Probabilistic human health risk assessment of PCDD/Fs near municipal solid-waste incinerator using Monte Carlo analysis coupled with triangular fuzzy numbers.

PCDD/Fs are dioxins produced by waste incineration and pose risks to human health. We aimed to detail the health risks of airborne and soil PCDD/Fs near a municipal solid-waste incinerator (MSWI) for the surrounding population and develop a new model that improves upon existing methods. Thus, we conducted field sampling and then investigated a MSWI in the Pearl River Delta (2016-2018). Our results showed that the carcinogenic and non-carcinogenic risk values of PCDD/Fs exposed to residents in nearby areas were acceptable, with hazard index (HI) values lower than 1.0 and a total carcinogenic risk lower than 1.0E-6. Notably, the results raised concerns regarding higher non-carcinogenic risks in children than in adults. Comparative analysis of the frequency accumulation diagram, accumulated probability risk, and the absolute value of error (δ) between the 95% confidence interval (CI) and the 90% CI of the Monte Carlo stochastic simulation-triangular fuzzy number (MCSS-TFN) and the MCSS model, respectively, demonstrated that the MCSS-TFN exhibited less uncertainty than the MCSS model, regardless of the health risk value of PCDD/Fs in ambient air or in soil. This observation underscores the superiority of the MCSS-TFN model over other models in assessing the health risks associated with PCDD/Fs in situations with limited data. Our new method overcomes the limited dataset size and high uncertainty in assessing the health risks of dioxin substances, providing a more comprehensive understanding of their associated health risks than MCSS models.

Health assessment of emerging persistent organic pollutants (POPs) in PM2.5 in northern and central Taiwan.

Over the last two decades, Taiwan has effectively diminished atmospheric concentrations of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) through the adept utilization of advanced technologies and the implementation of air pollution control devices. Despite this success, there exists a dearth of data regarding the levels of other PM2.5-bound organic pollutants and their associated health risks. To address this gap, our study comprehensively investigates the spatial and seasonal variations, potential sources, and health risks of PCDD/Fs, Polychlorinated biphenyls (PCBs), and Polychlorinated naphthalene (PCNs) in Northern and Central Taiwan. Sampling collections were conducted at three specific locations, including six municipal waste incinerators in Northern Taiwan, as well as a traffic and an industrial site in Central Taiwan. As a result, the highest mean values of PM2.5 (20.3-39.6 µg/m3) were observed at traffic sites, followed by industrial sites (14.4-39.3 µg/m3), and the vicinity of the municipal waste incinerator (12.4-29.4 µg/m3). Additionally, PCDD/Fs and PCBs exhibited discernible seasonal fluctuations, displaying higher concentrations in winter (7.53-11.9 and 0.09-0.12 fg I-TEQWHO/m3) and spring (7.02-13.7 and 0.11-0.16 fg I-TEQWHO/m3) compared to summer and autumn. Conversely, PCNs displayed no significant seasonal variations, with peak values observed in winter (0.05-0.10 fg I-TEQWHO/m3) and spring (0.03-0.08 fg I-TEQWHO/m3). Utilizing a Positive Matrix Factorization (PMF) model, sintering plants emerged as the predominant contributors to PCDD/Fs, constituting 77.9% of emissions. Woodchip boilers (68.3%) and municipal waste incinerators (21.0%) were identified as primary contributors to PCBs, while municipal waste incinerators (64.6%) along with a secondary copper and a copper sludge smelter (22.1%) were the principal sources of PCNs. Moreover, the study specified that individuals aged 19-70 in Northern Taiwan and those under the age of 12 years in Central Taiwan were found to have a significantly higher cancer risk, with values ranging from 9.26 x 10-9-1.12 x 10-7 and from 2.50 x 10-8-2.08 x 10-7respectively.

Short- and medium-chain chlorinated paraffins in breast milk in Shanghai, China: Occurrence, characteristics, and risk assessment.

