Human biomonitoring of dioxins, furans, and non-ortho dioxin-like polychlorinated biphenyls (PCBs) in blood plasma from Old Crow, Yukon, Canada (2019).

Dioxins, furans, and dioxin-like polychlorinated biphenyls (PCBs) are a group of persistent and toxic chemicals that are known to have human health effects at low levels. These chemicals have been produced for commercial use (PCBs) or unintentionally as by-products of industry or natural processes (PCBs, dioxins, and furans). Additionally, dioxin-like PCBs were formerly used in electrical applications before being banned internationally (2004). These chemicals are widely dispersed in the environment as they can contaminate air and travel hundreds to thousands of kilometers before depositing on land or water, thereafter, potentially entering food chains. Community concerns surrounding the safety of traditional foods prompted a human biomonitoring project in Old Crow, Yukon Territory (YT), Canada (2019). Through collaborative community engagement, dioxins and like compounds were identified as a priority for exposure assessment from biobanked samples. In 2022, biobanked plasma samples (n = 54) collected in Old Crow were used to measure exposures to seven dioxins, ten furans, and four dioxin-like PCBs. 1,2,3,6,7,8-HxCDD, 1,2,3,7,8,9-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, 1,2,3,6,7,8-HxCDF, PCB 126, and PCB 169 were detected in at least 50 % of samples. Among these analytes, the only congener at elevated levels was PCB 169, which was approximately ∼2-fold higher than the general population of Canada. No significant sex-based or body mass index (BMI) differences in biomarker concentrations were observed. Generally, the concentrations of the detected congeners increased with age, except for 1,2,3,4,6,7,8-HpCDD. For the first time, this research measures dioxin and like-compound exposures in Old Crow, advancing the information available on chemical exposures in the Arctic. Further research could be directed towards the investigation of PCB 169 exposure sources and temporal monitoring of exposures and determinants.

Photodegradation of 2-chlorodibenzo-p-dioxin (2-CDD) on the surface of municipal solid waste incineration fly ash: Kinetics and product analysis.

Considering that waste incineration fly ash is the main carrier of dioxins and can migrate over long distances in the atmosphere, it is of great significance to study the photochemical transformation behavior of dioxins on the surface of fly ash. In this work, 2-chlorodibenzo-p-dioxin (2-CDD) was selected to conduct a systematic photochemical study. The influence of various factors on the photodegradation of 2-CDD were first explored, and the results showed that small particle size of fly ash, low concentration of 2-CDD and appropriate level of humidity were more conducive to photodegradation, with the highest degradation percentage reaching 76%-84%. The components of fly ash (Zn (Ⅱ), Al (Ⅲ), Cu (Ⅱ) and SiO2) also had a certain promoting effect on the degradation of 2-CDD, which increases the degradation efficiency by 10%-20%, because they could act as effective photocatalysts to produce free radicals for reaction. With a higher total light exposure intensity, natural light environments led to a more complete degradation of 2-CDD than laboratory Xe lamp irradiation (90% degradation Vs. 79% degradation). Based on chemical probe and radical quenching experiment, hydroxyl radical also contributed to 2-CDD photodegradation on fly ash. A total of 16 intermediate products were detected by mass spectrometry analysis, and four initial reaction pathways of 2-CDD were speculated in the process, including dechlorination, ether bond cleavage, hydroxyl substitution, and hydroxyl addition. According to the results of density functional theory calculation, the reaction channels of ether bond cleavage and •OH attack were determined. The toxicity assessment software tool (TEST) was used to assess the toxicity and bioconcentration coefficient of reaction products, and it was found that the overall toxicity of the photodegradation products was reduced. This study would provide new insights into the environmental fate of dioxins during long-range atmospheric migration process.

Comprehensive characterization and prioritization of halogenated organic compounds in fish and their implications for exposure.

