Urban air PCDD/Fs: Atmospheric concentrations, temporal changes, gas/particle partitioning, possible sources and cancer risks.

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are pollutants of concern due to their toxic effects. No active sampling study on PCDD/Fs has been conducted in Bursa. This study aimed to fill this gap by measuring PCDD/F levels in the region. Accordingly, the samples were collected from an urban area in Bursa, covering four seasons between June 2022 and April 2023. The total (gas+particulate) ambient air concentrations were between 312.23 and 829.80 fg/m3 (mean: 555.05 ± 173.62 fg/m3). In terms of toxic equivalents (TEQ), the average concentration was 43.29 ± 9.18 fg WHOTEQ/m3. Based on the concentration values obtained, cancer and non-carcinogenic risk values of PCDD/Fs were calculated for three different age groups. The results indicated negligible health risks for all age groups. In addition, a seasonal assessment was also made and it was observed that PCDD/F concentration values varied with the ambient air temperatures. In general, higher values were measured in colder months compared to warmer months. This was probably due to the additional sources and adverse meteorological conditions. Moreover, the gas/particle partitioning of PCDD/Fs was investigated in detail. The average gas and particulate phase concentrations for PCDD/Fs were 101.81 ± 20.77 and 453.24 ± 172.50, respectively. It was found that an equilibrium state was not reached in the gas/particle partitioning. Two different gas/particle partition models based on adsorption and absorption mechanisms were compared, and the absorption model gave more consistent predictions. The Principal Component Analysis (PCA) was employed to identify the possible PCDD/F sources. The results indicated that the region was influenced by vehicle emissions, residential heating, organized industrial zones and metal recycling facilities. In addition, 72-hour backward air mass trajectory analyses were performed to understand the long-range transported air masses. However, it was found that the transported air masses did not significantly affect the concentration values measured in the sampling site.

Unintentional persistent organic pollutants in cremation process: Emissions, characteristics, and inventory.

Pollutants produced by cremation furnaces have gradually caused concern because of the increasing rate of cremation around the world. In this study, the levels, patterns, and emission factors of unintentional persistent organic pollutants (UPOPs) from cremation were investigated. The toxic equivalent (TEQ) concentrations (11 % O2 normalized) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in flue gas ranged from 0.036 to 22 ng TEQ/Nm3, while the levels of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in flue gas samples ranged from 0.0023 to 1.2 ng TEQ/Nm3 and 0.17-44 pg TEQ/Nm3, respectively. The average concentrations of UPOPs in flue gas from car-type furnaces were higher than those from flat-panel furnaces. Secondary chambers and air pollution control devices were effective for controlling UPOPs emissions. However, heat exchangers were not as effective for reducing UPOPs emissions. It was observed that the UPOPs profiles exhibited dissimilarities between fly ash and flue gas samples. HxCDF, OCDD, and PeCDF were the dominant homologs of PCDD/Fs in flue gas, while HxCDF, PeCDF, and HpCDF were the dominant homologs in fly ash. The fractions of MoCBs and MoCNs in fly ash were higher than those in flue gas. Finally, we conducted an assessment of the global emissions of UPOPs from cremation in the years of 2019 and 2021. The total emission of UPOPs in 47 countries was estimated at 239 g TEQ in 2021, which was during the peak period of the COVID-19 pandemic worldwide. The emissions in 2021 increased by approximately 24 % compared to 2019, with the impact of COVID-19 being a significant factor that cannot be disregarded.

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.

Spatial distributions, behaviors, and sources of PCDD/Fs in surface water and sediment from the Yangtze River Delta.

The Yangtze River Delta (YRD), one of the most economically developed and industrialized regions in China, is confronted with challenges arising from rapid urbanization, particularly environmental pollution. The collection of surface water and sediment samples from forty-nine sites in the YRD was conducted to analyze 2378-substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) congeners. The detected concentrations of PCDD/Fs were 0-5.3 pg TEQ/L in water and 0.12-1493 pg TEQ/g dw in sediment. The PCDD/Fs contamination in the sediment was widespread in the YRD. There were variations in the congener characteristics of PCDD/Fs in surface water and sediment. The proportion of OCDD was significantly lower in surface water samples compared to sediment, while the less chlorine-substituted homologs were found in larger proportions. To understand the partitioning and behavior of dioxins within the water-sediment system, we calculated the organic carbon normalized partition coefficients and fugacity fraction (ff) of PCDD/F congeners. The results revealed that the PCDD/Fs had not attained a state of distributional equilibrium, and the non-specific hydrophobic effect seemed minimally influential on their partitioning between sediment and water. The average ff values, which varied between 0.06 and 0.63, indicated differing migration directions for the PCDD/F congeners. Source identification analysis provided evidence that the dioxins in the river water were primarily attributed to industrial thermal processes. Iron and steel smelting, along with pesticide production and use, were likely responsible for the sediment contamination. This comprehensive analysis underscores the complex nature of PCDD/Fs pollution in the YRD and highlights the necessity for targeted environmental management strategies.