As novel contaminants, short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) have been of great concern in the past several years. Shanghai was one of the provinces with the largest chlorinated paraffins (CPs) emission in China; nevertheless, there is currently little information on the human exposure to SCCPs and MCCPs, particularly MCCPs. In this study, 25 breast milk samples were collected in Shanghai from 2016 to 2017. The concentrations of SCCPs and MCCPs were determined using two-dimensional gas chromatography coupled with orbitrap high-resolution mass spectrometry (GC × GC-orbitrap-HRMS) to investigate their characteristics and assess the associated health risks for breast-fed infants. Compared with the previous studies in other areas, the current study presented the higher CPs concentrations, with median concentrations of SCCPs and MCCPs up to 771 and 125 ng/g lipid weight (lw), respectively. The exposure profiles of the CPs were characterized by C10 and Cl6-7 as the predominant congeners of SCCPs, while C14 and Cl7-9 were identified as the dominant groups of MCCPs. CP-42 and CP-52 were identified as potential sources of CPs found in breast milk samples collected in Shanghai. The concentrations of MCCPs exhibited a positive correlation (p value < 0.05) with the dietary consumption of meat and poultry. No significant positive correlations were observed for SCCPs and MCCPs with polychlorinated dibenzodioxins/furans (PCDD/Fs) congeners. A preliminary exposure assessment showed that SCCPs in breast milk potentially posed high risks to the breast-fed infants in Shanghai.

Human health risk assessment of volatile organic compounds in oil-based drill cuttings of shale gas.

Waste oil-based drill cuttings contain dioxins and volatile organic compounds (VOCs), which have the potential to cause serious health effects in humans. Therefore, this paper took oil-based drill cuttings (OBDCs) as the research object and carried out the testing of VOCs and dioxins content by using GC-MS and HRGCS-HRMS and comprehensively evaluated the content, composition and distribution pattern of VOCs and dioxins and the risk to human health posed by the two pollutants in OBDCs. The results showed that the VOCs did not exceed the emission limits in ESPPI (GB 31571-2015), but it is vital to recognise that 1,2-dichloropropane has the potential to cause cancer risk, with soil and groundwater risk control values of 662.95 mg·kg-1 and 0.066 mg·kg-1, respectively. Benzene, 1,2-dichloropropane and 8 other VOCs pose a non-carcinogenic risk to humans. The levels of polychlorinated dibenzofurans (PCDFs) exceeded those of polychlorinated dibenzo-p-dioxins (PCDDs), which accounted for 95.76 percent of the total PCDD/Fs, 2,3,4,7,8-P5CDF (56.00%), 2,3,7,8-T4CDF (9.20%), 1,2,3,6,7,8-H6CDF (8.80%) and 1,2,3,7,8-P5CDF (8.00%) were the main contributing monomers. The findings of the assessment on exposure risk indicate that there is a respiratory risk to oil-based drill cuttings dioxins for adults and children exceeded the World Health Organisation (WHO) acceptable daily intake (ADI) (1-4 pgTEQ/kg/d). Finally, three aspects of solid waste pre-treatment prior to incineration, the incineration process and post incineration were used to reduce the environmental and human health risks from dioxins.

Polychlorinated naphthalenes in freshwater fish from Beijing markets: Species-specific differences, effects of cooking, and health risk assessment.

Fish are an important source of human dietary exposure to polychlorinated naphthalenes (PCNs). The occurrence and sources of PCNs in different species of freshwater fish are unknown, and few studies have assessed human exposure risks to PCNs through freshwater fish. In this study, 140 freshwater fish samples from 10 species were collected from Beijing markets, China. The Σ75CNs concentration range in the fish was 20.7-1310 pg/g wet weight (ww). The highest median Σ75PCNs concentration (80.4 pg/g ww) was found in mandarin fish (Siniperca chuatsi), and the lowest (29.6 pg/g ww) in snakehead (Channa argus). Di- and tri-CNs were the dominant PCN homologues with contributions of 35.3 % and 30.8 %, respectively. Unintentionally produced PCNs from metal smelting might be the source of PCN contamination in freshwater fish. The cooking temperature and time did not significantly affect the PCN concentrations in fish or the PCN homologue profiles. The highest toxic equivalent (TEQ) value was observed in sturgeon (Acipenser sinensis), followed by mandarin fish. Hexa-CNs were the most abundant homologue for the PCN TEQs. A risk assessment indicated that the dietary exposure risks for local residents to PCNs through freshwater fish were low. However, the relatively high concentrations of PCNs in the samples deserve attention to avoid PCNs exposure risks for groups with high fish consumption rates. Furthermore, freshwater fish likely contain a mixture of contaminants including dioxin and furans which also display a similar mode of toxicity as the PCNs and could enhance the risk to fish consumers.

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.

