollution control technology in new incinerators may be able to minimise potential exposure to slag and fly ash and thus the absorption of PCDDs and PCDFs from this source.     

Polychlorinated Dibenzo-p-Dioxins, Polychlorinated Dibenzofurans, and Coplanar Polychlorinated Biphenyls in Human Milk in Osaka City, Japan

Forty-eight human milk samples were collected from primiparous mothers in Osaka City from June 1999 to January 2000 and analyzed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like coplanar polychlorinated biphenyls (CoPCBs). Mean toxic equivalents (TEQs) in the milk were 13.86 pg I-TEQ/g fat or 16.50 pg World Health Organization (WHO)-TEQ/g fat for PCDDs and PCDFs; 9.87 pg WHO-TEQ/g fat for CoPCBs; and 23.74 pg TEQ/g fat using I-TEQ values of PCDDs and PCDFs or 26.36 pg TEQ/g fat using WHO-TEQ values of PCDDs and PCDFs for total PCDDs, PCDFs, and CoPCBs. The TEQ levels of these chemicals in human milk in Osaka City were in the range of levels in human milk surveyed in Japan, but the TEQ levels of PCDDs and PCDFs and total PCDDs, PCDFs, and CoPCBs from our study were slightly higher than average TEQ levels in human milk in Japan. When comparing our data with the latest data from the United States and some European countries, the TEQ levels of PCDDs and PCDFs in human milk from Osaka City were relatively high, whereas those of CoPCBs were ranked as being of intermediate level. Only TEQ values of CoPCBs in human milk were found to correlate with the increasing age of mothers and their estimated intake of seafood during the year before pregnancy. Concentrations of PCBs 105 and 118 contributed to TEQ values of CoPCBs associated with seafood intake, whereas those of PCBs 156, 157, 114, 189, 167, and 169 contributed to TEQ values of CoPCBs associated with increasing maternal age.     

PCDD/F Levels in the Vicinity of an Old Municipal Solid Waste Incinerator: Temporal Variation in Soils

In order to determine the temporal variation in the levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in soils in the vicinity of an old municipal solid waste incinerator (Montcada, Barcelona, Spain), in 1997 we collected 24 soil samples at the same sampling points in which samples were taken 1 year before. Each sample was analyzed for PCDDs and PCDFs by GC/MS. While in the previous study PCDD/F concentrations ranged from 0.30 to 44.26 ng TEQ/kg (dry matter), (median and mean values: 3.52 and 6.91 ng TEQ/kg), in the present study PCDD/F levels ranged from 0.15 to 29.27 ng TEQ/kg (median and mean values: 2.56 and 4.47 ng TEQ/kg). PCDD/F concentrations decreased in 14 of the 24 soil samples, while the remaining 10 samples showed increases of different orders. No statistically significant differences in PCDD/F levels according to the main wind directions in the area were noted. In both surveys, the highest PCDD/F concentrations were found 750 m from the stack to the south. The current levels of PCDD/Fs in soils, as well as those found in the previous survey are similar or even lower than PCDD/F concentrations reported for soil samples taken near to municipal solid waste incinerators from different places. Received: 2 May 1998/Accepted: 23 November 1998     

Prenatal exposure to PCDDs/PCDFs and dioxin-like PCBs in relation to birth weight

Several human studies have shown that low-level exposure to environmental contaminants, such as polychlorinated biphenyls (PCBs) and organochlorine pesticides, negatively influences birth outcomes. However, the effects of low-level exposure to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like PCBs (DL-PCBs) on birth outcomes have not been clarified in human studies.A prospective cohort study was established to investigate the possible adverse effects of PCDDs/PCDFs and DL-PCBs on fetal growth and neurodevelopment. We recruited 514 pregnant women between July 2002 and October 2005 in Sapporo, Japan. We measured 29 congener levels of PCDDs/PCDFs and DL-PCBs in maternal blood.Using multiple liner regression analysis of the association between birth weight and the levels of PCDDs/PCDFs and DL-PCBs with full adjustments for potential confounders, a significant adverse effect was observed regarding total PCDDs toxic equivalents (TEQ) levels (adjusted β=−231.5 g, 95% CI: −417.4 to −45.6) and total PCDFs TEQ levels (adjusted β=−258.8 g, 95% CI: −445.7 to −71.8). Among male infants, significant adverse associations with birth weight were found for total PCDDs TEQ level, total PCDDs/PCDFs TEQ level, and total TEQ level. However, among female infants, these significant adverse associations were not found. With regard to individual congeners of PCDDs/PCDFs and DL-PCBs, we found significantly negative association with the levels of 2,3,4,7,8-PeCDF (adjusted β=−24.5 g, 95% CI: −387.4 to −61.5).Our findings suggest that prenatal low-level exposure to PCDDs and PCDFs, especially 2,3,4,7,8-PeCDF, may accumulate in the placenta and retard important placental functions, which result in lower birth weight.     

