Dioxins, PFOS, and 20 other Persistent Organic Pollutants in Eggs of Nine Wild Bird Species from the Vaal River, South Africa.

The Vaal River catchment drains the largest and most populated industrial and mining region in Southern Africa. Heron, ibis, cormorant, egrets, and darter eggs, representing three habitats and four feeding guilds, were collected at four locations in 2009/10 to identify hotspots and hazards associated with persistent organic pollutants (POPs). The POPs included 21 organochlorine pesticides, five polybrominated diphenyl ether (PBDE) classes, 18 polychlorinated biphenyls (PCBs including six non-dioxin-like PCBs; NDL-PCB), and 12 dioxin-like PCBs (DL-PCBs), 17 polychlorinated dibenzo-p-dioxins and dibenzo-p-furans (PCDD/Fs), and perfluorooctane sulfonate (PFOS). Aquatic predators had higher PFOS and PCDD/F concentrations, while PCBs dominated in terrestrial eggs. Organochlorine pesticides, PBDEs, and PCBs were strongly associated with eggs from the industrial regions, while PCDD/F concentrations were evenly distributed. PCDD/F and PCB toxic equivalency quotient concentrations were low with no adverse effects expected. PFOS peaked at Bloemhof Dam with a maximum of 2300 ng/g wm in an African Darter egg, indicating an unexpected PFOS hotspot, the source of which is unknown. Despite order of differences in compound class concentrations, there was no association with egg size. To the best of our knowledge, this is the only study that analysed all 2010 POPs in bird eggs on a large geographic scale. This study highlighted the importance of multi-species studies sampling from multiple locations to assess the risk that POPs pose to avian populations as hotspots and species at risk may be missed by studies looking at one or few species.

Multi-media environmental fate of polychlorinated dibenzo-p-dioxins and dibenzofurans in China: A systematic review of emissions, presence, transport modeling and health risks.

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) are notorious persistent organic pollutants (POPs) with proven toxicity to human and ecosystems. This review critically evaluates existing research, emphasizing knowledge gaps regarding PCDD/F emissions, environmental behavior, human exposure, and associated risks in China. The current emission inventory of PCDD/Fs in China remains highly uncertain, both in terms of total emissions and emission trends. Moreover, existing monitoring data primarily focus on areas near pollution sources, limiting comprehensive understanding of the overall spatiotemporal characteristics of PCDD/F pollution. To address this, we propose a novel approach that integrates the Multi-media Urban Mode (MUM) model with an atmospheric chemical transport model that includes a dual adsorption model to capture gas-particle partitioning of PCDD/Fs in the atmosphere. This coupled model can simulate the transport and fate of PCDD/Fs in multi-media environments with high spatiotemporal resolution, facilitating a nuanced understanding of the impacts of emissions, climate, urbanization and other factors on PCDD/F pollution. Additionally, dietary ingestion, particularly from animal-derived foods, is identified as the predominant source (up to 98%) of human exposure to PCDD/Fs. While the changes in dietary structure, population distribution, and age structure can influence human exposure to PCDD/Fs, their impacts have not yet been quantified. The proposed model lays the foundation for a systematic assessment of health risks from PCDD/F exposure through various pathways by further incorporating a food chain model. Overall, this review offers a comprehensive strategy for assessing PCDD/F pollution, encompassing the entire continuum from emissions to environmental impacts.

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.

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.

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.

Insight into the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans in hazardous waste incineration and incinerators: Formation process and reduction strategy.

Incineration technology has been widely adopted to safely dispose of hazardous waste (HW). While the incineration process causes the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Due to its extreme toxicity, many scholars have been committed to determining the PCDD/F formation process and reducing emissions in incinerators. Previous studies ignored the impact of incineration and fluctuation of feeding materials on PCDD/F formation in hazardous waste incinerators (HWIs). In this study, differences in PCDD/F formation between HWIs and municipal solid waste incinerators (MSWIs) were pointed out. The incineration section in HWIs should be carefully considered. Laboratory experiments, conventional analysis and thermogravimetry experiments were conducted. An obvious disparity of PCDD/F formation between 12 kinds of HWs was found. Distillation residue was found with remarkably higher PCDD/F concentrations (11.57 ng/g). Except for the Cl content, aromatic rings and C-O bond organics were also found with high correlation coefficients with PCDD/F concentrations (>0.92). And PCDD/Fs were formed through a chlorination process and structure formation process. All of these are helpful to further understand the PCDD/F formation process during HW incineration, optimize the operation conditions in HWIs and reduce the emission pressure of PCDD/Fs in the future.