Development and application of a systematic and quantitative weighting framework to evaluate the quality and relevance of relative potency estimates for dioxin-like compounds (DLCs) for human health risk assessment.

The toxic equivalency factors (TEFs) approach for dioxin-like chemicals (DLCs) is currently based on a qualitative assessment of a heterogeneous data set of relative estimates of potency (REPs) spanning several orders of magnitude with highly variable study quality and relevance. An effort was undertaken to develop a weighting framework to systematically evaluate and quantitatively integrate the quality and relevance for development of more robust TEFs. Six main-study characteristics were identified as most important in characterizing the quality and relevance of an individual REP for human health risk assessment: study type, study model, pharmacokinetics, REP derivation method, REP derivation quality, and endpoint. Subsequently, a computational approach for quantitatively integrating the weighting framework parameters was developed and applied to the REP2004 database. This was accomplished using a machine learning approach which infers a weighted TEF distribution for each congener. The resulting database, weighted for quality and relevance, provides REP distributions from >600 data sets (including in vivo and in vitro studies, a range of endpoints, etc.). This weighted database provides a flexible platform for systematically and objectively characterizing TEFs for use in risk assessment, as well as providing information to characterize uncertainty and variability. Collectively, this information provides risk managers with information for decision making.

Persistent organic pollutants in Croatian breast milk: An overview of pollutant levels and infant health risk assessment from 1976 to the present.

This review article summarizes our research of persistent organic pollutants (POPs) in human milk from Croatian mothers over the last few decades. Our studies make up the bulk of all POPs research in human milk in Croatia and show a state-of-the art in the research area. The first investigations were made in 1970's. Aim of our review article is to document the comprehensive results over several decades as the best tool to: 1.) contribute to understanding of POPs and their potential health risks, 2.) evaluate effectiveness of legislative bans and restrictions on human exposure to POPs in Croatia, and 3.) to suggest further actions. In our review we discuss: 1.) Human milk between 2011 and 2014 - evaluation of interrelations of organochlorine pesticides (OCP) and polychlorinated biphenyls (PCB) in human milk and their association with the mother's age and parity using artificial intelligence methods; and our yet unpublished research data on health risks for infants assessed through daily PCB and OCP intake. 2.) Time trends of PCB and OCP in human milk between 1976 and 2014. 3.) polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofuran (PCDD/F) in human milk in 2000., and yet unpublished data on PCDD/F and polybrominated diphenyl ethers (PBDE) in 2014.

Proteomics coupled with AhR-reporter gene bioassay for human and environmental safety assessment of sewage sludge and hydrochar.

Today application of sewage sludge (SL) and hydrochar (HC) in agriculture is a common practice for soil conditioning and crop fertilization, however safety concerns for human and environmental health due to the presence of toxic compounds have recently been expressed. Our aim was to test the suitability of proteomics coupled with bioanalytical tools for unravelling mixture effects of these applications in human and environmental safety assessment. We conducted proteomic and bioinformatic analysis of cell cultures used in the DR-CALUX® bioassay to identify proteins differentially abundant after exposure to SL and the corresponding HC, rather than only using the Bioanalytical Toxicity Equivalents (BEQs) obtained by DR-CALUX®. DR-CALUX® cells exposed to SL or HC showed a differential pattern of protein abundance depending on the type of SL and HC extract. The modified proteins are involved in antioxidant pathways, unfolded protein response and DNA damage that have close correlations with the effects of dioxin on biological systems and with onset of cancer and neurological disorders. Other cell response evidence suggested enrichment of heavy metals in the extracts. The present combined approach represents an advance in the application of bioanalytical tools for safety assessment of complex mixtures such as SL and HC. It proved successful in screening proteins, the abundance of which is determined by SL and HC and by the biological activity of legacy toxic compounds, including organohalogens.

Buffering effect of the economizer against PCDD/Fs in flue gas from solid waste incineration plants.