Assessment of health effects in New York City firefighters after exposure to polychlorinated biphenyls (PCBs) and polychlorinated dibenzofurans (PCDFs): the Staten Island Transformer Fire Health Surveillance Project

Following an electrical transformer fire in Staten Island, New York, a health surveillance program was established for 60 New York City firefighters and emergency medical technicians exposed to polychlorinated biphenyls (PCBs) and polychlorinated dibenzofurans (PCDFs). Exposure potential was documented after high levels of PCBs and PCDFs were found on transformer and firefighters' uniforms. Personnel received comprehensive medical examinations, and the results were compared with preexposure values. Serum was analyzed for PCBs, PCDFs, and polychlorinated dibenzo-p-dioxins (PCDDs). Follow-up was conducted 9 mo later. Thirty-two of 58 (55%) firefighters reported initial symptoms, and 3 firefighters required brief medical leave. Pulmonary functions, exercise performance, serum liver functions, and serum lipid profiles were normal or unchanged from preexposure baselines. Serum PCBs averaged 2.92 +/- 1.96 ppb (range = 1.9-11.0 ppb). Five (8%) had serum PCBs that were greater than or equal to 6 ppb. Eight (73%) had a significant decrease (p = .05) in serum PCB level at the time of follow-up. Serum toxic equivalency (TEQ [1998 World Health Organization]) for total PCDDs and PCDFs averaged 39.0 +/- 21.5 (n = 48). Eighteen (38%) had elevated TEQs (i.e., > 40). All firefighters had no short-term heath effects. Modern firefighting uniforms are not meant to replace HAZMAT suits, but these uniforms provide protection from this chemical exposure for most firefighters.     

Assessment of Health Effects in New York City Firefighters after Exposure to Polychlorinated Biphenyls (PCBs) and Polychlorinated Dibenzofurans (PCDFs): The Staten Island Transformer Fire Health Surveillance Project

Following an electrical transformer fire in Staten Island, New York, a health surveillance program was established for 60 New York City firefighters and emergency medical technicians exposed to polychlorinated biphenyls (PCBs) and polychlorinated dibenzofurans (PCDFs). Exposure potential was documented after high levels of PCBs and PCDFs were found on transformer and firefighters' uniforms. Personnel received comprehensive medical examinations, and the results were compared with preexposure values. Serum was analyzed for PCBs, PCDFs, and polychlorinated dibenzo-p-dioxins (PCDDs). Follow-up was conducted 9 mo later. Thirty-two of 58 (55%) firefighters reported initial symptoms, and 3 firefighters required brief medical leave. Pulmonary functions, exercise performance, serum liver functions, and serum lipid profiles were normal or unchanged from preexposure baselines. Serum PCBs averaged 2.92 ± 1.96 ppb (range = 1.9-11.0 ppb). Five (8%) had serum PCBs that were greater than or equal to 6 ppb. Eight (73%) had a significant decrease (p = .05) in serum PCB level at the time of follow-up. Serum toxic equivalency (TEQ [1998 World Health Organization]) for total PCDDs and PCDFs averaged 39.0 ± 21.5 (n = 48). Eighteen (38%) had elevated TEQs (i.e., > 40). All firefighters had no short-term heath effects. Modern firefighting uniforms are not meant to replace HAZMAT suits, but these uniforms provide protection from this chemical exposure for most firefighters.     

