Polychlorinated Dibenzo-p-dioxins And Dibenzofurans Research Articles

Effect of Combustion Material on the Level of Persistent Organic Pollutants in Smoked Pork

Background: Although smoking has historically been one of the most prevalent methods for food preservation, it was considered a source of carcinogenic and mutagenic persistent organic pollutants (POPs), such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) due to incompletely combustion process. In this study, POPs in pork samples smoked with different materials: sawdust only (NP group), sawdust and polyethylene (PE group), sawdust and polystyrene (PS group), and mixed sawdust (M group) were detected and quantified. Method: The GC-MS method was applied to quantify several POPs in pork samples smoked by various materials. After that, multivariate statistics were used to elucidate differences among groups and chemical markers associated with each smoking material, underscoring the need to evaluate the implications of smoking materials on food safety and public health. Results: The total PAH and PCB contents were lowest in the NP samples (smoked with sawdust only), with PAH levels ranging from 500 to 2000 μg/kg lipid and PCB levels from 0.5 to 1.3 μg/kg lipid. In contrast, the PE, PS, and M groups, which were smoked with sawdust combined with different polymers and contaminants, showed higher levels. The PAH content in these groups exceeded 3000 μg/kg lipid, while PCB levels in PE and PS ranged from 1.5 to over 3.0 μg/kg lipid, and M samples had the widest variation, spanning from 0.6 to 3.2 μg/kg lipid. Regarding PCDD/Fs, none were detected in the NP samples, while the PE and PS groups contained between 1.2 and 1.5 pg/g lipid, with specific compounds identified (e.g., 234678-HxCDF in PE and 12378-PeCDF and 123478-HxCDF in PS). The M samples exhibited the highest PCDD/Fs content, ranging from 5.0 to 14.0 pg/g lipid, with up to six compounds formed, including one PCDD and five PCDFs. Conclusion: The analysis also revealed that the presence of polyethylene and polystyrene significantly elevated POP levels in the respective groups. Meanwhile, samples in the M group possessed various chemical compositions with multiple concentrations, presented by the large area on the PCA biplot and usually intermingled with samples of other groups. Especially, OCDD was the only PCDD that was detected only in M group simples.

Utilization of municipal solid waste incineration fly ash with different pretreatments with gold tailings and coal fly ash for environmentally friendly geopolymers.

Municipal solid waste incineration fly ash (MSWIFA) is considered a hazardous solid waste, traditionally disposed by solidified landfill methods. However, solidified landfills present challenges with leaching heavy metals, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). To address this issue, this study examined two pretreatment methods for MSWIFA: sintering at 850℃ for 30 min and washing with three water baths (20 min each) at a 3:1 liquid-solid ratio. Then, the pretreated MSWIFA was employed in geopolymer synthesis, along with gold tailings (GT) and coal fly ash (CFA). The optimal raw material ratio was GT:CFA:MSWIFA = 5:4:1 after pretreatment, which resulted in maximum compressive strengths of 20.95 and 25.87 MPa for the sintered and washed samples, respectively. Washing removed 87.3 % of soluble chlorides from MSWIFA, enhancing the compressive strength of the geopolymer. High-temperature treatment effectively reduced the leaching concentrations of heavy metals and the toxic equivalent quantity (TEQ) of PCDD/Fs. The leaching concentrations of heavy metals (Cu, Zn, Cd, Pb) and the TEQ of PCDD/Fs were all below the limits established by Chinese standards GB 5085.3-2007 and HJ 1134-2020. X-ray Diffraction, Fourier transform infrared spectrometry, scanning electron microscopy, and energy dispersive spectroscopy analyses revealed that the primary hydration products of the geopolymer are C-(A)-S-H gels. Washing treatment facilitated the formation of ettringite and Ca(OH)2, which enhanced the pore structure and optimized the performance of the geopolymer. Thermogravimetric analysis revealed the good thermal stability of the geopolymer, indicating that the high-temperature and washing pretreatments minimally impacted its thermal stability.

