Polychlorinated Dibenzo-p-dioxins And Dibenzofurans Research Articles

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.

Formation behavior of PCDD/Fs during waste pyrolysis and incineration: Effect of temperature, calcium oxide addition, and redox atmosphere

The clean and efficient utilization of municipal solid waste (MSW) has attracted increasing concerns in recent years. Pyrolysis of MSW is one of the promising options due to the production of high-value intermediates and the inhibition of pollutants at reducing atmosphere. Herein, the formation behavior of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during MSW pyrolysis and incineration was experimentally investigated and compared. The influence of reaction temperature, CaO addition, and redox atmosphere on PCDD/Fs formation were compared and discussed. The results showed as the pyrolysis temperature increased, the mass concentration and international toxicity equivalence quantity of PCDD/Fs initially peaked at ∼750 °C before declining. Most of the generated PCDD/Fs were concentrated in the liquid and gaseous products, accounting for ∼90% of the total. Among liquid products, octachlorodibenzo-p-dioxin (O8CDD), 2,3,4,7,8-pentachlorodibenzofuran and 1,2,3,4,6,7,8-heptachlorodibenzofuran (H7CDF) were the most crucial mass concentration contributors, while in gas products, high-chlorinated PCDD/Fs, such as O8CDD, octachlorodibenzofuran (O8CDF) and 1,2,3,4,6,7,8-H7CDF were predominant. Compared to incineration, the formation of PCDD/Fs was 7–20 times greater than that from pyrolysis. This discrepancy can be attributed to the hydrogen-rich and oxygen-deficient atmosphere during pyrolysis, which effectively inhibited the Deacon reaction and the formation of C–Cl bonds, thereby reducing the active chlorine in the system. The addition of in-situ CaO additives also decreased the active chlorine content in the system, bolstering the inhibiting of PCDD/Fs formation during MSW pyrolysis.

A novel, low-cost, and efficient separation strategy based on S-doped C3N4 for the analysis of PCDD/Fs and dioxin-like PCBs

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) are widespread and highly toxic persistent organic pollutants with similar chemical structure. The popular process for the separation of PCDD/Fs and dl-PCBs in one sample often relies on imported and expensive activated carbon, giving rise to an urgent need of inexpensive and efficient separation method. Herein, a novel, simple, and low-cost separation strategy based on sulfur-doped carbon nitride (S-C3N4) is reported. The S-C3N4 material was synthesized through simple thermal annealing with precursor of thiocyanuric acid. After recovery experiments, the optimal addition ratio of S-C3N4 was determined to be 40% mixed with silica gel. The recoveries for PCDD/Fs and dl-PCBs congeners are 32% - 105% and 60% - 70% respectively, which not only meets USEPA and Chinese standards but also shows comparable performance to activated carbon. Moreover, the proposed S-C3N4 strategy exhibits excellent performance for the analysis of PCDD/Fs and dl-PCBs in real complex samples (sediment and fish liver) in terms of detected concentrations and toxic equivalents. Overall, this study puts forward a new and low-cost avenue for the separation of PCDD/Fs and dl-PCBs, which is of remarkable meaning for motivating the development of detection techniques and domestic equipment for dioxins and other pollutants in the environment.

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 75.8ng/Nm3 for PCDDs, 219ng/Nm3 for PCDFs, and 763ng/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.

Characteristics of the pyrolytic products and the pollutant emissions at different operating stages from a pilot waste tire pyrolysis furnace

Pyrolysis is considered a highly practical, cost-effective, and environment-friendly technology for waste tires disposal. In this study, pyrolysis processes of waste tires were conducted in a pilot scale furnace feeding at 30 kg/h. The properties of pyrolytic products and the distribution patterns of pollutants generated in different operating stages (start-up, steady, and shut-down) were investigated. The pyrolytic gas in the steady state had a high caloric value of 10799 kJ/Nm3, valuable as heating source for pyrolysis. The elements of sulfur and zinc were effectively fixed as ZnS in the pyrolytic carbon. The basic properties of pyrolytic oil were in line with commercial diesel oil except for the lower flash point. Heavy metals were mainly concentrated in the pyrolytic carbon, with slightly higher concentrations in the steady state. Moreover, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were mainly concentrated in the pyrolytic oil, with predominated low-ring PAHs and high chlorinated PCDD/Fs. The concentrations of PAHs and PCDD/Fs in the gas phase were higher during the start-up stage due to the memory effect, whereas were effectively reduced during the steady stage. The concentration of PAHs in the solid phase was highest during the furnace start-up and lowest in the shut-down stage. In contrast to PAHs, the PCDD/Fs in the solid phase reached their highest concentration during the shut-down stage, which was mainly affected by temperature. The results provide guidance for the reducing of pollutant emissions and the recycling of pyrolytic products.