Fish are an important pollution indicator for biomonitoring of halogenated organic compounds (HOCs) in aquatic environments, and HOCs in fish may pose health threats to consumers. This study performed nontarget and comprehensive analyses of HOCs in fish from an e-waste recycling zone by gas chromatography-high-resolution mass spectrometry, and further prioritized their human exposure risks. A total of 1652 formulas of HOCs were found in the fish, of which 1222, 117, and 313 were organochlorines, organobromines, and organochlorine-bromines, respectively. The total concentrations of HOCs were 15.4-18.7 µg/g (wet weight), and organobromines were the predominant (14.1-16.8 µg/g). Of the HOCs, 41 % were elucidated with tentative structures and divided into 13 groups. The estimated total daily exposures of HOCs via dietary consumption of the fish for local adult residents were 3082-3744 ng/kg bw/day. The total exposures were dominated by several groups of HOCs with the following contribution order: polyhalogenated biphenyls and their derivatives > polyhalogenated diphenyl ethers > halo- (H-)alkanes/olefines > H-benzenes > H-dioxins > H-polycyclic aromatic hydrocarbons > H-phenols. The comprehensive characterization and prioritization results provide an overview of the species and distributions of HOCs in edible fish, and propose an inventory of crucial HOCs associated with high exposure risks.

Results of an international interlaboratory study on dioxin-like activities in drinking-, river surface- and wastewater using DR CALUX bioassay.

Aquatic animals and consumers of aquatic animals are exposed to increasingly complex mixtures of known and as-yet-unknown chemicals with dioxin-like toxicities in the water cycle. Effect- and cell-based bioanalysis can cover known and yet unknown dioxin and dioxin-like compounds as well as complex mixtures thereof but need to be standardized and integrated into international guidelines for environmental testing. In an international laboratory testing (ILT) following ISO/CD 24295 as standard procedure for rat cell-based DR CALUX un-spiked and spiked extracts of drinking-, surface-, and wastewater were validated to generate precision data for the development of the full ISO-standard. We found acceptable repeatability and reproducibility ranges below 36 % by DR CALUX bioassay for the tested un-spiked and spiked water of different origins. The presence of 17 PCDD/Fs and 12 dioxin-like PCBs was also confirmed by congener-specific GC-HRMS analysis. We compared the sum of dioxin-like activity levels measured by DR CALUX bioassay (expressed in 2,3,7,8-TCDD Bioanalytical Equivalents, BEQ; ISO 23196, 2022) with the obtained GC-HRMS chemical analysis results converted to toxic equivalents (TEQ; van den Berg et al., 2013).

Distributions of PCDD/Fs, PCBs, and PCNs in coastal sediments collected from major industrial bays in South Korea.

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) were assessed in coastal sediments from industrial bays in South Korea to evaluate the pollution levels and their environmental impact. The mean sediment concentrations of Σ17 PCDD/Fs, Σ18 PCBs, and Σ15 PCNs were 198 ± 140, 3427 ± 7037, and 85 ± 336 pg/g dw, respectively. Generally, pollutant concentrations in the inner bay were higher than those in the outer bay, indicating the influence of industrial emissions and harbor activities. The primary sources were identified as steel manufacturing and wastewater treatment plants for PCDD/Fs, harbor and shipbuilding activities for PCBs, and combustion-related sources for PCNs. Notably, PCDD/F concentrations exceeded sediment guideline values. The combined effects of PCDD/Fs and PCBs demonstrated adverse impacts on aquatic organisms. Hence, the release of toxic pollutants into the marine environment could have potential biological effects due to the combined impact of these various compounds.

Polychlorinated dibenzodioxins/furans and dioxin-like polychlorinated biphenyls in fish and crustaceans of a recreationally fished estuary, following targeted remediation.