Spatial distributions and source identification of PCDD/Fs and PCBs in soils and pine needles in the multi-industrial city of Ulsan, South Korea

The spatial distribution and contamination patterns of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) in soil and pine needles from the multi-industrial city of Ulsan, South Korea were assessed. The mean concentrations of Σ17 PCDD/Fs, Σ12 dl-PCBs, and Σ7 I-PCBs were 78 pg/g dw, 90 pg/g dw, and 453 pg/g dw in the soil and 6 pg/g ww, 31 pg/g ww, and 166 pg/g ww in the pine needles, respectively. The mean concentrations of PCDD/Fs, dl-PCBs, and I-PCBs in the soil at industrial sites (138, 184, and 453 pg/g dw) were significantly higher than those at urban (47, 33, and 186 pg/g dw) and suburban sites (48, 49, and 234 pg/g dw). In the pine needles, although PCDD/F and PCB levels were higher at several industrial sites, mean concentrations at the industrial (6, 31, and 166 pg/g ww), urban (4, 29, and 143 pg/g ww), and suburban (4, 31, and 169 pg/g ww) sites were comparable, indicating that atmospheric transport plays a crucial role in spreading contamination throughout the study area. Higher chlorinated PCBs were predominant in the soils, while PCDFs and lower chlorinated PCBs were more common in the pine needles, reflecting the distinct physicochemical properties and interactions of these chemicals with each medium. Principal Component Analysis (PCA) revealed industrial combustion as the main source of PCDD/Fs and PCBs, with Aroclors identified as an additional source of PCBs. Suburban areas were influenced by both local sources and pollutants transported from urban and industrial areas. This study highlights that industrial activities and atmospheric transport significantly contribute to the widespread contamination of PCDD/Fs and PCBs in Ulsan.

PFAS, PCBs, PCDD/Fs, PAHs and extractable organic fluorine in bio-based fertilizers, amended soils and plants: Exposure assessment and temporal trends

Bio-based fertilizers (BBFs) produced from organic waste contribute to closed-loop nutrient cycles and circular agriculture. However, persistent organic contaminants, such as per- and poly-fluoroalkyl substances (PFAS), polychlorobiphenyls (PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), as well as polyaromatic hydrocarbons (PAHs) can be present in organic waste or be formed during valorization processes. Consequently, these hazardous substances may be introduced into agricultural soils and the food chain via BBFs. This study assessed the exposure of 84 target substances and extractable organic fluorine (EOF) in 19 BBFs produced from different types of waste, including agricultural and food industrial waste, sewage sludge, and biowaste, and through various types of valorization methods, including hygienization at low temperatures (<150 °C) as well as pyrolysis and incineration at elevated temperatures (150–900 °C). The concentrations in BBFs (ΣPFOS & PFOA: <30 μg kg−1, Σ6PCBs: <15 μg kg−1, Σ11PAHs: <3 mg kg−1, Σ17PCDD/Fs: <4 ng TEQ kg−1) were found to be below the strictest thresholds used in individual EU countries, with only one exception (pyrolyzed sewage sludge, Σ11PAHs: 5.9 mg kg−1). Five BBFs produced from sewage sludge or chicken manure contained high concentrations of EOF (>140 μg kg−1), so monitoring of more PFAS is recommended. The calculated expected concentrations in soils after one BBF application (e.g. PFOS: <0.05 μg kg−1) fell below background contamination levels (PFOS: 2.7 μg kg−1) elsewhere in the literature. This was confirmed by the analysis of BBF-amended soils from field experiments (Finland and Austria). Studies on target legacy contaminants in sewage sludge were reviewed, indicating a general decreasing trend in concentration with an apparent half-life ranging from 4 (PFOS) to 9 (PCDD/Fs) years. Modelled cumulative concentrations of the target contaminants in agricultural soils indicated low long-term risks. Concentrations estimated and analyzed in edible plant part were low, indicating that exposure by plant consumption is well below tolerable daily intakes.

