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Objective: To analyze the level of PCDD/Fs exposure of occupational workers in the waste incineration industry and explore the risk of occupational exposure. Methods: In September 2021, literature on environmental PCDD/Fs exposure in waste incineration plants published from the establishment of the database to February 10, 2021 was retrieved from CNKI database. A total of 1365 literatures were retrieved, and 7 met the criteria for inclusion. The US Environmental Protection Agency (EPA) inhalation risk model was used to assess and analyze carcinogenic and non-carcinogenic risks of PCDD/Fs exposure among occupational workers in the waste incineration industry. Results: A total of 86 sampling sites were included in incineration plants in 7 regions. The study of Wuhan area showed that the concentration of working environment near the waste incinerator in the same factory was the highest, followed by the rest and office area in the factory. The concentration of PCDD/Fs in waste incinerators was the highest in Southwest China (4880.00-24880.00 pg TEQ/m(3)), and the lowest in Shenzhen (0.02-0.44 pg TEQ/m(3)). According to the cancer risk assessment, with the increase of exposure years, the risk of cancer increased. The highest risk of cancer was found in the waste incineration plants in Southwest China. When the exposure period was 1 year, the risk was moderate (22.40×10(-6)-114.20×10(-6)). When the exposure time was more than 5 years, the risk of cancer was high. In Jinan, workers working near the incinerator had a moderate risk of cancer after five years of exposure. In Zhejiang, workers were at medium risk of cancer after exposure for more than 20 years. Workers in Wuhan, Shanghai, Zhejiang Province, Shenzhen and the Pearl River Delta were still at low risk of cancer after 40 years of occupational exposure. HQ>1 of workers working near the waste incinerators in Jinan, Zhejiang Province and Southwest China, and the qualitative evaluation results showed that the non-carcinogenic risk was unacceptable. Conclusion: There are great differences in PCDD/Fs of occupational exposure in waste incineration industry, and the occupational exposure exceeding the occupational exposure limit has higher carcinogenic and non carcinogenic risks.

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Objective: To analyze the level of PCDD/Fs exposure of occupational workers in the waste incineration industry and explore the risk of occupational exposure. Methods: In September 2021, literature on environmental PCDD/Fs exposure in waste incineration plants published from the establishment of the database to February 10, 2021 was retrieved from CNKI database. A total of 1365 literatures were retrieved, and 7 met the criteria for inclusion. The US Environmental Protection Agency (EPA) inhalation risk model was used to assess and analyze carcinogenic and non-carcinogenic risks of PCDD/Fs exposure among occupational workers in the waste incineration industry. Results: A total of 86 sampling sites were included in incineration plants in 7 regions. The study of Wuhan area showed that the concentration of working environment near the waste incinerator in the same factory was the highest, followed by the rest and office area in the factory. The concentration of PCDD/Fs in waste incinerators was the highest in Southwest China (4880.00-24880.00 pg TEQ/m(3)), and the lowest in Shenzhen (0.02-0.44 pg TEQ/m(3)). According to the cancer risk assessment, with the increase of exposure years, the risk of cancer increased. The highest risk of cancer was found in the waste incineration plants in Southwest China. When the exposure period was 1 year, the risk was moderate (22.40×10(-6)-114.20×10(-6)). When the exposure time was more than 5 years, the risk of cancer was high. In Jinan, workers working near the incinerator had a moderate risk of cancer after five years of exposure. In Zhejiang, workers were at medium risk of cancer after exposure for more than 20 years. Workers in Wuhan, Shanghai, Zhejiang Province, Shenzhen and the Pearl River Delta were still at low risk of cancer after 40 years of occupational exposure. HQ>1 of workers working near the waste incinerators in Jinan, Zhejiang Province and Southwest China, and the qualitative evaluation results showed that the non-carcinogenic risk was unacceptable. Conclusion: There are great differences in PCDD/Fs of occupational exposure in waste incineration industry, and the occupational exposure exceeding the occupational exposure limit has higher carcinogenic and non carcinogenic risks.