The emission of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from solid waste incineration is always a crucial concern for the society. Less attention has been paid to differentiate its formation and migration in the low temperature range of economizer, leading to a fuzzy understanding on the control of PCDD/Fs before flue gas cleaning. This study first reveals the buffering effect against PCDD/Fs in the economizer, which is contrary to the well-known memory effect, and first recognizes the intrinsic mechanism by 36 sets of full-scale experimental data under three typical operating conditions. Results indicated that the buffering effect, which includes interception and releasing, could remove averagely 82.9 % of PCDD/Fs in flue gas and reconcile PCDD/Fs profiles. The interception effect is dominant and in compliance with the condensation law. The low temperature range of economizer is exactly suitable for the condensation of lowly chlorinated congeners, which condense behind highly chlorinated ones. The releasing effect was non-staple but stimulated by the sudden change of operating condition, proving that PCDD/Fs formation rarely exists in the economizer. The buffering effect is mainly controlled by the physical migration of PCDD/Fs among different phases. The condensation of PCDD/Fs leads to their migration from vapor phase to aerosol and solid phases during flue gas cooling in the economizer. There is no need for excessive anxiety about PCDD/Fs formation in the economizer because it rarely exists. Intensifying the condensation process of PCDD/Fs in the economizer can help relieve the pressure of end-of-pipe measures for PCDD/Fs control.

[Quantitative risk assessment of occupational exposure to PCDD/Fs in the waste incineration industry].

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.

Ecological risk assessment and corrective actions for dioxin-polluted sediment in a chemical plant's brine water storage pond.

Despite the known high toxicity of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, or dioxins), there are few case studies of PCDD/Fs contamination in sediment and there remains much to learn regarding their ecological impact. In this study, we performed an environmental risk assessment of a brine water storage pond near a chemical plant with high PCDD/Fs pollution potential before and after corrective actions. We found PCDD/F accumulation in the pond's fish and crab from the brine water storage pond, and the PCDD/Fs concentrations in biota higher than Taiwan's food safety standard (3.5 pg-TEQ/g). Furthermore, we found a high degree of pollution using different indices, including contamination factor (CF), modified degree of contamination (mCd), and pollution index (PI), in the pond's sediment. Before corrective actions, we also found high risk in the PCDD/F contamination in the sediment using various biological risk indices, including potential ecological risk index (RI) and risk quotient (RQ). After the corrective actions, including institutional/engineering control and remediation, the CF, mCd, and PI had decreased by 20-41 % and RI and RQ by 41-56 %. In addition, despite the slight reduction of pollution and risk index values in the whole pond, significant reduction was observed in the sediment of highly polluted area A owing to the lower disturbing suction dredging. In conclusion, the corrective actions used in this study helped decrease the pollution and ecological risk associated with this site's PCDD/Fs polluted sediment to some extent, suggesting that contamination and risk could be reduced to acceptable levels if these corrective actions are continued.

Dioxin transfer simulation from feed to animal tissues and risk assessment.

Dioxins might be introduced into the food chain through a direct or an indirect pathway. The main source of human exposure to dioxins is food of animal origin, whereas feeds are the main route of exposure of farmed animals to dioxins and polychlorinated biphenyls. The aim of the study was to simulate dioxin passage from feed to tissues on farm animals using transfer models, and, in addition, to assess the risk to consumers of food of animal origin. From over 700 feed samples analyzed over the course of 9 years (2013-2021), those exceeding the maximum permissible levels set down in Commission Regulation No 277/2012/EU were selected. These samples being derived from real cases of dioxin contamination made it possible to present the most realistic picture of the effects these feed materials could have had if they had entered the food chain. Three species of animals were selected (laying hens, dairy cattle and slaughter pigs), for which feed materials with dioxin contents exceeding the maximum permissible level were selected in accordance with the nutritional recommendations. The calculated PCDD/PCDF concentrations in chicken eggs, cow's milk and pork were above the maximum permissible level in most cases.

Polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and furans in imported canned fish in Nigeria and risk assessment.

Concentrations of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) were measured in imported canned fish such as mackerel, sardine and tuna to evaluate the risk relating to human consumption of these products. Gas chromatography-mass spectrometry (GC/MS) was used to evaluate the concentrations of PCBs and PCDD/Fs in the samples. The ∑28 PCB concentrations in the canned mackerel, tuna and sardine ranged from 0.33 to 9.48 ng g -1,

Transfer of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) from oral exposure into cow's milk - part II: toxicokinetic predictive models for risk assessment.

Understanding the transfer of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) as well as polychlorinated biphenyls (PCBs) from oral exposure into cow's milk is not purely an experimental endeavour, as it has produced a large corpus of theoretical work. This work consists of a variety of predictive toxicokinetic models in the realms of health and environmental risk assessment and risk management. Their purpose is to provide mathematical predictive tools to organise and integrate knowledge on the absorption, distribution, metabolism and excretion processes. Toxicokinetic models are based on more than 50 years of transfer studies summarised in part I of this review series. Here in part II, several of these models are described and systematically classified with a focus on their applicability to risk analysis as well as their limitations. This part of the review highlights the opportunities and challenges along the way towards accurate, congener-specific predictive models applicable to changing animal breeds and husbandry conditions.