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) are a suite of harmful chemicals (hereafter collectively referred to as 'dioxins'), and their emission into aquatic habitats leads to persistent contamination of sediments, aquatic food-webs, and seafoods. Quantifying contaminant levels in seafood species is important for the ongoing management of exposure risk by fishers, particularly after any remediation actions. We present dioxin concentrations in four seafood species (Yellowfin Bream Acanthopagrus australis, Sea Mullet Mugil cephalus, Eastern School Prawn Metapenaeus macleayi, and Eastern King Prawn Penaeus plebejus) in a recreationally fished estuary, in relation to a contaminated site that has undergone a remediation process, partially removing contaminated sediments (Homebush Bay, Port Jackson, New South Wales, Australia). Dioxin concentrations in these species were measured before (2005/6) and after (2015/16) remediation at a range of locations in and around the remediated site. Dioxin concentrations and congener profiles differed substantially among taxa, and concentrations were frequently higher than Australian screening criteria. The two prawn species showed evidence of a decline in dioxin concentrations after remediation, but the fish species only showed a declining dioxin concentration with distance from the contaminated site (not between periods). There were some minor changes in the congener profile for some species following remediation. While there was evidence for greatly reduced dioxin concentrations in prawn species following remediation, the complex patterns for fish were likely affected by environmental changes, species-specific and temporal changes in lipid content, and animal movement patterns. Future monitoring may aid interpretation of the patterns and modelling of exposure risk associated with seafood consumption into the future.

Distribution of gasification products and emission of heavy metals and dioxins from municipal solid waste at the low temperature pyrolysis stage.

Gasification is widely regarded as one of the most practical, economical, and environmentally friendly waste disposal technologies for municipal solid waste (MSW). The pyrolysis stage (300-500 °C) is crucial for weight loss during MSW gasification, as a considerable amount of organic matter breaks down, producing high-value synthesis gas. This study investigated the product distribution and pollutant emission characteristics within this temperature range and its influencing factors during MSW gasification using a self-designed MSW gasification device. Results indicated that MSW underwent approximately 70% weight loss within this temperature range, yielding low amounts of inorganic and short-chain organic products, with mainly long-chain organic compounds of C16-C34. The atmosphere variation had minimal effect on the elemental composition and content of solid phase products. X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS) analyses showed that Mn and Zn were the primary components of heavy metal leaching toxicity in solid phase products, with their contents increasing as temperature increased. Synthesis gas showed the highest content of heavy metal As element, reaching a peak at 400 °C. Higher gasification temperature and lower oxygen flow rate significantly reduced the dioxin content and I-TEQ values, with highly chlorinated isomers being the predominant dioxin isomers. Nonetheless, low-chlorinated dioxins accounted for more than 50% of the I-TEQ. This study improves our understanding of the gasification process of MSW.

Dietary exposure levels to polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and non-ortho-polychlorinated biphenyls in US meat, poultry and siluriform fish from 2018 to 2019.

Daily dietary exposure estimates from beef, pork, chicken, turkey and siluriform fish were calculated using toxic equivalency (TEQ) data from the U.S. Department of Agriculture's survey of dioxins and dioxin-like compounds (DLCs) in the domestic meat supply and consumption data. Exposure estimates for the whole population and age groups were based on mean consumption of a commodity and mean or 90th percentile TEQ dioxin levels from the survey. Ratios of the exposure estimates to the U.S. EPA oral reference dose (RfD) of 0.7 pg TEQ/kg bw/day were calculated to determine if domestic meat might contribute materially to consumer exposure. In general, normal consumption of lean beef, pork, chicken and turkey will not cause exposures exceeding the RfD. Non-lean meats will have higher dioxin levels as dioxins accumulate in fat, therefore consumption of non-lean meat might cause higher exposure than compared to lean meat. However, on a mean basis, none of the exposure estimates for non-lean beef, pork, chicken or turkey exceeded the RfD for any of the age groups. For some age groups, especially toddlers, there are commodities such as non-lean beef in the 90th percentile of dioxin TEQs and siluriform fish that might exceed the RfD on occasion.

Dioxins and furans maternal transfer: A study of breast milk and cord serum levels among Lebanese mothers and associations with newborn anthropometric measurements.