Effects of industrial solid waste on the generation of PCDD/Fs, dl-PCBs and PAHs tuned by waste pseudo-components during engineering co-combustion

Co-combustion of municipal solid waste (MSW) with industrial solid waste (ISW) is becoming prevailing. But its effects on generation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polycyclic aromatic hydrocarbons (PAHs) remain unclear, hindering their efficient control. Hence, six batches of engineering incineration tests containing diverse blending types and ratios of ISW were designed in an incinerator of 650 t/d. To target the relationship between complex waste components and contaminants, a pseudo-component matrix model was innovatively incorporated, with nine plastic and biomass pseudo-components quantitatively extracted. Compared to raw MSW incineration, co-combustion generally increased generation of 17 PCDD/Fs and 12 dl-PCBs in fly ash up to six-fold, with the highest TEQ concentrations of 843 ng/kg and 68.1 ng/kg, respectively, while exerted less impact on generation of 16 PAHs. Among nine pseudo-components, polyethylene glycol terephthalate (PET), polyvinyl chloride (PVC) and cellulose were identified as the key to generation of PCDD/Fs and dl-PCBs. Combustion of PET and cellulose served to provide benzene derivatives, while PVC contributed more chlorine. Tracking the original waste, blending with waste plastics, polyester textile, artificial leather and paper should be strictly regulated. This study was of significance to optimize co-combustion for source reduction of toxic pollutants.

Degradation of dioxins in chelated municipal solid waste incineration fly ash by low-temperature pyrolysis

In this study, low-temperature pyrolysis is applied to raw and chelated municipal solid waste incinerator fly ash to degrade and remove PCDD/F (polychlorinated dibenzo-p-dioxins, and dibenzofurans) and corresponding I-TEQs (international toxic equivalents), respectively. Additionally, PCDD/F degradation pathways are identified based on PCDD/F signatures. From the analysis of the average signal intensity of dioxin isomers in thermally treated fly ashes, the PCDD/F degradation rate was between 89.97 and 99.80 %, and the I-TEQs removal rate was 98.96 and 99.90% across all samples compared to untreated raw fly ash. The chelating agent EDTA enhanced the thermal degradation of PCDD/F, but the addition of Na2HPO4 in chelated fly ash as an inhibitor promoted PCDD/F regeneration. Further, there is a variable output of dioxins and corresponding I-TEQs under different temperatures and reaction times; however, longer reaction duration and higher temperatures proved highly effective. The overall toxicity of all thermally tested fly ashes was lesser than the permissible value of 50 ng I-TEQ/kg for resource utilization and observed in the range of 1.84 ± 0.15 to 19.45 ± 0.89 ng I-TEQ/kg. The investigation of the PCDD and PCDF signatures suggests that thermal destruction was a major pathway of degradation by breakage of the C-O bond, compared to dechlorination as observed by a high percentage contribution of HpCDD/F and OCDD/F congeners in thermally treated fly ashes. Low-temperature pyrolysis is an auspicious disposal technology that requires additional studies for large-scale applications.

Low-Temperature NH3-SCR Technology for Industrial Application of Waste Incineration: An Overview of Research Progress

Selective catalytic reduction of nitrogen oxides with NH3 (NH3-SCR) was investigated deeper and deeper with poisoning factors such as H2O, SO2, heavy metals, etc. In order to remove the reheating process before the SCR reactor, the application trend of NH3-SCR technology in the non-power industry is concentrated on the condition of low temperature even ultra-low temperature. The present study summarizes the research process of SO2 and H2O resistance of NH3-SCR catalysts under low temperatures related to the working conditions of municipal solid waste incineration plants. In detail, the effects of a high content of H2O and low concentration of SO2 are reviewed. Other factors such as heavy metals, alkali, or alkaline earth metals in the reaction system, synergistic removal of NOx, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are addressed. Finally, the catalytic performance of assembled monolithic catalysts and pilot-scale experiments are also analyzed for the possibility of industrial application. Hopefully, in view of the questions outlined in this study, valuable insights could be taken into consideration for the development of NH3-SCR in waste incineration.