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.

Historical production and release inventory of PCDD/Fs in China and projections upon policy options by 2025.

Using the source identification and classification methodology described in UNEP standardized toolkit for dioxin releases, combined with research data over the past decade, the production and release of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) from 6 major sectors in China were inventoried from 2003 to 2020, and were projected until 2025 based on current control measures and relevant industrial plans. The results showed that after ratification of the Stockholm Convention, China's production and release of PCDD/Fs began to decline after peaking in 2007, demonstrating the effectiveness of preliminary control measures. However, the continual expansion of manufacturing and energy sectors, along with the lack of compatible production control technology, reversed the declining trend of production after 2015. Meanwhile, the environmental release continued to decrease, but at a slower rate after 2015. If subject to current policies, production and release would remain elevated with an expanding gap in between. This study also established the congener inventories, revealing the significance of OCDF and OCDD in terms of both production and release, and that of PeCDF and TCDF in terms of environmental impacts. Lastly, through comparison with other developed countries and regions, it was concluded that room for further reduction exists, but can only be achieved through strengthened regulations and improved control measures.

Dietary intake of polychlorinated dibenzo-p-dioxins and furans, adiposity and obesity status.

INTRODUCTION: The principal source of exposure to Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo-p-furans (PCDD/Fs) in humans comes from food intake. PCDD/Fs, are a family of potential endocrine disruptors and have been associated with different chronic diseases such as diabetes and hypertension. However, studies assessing the relationship between dietary exposure to PCDD/Fs and adiposity or obesity status in a middle-aged population are limited. OBJECTIVE: To assess cross-sectionally and longitudinally the associations between estimated dietary intake (DI) of PCDD/Fs and body mass index (BMI), waist circumference, and the prevalence/incidence of obesity and abdominal obesity in a middle-aged population. METHODS: In 5899 participants aged 55-75 years (48% women) living with overweight/obesity from the PREDIMED-plus cohort, PCDD/Fs DI was estimated using a 143-item validated food-frequency questionnaire, and the levels of food PCDD/F expressed as Toxic Equivalents (TEQ). Consequently, cross-sectional and prospective associations between baseline PCDD/Fs DI (in pgTEQ/week) and adiposity or obesity status were assessed at baseline and after 1-year follow-up using multivariable cox, logistic or linear regression models. RESULTS: Compared to participants in the first PCDD/F DI tertile, those in the highest tertile presented a higher BMI (ß-coefficient [confidence interval]) (0.43kg/m2 [0.22; 0.64]; P-trend <0.001), a higher waist circumference (1.11 cm [0.55; 1.66]; P-trend <0.001), and a higher prevalence of obesity and abdominal obesity (1.05 [1.01; 1.09] and 1.02 [1.00; 1.03]; P-trend = 0.09 and 0.027, respectively). In the prospective analysis, participants in the top PCDD/F DI baseline tertile showed an increase in waist circumference compared with those in the first tertile after 1-year of follow-up (ß-coefficient 0.37 cm [0.06; 0.70]; P-trend = 0.015). CONCLUSION: Higher DI of PCDD/Fs was positively associated with adiposity parameters and obesity status at baseline and with changes in waist circumference after 1-year of follow-up in subjects living with overweight/obesity. Further large prospective studies using a different population with longer follow-up periods are warranted in the future to strengthen our results.

Terrestrial animal livers as a source of PCDD/Fs, PCBs and PBDEs in the diet.

The livers of terrestrial animals are an important source of vitamins and minerals, but with the liver being the major filtering and detoxifying organ, it retains xenobiotic material, especially persistent organic pollutants (POPs). The aim of the study was human health risk assessment related to the presence of certain POPs, namely polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in terrestrial animals' livers. HRGC-HRMS was used to determine analyte concentrations in 99 liver samples of chicken, pork, beef, and mutton livers obtained from Polish farms. The ovine livers were the most contaminated by ∑PCDD/F/dl-PCBs (0.06-2.21 pg WHO-TEQ g-1 wet weight), ∑ndl-PCBs (0.036-1.54 ng g-1 wet weight) and ∑PBDEs (0.21-2.27 ng g-1 wet weight). Samples were found of ovine and pork livers that exceeded the maximum concentration limits established for PCDD/Fs. The Kruskal-Wallis test showed that there were statistical differences between regions in the concentrations of the ∑PCDD/Fs and ∑PCDD/F-PCBs, but none in those of the ∑dl-PCBs, ∑ndl-PCBs or ∑PBDEs. According to Dunnett's test results, ovine liver samples from the Podlaskie province contained fewer ∑PCDD/F than those from the Dolnoslaskie (p < 0.027) and Malopolskie (p < 0.0342) voivodeships. Taking into account PCDD/F contents and Tolerable Weekly Intake (2 pg WHO-TEQ/kg BW) (TWI2018), the lowest risk was associated with chicken liver consumption (TWI up to 11 % in the 95th percentile), pork (62 %) and bovine (92 %) livers should be eaten in limited amounts for risk avoidance, while mutton liver (400 %) should not be eaten at all. Additionally, there is no risk of ingestion of a harmful amount of PBDEs associated with consumption of the livers of terrestrial animals from Poland based on the margin of exposure values (>15).