Dioxins and furans (PCDD/Fs) are anthropogenic pollutants that persist in the environment for long years, bioaccumulating in food & contaminating humans. In pregnancy, they can transfer through the placenta and reach the fetus, which negatively affects fetal growth. They can also reach newborns through breastfeeding. In this study, we focused on this critical subpopulation and identified the presence of PCDD/Fs among pregnant women in breast milk (n = 41) and cord serum (n = 49); we assessed the correlation between different matrices, evaluated the predictors and associations with newborn anthropometric measurements. Over 70.7 % of PCDD/Fs were detected in breast milk and 46.9-55.1 % in cord serum. Cord/maternal serum and breast milk to maternal serum ratios were > 1 with a significant positive Spearman correlation (0.669-0.729). Breast milk & maternal serum PCDD/Fs were associated inversely with age and positively with red meat intake. Cord serum PCDD/Fs were inversely associated with pre-pregnancy weight loss and passive smoking. Parity and gestational weight gain showed positive associations with Z-scores at birth. Z-score differences showed negative and positive associations with passive smoking and pre-pregnancy BMI respectively.

Levels, patterns and risk assessment of PCDD/Fs and dl-PCBs through dietary exposure in the Valencian Region (Spain).

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin like polychlorinated biphenyls (dl-PCBs) levels were measured in representative vegetable oils and animal origin foodstuffs collected in a Total Diet Study carried out in the Valencian Region (Spain). A total amount of 3,300 food samples were collected and grouped into 5 main food groups: vegetable oils, meat and meat products, eggs, milk and dairy products and fish and sea products. The samples were analysed using gas chromatography coupled to high-resolution mass spectrometry (GC-HRMS). The food group which presented the highest concentration in wet weight (ww) for the sum of PCDD/Fs and dl-PCBs was fish and sea products (0.5 pg TEQ g-1 ww), whereas meat and meat products (0.6 pg TEQ g-1 lipid) showed the highest levels expressed in lipid terms. Occurrence data of PCDD/F and dl-PCBs were combined with consumption data to estimate the dietary exposure of adults (>15 years) and children (6-15 years). Finally, the estimated weekly intake (EWI) was calculated using a deterministic approach and considering the food consumption of the population, with fish and sea products being the main food group contributor. Likewise, considering the worst-case scenario (Upper Bound, UB), average EWI were 1.8 and 3.4 pg TEQ kg-1 body weight (bw) week-1 for adults and children, respectively. For children, the average EWI was almost twice above the tolerable weekly intake (TWI) of 2 pg TEQ kg-1 bw week-1 set by EFSA in 2018. In terms of risk characterisation, the overall obtained results showed that 19 % of adults and 43 % of children may exceed the TWI when using UB.

Feed materials - Levels and characteristic profiles of dioxins and PCBs.

Dioxins (PCDD/PCDF) are toxic compounds that are ubiquitous in the environment; although present in low concentrations, they are persistent and highly toxic and they bioaccumulate in food chains. Therefore, it is very important that feed is free of these types of contaminants, because otherwise they can become a source that can negatively affect animal health and the safety of food of animal origin. The aim of the study was to comprehensively assess the concentrations of dioxins and polychlorinated biphenyls (PCBs) in a variety of feed materials available on the Polish market. In addition, characteristic profiles of congeners for given categories of feeds were investigated and defined. Approximately 95 % of the 523 samples of various feed materials tested over seven years (2013-2018 and 2022) met the requirements of European Union feed law (Commission Regulation 277/2012/EU). The highest average PCDD/PCDF/dl-PCB concentrations were found in fish oils and meal and were respectively 1.17 ± 0.78 and 5.51 ± 4.51 ng WHO-TEQ/kg of feed at 12 % moisture. Median and background level concentrations of PCDD/PCDFs, dl-PCBs, PCDD/PCDF/dl-PCBs, and ndl-PCBs were significantly lower than their average concentrations for each individual feed material category. The WHO-TEQ profiles enabled the identification of three different characteristic profiles in feed materials.

Distribution of PCDD/Fs and PCBs at different locations in a circulating fluidised bed municipal solid waste incinerator.