Health risks and sources of PCDD/Fs and PCBs residue in cultured crabs

The Chinese mitten crab (Eriocheir sinensis) holds significant importance as a popular aquaculture food source; however, there are concerns about its potential contamination with polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) from both food and aquatic environment. To assess the associated health risks and identify potential sources of contamination in crabs, a comprehensive investigation was conducted, including a total of 70 samples from the crab food web. The results demonstrated that crabs predominantly exhibited elevated concentrations of PCBs and dl-PCBs, with mean concentrations of 12 207 ± 11 962 pg g-1 and 554 ± 203 pg g-1, respectively, while PCDD/Fs concentrations were comparatively lower at 20 ± 17 pg g-1. The accumulation of PCBs in crabs significantly surpassed that of PCDD/Fs. The material balance of PCDD/Fs and PCBs in the crab food web was estimated, indicating that sediments and feeds likely constitute the two primary sources of PCDD/Fs and PCBs in crabs. The monthly intake of PCDD/Fs and PCBs through crab consumption accounted for 30% of the dietary intake, which was well below the provisional tolerable monthly intake (PTMI) limit. The weekly intake of PCDD/Fs and PCBs for adults consuming one crab (100 g) does not pose health risks and the recommended weekly intake of white crabmeat and brown crabmeat is 443 g and 21 g, respectively.

Modification of activated carbon to enhance the absorption of PCDD/F and dl-PCBs emissions in flue gas in South Africa

Activated carbon (AC) adsorption is commonly used for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) removal from flue gas. However, the AC available in the market predominantly possesses a substantial specific surface area and numerous micropores leading to significant variations in their adsorption characteristics. In this study, three types of activated carbon (AC) impregnated with different activating agents, namely K2CO3, KOH, and H3PO4 were evaluated for their effectiveness in removing PCDD/Fs and dl-PCBs compounds. For dl-PCBs, AC impregnated with H3PO4 resulted in a substantial reduction of PCB concentrations with an impressive 98% reduction achieved. Impregnation with KOH proved even more effective attaining a remarkable 99% reduction. In contrast, impregnation with K2CO3 while still effective achieved a slightly lower reduction rate of 95%. For PCDD/F, LACH3PO4 showed selectivity in achieving high reductions across both CDD and CDF congeners however proved effective in reducing the ∑PCCDF from 403.94 ng/Nm3 to 3.463 ng/Nm3 and ∑TEQ from 41.34 ng I-TEQ/Nm3 to 0.35 ng I-TEQ Nm3. LACKOH proved effective in reducing the ∑PCCDF from 540.45 ng/Nm3 to 0.25 ng/Nm3 and ∑TEQ from 57.42 ng I-TEQ/Nm3 to 0.12 ng I-TEQ Nm3 obtaining the overall removal efficiency of 99.5%. While the LACKOH injections were successful in the absorption of PCDD/Fs from the gas phase, it was observed that certain PCDD/F congeners became desorbed and entrapped within the ash necessitating further treatment of the ash residue. The ash underwent a thermal treatment first at 300 °C and 500 °C. The thermal treatment at 500 °C achieved a remarkable degradation of 99.7% removal efficiency rendering the ash and residue safe for disposal in a landfill site.Graphical

Robust online monitoring system for PCDD/Fs in a full-scale MSWI by Deans switch: Efficiently separation and purification

Existing online monitoring system for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), technically named Thermal Desorption-Gas Chromatography-Tunable Laser Ionization-Time of Flight Mass Spectrometry (TD-GC-TLI-TOFMS), has been applied in several incinerators in China. TD-GC-TLI-TOFMS can realize rapid detection of PCDD/Fs emissions from incineration sources. However, the long-term measurement of unclean flue gas will pollute the instruments in TD-GC-TLI-TOFMS, and interfere with the peak output of the target 1,2,4-trichlorobenzene (1,2,4-TrCBz). In this study, Deans switch (DS) was utilized for the first time in an online monitoring system for PCDD/Fs to separate 1,2,4-TrCBz signal from impurity signals, which improved the anti-interference capability of the system. Laboratory standard gas experiments showed that after adding a DS device between GC and TLI pulse valve, when the pressure set in DS was 4 psi and switched before or near the peak output of 1,2,4-TrCBz, the change of 1,2,4-TrCBz signal intensity was minimal. The impurities near the target peak were removed, and TLI-TOFMS was highly stable during continuous measurement. Moreover, the maximum intensity peak time of 1,2,4-TrCBz was stable after using DS in different switching time intervals. When connecting DS to TD-GC-TLI-TOFMS for field validation on the tail flue gas of a municipal solid waste incinerator (MSWI), results showed that a better 1,2,4-TrCBz signal could be obtained with a 69.52 % reduction of impurity peaks at the moments closer to the target peak. Furthermore, DS improved the sensitivity of the system to low concentration variations of 1,2,4-TrCBz in the flue gas. The robust system developed in this study can be better applied to incineration factories with poor combustion or suboptimal purification technology, facilitating online PCDD/Fs monitoring.