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.

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).

Polychlorinated Naphthalenes in Foods from the French Market: Occurrence, Dietary Exposure, and Evaluation of Relative Contributions to Dioxin-like Contaminants.

Despite the growing interest in PCNs and the dioxin-like toxicity exhibited by a number of congeners, a comprehensive assessment of their contribution to the cocktail of dioxin-like contaminants is still lacking. To address such a shortcoming, this study investigated the PCN contamination in foodstuffs recently acquired in France, together with that of the regulatory polychlorinated dibenzodioxins/furans (PCDD/Fs) and polychlorinated biphenyls (PCBs). PCNs were ubiquitous at levels (∑70 PCNs = 2.5-150 pg g-1 wet weight) similar to those reported in other countries, with maximum concentrations observed in fish and fishery products from the North-East Atlantic Ocean. Their congener patterns further suggested unintentional releases of PCNs, while those of the other foodstuffs were correlated to the historical PCN profiles. Low risk from dietary exposure was estimated (∑70 PCNs-EDIs of 60-360 pg kg-1 bw d-1, ∑24 PCNs-TEQ-EDIs of 8 × 10-3-2.2 × 10-2 pg TEQ kg-1 bw d-1), with milk and dairy products being the highest contributors, followed by meat and meat products. Finally, the rather high contributions of PCNs to the total PCNs+PCDD/Fs+PCBs concentrations (0.9-50%, average of 9%) and the toxic equivalents (0.2-24%, average of 5%) show that these substances are not minor components of the PCNs+PCDD/Fs+PCBs cocktail.

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.

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.

Dioxins emissions from bio-medical waste incineration: A systematic review on emission factors, inventories, trends and health risk studies.

COVID-19 has aggravated the biomedical waste generation all over the world and the concern for its safe disposal is on the rise. The vast majority of healthcare systems employ incineration as their treatment method considering its agility to reduce the waste volume by up to 95-96% and high-temperature inactivation of infectious biological materials. However, incinerator emission is a significant contributor of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) according to various national inventories across the globe. Bio-Medical Waste Incinerators (BMWIs) are the dominant form of incinerator plants in developing nations and hence BMWI emissions were found to contribute lion's share of national dioxins inventories in most of these countries. The Stockholm Convention on POPs played a key role in imbibing significant urge on the dl-POPs monitoring studies of incinerators internationally and on controlling the average incinerator emission levels. Though many national/international agencies endorse a stringent incinerator stack emission standard of 0.1 ngTEQ/Nm3, there are some differences observed in nation-to-nation regulatory scenarios. This paper reviews and reports on the dioxins emission and health risk studies associated with bio-medical waste incineration over the last three decades (1990-2020) with a comprehensive spatial and temporal emission trend analysis. An overview of important national and international regulations, national inventories and emission factors for the biomedical waste incineration sector is also reviewed in detail. The study observes that continuous regulatory monitoring and logical relaxations can enhance the performance of the existing facilities ensuring low emissions and minimal risk.

Serum PCDD/F levels in metropolitan populations living near a municipal solid waste incinerator in Eastern China.

Ambient exposure to polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) is suspected to cause adverse human health outcomes. Herein, serum samples from 40 residents in the neighborhood of a municipal solid waste incinerator (MSWI) in the metropolitan area were measured for PCDD/Fs. The mean toxic equivalent (TEQ) concentration of total PCDD/Fs in human serum samples was 16.8 pg TEQ/g lipid. Serum PCDD/F levels were significantly higher in residents adjacent to the MSWI than in those from areas far from the emission source (p < 0.01). In addition, there were no significant associations between serum PCDD/Fs levels and factors, such as gender, age, and BMI in donors. For non-occupationally exposed populations, OCDD and 1,2,3,7,8-PeCDD in serum are available as indicators of total PCDD/Fs and total TEQ, respectively. The atmospheric PCDD/Fs levels were within a relatively low range in areas upwind and downwind of the MSWI. The results of the principal component analysis showed a distinct difference in PCDD/F congener patterns between air and serum samples, suggesting inhalation exposure could have a limited influence on the human body burden. Our findings will deepen the current knowledge of endogenous PCDD/F exposure in urban populations, and also facilitate public health protection strategies near MSWIs.

Abandonment of fibreglass reinforced plastic fishing boats in Kerala, India, and chemical emissions arising from their burning.