This study investigates a circulating fluidised bed (CFB) incineration plant to examine the concentrations and fingerprints of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) at five locations downstream of the post-combustion zone. Sampling encompassed both flue gas and ash, spanning from the high-temperature superheater to the outlet of the baghouse filter, thus covering a wide range of flue gas temperatures. The analysis reveals a continuous increase in PCDD/F and PCB concentrations in the flue gas from the superheater to the inlet of the air pollution control system (APCS). The maximum concentrations observed were 75.8 ng/Nm3 for PCDDs, 219 ng/Nm3 for PCDFs, and 763 ng/Nm3 for PCBs. These values represent 9.14, 11.5, and 6.37 times their respective concentrations at the outlet of the high-temperature superheater. Concurrently, the levels of PCDD/Fs and dioxin-like PCBs (dl-PCBs) in the ash steadily increased along the cooling path of the flue gas within the plant. Comparing dl-PCBs to the total amount of 209 PCB congeners, it was evident that dl-PCBs exhibited a trend more akin to that of PCDD/Fs. A robust linear correlation was observed between dl-PCBs and PCDD/Fs (R2 = 0.99, p < 0.001), surpassing that between PCBs and PCDD/Fs (R2 = 0.92, p < 0.01), suggesting that dl-PCBs share closer formation pathways with PCDD/Fs. Additionally, elemental composition analysis of fly ash samples aimed to explore potential links between fly ash characteristics and PCDD/F and PCB formation. The Cl/S ratio increased from 1.58 to 5.13 with decreasing flue gas temperature. Principal component analysis (PCA) was employed to visualise the concentrations of PCDD/Fs and PCBs in the flue gas alongside elemental contents in the fly ash. With the exception of PCBs in ash, all other PCDD/Fs and PCBs in fly ash exhibited positive correlations with both carbon (C) and chlorine (Cl). Furthermore, a positive relationship between C/Cl and PCDD/Fs-PCBs in fly ash implies that fly ash serves as the primary reaction surface for dioxin generation during low-temperature heterogeneous catalytic reactions.

Dietary intakes of dioxins and polychlorobiphenyls (PCBs) and mortality: EPIC cohort study in 9 European countries.

Dioxins and polychlorinated biphenyls (PCBs) are toxic, endocrine disruptors and persistent chemicals for which the main exposure source is diet due to their bioaccumulation and biomagnification in food chains. Cohort studies in the general populations have reported inconsistent associations between these chemicals in serum/plasma and mortality. Our objective was to study the association between dietary intake of 17 dioxins and 35 PCBs and all-cause, cancer-specific and cardiovascular-specific mortalities were assessed in the European Prospective Investigation into Cancer and Nutrition (EPIC) cohort. Dietary intake of dioxins and PCBs was assessed combining EPIC food consumption data with European food contamination data provided by the European Food Safety Authority. We applied multivariable Cox regressions. The analysis included 451,390 adults (mean ± SD age:51.1 ± 9.7 years) with 46,627 deaths and a median follow-up of 17.4 years (IQR = 15.2-19.1). A U-shaped non-linear association with all-cause mortality for dietary intake of dioxins (Pnon-linearity<0.0001), DL-PCB (Pnon-linearity = 0.0001), and NDL-PCBs (Pnon-linearity<0.01) was observed. For example, the hazard ratios (95%Confidance interval) for all-cause mortality obtained with the spline model was equal to 1.03 (1.02-1.05) for low levels of intake to dioxins (7 pg TEQ/day), 0.93 (0.90-0.96) for moderate levels of intake (25 pg TEQ/day), while for high levels of intake (55 pg TEQ/day) it was 1.03 (0.97-1.09). Intake of dioxins, DL-PCBs and NDL-PCBs was not associated with cardiovascular mortality. There was no association between intakes of dioxins and cancer mortality, but a U-shaped association was observed for intake of DL-PCBs and intakes of NDL-PCBs and cancer mortality. The PCBs and dioxins are known to have endocrine disrupting properties which can lead to non-monotonic dose responses. These results need to be interpreted with caution and further studies are needed to better clarify the association between dietary intake of dioxins and PCB and mortality in the general population.

Estimation of dietary intake of polychlorinated dibenzo-p-dioxins and dibenzofurans and dioxin-like polychlorinated biphenyls from the Thai total diet study in 2019.