Dietary exposure to metals/metalloids and persistent organic pollutants in Spanish preschool and primary school children

Diet is a primary source of pollutant exposure. Given children's vulnerability to their effects, this study assessed dietary intake of metals/metalloids and different persistent organic pollutants in children in Tarragona (Spain), compared it with the health-based guideline values (HBGV), and identified the main dietary sources. The analysis included 533 preschoolers and 443 primary school children from the EPINED and ECLIPSES studies. Dietary intake of cadmium (Cd), methylmercury (MeHg), lead (Pb), inorganic arsenic (inAs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DL-PCBs), and non-dioxin-like polychlorinated biphenyls (NDL-PCBs) was estimated using validated food frequency questionnaires and a database from the Catalan Agency for Food Safety. Preschoolers and primary school children exceeded the relevant reference value for InAs and DL-PCBs. Only preschoolers exceeded the limit for MeHg and PCDD/Fs. Cd, Pb, and NDL-PCBs intakes did not exceed the limits in either age group. Salted cereals/potatoes were the main source of InAs; fish for MeHg and DL-PCBs; and milk/yogurt for PCDD/Fs, followed by white fish in preschoolers and fatty fish in primary school children. The findings highlight that dietary exposure to some pollutants poses a significant risk to these children, emphasizing the need for public health policies to reduce pollutants in their diets.

Environmental Levels of PCDD/Fs near Cement Plants in Catalonia, Spain. An Update of Human Health Risks

Cement production is an important industrial activity that generates large amounts of pollutants, including, among others, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). These environmental contaminants are persistent and bioaccumulative, potentially causing serious adverse effects on human health, including cancer. The present paper was aimed at providing an update of the environmental concentrations of PCDD/Fs around various cement plants located in Catalonia, Spain. The non-carcinogenic and the carcinogenic risks associated to PCDD/Fs exposure were also assessed for the population living near the facilities. According to the present results, the environmental burdens of PCDD/Fs were highly dependent on the surroundings, rather than the technical specifics characteristics of each facility. Thus, higher concentrations were found near cement plants located in urban areas, where other emission sources (e.g., heavy traffic, domestic heating, etc.) may be present. The surveillance studies showed long-term stable concentrations in air, while PCDD/Fs levels in soil and vegetation were more variable. Although inhalation was the most relevant pathway of environmental exposure, the main uptake of PCDD/Fs occurs -in general- via dietary intake. Cancer risks were higher for people living near cement plants in urban areas than in rural environments, but at levels that are considered as acceptable by international regulations. In turn, the non-carcinogenic risks suggest a low concern, as the hazard quotient was &lt;1. Long-term surveys conducted in Catalan cement plants indicate that these facilities, which are periodically (every two years) monitored, should not be of concern for human health, in terms of PCDD/F exposure.

Unveiling the competitive mechanism between SO2 and PCDD/Fs on activated carbon adsorption

In municipal solid waste incineration (MSWI) plants, activated carbon (AC) adsorption is the key technique for eliminating Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from flue gases. This research thoroughly investigates the potential competitive adsorption between SO2 and PCDD/Fs and examines how adsorption at the center and the edge of the AC layer impacts the adsorption process. The findings show a decline in the removal efficiency of PCDD/Fs from 86.8 % to 84.2 % and further to 74.4 % when using SO2 pre-treated (AC-A3) and H2SO4-impregnated (AC-B2) activated carbon, respectively. Multiple characterization methods reveal that sulfur elements occupy active sites within the inner pores of the activated carbon, reducing the availability of its pore structure, particularly affecting microporous more than mesoporous structures. DFT calculations suggest that the π-π EDA effect facilitates the adsorption of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), whereas dispersion force drive SO2 adsorption. Comparisons among various oxygenated functional groups show that the organic acid anhydride (CO-CO) has better adsorption selectivity toward TCDD and less adsorption to SO2. This study provides a novel perspective on the adsorption mechanisms of PCDD/Fs on AC and the competitive dynamics of sulfur in the flue gas.