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) soil contamination in Lausanne, Switzerland: Combining pollution mapping and human exposure assessment for targeted risk management.

In December 2020, high soil concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were discovered across large parts of Lausanne, Switzerland. Concentrations reached up to 640 ng TEQWHO-2005/kg dry weight. The most likely source was a former municipal waste incinerator. A three-step, multidisciplinary approach to human health risk assessment was conducted to determine the potential population exposure to PCDD/Fs and identify appropriate preventive measures. First, exposure scenarios were developed based on contaminated land uses. Second, the toxicological risks of different scenarios were evaluated using a toxicokinetic model estimating increases in blood serum PCDD/F concentrations over background concentrations from the general population's food consumption. Third, a detailed geostatistical mapping of PCDD/F soil contamination was performed. Stochastic simulations with an external drift and an anisotropic model of the variogram were generated to incorporate the effects of distance from emission source, topography, and main wind directions on the spatial distribution of PCDD/Fs in topsoil. Three main scenarios were assessed: i) direct ingestion of soil by children in playgrounds; ii) consumption of vegetables from private gardens by children and adults; and iii) consumption of food from livestock and poultry raised on contaminated soil. The worst exposure scenario involved the consumption of eggs from private hen houses, resulting in PCDD/F concentrations in serum an order of magnitude higher than might normally be expected. No relevant increases in serum concentrations were calculated for direct soil ingestion and vegetable consumption, except for cucurbitaceous vegetables. Combining mapping and exposure scenario assessment resulted in targeted protective measures for land users, especially concerning food consumption. The results also raised concerns about the potential unsafe consumption of products derived from animals raised on land with PCDD/F concentrations only moderately over environmental background levels.

Changes in Polychlorinated Biphenyl Residues in Milk during Lactation: Levels of Contamination, Influencing Factors, and Infant Risk Assessment.

Given the importance of breastfeeding infants, the contamination of human milk is a significant public concern. The aim of this study was to assess the contamination of human milk with dioxin-like PCBs (dl-PCBs) and non-dioxin-like PCBs (ndl-PCBs) in relation to the duration of lactation and other influencing factors, especially the frequency of the consumption of selected foods during pregnancy. Based on this, the health risk to infants was assessed and compared to the tolerable daily intake (TDI). PCB determinations were performed using gas chromatography/mass spectrometry. The ∑ndl-PCB content ranged from 0.008 to 0.897 ng/g w.w., at an average of 0.552 ng/g wet weight, which was 55% of the maximum level according to the EU guidelines for foods for infants and young children. The toxic equivalent (TEQ) was in the range of 0.033-5.67 pg-TEQ/g w.w. The content of non-ortho, mono-ortho, and ndl-PCBs in human milk decreased the longer lactation continued. Moreover, when pregnant women smoked tobacco, this correlated significantly with increases in the concentrations of PCB congeners 156, 118, and 189 in human milk. The human milk contents of PCB congeners 77, 81, 186, 118, and 189 were strongly positively correlated with the amount of fish consumed. The content of stable congeners PCB 135 and PCB 153 increased with age.

Determination of the relative potencies of brominated dioxins for risk assessment in aquatic environments using the early-life stage of Japanese medaka.

World Health Organization toxic equivalency factors (WHO-TEFs) are recommended for risk management of brominated dioxins in aquatic environments because limited information is available on their toxicity to fish. To validate this approach, we obtained the relative potencies of polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans and mixed-halogenated furans (PXDF, X = Cl/Br) against 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) based on their toxicity to the early-life stage of Japanese medaka (Oryzias latipes). 2,3,7,8-substituted brominated dibenzofurans caused typical dioxin exposure effects, such as blue-sac disease. The TCDD-relative potency factors (REPs) of test substances were calculated based on the concentrations in water and eggs that caused 20% lethality on day 28 post-fertilization, and were in the order of: 2-chloro-3,7,8-tribromodibenzofuran (REPwater 3.3, REPegg 4.6) > 2,3,7,8-tetrabromodibenzofuran (0.85, 0.92) > 2,3,4,7,8-pentabromodibenzofuran (0.053, 0.55) > 1,2,3,7,8-pentabromodibenzofuran (0.0091, 0.19). The transfer rate from water to eggs was lower for pentabrominated furans than tetrabrominated congeners, and was expected to decrease with the log Kow of the test substance. Although the REPegg value can be used to compare the toxicity potential of brominated dioxins, REPwater may be more suitable for environmental risk assessment because the uptake potential of these compounds from water should be considered. This study is the first to report higher toxicity of a PXDF congener compared with TCDD in vivo, further investigations of the toxicity of mixed-halogenated dioxins and environmental behavior are necessary for environmental risk assessment.