Dietary intakes of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) were assessed in the Thai Total Diet Study (TDS) in 2019. Food samples including portable water (n = 1048) were collected from four regions of Thailand to represent a whole diet of Thai population, prepared as consumed and analyzed. To estimate the dietary intakes of PCDD/Fs and DL-PCBs, the concentrations in 18 food groups were combined with the respective food consumption from the national consumption data of Thailand and with a mean body weight of 57.57 kg for Thai population aged ≥ 3 years. The dietary intakes of PCDD/Fs, DL-PCBs and ∑PCDD/Fs/DL-PCBs were estimated to be 8.09, 4.93 and 13.02 pg WHO2005-TEQ kg-1 body weight month-1, respectively (upper bound). The major contributors to the total dietary intake were marine animals, followed by milk and milk products, freshwater animals, pork and pork products, and eggs, corresponding to 26, 22, 21, 10 and 9%, respectively. In comparison to health-based guidance value (HBGV), the intake of ∑PCDD/Fs/DL-PCBs (upper bound) was equal to 19% of the provisional tolerable monthly intake set by JECFA in 2001. Moreover, a comparison with other HBGVs was additionally presented and discussed.

Troubleshooting dioxins stack emissions in an industrial waste gas incinerator.

An important source of dioxins and furans at present is waste incineration, utmost formed during combustion processes and emitted to the environment without being fully captured by waste-gas treatment equipment. In this study, monitoring campaign of International Toxic Equivalents for dioxins and furans (I-TEQDF), was carried out at pharmaceutical industrial waste incinerator to find a correlation between combustion parameters and feed composition with potential emission. Principal Component Analysis (PCA) shows that high values of dioxin emission correlate with short residence time of the flue gas in the furnace as well as low oxygen concentration. These operating conditions were further investigated, using COMSOL Computational Fluid Dynamics (CFD) simulation to calculate the temperature profiles along the furnace. The results suggest that the flame temperature profile is anticipated to exhibit cold areas (cold spots), which may be used as a proxy for dioxin formation due to incomplete combustion. Additionally, the calculated congeners furan to dioxin concentration ratio, points to their formation via de novo mechanism. SEM-EDS analysis preformed on the bag filter upstream the feed following its filtration, have shown large amount of iron, which may have served as a metal catalytic source for dioxin formation. The iron origin is most likely from corrosion of the feeding pipe, drifted with the waste gas and trapped on the bag filter. The results of this study provide a better understanding of the parameters controlling dioxin formation and emission from the plant and may assist a planning of process optimization in such a plant.

Development of a field-deployable analytical workflow for determining current status and indicative human health risks at a historic dl-POPs hotspot.

This paper introduces an integrated workflow that effectively evaluates environmental and health risks of dioxin-like Persistent Organic Pollutants (dl-POPs) at industrial hotspot regions. The developments of validated, cost effective and user-friendly analytical strategies which can be field deployable are quintessential for routine monitoring of dl-POPs, particularly in developing countries. This study addresses the lacunae by enabling an exclusive gas chromatography triple quadrupole mass spectrometer based analytical workflow substituting conventional magnetic sector high resolution mass spectrometer technique and validated the methodology as per the European Union regulation 644/2017. The viable monitoring utility of the methodology for predicting enviro-food-health nexus was field-tested by analyzing fish and sediment samples from the Eloor-Edayar industrial belt, a solitary POPs hotspot in India. The profiles of congeners indicate that dl-POPs were formed through precursor pathways, suggesting the potential release of chlorinated precursor species from surrounding industrial area as the root cause. Fish samples from hotspots were observed to have 8 times higher levels of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) and 30 times higher levels of polychlorinated biphenyls (PCBs) than the control sites. A strong statistically significant (p < 0.05) positive correlation was observed between dl-POPs levels in fish and sediment samples at the study site and the Biota sediment accumulation factors for PCDD/Fs and dl-PCBs ranged from 0.019 to 0.092 and 0.004 to 0.671 respectively. The estimated weekly intake from fish consumption in the study region was observed to be 3 to 24 times higher than the maximum levels set by the European food safety authority (2 pgTEQ kg-1bwweek-1). Hence, the periodic surveillance of dl-POPs employing user friendly/validated confirmatory tools stands highly imperative to safeguard human health and environment. Keywords: Dioxin and PCBs, GC-MS/MS, POPs Hotspot, Biota-sediment accumulation factor, Correlation analysis, Health risk assessment.