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The concentrations of PCDD/Fs, PCBs, and PCNs in the soil samples around a typical secondary copper smelter were determined simultaneously, and then the impact of the smelter on the surrounding environment and the health risks of workers in the study area were analyzed and evaluated. PCDD/F, PCB, and PCN concentrations were in the range of 17.2-370, 1.20-14.2, and 70.9-950 pg·g-1 in the soil around the smelter, respectively. High concentrations of PCDD/Fs and PCNs were observed at the sample sites close to the secondary copper smelter (<300 m), and their concentrations exponentially decreased with an increase in distance from the smelter. The results of the source analysis showed that the secondary copper smelter had a significant impact on the PCDD/Fs and PCNs content and congener profiles of the soil within 300 m of its surroundings. In addition, the PCDD/Fs pollution in the surrounding soil may also have been affected by the historical use of pentachlorophenol or sodium pentachlorophenol in addition to the secondary copper smelter. The health risk assessment results showed that the non-carcinogenic and carcinogenic risks of workers exposed to PCDD/Fs, PCBs, and PCNs in the surrounding soil were within acceptable levels, and that oral ingestion was the main exposure route. Although the health risk assessment only considered the exposure of workers to these pollutants in an outdoor environment during working hours, the carcinogenic risk values of the two soil samples had reached 0.47×10-6 and 0.15×10-6 (threshold value 10-6), so they should attract our attention. PCDD/Fs had the highest contribution rate (96%) to the total carcinogenic risk (PCDD/Fs+PCBs+PCNs), and they were the dioxins that need to be the primary concern and control in the study area.

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All the possible polychlorinated aromatic compounds in the classes of dibenzodioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) were studied by the quantum chemical methods of HF/6-311++G(d,p), B3LYP/6-311++G(d,p), and MP2/cc-pVTZ. The calculated stabilities and structures of these compounds were compared with the available data on their abundance and toxicity. Prediction models for trends in energy and planarity among these congeners were proposed. The results discussed here can help contribute to the understanding of the role of dioxin-like compounds (DLCs) in the environment.

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The Anniston Community Health Survey (ACHS-I) was initially conducted from 2005 to 2007 to assess polychlorinated biphenyl (PCB) exposures in Anniston, Alabama residents. In 2014, a follow-up study (ACHS-II) was conducted to measure the same PCBs as in ACHS-I and additional compounds e.g., polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like non-ortho (cPCBs) substituted PCBs. In this epigenome-wide association study (EWAS), we examined the associations between PCDD, PCDF, and PCB exposures and DNA methylation. Whole blood DNA methylation was measured using Illumina EPIC arrays (n=292). We modeled lipid-adjusted toxic equivalencies (TEQs) for: ΣDioxins (sum of 28 PCDDs, PCDFs, cPCBs, and mPCBs), PCDDs, PCDFs, cPCBs, and mPCBs using robust multivariable linear regression adjusting for age, race, sex, smoking, bisulfite conversion batch, and estimated percentages of six blood cell types. Among all exposures we identified 10 genome-wide (Bonferroni p≤6.74E-08) and 116 FDR (p≤5.00E-02) significant associations representing 10 and 113 unique CpGs, respectively. Of the 10 genome-wide associations, seven (70%) occurred in the PCDDs and four (40%) of these associations had an absolute differential methylation ≥1.00%, based on the methylation difference between the highest and lowest exposure quartiles. Most of the associations (six, 60%) represented hypomethylation changes. Of the 10 unique CpGs, eight (80%) were in genes shown to be associated with dioxins and/or PCBs based on data from the 2019 Comparative Toxicogenomics Database. In this study, we have identified a set of CpGs in blood DNA that may be particularly susceptible to dioxin, furan, and dioxin-like PCB exposures.