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

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

Bio-treatment of municipal solid waste incineration fly ash: A sustainable path for recyclability

This study investigates the impact of bio-treatment on Municipal Solid Waste Incineration Fly Ash (MSWIFA), comparing bio-treated MSWIFA (BFA) to raw MSWIFA (RFA). BFA exhibited a larger particle size and the presence of microbial-induced calcium carbonate precipitation (MICP) gels. Both RFA and BFA maintained highly alkaline pH levels, with mineral analysis showing reduced chlorine content in BFA and the presence of Monocarboaluminate (Mc), suggesting potential concrete strength improvements. Bio-treatment effectively reduced polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) levels, meeting standards. Biomineralization stabilized heavy metals in MSWIFA, reducing leaching concentrations and meeting national standards. Blending BFA with magnesium phosphate cement (MPC) improved compressive strength, especially in early stages, further enhanced by calcium acetate. SEM images confirmed MICP gels on paste surfaces, contributing to increased strength. Analytical techniques (X-ray diffraction, Fourier transform infrared, and thermal gravimetric analysis) supported superior performance in hydration and strength. SEM-EDS analysis showed effective solidification/stabilization of heavy metals, reduced chlorine content, and enhanced biomineralization. Leaching tests confirmed reduced heavy metal concentrations in leachate. In summary, bio-treatment enhances the properties and environmental impact of MSWIFA, offering sustainable waste management opportunities.

Toxicokinetic modeling of the transfer of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) into milk of high-yielding cows during negative and positive energy balance

A toxicokinetic modeling approach was used to study the transfer of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 dibenzofurans (PCDFs), 12 dioxin-like polychlorinated biphenyls (dl-PCB) and 3 non-dioxin like (ndl) PCBs in dairy cows. The model describes the concentration–time profile of each congener in milk and blood of high-yielding dairy cows. It was parametrized using an in-house transfer study with 3 cows exposed to a defined synthetic congener mixture for two dosing periods, as well as 3 control cows to account for background exposure. The first dosing was administered during negative energy balance (NEB) after calving, and the second during positive energy balance (PEB) in late lactation. Results include extrapolated steady-state transfer rates and elimination half-lives, many of which have never been reported before. Transfer rates (TRs) were significantly higher during the NEB by a median of 27%, likely due to an increase in non-milk elimination during PEB. The difference draws attention to the influence of the metabolic state of food-producing animals in risk assessment. Comparison of the TRs derived here with those reported in the literature showed that they were, in median, 43% higher in the NEB phase and 16% higher in the PEB phase probably because we report TRs in steady-state unlike most literature sources.

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.

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.

Electrochemical degradation of key drugs to treat COVID-19: Experimental analysis of the toxic by-products formation (PCDD/Fs)

Drug consumption has grown exponentially in recent decades, particularly during the COVID-19 pandemic, leading to their presence in various water sources. In this way, degradation technologies for pollutants, such as electrochemical oxidation (ELOX), have become crucial to safeguard the quality of natural resources. This study has as its starting point a previous research, which demonstrated the efficacy of ELOX in the removal of COVID-19 related-drugs, such as dexamethasone (DEX), paracetamol (PAR), amoxicillin (AMX), and sertraline (STR), using the electrolytes NaCl and Na2SO4. The present research aims to study the potential risks associated with the generation of toxic by-products, during the ELOX of cited drugs, specifically focusing on the highly chlorinated persistent organic pollutants (POPs), such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Dioxins and furans can be formed potentially in electrochemical systems from precursor molecules or non-precursor molecules in chloride medium. First, the degradation of the parent compounds was found to be complete. At this point, a comprehensive investigation was conducted to identify and analyse the by-products formed during the degradation process; precursors of PCDD/Fs, such as chlorophenols or hydroquinones were identified. Additionally, in continuation of the previous study, PCDD/Fs congeners were investigated, revealing elevated concentrations; the highest concentration obtained was for the congener 1,2,3,4,6,7,8-HpCDF (234.6 pg L−1 in NaCl) during degradation of the AMX. Finally, an assessment of the toxicity based on TEQ values was conducted, with DEX exhibiting the highest concentration among all compounds: 30.1 pg L−1 for NaCl medium. Therefore, the formation of minor by-products should not be underestimated, as they can significantly enhance the toxicity of the final sample, so the selection of the appropriate remediation technology, as well as the optimization of experimental operating variables, is determining in the treatment of pharmaceutical-contaminated waters.