Formation pathways, gas-solid partitioning, and reaction kinetics of PCDD/Fs associated with baghouse filters operated at high temperatures: A case study.

The application of the 3T method during combustion (i.e., a Temperature > 850 °C, a residence Time > 2 s, and sufficient Turbulence) can lead to elevated operating temperature in the baghouse filter for the municipal solid waste incineration (MSWI) systems without sufficient heat exchange capacity, which is potentially detrimental to the emission control of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Herein, a field study focusing on the distribution and variation of PCDD/Fs in gaseous and solid phases in a baghouse filter with high operating temperature (225-230 °C) was carried out. The concentration of PCDD/Fs in gases at the outlet of the baghouse filter was around 1 order of magnitude higher than that in inlet gases (i.e., noticeable memory effect of PCDD/Fs), because of the significant PCDD/Fs formation in filter fly ash (primarily contributed by the precursor pathway) followed by PCDD/Fs desorption. In addition, the mechanisms and factors resulting in the memory effect of PCDD/Fs were identified based on a laboratory study that carefully investigated the formation and desorption of PCDD/Fs at potential operating temperatures of baghouse filters (i.e., 180, 200, and 225 °C). The temperature was identified as the key factor inducing the memory effect of PCDD/Fs, because: i) PCDD/Fs memory effect was not observed for baghouse filters with low operating temperatures of ~150 °C in previous studies; ii) both the formation and desorption of PCDD/Fs were noticeably favored by rising temperature from 180 to 225 °C; iii) increasing temperature appeared to facilitate the transformation from inorganic Cl to organic Cl and the conversion from aliphatic carbon to aromatic carbon or unsaturated hydrocarbons, both of which were favorable to PCDD/Fs formation; and iv) the release rate of PCDD/Fs from fly ash was exponentially dependent on temperature based on the modeling results of reaction kinetics.

Suppression on PCDD/Fs formation by a novel inhibition system consisting of phosphorous-based compounds coupled with a chlorine-deactivation material.

The SN-containing inhibitors are effective for suppressing the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the post-combustion zone of municipal solid waste incineration systems, but the industrial application of the SN-containing inhibitors is restricted by the high cost and the generation of corrosive by-products (e.g., SOx). To develop cost-effective and environmentally friendly inhibitors, a new inhibition system consisting of P-based compounds (i.e., NH4H2PO4 (ADP) and KH2PO4 (PDP)) and a chlorine-deactivation material (CaO) was proposed in this study. Also, the performance of this inhibition system in terms of suppressing PCDD/Fs formation was evaluated in an experimental system which simulated PCDD/Fs generation in the post-combustion zone. Generally, the formation of PCDD/Fs was effectively suppressed by over 95 % by the mixed inhibitors (ADP/CaO and PDP/CaO) and the individual inhibitor of ADP. Based on the observation on PCDD/F-fingerprints and the chemical speciation of Cl and Cu, the mechanisms of inhibitors were identified as: (i) passivating metal catalyst by converting the speciation of Cu from chlorides and Cu2+ with high reactivities to phosphates, oxides, and Cu+ with low reactivities, and (ii) deactivating Cl by CaO to prevent the formation of organic Cl which was critical for PCDD/Fs formation. In addition, both mechanisms were supported by (i) the better performance of inhibitors on suppressing the PCDD/F-congeners formed via de novo pathway than congeners synthesized from chlorophenols and (ii) lower degrees of chlorination of PCDD/Fs for reaction systems with CaO involved than other systems.

Investigation on dioxins emission characteristic during complete maintenance operating period of municipal solid waste incineration.