Calcium oxide adsorption of gas phase PCDD/Fs and its impact on the adsorption properties of activated carbon

Calcium oxide (CaO), utilized in semi-dry/dry desulfurization systems at municipal solid waste incineration (MSWI) plants, demonstrates some capability to remove polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). This study assessed the gas-phase PCDD/F removal performance of CaO, activated carbon (AC) and CaO-AC mixtures. Alone, CaO achieved removal efficiencies of only 31.9% for mass and 50.8% for I-TEQ concentration. However, CaO-AC mixtures exhibited significantly higher efficiencies, reaching 96.0% and 92.5% for mass and I-TEQ concentrations, respectively, surpassing those of AC alone, which were 74.7% and 58.5%. BET analysis indicated that CaO's limited surface area and pore structure are major constraints on its adsorption performance. Density functional theory (DFT) calculations revealed that the π-π electron donor-acceptor (EDA) interaction enhances the adsorption between AC and PCDD/F, with adsorption energies ranging from −1.02 to −1.24 eV. Additionally, the induced dipole interactions between CaO and PCDD/F contribute to adsorption energies ranging from −1.13 to −1.43 eV. Moreover, with increasing chlorination levels, PCDD/F molecules are more predisposed to accept electron transfers from the surfaces of AC or CaO, thereby facilitating adsorption. The calculation for mixed AC and CaO showed that CaO modifies AC's properties, enhancing its ability to adsorb gas phase PCDD/Fs, with the higher adsorption energy and more electrons transfer, aligning with gas phase PCDD/Fs adsorption experiments. This study provides a comprehensive understanding of how CaO influences the PCDD/F adsorption performance of AC.

Insight into the inhibition mechanisms of Ca-, N-, S-containing compounds on persistent organic pollutant formation from the thermal reaction of anthracene on copper chloride

Four inhibitors (CaO, CaS, CH4N2S, and (NH4)2SO4) were employed to inhibit the formation of multiple unintentional persistent organic pollutants (POPs) and environmentally persistent free radicals (EPFRs) using anthracene as a precursor, with CuCl2 serving as both a transition metal catalyst and chlorine source. The inhibition mechanisms were elucidated in terms of chlorine immobilization, catalyst deactivation, and free radical regulation. The inhibition efficiency of the four inhibitors on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) ranged from 64.7 % to 98.4 %, with the corresponding inhibition rates on toxic equivalency quantity ranging from 86.3 % to 99.7 %. The distribution of homologs shifted towards less chlorinated species, indicating effective suppression of chlorination. Calcium- and nitrogen-containing compounds consumed chlorine sources by forming CaCl2, CaClOH, and NH4Cl, while sulfur-containing compounds deactivated catalysts by forming CuSO4. EPFRs derived from anthracene were identified as carbon-centered anthracene-type and anthraquinone-type radicals. Positive correlations were observed between POPs and EPFRs concentrations, suggesting the pivotal role of organic free radicals as intermediates in POPs formation. Anthraquinones derived from anthracene underwent decomposition, recombination and chlorination, leading to the formation of PCDD/Fs and PCBs. The addition of inhibitors reduced EPFRs concentrations by 74.2–95.1 %. Sulfur- and nitrogen-containing inhibitors generated radicals that attacked POPs precursors and intermediates, forming heteroatomic compounds and inhibiting POPs formation. These findings enhanced the understanding of the source control mechanisms of POPs and provided theoretical and technical support for the synergistic inhibition of POPs and EPFRs in industrial thermal processes.