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Anniston, Alabama was home to a major polychlorinated biphenyl (PCB) production facility from 1929 until 1971. The Anniston Community Health Survey I and II (ACHS-I 2005-2007, ACHS-II 2013-2014) were conducted to explore the effects of PCB exposures. In this report we examined associations between PCB exposure and DNA methylation in whole blood using EPIC arrays (ACHS-I, n = 518; ACHS-II, n = 299). For both cohorts, 35 PCBs were measured in serum. We modelled methylation versus PCB wet-weight concentrations for: the sum of 35 PCBs, mono-ortho substituted PCBs, di-ortho substituted PCBs, tri/tetra-ortho substituted PCBs, oestrogenic PCBs, and antiestrogenic PCBs. Using robust multivariable linear regression, we adjusted for age, race, sex, smoking, total lipids, and six blood cell-type percentages. We carried out a two-stage analysis; discovery in ACHS-I followed by replication in ACHS-II. In ACHS-I, we identified 28 associations (17 unique CpGs) at p ≤ 6.70E-08 and 369 associations (286 unique CpGs) at FDR p ≤ 5.00E-02. A large proportion of the genes have been observed to interact with PCBs or dioxins in model studies. Among the 28 genome-wide significant CpG/PCB associations, 14 displayed replicated directional effects in ACHS-II; however, only one in ACHS-II was statistically significant at p ≤ 1.70E-04. While we identified many novel CpGs significantly associated with PCB exposures in ACHS-I, the differential methylation was modest and the effect was attenuated seven years later in ACHS-II, suggesting a lack of persistence of the associations between PCB exposures and altered DNA methylation in blood cells.

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Polychlorinated-dibenzo-para-dioxins (PCDDs) and Polychlorinated-dibenzofurans (PCDFs) contamination in ecosystems has been a major concern, however, no information is available about the atmospheric contents and emission profiles in different types of fuels from industrial boilers in Thailand, Lao PDR, and Cambodia. Nine air and bottom ash samples (n = 18) were collected from three industrial boilers using U.S.EPA Method 23 and U.S.EPA Method 8290, respectively. All samples were successfully quantified by two High Resolution Chromatography-High Resolution Mass Spectrometry (HRGC-HRMS) namely Waters Autospec Premier and Waters Autospec Ultima. This investigation elucidates the impacts of fuel type on the emissions of PCDDs and PCDFs from three different industrial boilers. It appears plausible to affirm that fuel types play an important role on PCDD/PCDF emission levels from industrial boilers. The results of PCDD/PCDF concentrations should be considered as baseline data for promoting Best Available Technique (BAT) and Best Environmental Practise (BEP) in order to reduce dioxin emissions from industrial boilers in Southeast Asian countries.

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Removal/destruction of aqueous-phase octachlorodibenzo-p-dioxin (OCDD) and octachlorodibenzofuran (OCDF) via hydrodechlorination process (HDC) is experimentally evaluated over palladium/activated carbon (Pd/AC) catalyst. Pd catalyst is mainly used as active component for effectiveness in removing dioxin from wastewater. Studies on the removal of PCDD/Fs accomplished with HDC reaction in aqueous phase are limited and the influencing factors have not been clarified. In this study, high-concentration OCDD/F are selected as targets, and the effects of solvent and operating temperature on dechlorination efficiency are investigated via experimental tests. The results indicate that the highest hydrodechlorination efficiency is achieved with isopropanol as solvent. The OCDD/F removal efficiency achieved with the solution of 80% isopropanol is higher than that of 50% isopropanol, whereas the destruction efficiency of OCDD/F reveals the opposite trend. Generally, the removal and destruction efficiencies of PCDFs are higher than those of PCDDs. In addition, the activation energies of OCDD and OCDF are calculated with the Arrhenius equation as 24.8 and 23.1 kJ/mol, respectively. Stability tests are conducted with three cycles. Overall, the results indicate that a high performance (≥99%) can be achieved by combining hydrodechlorination with Pd/AC at a temperature range of 303-353 K, demonstrating that Pd/AC has good potential for removing PCDD/Fs from wastewater.