The dioxins (DXN) are a set of pollutants encompass polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F), their emissions from municipal waste incineration processes (MSWI) are normally detected under steady operating conditions. However, limited studies have focused on the PCDD/F emission characteristics under a complete maintenance operating period (CMOP), which includes shut-down, cooling, maintenance, heating, startup, and normal operations. In this article, the shutdown process (SDP) starts from the normal operation, followed by shutdown, and then cooling; while the startup process (SUP) commences from heating, followed by startup, and then normal operation. The detection and analysis were conducted at the SDP and SUP stages. The PCDD/F mass and total toxic equivalent quantity (TEQ) concentrations were measured in the flue gas and bag filter fly ash (BF-FA) during a CMOP of Beijing MSWI plant. The highest PCDD/F concentrations in the flue gas were found in the "cooling" and "startup" phases; in the FA, this condition occurred in the "startup" phase. Further, the results show that the most heightened concentrations were observed for 5-6 chlorinated PCDF and 4-5 chlorinated PCDD among the 17 PCDD/F congeners in most cases. More importantly, the air pollution control devices (APCDs) which include activated carbon, lime, and BF, have high removal efficiency for PCDD/F (especially PCDD) during the "startup" phase. APCDs also easily release a considerable amount of PCDD/F because of the memory effect, which emits more PCDD/F at the "shutdown" phase than at the "startup" one. Besides, the annual PCDD/F emission in the flue gas of the MSWI plant was estimated to be 67.72 mg I-TEQ, of which the emission accounts for approx. 20% during the CMOP. Moreover, the experiment shows that the PCDD/F emissions of the MSWI plant in Beijing under unsteady conditions are more miniature than those reported earlier in other areas.

Polychlorinated dioxins and dibenzofurans (PCDD/F), polybrominated dioxins and dibenzofurans (PBDD/F), polychlorinated biphenyls (PCB), polybrominated diphenyl ethers (PBDE), and per- and polyfluoroalkyl substances (PFAS) in German breast milk samples (LUPE 8).

Most organic pollutants (POP) are persistent in the environment, accumulate in fatty tissues, and so a transfer through the food chain is probably, thereby causing various health effects. We quantified PCDD/F, PBDD/F, PCB, PBDE, perfluorinated substances, and ADONA in breast milk samples collected in two German federal states and breast milk and blood samples from subjects additionally exposed to PFOA. The median (95th percentile) concentrations were 2.43 (6.58) pgWHO2005TEQ/g l.w. for PCDD/F, 2.45 (4.82) pgWHO2005TEQ/g l.w. for dioxin-like PCB (dl-PCB), and 0.62 (2.69) pgWHO2005TEQ/g l.w. for PBDD/F. The relative contributions of the median values of PCDD/F, dl-PCB, and PBDD/F to the total-TEQ were approximately 41%, 42%, and 11%, respectively. Nondioxin-like PCB (ndl-PCB) concentrations were clearly dominated by the higher chlorinated PCB congeners, with medians of 23.2 ng/g l.w. for PCB 153, 13.9 ng/g l.w. for PCB 138, and 13.0 ng/g l.w. for PCB 180. The sum of the 3 congeners (PCB 138, 153, and 180) were multiplied with 1.64 (total PCB) and showed a median of 82.16 ng/g l.w. and a 95th percentile of 173.3 ng/g l.w. Only PFOA and PFOS could be quantified in 29% and 17% of in total 180 samples with 95th percentiles of 53 ng/l and 33 ng/l, respectively. Milk samples (n = 13) from subjects living on PFOA contaminated sites showed higher levels between 33 and 854 ng/l PFOA (mean: 199 ng/l), whilst PFOS could be quantified only in three samples. The sum of 17 PBDE congeners showed medians (95th percentile) of 1737 pg/g l.w. (22,806 pg/g l.w.), with the highest medians of 422 pg/g l.w. for BDE 209 and 378 pg/g l.w. for BDE 153. Overall, our study confirms the declining contamination level in breast milk during the last decade, but points out the need to further reduce the environmental contamination with persistent substances and subsequently the exposure in childhood.

PCDD/F removal at low temperatures over vanadium-based catalyst: insight into the superiority of mechanochemical method.