Enabling efficient and economical degradation of PCDD/Fs in MSWIFA via catalysis and dechlorination effect of EMR in synergistic thermal treatment

Catalytic thermal treatment is an efficient and low-energy consumption method for degrading polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in municipal solid waste incineration fly ash (MSWIFA). However, catalysts with high activity are expensive, difficult to separate and reuse from the treated MSWIFA, and they usually pose a risk of heavy metal pollution. Herein, a synergistic thermal treatment method of MSWIFA and electrolytic manganese residue (EMR) at relatively low temperatures was proposed after an in-depth analysis of their mineralogy composition to achieve detoxification of PCDD/Fs in MSWIFA. The mass and WHO-TEQ degradation efficiencies of PCDD/Fs significantly increased from −92.79% and −51.46%–98.57% and 96.10%, respectively, by the addition of electrolytic manganese residue (EMR) with an MSWIFA/EMR ratio of 3:7 in the thermal treatment of MSWIFA at 250 °C for 60 min. The WHO-TEQ concentration of PCDD/Fs in the treated sample decreased to 3.7 ng WHO-TEQ/kg, meeting the European end-of-waste criteria (20 ng WHO-TEQ/kg). The excellent degradation effect of EMR on PCDD/Fs in MSWIFA could be attributed to two aspects: 1) the manganese oxides in EMR has a catalytic effect on the degradation of PCDD/Fs; 2) the NH3 generated by the decomposition of (NH4)2SO4 in EMR is conducive to the degradation and resynthesis inhibition of PCDD/Fs. Besides, the thermodynamic calculations indicated that CaClOH in MSWIFA played a crucial role in the decomposition of (NH4)2SO4 in EMR. In addition, the degradation pathways and mechanisms of PCDD/Fs-homologues under the synergistic effect of manganese oxides, ammonia, and thermal field were investigated through comparative analysis of concentration and fingerprint of PCDD/Fs.

Heterogeneous photochemical conversion of chlorobenzene on γ-Al2O3: A chamber experiment study

Atmospheric photochemical conversion of chlorinated volatile organic compounds (CVOCs) is crucial for secondary aerosol formation and tropospheric chlorine chemistry. However, their corresponding conversion pathways and the reaction products are lack of sufficient exploration. Herein, the photochemical conversion of chlorobenzene (CB) on the mineral γ-Al2O3 particulates was chosen as a model reaction to unveil the atmospheric chemistry of CVOCs. Chamber experiments were performed to determine the decay rates of CB with/without SO2 or NH3 under light irradiation. Reaction products were evaluated, along with the in situ diffuse reflectance infrared Fourier transform spectroscopy measurements, to explore the CB conversion pathways under different conditions. We showed that the CB could be greatly degraded by γ-Al2O3 under light irradiation, and the added SO2 significantly inhibited this conversion owing to surface acidification. However, the presence of NH3 was shown to facilitate the CB conversion by immobilizing Cl− as NH4Cl, and recovering surface oxygen vacancies for oxygen activation. In particular, we found that polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) could be generated from the photochemical CB conversion over γ-Al2O3, regardless of SO2 or NH3 coexistence, indicating a potential origin of PCDD/Fs on the atmospheric particulates from the heterogeneous photochemical CVOC conversion.

Experimental Study on the Transfer of Polychlorinated Biphenyls (PCBs) and Polychlorinated Dibenzo-p-dioxins and Dibenzofurans (PCDD/Fs) into Milk of High-Yielding Cows during Negative and Positive Energy Balance.

Dioxin-like polychlorinated biphenyls (dl-PCBs) as well as polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are a major concern for food safety, especially in fat-containing foods of animal origin, such as milk. Due to the lipophilic character of PCDD/Fs and PCBs, it is of special interest to explore whether the metabolic state of high-yielding cows influences the transfer rates into milk. Five German Holstein cows were orally exposed to a mixture of 17 PCDD/Fs, 12 dl-PCBs, and 6 non-dioxin-like PCBs (ndl-PCBs) for two dosing periods of 28 days each. The first period covered the negative energy balance (NEB) after calving, while the second period addressed the positive energy balance (PEB) in late lactation. Each dosing period was followed by a depuration period of around 100 days. During the NEB phase, the transfer rates of 14 PCDD/Fs and 7 dl-PCBs quantified were significantly (p ≤ 0.1) higher compared to the PEB phase, indicating an influence of the metabolic state on the transfer. Furthermore, the congener-specific transfer rates (0.3-39%) were in the range of the results from former studies. This indicates that the milk yield of the exposed cows is not the only determining factor for the transfer of these congeners into milk.