Associations between serum levels of selected organochlorine compounds and endometriosis in infertile Japanese women

Endocrine-disrupting chemicals (EDCs) have been proposed as risk factors for endometriosis. Persistent organochlorine compounds, a group of suspected EDCs, are present to some extent in almost all human adipose tissue and blood via the food chain. A few animal studies have confirmed that exposure to these compounds can increase the incidence of endometriosis. In this study, we examined the associations between endometriosis and exposure to selected organochlorine compounds, including 8 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), 4 coplanar polychlorinated biphenyls (cPCBs), 36 ortho-substituted polychlorinated biphenyls (PCBs), and 13 chlorinated pesticides or their metabolites. The participants were 139 infertile Japanese women who were examined by laparoscopy and diagnosed as either endometriosis cases (Stages II-IV) or controls (Stages 0-I). The serum levels (lipid adjusted) of the targeted organochlorine compounds were in both 58 cases and 81 controls. There were very few differences in the various levels between endometriosis cases and controls. The total serum toxic equivalency (TEQ) value of PCDDs was significantly higher in the controls than in the cases (P=0.02). No other total TEQ values differed between cases and controls. For PCDDs, PCDFs, cPCBs, and PCBs, the multivariate odds ratio was 0.38 [95% confidence interval (CI), 0.12-1.17] and 0.41 (95% CI, 0.14-1.27) for the third and highest quartiles, respectively, compared to the lowest quartile of total TEQ values. A weak, negative dose-response relationship was evident for total TEQs (P for trend of 0.06). The results of this study provide some evidence that serum levels of these organochlorine compounds are not associated with an increased risk of endometriosis in infertile Japanese women.     

A Survey of Dietary Intake of Polychlorinated Dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins,Polychlorinated Dibenzofurans,and Dioxin-like Coplanar Polychlorinated Biphenyls from Food During 2000–2002 in Osaka City,Japan

Studies of the dietary intake of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like coplanar polychlorinated biphenyls (dioxin-like PCBs), collectively referred as dioxins, were conducted using the total diet study (TDS) method with food purchased in Osaka City, Japan during 2000–2002. The daily intake of dioxin-TEQ (toxic equivalent) from food per adult person was estimated respectively as 104.24 pg TEQ/person/day in 2000, 72.73 pg TEQ/person/day in 2001, and 87.28 pg TEQ/person/day in 2002, corresponding to 2.08, 1.45, and 1.74 pg TEQ/kg body weight (bw)/day for an adult weighing 50 kg. The highest contribution ratio to the total intake of dioxin-TEQ was from fish and shellfish (group 10) in each year, accounting for 77–92%. The next highest contributor was meat and eggs (groups 11-A and 11-B). An annual decrease of the intake of dioxin-TEQ was not observed clearly. Otherwise, the dietary intake of non-2,3,7,8-substituted PCDDs/PCDFs were estimated together. The intake of 1,3,6,8-TeCDD came mostly from intake of fish and shellfish (group 10), green vegetable (group 7), and the other vegetables, including mushrooms and seaweed (group 8). In addition, the intake of 1,3,6,8-TeCDF, which reportedly antagonizes 2,3,7,8-TeCDD-mediated aryl hydrocarbon hydroxylase (AHH) and ethoxyresorufin O-deethylase (EROD) induction activities, was an insufficient amount to suppress 2,3,7,8-TeCDD-mediated activities. Furthermore, we discussed different TEQ compositions of PCDDs/PCDFs to dioxin-like PCBs from food intake and in human samples and inferred that the difference was caused by low bioaccumulation properties of 3,3′,4,4′,5-PeCB (PCB 126).     

Dioxinlike components in incinerator fly ash: a comparison between chemical analysis data and results from a cell culture bioassay.

Potent polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxinlike polychlorinated biphenyls (PCBs) are among the most relevant toxic emissions from incinerators. Induction of cytochrome P450 1A1-catalyzed 7-ethoxyresorufin O-deethylase (EROD) activity in mammalian cell culture (EROD bioassay) is thought to be a selective and sensitive parameter used for the quantification of dioxinlike compounds. Fly ash extracts from municipal waste incinerators (MWI), a crematorium, wood combustors, and a noble metal recycling facility were analyzed in the EROD bioassay using rat hepatocytes in primary culture. Fractions containing 2,3,7,8-substituted PCDDs/PCDFs, dioxinlike PCBs, and 16 major polycyclic aromatic hydrocarbons (PAHs) were isolated from the extract and analyzed by gas chromatography-mass spectrometry (GC-MS) and by the EROD bioassay. It was found that with MWI samples the bioassay of the extract resulted in a two- to fivefold higher estimate of TCDD equivalents (TEQ) than the chemical analysis of PCDDs/PCDFs and PCBs. However, the outcome of both methods was significantly correlated, making the bioassay useful as a rough estimate for the sum of potent PCDDs/PCDFs and dioxinlike PCBs in extracts from MWI fly ash samples and in a fly ash sample from a crematorium. In noble metal recycling facility and wood combustor samples, higher amounts of PAHs were found, contributing to more pronounced differences between the results of both methods. The remaining unexplained inducing potency in fly ash samples probably results from additional dioxinlike components including certain PAHs not analyzed in this study.The hypothesis that emissions from MWI of hitherto unidentified dioxinlike compounds are higher by orders of magnitude than emissions of potent PCDDs/PCDFs and dioxinlike PCBs could not be confirmed. We found no indication for a marked synergistic interaction of dioxinlike fly ash components in the bioassay.     