Polychlorinated dibenzo-p-dioxin and dibenzofuran contamination of free-range eggs: estimation of the laying hen’s soil ingestion based on a toxicokinetic model, and human consumption recommendations

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are ubiquitous in the environment. The main route of human exposure is through food consumption. Soil contamination can be problematic for sanitary safety depending on the usage of the soil, such as farming. In case of environmental soil contamination with PCDD/Fs, hen’s eggs may be contaminated due to soil ingestion by hens. For this reason, it is important to understand the parameters that influence eggs’ contamination when hens are raised in contaminated areas. After the discovery of a contaminated area in Lausanne (Switzerland), we collected hens’ eggs from ten domestic-produced eggs and one farm. Based on PCDD/F measurements of eggs and soil, and a toxicokinetic model, we estimated individual hen’s soil intake levels and highlighted appropriate parameters to predict the dose ingested. Recommended weekly consumption for home-produced eggs was calculated based on the tolerable weekly intake proposed by EFSA in 2018. The most important parameter to assess the soil ingestion does not seem to be the soil coverage by vegetation but rather the hen’s pecking behaviour, the latter being difficult to estimate objectively. For this reason, we recommend using a realistic soil ingestion interval to assess the distribution of egg PCDD/F concentration from free-range hens reared on contaminated soil. The addition of soil contamination in the toxicokinetic model can then be used to recommend to the general population weekly consumption of eggs. The consumption by adults of free-range eggs produced on land with soil containing >90 ng toxic-equivalent (TEQ)/kg dry soil should be avoided. Even with a low level of soil contamination (1–5 ng TEQ/kg dry soil), we would recommend consuming not more than 5 eggs per week for adults and no more than 2 eggs for children below 4 years old.

Mixture analysis of associations between environmental and workplace toxins and liver damage and telomere length, stratified by race/ethnicity

This study aimed to identify the worst “bad actors” in mixtures of pollutants contributing to liver damage and shorter telomeres in the U.S. population, using Weighted Quantile Sum (WQS) modeling with stratification by race/ethnicity. We conducted a comprehensive cross-sectional analysis of mixtures of pollutants in National Health and Nutrition Examination Survey datasets: a) 33,979 adults with blood levels of cadmium (Cd), lead (Pb), and mercury, including subsets with measurements of per-/polyfluoroalkyl substances (PFAS), and polychlorinated biphenyls (PCBs)/polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs); and b) 7360 adults with measurements of telomeres, Cd, and Pb. Multivariable-adjusted WQS regression examined associations between WQS mixture indices and liver injury [alanine aminotransferase (ALT)-elevation], advanced liver-fibrosis (LF), and telomere length. WQSmetal indices were associated with advanced-LF in all racial/ethnic groups. The top contributor was Cd in the total population and in non-Hispanic Whites (NHW), while Pb was the top contributor in non-Hispanic Blacks (NHB). The WQSmetal-PCB-PCDD/F index was associated with ALT-elevation, with PCB126, Cd and Pb as main contributors; the odds ratio (OR) per decile was 1.50 (95%CI, 1.26-1.78), while the OR per decile of the WQSmetal-PFAS index was 1.03 (95%CI, 0.98-1.05), not significant. WQSmetal indices were associated with shorter telomeres. Cd was main contributor associated with advanced-LF in NHW, while Pb was the major bad actor in NHB, suggesting that NHB may be especially susceptible to Pb toxicity. Metals were associated with shorter telomeres. Metal and PCB/PCDD/F mixtures were associated with ALT-elevation. Heavy metals and organic chemicals may contribute to liver-related morbidity and healthcare disparities.