Pollution profile, source identification, and risk assessments of persistent organic pollutants (POPs) and toxic elements in the sediments of one of the water supply areas (Sultanbahçedere lake) to Istanbul, Türkiye

This study was done to comprehensively exhibit the pollution level of surface sediments taken from Sultanbahçedere dam lake in terms of some persistent organic pollutants (POPs) and toxic elements, to decide the possible sources of polycyclic aromatic hydrocarbons (PAHs), to perform the ecological and human health risk assessments, and to evaluate the pollution profile with the hierarchically clustered heatmap (HCHM) analysis and principal component analysis (PCA). Naphthalene, Benzo(b)fluoranthene, Fluoranthene, Pyrene for PAHs; p,p-DDE, p,p-DDD, alpha-HCH, p,p-DDT, Endrin for OCPs; hexa and hepta chlorinated congeners accounting for 50.63% and 28.44% for polychlorinated biphenyls (PCBs); 1234678-HpCDD, OCDD for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs); PCB 118, PCB 105, PCB 167 for dioxin like-PCBs (DL-PCBs) and Al, Fe, Ca for elements were predominant in almost all of the sediments with a few exceptions. S4 site, which is one of the mid-sites of reservoir, has high concentrations in most of these pollutants. According to PAH diagnostic analysis, PAHs in the surface sediments are mostly affected by pyrogenic sources. The concentrations of POPs do not pose any toxic risk to aquatic organisms according to sediment quality guideline (SQG) and the limit values of other countries accepted in the world. Also, since none of the elements exceeded the effect range median (ERM) values, they do not pose a significant toxic risk to aquatic organisms. There is no risk for non-carcinogenic and carcinogenic hazards both for children and for adults considering hazard quotient (HQ), hazard index (HI), and lifetime cancer risk (LCR) values of all pollutants.

Legacy persistent organic pollutants (POPs) in eggs of night herons and poultries from the upper Yangtze Basin, Southwest China.

Black-crowned night heron (Nycticorax nycticorax) eggs have been identified as useful indicators for biomonitoring the environmental pollution in China. In this study, we investigated thirty eggs of black-crowned night heron collected from the upper Yangtze River (Changjiang) Basin, Southwest China, for the occurrence of legacy persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Our results showed a general presence of POPs in night heron eggs with OCPs being the dominant contaminants, having a geometric mean concentration of 22.2 ng g-1 wet weight (ww), followed by PCBs (1.36 ng g-1 ww), PBDEs (0.215 ng g-1 ww), and PCDD/Fs (23.0 pg g-1 ww). The concentration levels were found to be significantly higher in night heron eggs than in poultry eggs by one or two magnitude orders. Among OCP congeners, p,p'-DDE was found to be predominant in night heron eggs, with a geometric mean concentration of 15.1 ng g-1 ww. Furthermore, species-specific congener patterns in eggs suggested similar or different sources for different POPs, possibly associated with contaminated soil and parental dietary sources. Additionally, estimated daily intakes (EDIs) were used to evaluate non-carcinogenic and carcinogenic risk associated with consumption of bird eggs. Our results revealed non-negligible non-cancer and cancer risk for humans who consume wild bird eggs as a regular diet instead of poultry eggs.

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.

Biological wastewater treatment plants as sources of environmental pollution by persistent organic pollutants (on the example of Odesa industrial-and-urban agglomeration)