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Lindane (γ-hexachlorocyclohexane) manufacture in Spain generated nearly 200,000tonnes of HCH wastes; near 160,000tonnes were originated by the Inquinosa factory located in Sabiñánigo (northern Spain) and were deposited in unlined landfill sites. This study reports for the first time the content of polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/Fs) in non-recycled HCH wastes that had been disposed in the Bailín landfill site in Sabiñánigo. Samples from solid HCH powder residues (white HCH and δ-paste wastes) and the dense non-aqueous phase liquids (DNAPLs), as well as landfill leachates, soil and sediments have been characterized. White HCH wastes exhibited a toxicity of 1488ngWHO-TEQ2005·kg-1 (Σ17 PCDD/Fs), while δ-paste wastes presented a noticeable higher toxicity (12,094ngWHO-TEQ2005·kg-1). Nevertheless, the maximum toxicity value was found for DNAPLs (37,353ngWHO-TEQ2005·L-1). Dioxins were predominant in the DNAPL waste whereas furans predominated in the landfill leachates, soil and sediments. However, in solid HCH wastes, PCDD and PCDFs contributed in a similar proportion. The PCDD/Fs congener profiles in landfill leachates, soil and sediments do not resemble the PCDD/Fs profiles found for the HCH wastes. These preliminary results will be of paramount importance in order to estimate the total quantities of PCDD/Fs disposed to the landfill site and to assess the potential mobility of PCDD/Fs, especially to groundwater and landfill leachates. Besides, this information is of great value to design periodical monitoring plans to evaluate the presence of PCDD/Fs in the impacted groundwater and leachates and finally, to evaluate the risk of PCDD/Fs for the environment and human health.

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Dietary exposure of the Valencia Region population to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and PCBs was assessed in the Region of Valencia in 2010-2011. A total of 7700 food samples were collected. Occurrence data were combined with consumption data to estimate dietary exposure in adults (>15 years of age) and young people (6-15 years of age). The estimated intake was calculated by a probabilistic approach. Average intake levels (upper-bound scenario) were 1.58 and 2.76 pg toxic equivalent (TEQ) kg-1 body weight (bw) day-1 for adults and young people, respectively. These average intakes are within range of the tolerable daily intake of 1-4 pg WHO-TEQ kg-1 bw day-1 recommended by WHO, and slightly above the tolerable weekly intake (TWI) of 14 pg TEQ kg-1 bw week-1 and the Provisional tolerable monthly intake of 70 pg TEQ kg-1 bw month-1 set by the Scientific Committee on Food and the Joint FAO/WHO Expert Committee on Food, respectively. These results show that the contamination levels in food and therefore the exposure of the general population to PCDD/Fs and PCBs have declined in this region and therefore show the efficiency of the European risk-management measures. In terms of risk characterisation, the results showed that, under the upper-bound scenario, 22% of the adult and 58% of the young people population could exceed the TWI.

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The atmospheric chemical reactions of some polyfluorinated dibenzofurans (PFDFs) and polychlorinated dibenzofurans (PCDFs), initiated by OH radical, were investigated by performing theoretical calculations using density functional theory (DFT) and B3LYP/6-311++G(2df,p) method. The obtained results indicate that OH addition reactions of PFDFs and PCDFs occurring at C1∼4 and CA sites are thermodynamic spontaneous changes and the branching ratio of the PF(C)DF-OH adducts is decided primarily by kinetic factor. The OH addition reactions of PFDFs taking place at fluorinated C1∼4 positions are kinetically comparable with those occurring at nonfluorinated C1∼4 positions, while OH addition reactions of PCDFs occurring at chlorinated C1∼4 sites are negligible. The total rate constants of the addition reactions of PFDFs or PCDFs become smaller with consecutive fluorination or chlorination, and substituting at C1 position has more adverse effects than substitution at other sites. The succedent O2 addition reactions of PF(C)DF-OH adducts are thermodynamic nonspontaneous processes under the atmospheric conditions, and have high Gibbs free energies of activation (ΔrG≠). The substituted dibenzofuranols are the primary oxidation products for PCDFs under the atmospheric conditions. However, other oxidative products may also be available for PFDFs besides substituted dibenzofuranols.