Unveiling respiratory health risks: PCDD/Fs adhering to particulate matter (PM10 and PM2.5) in Bien Hoa City, Dong Nai, Vietnam

This study investigates the concentrations of atmospheric aerosol particles (PM, including PM2.5 and PM10), as well as the presence and distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in ambient air in Bien Hoa City (Dong Nai province, Vietnam) during the dry and rainy seasons in 2023. The concentrations of 7 PCDDs and 10 PCDFs congeners in PM10 or PM2.5 were determined using gas chromatography-mass spectrometry (GC-MS). The results show that the concentration of PM10 and PM2.5 were 54.7 ± 9.4 µg/m3, 65.3 ± 7.6 µg/m3, and 39.6 ± 7.9 µg/m3, 58.9 ± 12.6 µg/m3, in the rainy season and dry season, respectively. This reveals that while only PM2.5 concentration levels in the dry seasonexceed national ambient air quality standards, but all of PM2.5 concentration levels consistently exceeded WHO guidelines. The study highlights the dominance of PM2.5 and its adverse health implications, as evidenced by the PM2.5/PM10 ratio (0.74 and 0.85 for the rainy and dry seasons, respectively) and its association with worse air quality. Analysis of PCDD/Fs concentrations in PM samples demonstrates their comparable levels in both seasons, with OCDD being the most abundant species. Furthermore, the study estimates the toxic equivalency (TEQ) of PCDD/Fs and assesses health risks, revealing a potentially high cancer risk from exposure to these pollutants, particularly PM2.5 under WHO2005-TEQ. Several PCDD/Fs- WHO2005-TEQ congeners exhibit higher concentration levels in PM2.5 compared to PM10, suggesting differential particulate matter dynamics and potential environmental implications. These findings underscore the urgent need for mitigation strategies to alleviate air pollution and reduce associated health risks in the dioxin hotspot of Vietnam.

Accumulation Rate, Depuration Kinetics, and Tissue Distribution of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans (PCDD/Fs) in Suckler Ewes (Ovis aries).

Understanding the transfer of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in farm animals is essential for ensuring food safety, but such information for suckler ewes (Ovis aries) has been lacking. This work quantifies the accumulation, tissue distribution, and depuration kinetics of PCDD/Fs in these animals. Six suckler ewes (EXP group) were exposed to PCDD/Fs through contaminated hay (2.3-12.7 ng toxic-equivalent kg-1 dry matter) and then allowed to depurate by switching to noncontaminated hay from 29 days of lactation. Four control ewes were fed continuously with noncontaminated hay. At different time points covering depuration, weaning and slaughter, PCDD/F analysis of milk (three time points), blood and sternal adipose tissue (five time points), Longissimus thoracis muscle, liver, and empty body homogenate at slaughter (188 days of depuration) was performed. A relevant PCDD/F bioaccumulation was observed from oral intake in milk and adipose tissue (biotransfer factors of 1.24 and 1.06 day kg-1 lipids for the sum toxic-equivalent, respectively) in the EXP ewes, especially for penta- and hexa-chlorinated congeners. The EXP ewes' adipose tissue started at 10-fold the EU maximum level (ML) and showed depuration below the ML after 130 days. Specific PCDD/F accumulation in the ewe liver was observed, especially for dibenzofurans. These toxicokinetic data can inform recommendations to ensure the chemical safety of sheep food products.

Regulatory compliance of PCDD/F emissions by a municipal solid waste incinerator. A case study in Sant Adrià de Besòs, Catalonia, Spain

Despite incineration is an important emission source of toxic pollutants, such as heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), it is still one of the most widely used methods for the management of municipal solid waste. The current paper summarizes the results of a 20-year follow-up study of the emissions of PCDD/Fs by a municipal solid waste incinerator (MSWI) in Sant Adrià de Besòs (Catalonia, Spain). Samples of ambient air, soils and herbage were periodically collected near the facility and the content of PCDD/Fs was analyzed. In the last (2017) survey, mean levels in soil were 3.60 ng WHO-TEQ/kg (range: 0.40–10.6), being considerably higher than the mean concentrations of PCDD/Fs in soil samples collected near other MSWIs in Catalonia. Moreover, air PCDD/F concentrations were even higher than those found in a previous (2014) survey, as they increased from 0.026 to 0.044 pg WHO-TEQ/m3. Ultimately, the PCDD/F exposure would be associated to a cancer risk (2.5 × 10−6) for the population living in the surrounding area. Globally, this information indicates that the MSWI of Sant Adrià de Besòs could have had a negative impact on the environment and potentially on public health, being an example of a possible inappropriate management for years. The application of Best Available Techniques to minimize the emission of PCDD/Fs and other chemicals is critical.