Formulation of the problem. Effective mechanism of wastewater treatment (WT) are important components of reducing anthropogenic load on the environment. One of the most widespread mechanisms of urban wastewater treatment is the biological treatment on a Biological Wastewater Treatment Plant (BWTP). However, increasing the nomenclature of pollutants concentrated in urban wastewater seriously affects the effectiveness of WT on BWTPs, which are not intended for such a wide spectrum of specific pollutants such as, in particular, Persistent Organic Pollutants (POPs). The control of their intake into the environment must be regulated according to the Stockholm convention. The goal of the research is the evaluation of the intake of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) into the environment from the wastewater of Odesa Industrial-and-Urban Agglomeration (IUA) and determining the volumes of their accumulation in the sea environment. Purpose. The assessment of the amount of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) entering the environment with the wastewater from Odesa IUA and determining the amount of their accumulation in the sea environment. Methods. In our research, all available official methods of calculation of the unintentional formation of POPs were reviewed, as a result – the main and most complete methods were selected: «UNEP (2013). Toolkit for Identification and Quantification of Releases of Dioxins, Furans and Other Unintentional POPs» and «EMEP/EEA air pollutant emission inventory guidebook. Technical guidance to prepare national emission inventories, 2019». For evaluation of PCDD/F accumulation in the sea environment an improved by authors methodology for calculation of PCDD/F accumulation with their cumulative effect and half life taken into account was used. Results. The work provides justification for the necessity of use of calculation methodologies for determing the intake of PCDD/F to the sea environment adjacent to Odesa IUA; annual massed of PCDD/F entering the sea environment as part of treated, insufficiently treated and untreated wastewater are calculated; massed of PCDD/F that accumulate in waste activated sludge (WAS) on BWTP are calculated; volumes and specifics of PCDD/F accumulation in the sea basin, where the wastewater of Odesa IUA is being discharged to are determined using the improved methodology that enables taking into account the cumulative effect and half life period of these substances; mass and concentration of PCDD/F, immobilized in WAS, are determined, the excess level of concentration of PCDD/F in WAS compared to the maximum permissible concentration is determined. The total accumulation of PCDD/F in the sea environment over 2007-2017 period is determined. Conclusions. It was established that the use of calculation methodologies for evaluating PCDD/F volumes in the water environment is the only and necessary condition for satisfying the requirements of the Stockholm convention due to the impossibility of performing a regular instrumental monitoring of PCDD/F intake into the water environment. The use of suggested by us improved methodology for calculation of PCDD/F accumulation with their cumulative effect and half-life period taken into account allows for calculation of PCDD/F masses that were formed throughout the year under consideration, taking into account the PCDD/F masses that were formed during previous years as well.

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

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

Full replacement of fish oil with algae oil in farmed Atlantic salmon (Salmo salar) – Debottlenecking omega 3

The global goal of developing sustainable aquafeed has faced increased complexity in sourcing raw materials. The limited availability of fish oil (FO) is a well-known bottleneck for the aquaculture industry and pairing it with EFSA (EFSA CONTAM, 2018) reduced tolerable weekly intake of marine contaminants [polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and dioxin-like polychlorinated biphenyls (DLPCB)] creates another challenge for wild caught FO and its use in fish feed. In recent years, commercial algal alternatives have increasingly become available. Not only would omega-3 sources from algae reduce the reliance on FO; it would allow for restoration of the long chain omega-3 levels in farmed salmon. To this end, a study was conducted to establish knowledge on full replacement of FO by algae oil (Schizochytrium sp.) in Atlantic salmon with the aim of reducing contaminants levels in the fillet and maintaining the level of omega-3 fatty acid (FA), growth performance, health, and final product quality. Atlantic salmon (531 g) were distributed into twelve 5 × 5 × 5 m sea cages and fed one of four diets for 369 days: a control diet (Control) containing FO + rapeseed oil (VO1); a diet where AlgaPrime (AP) replaced 50% of the sum of EPA + DHA from FO (50AP + VO1); a diet where AP replaced 100% of the sum of EPA + DHA from FO (100AP + VO1), and a diet the same as the previous but using linseed instead of rapeseed oil (VO2; 100AP + VO2). All diets were balanced for key micronutrients. At the end of the trial, zootechnical parameters were obtained, health and welfare assessed, and final fillet quality analysed for contaminants and fillet quality post slaughter. Full replacement of FO significantly reduced the levels of PCDD/F and DLPCB in the fillet of 4 kg salmon by 70% and 79% respectively for 100AP + VO1 and 40% and 43% respectively for 100AP + VO2 fed fish. Fish gained an average of 3.7 kg across treatments (average final weight 4235.8 g ± 191.8); almost an 8-fold increase for all treatments. No significant differences were found among diets for performance, feed intake, gut health, histology, welfare, pigmentation, or fillet quality. This study demonstrates that AlgaPrime can be used to fully replace FO in Atlantic salmon grower feed without negative effects, achieving an important impact on food safety and sustainability for aquafeed producers and salmon consumers.