Occurrence and carcinogenic potential of airborne PBDD/Fs and PCDD/Fs around a large-scale municipal solid waste incinerator: A long-term passive air sampling study.

Municipal solid waste incinerator (MSWI) not only is deemed one of the uppermost sources of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), but also produces substantial amount of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) owing to the existence of brominated flame retardants (BFRs) in the waste. So far, however, PBDD/Fs in the vicinal environments of MSWI and their associated risks remain rarely studied. Based on a one-year passive air sampling (PAS) scheme, we investigated airborne PBDD/Fs and PCDD/Fs around a large-scale MSWI that has been operated for multi-years. Both the concentrations of PBDD/Fs and PCDD/Fs showed spatially decreasing trends with the distance away from the MSWI, confirming the influence of the MSWI on the dioxin levels in its ambient air. But its influence on PBDD/Fs was less because PBDD/Fs exhibit lower volatility and therefore lower gaseous concentrations than PCDD/Fs. Compared to the existing global data of airborne PCDD/Fs and PBDD/Fs, our data of the MSWI vicinity were at medium levels, despite PAS samples only represent the concentrations of gaseous dioxins in theory. The seasonal data suggest that meteorological conditions exerted apparent influences over the concentrations and sources of airborne dioxins around the MSWI. As for PCDD/Fs, the MSWI was diagnosed as their uppermost source, followed by local traffic and volatilization/deposition. Whereas the top three PBDD/F sources were related to PBDEs, bromophenol/bromobenzene, and traffic vehicles, respectively. The bioassay-derived TEQs based on the aryl hydrocarbon receptor activation of airborne dioxins around the MSWI were one or two orders of magnitudes higher than their concentration-based TEQs, and the corresponding carcinogenic risks at some MSWI-vicinal sites exceeded the acceptable threshold proposed by the U. S. EPA (10-6 âˆ¼ 10-4) and deserve continuous attention.

Global survey of dioxin- and thyroid hormone-like activities in consumer products and toys.

BACKGROUND: Children and consumers are exposed to increasingly complex mixtures of known and as-yet-unknown toxic chemicals from toys and products. However traditional chemical analysis methods only evaluate a small number of chemicals at a time thereby restricting consumer awareness of the full range of potentially harmful chemicals in products. METHODS: We used high-throughput effect-based non-animal methods to investigate exposures to complex chemical mixtures of several kinds of brominated flame retardants (BFRs) for their dioxin- and thyroid hormone-like activities in various kinds of consumer products and toys from 26 different countries, on four continents (Africa, America, Asia and Europe) in combination with chemical analysis of various polybrominated flame retardants (BFRs) and their impurities (such as polyhalogenated PCDD/Fs and PBDD/Fs). RESULTS: We found high levels of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in toys and now, for the first time, also in consumer products that are manufactured from black plastics containing certain brominated flame retardants (BFRs). The presence of PBDD/PBDFs as well as other BFRs in various black plastic materials from additional countries as well as additional kinds of consumer products as confirmed by effect-based in vitro reporter gene DR CALUX and TTR-TRß CALUX assays as well as congener-specific chemical analysis. We compared total Toxicity Equivalent (TEQ) levels of PBDD/F-TEQs analysed by chemical analysis to by CALUX bioassay measured Biological equivalence (BEQ) concentrations (for further info see at ISO 23196, ISO, 2022). In the case of TBBPA, both chemical and TTR-TRß CALUX analysis measure direct the amount of TBBPA. Finally, the daily ingestion of 2,3,7,8-TCDD equivalents from PBDD/Fs-contaminated plastic toys by child mouthing habits have been related to our earlier study (Budin et al., 2020). CONCLUSIONS: Interaction of children with such contaminated plastics may significantly contribute to the daily uptake of dioxin- and thyroid hormone transport disrupting-like compounds. Effect-based bioassays for dioxin- and thyroid hormone-like activities are relevant to pick-out such complex mixtures of known and yet unknown (and therefore not regulated) substances for safer and more sustainable plastics. Low POPs Content Levels and other mechanisms set under the Basel and Stockholm Conventions are set far too high to prevent a significant flow of BFRs and PBDD/Fs into consumer products.