Little information exists on the fate and impacts of boats constructed of fibreglass reinforced plastic (FRP) once they reach their end-of-life. In this study, the number of abandoned fishing boats constructed of FRP or constructed of plywood-wood and sheathed by FRP has been determined along the coast of Kerala, India, and chemical emissions have been estimated when boats are burned as a means of disposal. A total of 292 abandoned boats were observed across eight coastal transects constructed around selected landing centres, with abandonment ranging from 13 to 48 per km (average = 29 km-1). This results in the generation of 1420 kg of FRP debris (glass mat and epoxy resin) per km of coastline. A controlled combustion experiment, simulating open burning, revealed that 63% of original boat mass is emitted to the atmosphere, with the remainder forming a burnt residue. Total concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans emitted and remaining were found to be 2.6 ng Nm-3 and 249.6 µg kg-1, respectively, with respective calculated toxicity equivalence (TEQ) levels of 437.6 pg TEQ Nm-3 in air emissions and 26.6 µg TEQ kg-1 in the residue. These figures are equivalent to the total emission from FRP boat burning of about 17,000 µg TEQ t-1. Burning also generates significant quantities of potentially toxic metals, with resulting concentrations of Co, Cr and Cu close to or exceeding soil guideline values. The study calls for a greater awareness of the impacts arising from boat abandonment and burning amongst fishermen, and guidelines or regulatory protocols regarding safe and sustainable boat disposal or recycling.

Identification and verification of PCDD/Fs indicators from four typical large-scale municipal solid waste incinerations with large sample size in China.

Monitoring PCDD/Fs emissions from municipal solid waste incinerations (MSWIs) is of paramount importance, yet it can be time-consuming and labor-intensive. Predictive models offer an alternative approach for estimating their levels. However, robust models specific to PCDD/Fs were lacking. In this study, we collected 190 PCDD/Fs samples from 4 large-scale MSWIs in China, with the average PCDD/Fs levels and TEQ levels of 0.987 ng/m3 and 0.030 ng TEQ/m3, respectively. We developed and evaluated predictive models, including traditional statistical methods, e.g., linear regression (LR) as well as machine learning models such as back propagation-artificial neural networks (BP ANN) and random forest (RF). Correlation analysis identified 2,3,4,7,8-PeCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF were better indicator congeners for PCDD/Fs estimation (R2 > 0.9, p < 0.001). The predictive results favored the RF model, exhibiting a high R2 value and low root mean square error (RMSE) and mean absolute error (MAE). Additionally, the RF model showed excellent prediction ability during external validation, with low absolute relative error (ARE) of 10.9 %-12.6 % for the three indicator congeners in the normal PCDD/F TEQ levels group (<0.1 ng TEQ/m3) and slightly higher ARE values (13.8 %-17.9 %) for the high PCDD/F TEQ levels group (>0.1 ng TEQ/m3). In conclusion, our findings strongly support the RF model's effectiveness in predicting PCDD/Fs TEQ emission from MSWIs.

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.

Occurrence and Formation Mechanism of PCDD/Fs and SCCPs in Chlorinated Paraffin Products.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and short-chain chlorinated paraffins (SCCPs) can be formed during the production of chlorinated paraffins (CPs). Detection and accurate quantification of PCDD/Fs in CPs are challenging because of their matrix complexity. Therefore, the occurrence and formation mechanisms of PCDD/Fs from CPs have not been studied extensively in the past. In this study, 15 commercial samples including solid and liquid CPs were collected in 2022 from China. The average ΣSCCP concentrations detected in the solid and liquid CPs were 158 and 137 mg/g, respectively. The average International Toxic Equivalent (I-TEQ) values of 2,3,7,8-PCDD/F in solid and liquid CPs were 15.8 pg I-TEQ/g and 15.0 pg I-TEQ/g, respectively. The solid and liquid CPs had different predominant congener groups for SCCPs and PCDD/Fs. Possible formation routes for the generation of PCDD/Fs were analyzed by screening precursors in paraffin and laboratory-scale thermochemical experiments of CPs. The transformation between 2,3,7,8-PCDD/Fs and non-2,3,7,8-PCDD/Fs was recognized by calculating the successive chlorination preference. The first reported occurrence of PCDD/Fs in CP commercial products indicated that exposure to CPs and downstream products might be an assignable source of PCDD/F emission, which is of great significance to further explore the control factors of PCDD/Fs in the whole life cycle of CPs.

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.

Influence of different loads on PCDD/F removal by SCR during municipal solid waste incineration.

This study was conducted on a full-scale (500 t/d) municipal solid waste incinerator (MSWI), investigating the influence of different loads on the emission of polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs) and their removal by selective catalytic reduction (SCR) system. The total concentration of PCDD/Fs at the SCR inlet under 100% load was higher than that under 80% load. The changing loads caused different distribution characteristics of PCDD/Fs at the SCR inlet, and the dominant congeners changed from high-chlorinated PCDDs (80% load) to low-chlorinated PCDFs (100% load). Moreover, the increased load enhanced the removal efficiency of PCDD/Fs by SCR from 17.3% to 64.2%, which was influenced by the inlet PCDD/F distribution and the moisture content. The high-chlorinated PCDD/Fs with the more stable structure were more difficult to be deteriorated and the high moisture content can weaken the catalytic activity of SCR catalysts. Correlation analysis was used to study the relationship between major air pollutants and PCDD/F emissions. The results showed that HCl positively correlated with PCDD/F emission concentrations, while NOx and SO2 negatively correlated. The results of this study can provide a reference for MSWI to operate properly under variable loads.

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.