Chemical Characterization of Polychlorinated Biphenyls, -Dibenzo-p-Dioxins, and -Dibenzofurans in Technical Kanechlor PCB Formulations in Japan

Technical polychlorinated biphenyl (PCB) formulations—Kanechlor KC-200, KC-300, KC-400, KC-500, KC-600 and KC-1000—produced in Japan were analyzed for the chemical characterization of PCBs, -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) using high-resolution gas chromatography–high-resolution mass spectrometry (HRGC-HRMS) by isotope dilution technique. The homologue/congener profiles of Kanechlor formulations resembled those of Clophen, Aroclor, and Delor, respectively, from Germany, the United States, and Czechoslovakia. Twenty-seven major PCB congeners contributed 50% (in KC-200) to 69–71% (in KC-600, 1000, and 500) to total PCBs. Average total PCB concentrations were 510,000, 800,000, 830,000, 840,000, 870,000, and 880,000 μg/g in KC-1000 (51%), KC-200 (80%), KC-500 (83%), KC-400 (84%), KC-300 (87%), and KC-600 (88%), respectively. Kanechlors also contained PCDDs and PCDFs (4.3 to 0.35 μg/g) as impurities which were approximately 1/10,000 to the PCB concentrations. Congener characterization and concentrations of PCBs and PCDFs were considerably varied in between Kanechlor formulations. The potential for the emissions of PCDDs and PCDFs from Kanechlor was estimated to be 1.94 kg and 464.4 kg, respectively. The average WHO-toxic equivalent (TEQ) was 16 (KC-500) >12 (KC-400) >10 (KC-1000) >4.1 (KC-600) >3.5 (KC-300) >1.9 (KC-200) on μgTEQ/g. Non- and mono-ortho PCBs were the major contributors to the total TEQ in Kanechlor formulations, whereas the PCDD/DF contribution was <2.0%. The environmental input of TEQs from Kanechlors can be estimated to be between 112 and 941 kg.     

Risk Factors Affecting Blood PCDDs and PCDFs in Residents Living near an Industrial Incinerator in Korea

The contamination sources of polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), such as industrial incinerators, can potentially change the blood levels and isomer patterns of PCDD/DFs in residents living near the incinerators. In this study, we estimated whether the blood levels and isomer patterns of PCDD/DFs in residents living near an incinerator were affected by its presence and investigated factors that characterize the risk of high exposure to PCDD/DFs in the area. We estimated the blood levels and homologue patterns of PCDD/DFs in a group of 40 residents living within 5 km of an industrial incinerator and in a group of 20 residents living 20 km away from an incinerator. We cannot assert that the operation of incinerator facilities was only cause of increased PCDD/DFs in these residents; however, the operation of incinerator facilities in agricultural areas increased PCDD/DF exposure to individuals. The group living next to the industrial incinerator especially represented the typical isomer pattern in which the proportions of OCDDs were lower and those of PCDFs higher than those in the other groups. The high-risk population with increased blood levels of PCDD/DFs included those who had lived longer in the contaminated area as well as those who frequently ate contaminated foods.     