Nontarget and Comprehensive Analyses of Halogenated Organic Additives in Electrical Product Plastics by GC-NCI-Q-Orbitrap-HRMS and Cl/Br-Screening Algorithms.

Halogenated organic additives (HOAs) are used in plastic components of various electrical products, potentially causing detrimental effects on the eco-environment and humans. Besides reported HOAs, many unknown HOAs may be present in electrical product plastics and urgently require identification and characterization. This study performed nontarget analysis and comprehensive characterization of HOAs in three typical electrical product plastics by nontarget analysis using gas chromatography-negative chemical ionization-high-resolution mass spectrometry in association with in-house-developed chlorine/bromine-specific data-processing algorithms. A total of 674 formulas of HOAs were identified in the plastics dismantled from three electrical products, among which 166, 362, and 146 were organochlorines, organobromines, and mix-chlorinated/brominated organic compounds, respectively. The identified HOAs were semiquantified, and the total concentrations of HOAs in individual plastics were 445-1549 ng/g. Organobromines showed the most species and the highest abundances in all of the plastics, of which the abundances accounted for 86.6-98.0% of the total HOAs. Partial HOAs (209 formulas) were tentatively structurally elucidated, which were classified into 13 groups, i.e., halogenated alkyl phenoxyethyls (H-alkyl phenoxyethyls), H-alkylbenzenes, H-benzenes, H-bisphenol A (H-BPAs), H-dioxins, H-diphenyl ethers, H-biphenyls/terphenyls, H-polycyclic aromatic hydrocarbons, H-phenols, H-phenyl esters, H-phenyl-aldehydes/ketones, H-quinones, and an undefined group containing the HOAs such as dechlorane plus and chlordane. H-BPAs were the predominant HOAs in the plastics, showing relatively high concentrations (13-281 ng/g), and tetrabromobisphenol A was the most abundant H-BPA, with the concentrations of 9-196 ng/g. The comprehensive characterization results represent a holistic picture on the species features and abundance distributions of HOAs in electrical product plastics and provide an inventory of crucial HOAs worthy of concern. HOAs may migrate from plastics and release into the environment and are possibly an important source of halogenated organic pollutants in the environment, thus calling for further investigation and proper regulation.

Polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs) contamination in sediments and fish from Msimbazi River in Dar es Salam, Tanzania: patterns, sources, and their exposure to humans.

Results of a two-dimensional gas chromatograph time of flight mass spectroscopy (GCXGC-TOFMS) determination of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDF) in sediments and catfish samples collected from the Msimbazi River are presented here. Samples were extracted using USEPA Method 1613. PCDD/Fs congeners in sediments ranged from 2.0 to 393.0 and 0.7 to 654.8 pg/g in the dry and wet seasons, respectively. 1,2,3,4,7,8,9-HepCDF was detected at the highest concentration, but all were lower than the USA action level of 1000 pg/g. Toxicity for each of the sampling points ranged from 19.7 to 36.5, with a mean concentration of 27.0 pg WHO 2005-TEQ g-1 in the dry season and 2.0 to 38.7 with a mean concentration of 20.7 pg WHO 2005-TEQ g-1 in the wet season. Analysis of variance (ANOVA) showed that there was no significant difference between PCDD/Fs TEQ during the dry and wet seasons (p = 0.08; α = 0.05). The highest TEQ value was estimated at Jangwani in the wet season. Toxicity of PCDD/Fs in catfish collected from the Msimbazi River ranged from 9.3 to 145.2, with a mean of 61.2 pg WHO2005-TEQg-1. Tetrachlorodibenzo dioxin (2, 3, 7, and 8-TCDD) was detected in all fish samples and ranged from 3.5 to 12.7 with a mean of 8.1 pg/g. The concentration of TCDD in fish exceeded the Agency for Toxic Substance and Diseases Registry MRL, thus posing a probable high risk to people whose dietary requirements depend on fish from the Msimbazi River.