The high toxicity and low volatility of PCDD/Fs prevent detailed study of their catalytic degradation removal characteristics. In this study, 1,2-dichlorobenzene (1,2-DCBz) was initially used as a model to investigate the catalytic characteristics of various vanadium-based catalysts prepared by different methods. Then, the optimized catalyst was used for catalytic degradation of real PCDD/Fs at low temperatures based on a self-made stable source. The VOx/TiO2 catalysts synthesized by the mechanochemical method (VTi-MC2) had a higher 1,2-DCBz removal efficiency (>85%) and stability (> 420 min) at low temperatures (< 200 °C) compared to VTi-SG (sol-gol method) and VTi-WI (wetness impregnation method). The physicochemical properties of catalysts were studied using comprehensive characterization. It was found that the VTi-MC2 has better VOx species distribution and possesses the highest V5+ species and surface adsorbed oxygen content, which are the key factors that contributed to the higher removal efficiency. Accordingly, the mechanochemical method can be used to control the physicochemical properties of catalysts by adjusting the milling parameters. The optimum ball milling time is 2 h and a suitable precursor is NH4VO3 for VOx/TiO2. Moreover, the removal efficiency and catalytic degradation efficiency of PCDD/Fs in gas phase catalyzed by VTi-MC2 were 97% and 50% respectively, within a range of temperatures below 200 °C, which are both higher than those reported research. In general, the mechanochemical strategy employed in this study provides a means for seeking more efficient catalysts used for low-temperature degradation of various trace organic pollutants.

Prenatal exposure to endocrine disrupting chemicals is associated with altered DNA methylation in cord blood.

Prenatal exposure to endocrine disrupting chemicals can interfere with development, and has been associated with social-cognitive functioning and adverse health outcomes later in life. Exposure-associated changes of DNA methylation (DNAm) patterns have been suggested as a possible mediator of this relationship. This study investigated whether prenatal low-dose exposure to polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) is associated with altered DNAm patterns across the genome in a Western urban-industrial population. In 142 mother-infant pairs from the Duisburg Birth Cohort Study, PCBs and PCDD/Fs levels were quantified from maternal blood during late pregnancy and associated with DNAm levels in cord blood using the Illumina EPIC beadchip. The epigenome-wide association studies (EWAS) identified 32 significantly differentially methylated positions (DMPs) and eight differentially methylated regions (DMRs) associated with six congeners of PCB and PCDD in females or males (FDRs < 0.05). DMPs and DMRs mapped to genes involved in neurodevelopment, gene regulation, and immune functioning. Weighted gene correlation network analysis (WGCNA) showed 31 co-methylated modules (FDRs < 0.05) associated with one congener of PCDF levels in females. Results of both analytical strategies indicate that prenatal exposure to PCBs and PCDD/Fs is associated with altered DNAm of genes involved in neurodevelopment, gene expression and immune functioning. DNAm and gene expression levels of several of these genes were previously associated with EDC exposure in rodent models. Follow-up studies will clarify whether these epigenetic changes might contribute to the origin for adverse mental and health outcomes.

Generalized prediction and optimal operating parameters of PCDD/F emissions by explainable Bayesian support vector regression.

The current derived models for predicting polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) emissions from incineration can only be applied to a specific incinerator due to high deviation or systematic errors. And the models fail to provide quantized guidance for the operation of full-scale municipal solid waste incinerators. To address the problem, explainable Bayesian support vector regression (E-BSVR) has been established to generalized predict and maximumly reduce the PCDD/F emissions. First, forty-two PCDD/F samples were determined from a whole year experiment in a full-scale incinerator. Meanwhile, 1,2,4-trichlorobenzene(1,2,4-TrCBz), carbon monoxide, sulfur dioxide, oxynitride, particulate matter, fluoride, and hydrogen chloride were measured, as input features. Second, after box-cox transformation normalization, and hyperparameters tuning, the R-Squared and root mean square error (RMSE) of the proposed method are 0.983 and 0.044, exhibiting high accuracy. The high accuracy (R-Squared = 0.992) and generalization are also proven on the dataset with high PCDD/F emissions. Then, the performances of BSVR are compared with kernel ridge regression, multiple linear regression, and unary linear regression, indicating afar smaller RMSE of BSVR. Finally, the optimal operating parameters are calculated through local interpretable model-agnostic explanations and the partial dependence plot. Results indicate that reducing the content of organic chlorine in municipal solid waste and inhibiting the deacon reaction are important methods for reducing PCDD/F emissions. The optimal operating parameters for the maximal reduction of PCDD/F emissions are 1,2,4-TrCBz < 0.098 ug/m3, fluoride > 0.452 mg/m3. As a whole, the E-BSVR method can be used as a reliable and accurate approach for the prediction and reduction of PCDD/F emissions.

Thermal cotreatment of municipal solid waste incineration fly ash with sewage sludge for PCDD/Fs decomposition and reformation suppression.