Health risk assessment to polychlorinated naphthalenes dioxin-like compounds in French sea food consumers.

There has been a recent revival of interest in some historical contaminants such as polychlorinated naphthalenes (PCNs). However, occurrence data are still lacking in some countries although industrial production of PCNs has been reported. This observation led to the first ever assessment of their presence in fish and seafood products in France in the present work. Their analysis was integrated in an already validated method applied for polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs), based on the structural similarity existing between these POPs. Performances of the method (LODs in the range 0.10-0.28 pg g-1 wet weight (ww), LOQs in the range 0.33-0.93 pg g-1 ww), enabled monitoring 69 di-to octachlorinated congeners in a large representative set of fish and seafood samples collected in 2005 in four coastal areas of the French mainland (n > 30). Their systematic presence was demonstrated in all the investigated seafood products, with levels (ΣPCNs in the range 2-440 pg g-1 wet weight) close to those already reported in other European fish and seafood sampled at a similar period. In addition, the robust measurement of almost all possible PCNs (69/75) allowed a fine interpretation of the observed profiles, highlighting in particular the specificities between species and fishing areas. Compared to the PCDD/Fs, PCBs, and polybrominated diphenylethers levels also measured for this set of samples, PCNs were observed as minor contributors to total concentrations (0.05-3.2%). The specific PCN related dietary dioxin-like exposure could be evaluated at 0.028-0.051 pg of toxic equivalent (TEQ) per kg of body weight per week for an adult, based on fish and seafood consumption only. Overall, this study provides the first baseline data on the occurrence of a large number of PCNs in France, which will allow future evaluation of temporal trends and associated risks.

PCDD/Fs and heavy metals in the vicinity of landfill used for MSWI fly ash disposal: Pollutant distribution and environmental impact assessment.

This study focused on the syngenetic control of polychlorinated-ρ-dibenzodioxins and dibenzofurans (PCDD/Fs) and heavy metals by field stabilization/solidification (S/S) treatment for municipal solid waste incineration fly ash (MSWIFA) and multi-step leachate treatment. Modified European Community Bureau of Reference (BCR) speciation analysis and risk assessment code (RAC) revealed the medium environment risk of Cd and Mn, indicating the necessity of S/S treatment for MSWIFA. S/S treatment significantly declined the mass/toxic concentrations of PCDD/Fs (i.e., from 7.21 to 4.25 µg/kg; from 0.32 to 0.20 µg I-TEQ/kg) and heavy metals in MSWIFA due to chemical fixation and dilution effect. The S/S mechanism of sodium dimethyldithiocarbamate (SDD) and cement was decreasing heavy metals in the mild acid-soluble fraction to reduce their mobility and bioavailability. Oxidation treatment of leachate reduced the PCDD/F concentration from 49.10 to 28.71 pg/L (i.e., from 1.60 to 0.98 pg I-TEQ/L) by suspension absorption or NaClO oxidation decomposition, whereas a so-called "memory effect" phenomena in the subsequent procedures (adsorption, press filtration, flocculating settling, slurry separation, and carbon filtration) increased it back to 38.60 pg/L (1.66 pg I-TEQ/L). Moreover, the multi-step leachate treatment also effectively reduced the concentrations of heavy metals to 1-4 orders of magnitude lower than the national emission standards. Furthermore, the PCDD/Fs and heavy metals in other multiple media (soil, landfill leachate, groundwater, and river water) and their spatial distribution characteristics site were also investigated. No evidence showed any influence of the landfill on the surrounding liquid media. The slightly higher concentration of PCDD/Fs in the soil samples was ascribed to other waste management processes (transportation and unloading) or other local source (hazardous incineration plant). Therefore, proper management of landfills and leachate has a negligible effect on the surrounding environment.