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Until recently, European Union (EU) legislation required the use of high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC-HRMS) based on magnetic sector analyzers as a standard approach for confirmatory analysis of dioxins (PCDDs) and furans (PCDFs) in feed and food. However, recent technological advances in MS instruments enabled other alternative analytical techniques to meet the same analytical criteria as those requested for HRGC-HRMS. In this sense, triple quadrupoles (GC-MS/MS) can be a realistic alternative for the analysis of dioxins. In this work, the performance of GC-MS/MS technology was evaluated against the criteria demanded by the EU for confirmatory analysis of dioxins and PCBs in food and feed. Thus, the study comprises a number of parameters including chromatographic separation, limit of quantification, linearity, repeatability, and ion ratio precision. Analyses of solvent standards as well as sample extracts (inter-calibration extracts and certified reference materials) were also considered within the scope of this study. Additionally, direct comparisons of the results obtained by GC-MS/MS with those from GC-HRMS were made. The results of this work suggested that GC-MS/MS was highly sensitive and selective for confirmatory analysis of PCDD/Fs and related compounds in food and feed samples and meets all the criteria requested by the European Commission.

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In the present study, we report on the co-occurrence of persistent organic pollutants (POPs) adsorbed on nanoparticular titanium dioxide (TiO2). We report on the finding of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) on the surface of commercially available TiO2 nanoparticles, being formed during the fabrication process of the TiO2. Thereby, the samples comprise PCBs with higher congener numbers or, in the absence of PCBs, a high concentration of PCDDs and PCDFs. This new class of POPs on an active catalytic surface and the great range of applications of nanoparticular TiO2, such as in color pigments, cosmetics, and inks, give rise to great concern due to their potential toxicity.

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Dioxins include polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and part of polychlorinated biphenyls (PCBs). Only the compounds that are chlorinated at the 2,3,7, and 8 positions have characteristic dioxin toxicity. PCDDs, PCDFs and PCBs accumulate in the food chain due to their high lipophilicity, high stability, and low vapor pressure. They are not metabolized easily; however their hydroxylated metabolites are detected in feces. They cause a wide range of endocrine disrupting effects in experimental animals, wildlife, and humans. Endocrine related effects of PCDDs, PCDFs and PCBs on thyroid hormones, neurodevelopment and reproductive development were referenced. In addition, some studies of contamination of foods, bioaccumulation, dietary exposure assessment, as well as challenges of scientific research in these compounds were reviewed.

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The UPPER (Unified Physicochemical Property Estimation Relationships) model uses enthalpic and entropic parameters to estimate 20 biologically relevant properties of organic compounds. The model has been validated by Lian and Yalkowsky on a data set of 700 hydrocarbons. The aim of this work is to expand the UPPER model to estimate the boiling and melting points of polyhalogenated compounds. In this work, 19 new group descriptors are defined and used to predict the transition temperatures of an additional 1288 compounds. The boiling points of 808 and the melting points of 742 polyhalogenated compounds are predicted with average absolute errors of 13.56 K and 25.85 K, respectively.

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A total of 126 food samples, categorised into three groups (seafood and seafood products, meat and meat products, as well as milk and dairy products) from Malaysia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). The concentration of PCDD/Fs that ranged from 0.16 to 0.25 pg WHO05-TEQ g(-1) fw was found in these samples. According to the food consumption data from the Global Environment Monitoring System (GEMS) of the World Health Organization (WHO), the dietary exposures to PCDD/F from seafood and seafood products, meat and meat products, as well as milk and dairy products for the general population in Malaysia were 0.064, 0.183 and 0.736 pg WHO05-TEQ kg(-1) bw day(-1), respectively. However, the exposure was higher in seafood and seafood products (0.415 pg WHO05-TEQ kg(-1) bw day(-1)) and meat and meat products (0.317 pg WHO05-TEQ kg(-1) bw day(-1)) when the data were estimated using the Malaysian food consumption statistics. The lower exposure was observed in dairy products with an estimation of 0.365 pg WHO05-TEQ kg(-1) bw day(-1). Overall, these dietary exposure estimates were much lower than the tolerable daily intake (TDI) as recommended by WHO. Thus, it is suggested that the dietary exposure to PCDD/F does not represent a risk for human health in Malaysia.

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