Dietary intake of PCDDs/PCDFs and coplanar PCBs among the Japanese population estimated by duplicate portion analysis: a low proportion of adults exceed the tolerable daily intake

Dietary intake of dioxins was estimated by duplicate portion analysis of consecutive 3-day food samples among 86 men and 288 women (aged 17-72 years), who were living in 75 different areas of 25 prefectures in Japan. The mean (median) intake of PCDDs+PCDFs, coplanar PCBs (co-PCBs), and total dioxins, expressed on the basis of toxicity equivalents (TEQ), was 0.46 (0.34), 0.59 (0.39), and 1.06 (0.79) pg/kg body weight/day, respectively. Dietary intake was highest in fishing areas, followed by farming and urban areas. In multiple regression analysis, TEQs of PCDDs+PCDFs, co-PCBs, and total dioxins were positively associated with age and intake amount of fish and shellfish, and milk and dairy products, and negatively associated with survey year. There were significant positive correlations between dietary intake and blood levels for TEQs of PCDDs+PCDFs, co-PCBs, and total dioxins (Pearson r=0.35-0.36). The proportion of those whose dietary intake exceeded the tolerable daily intake (TDI), set by the World Health Organization (4 pg TEQ/kg/day) and European Union (2 pg TEQ/kg/day), was estimated at 2.1% and 10.4%, respectively. However, these proportions were considered to be overestimated because of the effect of day-to-day within-person variation. Therefore, the ratio of within- and between-person variance was estimated by applying random effects one-way analysis of variance to repeated measurements for another group of 35 persons. When the effect of within-person variation of dietary intake was accounted for, the proportion of subjects whose long-term intake exceeded the TDI of WHO and EU decreased to 0.06% and 2.9%, respectively.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran levels and patterns in polyvinylchloride and chloralkali industry workers

 The production of chlorine and vinyl chloride (VCM) is associated with the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The objective of the present study was to determine whether the levels and congener patterns of PCDDs and PCDFs in the blood of workers involved in the production of such substances could be related to their occupational environment. PCDD and PCDF levels in blood plasma from VCM and chloralkali workers and in referents were determined by means of high-resolution gas chromatography/high resolution mass spectrometry (HRGC/ HRMS) techniques and the results were evaluated through principal component analysis (PCA). The overall levels of PCDDs and PCDFs were low, but the relative congener distribution detected in the workers differed from that found in the referents. 1,2,3,4,6,7,8-HpCDF, 1,2,3,4,7,8- and 1,2,3,6,7,8-HxCDFs are congeners related to work in VCM and chloralkali industries. Exposure to PCDDs and PCDFs in these industrial environments changes the congener-distribution pattern in the blood of workers as compared with referents. A combination of isomer-specific analysis of PCDDs and PCDFs in blood plasma and PCA is suitable for the differentiation between nonoccupational and occupational exposure and provides a means of assessing workers’ exposure situation in different occupational settings. Received: 18 October 1996/Accepted: 29 November 1996     

Toxicity reference values for mink exposed to 2,3,7,8-tetrachlodibenzo-p-dioxin (TCDD) equivalents (TEQs)

Dietary and tissue residue-based toxicity reference values (TRVs) were derived for mink from the published results of studies in which mink were exposed to polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), or related compounds. Because the primary mechanism of toxic action at the least concentration for these compounds is related to activation of the aryl hydrocarbon receptor (AhR), TRVs were described on the basis of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQ). Each published study was critically reviewed for its usefulness in deriving a TRV based on the following criteria: (1) close relatedness of the test species to the wildlife receptor of concern (only mink studies were reviewed in this paper); (2) chronic duration of exposure which included sensitive life stages to evaluate potential developmental and reproductive effects; (3) measurement of ecologically relevant endpoints; (4) availability of congener-specific data to calculate TEQ concentrations; and (5) minimal impact of co-contaminants. Dietary TRVs for mink exposed to TEQ ranged from 12.1 to 56.6 ng TEQ/kg feed (wet weight) for the no observable adverse effect level (NOAEL) and from 50.4 to 242 ng TEQ/kg feed (wet weight) for the lowest observable adverse effect level (LOAEL). TRVs based on tissue residue concentrations ranged from 50.2 to 77.8 ng TEQ/kg liver (wet weight) for the no observable adverse effect concentration (NOAEC) and the value was 189 ng TEQ/kg liver (wet weight) for the lowest observable adverse effect concentration (LOAEC). Selection of a TRV should be based on studies of compounds that are most similar to those at a site of interest. In particular, it was determined that the effects of PCDFs could not be accurately predicted from the use of TEQ-based TRVs developed from studies of PCDDs or PCBs. Risk assessors should be aware that exceedance of these TRVs would not necessarily be expected to lead to ecologically relevant adverse effects because of the inherently conservative assumptions made in the TRV derivation process.