Thermal treatment of municipal solid waste incineration fly ash (FA) is an effective method to detoxicate FA and produce secondary material with good utilization properties, but the high temperature induced migration of carbon, chlorine, and catalytic metals from FA to flue gases can result in a considerable reformation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Herein, two typical fly ashes were thermally cotreated with sewage sludge (SS), respectively, and the decomposition and reformation of PCDD/Fs were systematically investigated. Thermal treatment effectively decomposed PCDD/Fs in all samples to a low level well meeting the reutilization criterion of 50 ng WHO-TEQ g-1. Cleavage of the oxygen bridge was identified as the primary decomposition pathway. Compared to mono-treating FA, cotreating FA with SS resulted in a better CaO-Al2O3-SiO2 ternary system for vitrification and effectively suppressed the reformation of PCDD/Fs in off-gases with inhibition efficiencies up to 96%. Based on the variation of chemical speciation of N, P, and S in SS after thermal treatment, SS appeared to be a S-N-containing inhibitor which passivated catalytic metals to suppress PCDD/Fs synthesis. The better suppression on de novo pathway than on chlorophenol-route identified by monitoring PCDD/F-fingerprints evolution further verified the suppression mechanism of passivating catalytic metals.

Stable and Effective Online Monitoring and Feedback Control of PCDD/F during Municipal Waste Incineration.

For the long-term operation of municipal solid waste incineration (MSWI), online monitoring and feedback control of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) can be used to control the emissions to national or regional standards. In this study, 500 PCDD/F samples were determined by thermal desorption gas chromatography coupled to tunable-laser ionization time-of-flight mass spectrometry (TD-GC-TLI-TOFMS) for 168 h. PCDD/F emissions range from 0.01 ng I-TEQ/Nm3 to 2.37 ng I-TEQ/Nm3, with 44% of values below 0.1 ng I-TEQ/Nm3 (the national standard). In addition, the temperature of the furnace outlet, bed pressure, and oxygen content are considered as key operating parameters among the 13 operating parameters comprising four temperature parameters, four pressure parameters, four flow parameters, and oxygen content. More specifically, maintaining the furnace outlet temperature to be higher than 800 °C, or bed pressure higher than 13 kPa, or the oxygen content stably and above 10% are effective methods for reducing PCDD/F emissions. According to the analysis of the Pearson coefficients and maximal information coefficients, there is no significant correlation between operating parameters and PCDD/F I-TEQ. Only when there is a significant change in one of these factors will the PCDD/F emissions also change accordingly. The feedback control of PCDD/F emissions is realized by adjusting the furnace outlet temperature, bed temperature, and bed pressure to control the PCDD/F to be less than 0.1 ng I-TEQ/Nm3.

Evolution of fusion and PCDD/F-signatures of boiler ash from a mechanical grate municipal solid waste incinerator.

Boiler ash formed at different temperature ranges in a typical mechanical grate incinerator is collected and systemically studied, with the aim of providing a reference for ash disposal and revealing the formation routes and distribution of polychlorinated ρ-dibenzodioxins and dibenzofurans (PCDD/Fs). Key physical and chemical properties are carefully analyzed, including chemical component, ash fusion temperatures (AFTs), crystalline phases, chemical species, and PCDD/Fs. Several fouling and slagging indices are introduced and their relationships with AFT are revealed. The fouling index (Fu) and a slagging index (Rb/a×Na) are well fitted with ash flow temperatures, with correlation coefficient (R2) of 0.82 and 0.82, respectively; these could be better potential indices for disposal applications of municipal solid waste incineration fly ash. CC/C-C/C-H (69.25-80.93%) and inorganic chlorine (94.23-98.68%) are the dominant carbon and chlorine species, respectively. The increasing AFT is mainly attributed to the changing components, the increasing proportions of crystalline CaSO4, NaCl and KCl and the decreasing crystallinity and content of SiO2. Twice as much PCDD/Fs is generated by the low-temperature heterogeneous reaction (6.71-19.22 ng/g) than by the high-temperature homogeneous reaction (0.59-6.71 ng/g). The proportions of highly chlorinated homologues increase and gradually become the main component. Principal component analysis reveals that PCDD/Fs is positively correlated with Cl, Cu, Pb, Sn, Sb, Zn and CC/C-C/C-H but negatively correlated with less volatile elements, e.g., Ni, Mn, Al, Ti, Si, and Cr. These results can benefit further research on boiler ash disposal and PCDD/F formation routes in the post-combustion area of incinerators.