PCDDs), Dibenzofurans Research Articles

Formation, migration, and removal mechanisms of PCDD/Fs throughout the temperature range (850°C–150°C) in a full-scale MSW incinerator: The invention of novel high-temperature PCDD/F sampling device

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) emitted from municipal solid waste (MSW) incineration have detrimental effects on the ecological environment. This study innovatively invented a high-temperature sampling device for PCDD/Fs, followed by a process tracing experiment conducted in a full-scale MSW incinerator to investigate the formation and migration mechanisms of PCDD/Fs throughout the temperature range (850°C–150°C). The results highlighted the considerable PCDD/F level of 0.446 ng I-TEQ Nm−3 at the @1 furnace outlet (850°C). The distribution characteristics of PCDD/Fs suggested a prevalence of high-temperature homogeneous reactions in the flue zone between sites @1 and #1 (850°C–600°C). In the low-temperature zone, de novo synthesis emerged as the dominant formation mechanism, primarily occurring near the @2 superheater outlet (∼368°C) and inside the SCR system (∼230°C). The impact and removal efficiency of individual air pollutant control devices on PCDD/Fs was systematically analyzed, yielding an overall PCDD/F reduction of 99.7%. Remarkably, the buffering effect of economizer, the co-removal of semi-dry deacidification system, and the adsorption-filtration effect of activated carbon injection and fabric filter individually reduced PCDD/F concentrations by 23.9%, 35.3%, and 99.7%, respectively; while de novo synthesis inside the SCR system negatively impacted PCDD/F removal, demonstrating an efficiency of −43.2%. Consequently, these comprehensive insights inspired industrial operation optimization and ultra-low PCDD/F emission control.

Free-radical triggered formation of dioxins from 2-chlorophenol pyrolysis investigated by synchrotron radiation photoionization mass spectrometry

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated naphthalenes (PCNs) are a category of highly toxic and environmentally persistent pollutants released particularly via thermal processes of chlorine-containing materials. However, the detailed reaction mechanism, especially the evolution of related radicals remains elusive for decades. Herein we have for the first time characterized the radicals and intermediates during pyrolysis of 2-chlorophenol resulting in PCDD/Fs and PCNs, using a flow tube reactor coupled with in-situ synchrotron radiation photoionization mass spectrometry (SR-PIMS). Transient species including 2-chlorophenoxy (C6H4ClO•), phenoxy (C6H5O•), chloro-cyclopentadienyl (•C5H4Cl), chloro-cyclopentadiene (C5H5Cl), fulvenone ketene (C6H4O) and o-benzyne (o-C6H4), were identified via m/z and photoionization efficiency profile. Potential energy surfaces of the early-stage mechanism and the associated rate constants and branching ratios were elucidated. Successively, the formation mechanisms of PCDD/Fs and PCNs from these transient intermediates at high temperatures were proposed which have experimentally validated and refined the previous mechanism. The results suggested that the combination of 2-chlorophenoxy radicals with another 2-chlorophenoxy, phenoxy, phenyl, or o-benzyne leads to the formation of PCDD/Fs, while PCNs are generated from the self-coupling of chloro-cyclopentadienyl.

Emissions of Polychlorinated Dibenzo-p-Dioxins/Dibenzofurans during Coffee Roasting: Exploring the Influence of Roasting Methods and Formulations

Polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) emissions during the roasting of green Arabica coffee and coffee formulations containing alcohol, sugar, and honey were investigated in this study. Fast and slow roasting methods, which took 5.62 and 9.65 min to achieve a light roast, respectively, were used to evaluate the emissions. The concentrations in the flue gas during the fast roasting of green coffee (0.0296 ng Nm−3 and 0.00364 ng WHO-TEQ Nm−3) were 13.9% and 70.5% higher than during slow roasting, respectively. However, this was only the trend for some formulations, and no significant differences in concentrations were found between the methods at p = 0.05. Thus, the slow roasting method might not necessarily reduce formation when additives are included. The emission factors were 2.86 ng kg−1 and 0.352 ng WHO-TEQ kg−1, and 4.17 ng kg−1 and 0.176 ng WHO-TEQ kg−1 for the fast and slow roasting of green coffee, respectively. Further investigations are warranted to understand the formation mechanism, assess potential health risks, and explore mitigation strategies. These findings have implications for both coffee processing industries and regulatory bodies, as understanding the impact of roasting methods and additives could inform the development of cleaner production practices and targeted emission reduction policies.

Br-to-Cl Transformation Guided the Formation of Polyhalogenated Dibenzo-p-dioxins/Dibenzofurans.

Polyhalogenated dibenzo-p-dioxins/dibenzofurans (PXDD/Fs) are commonly released into the environment as byproducts of combustion processes, accompanied by flue gases. Chlorinated (Cl) and brominated (Br) precursors play crucial roles in forming PXDD/Fs. However, the specific contributions of Cl-precursors and Br-precursors to PXDD/Fs formation have not been fully elucidated. Herein, we demonstrate that the formation of Br-precursors can increase the fraction of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) congeners substituted at specific positions, such as 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF. This is attributed to the electrophilic chlorination reaction of the Br-precursors, which includes the Br-to-Cl transformation pathway, following the principle of regioselectivity. The observed formation of polybrominated/chlorinated dibenzo-p-dioxins/benzofurans (PBCDD/Fs) from 1,2-dibromobenzene (1,2-DiBBz) as a Br precursor provides direct evidence supporting the proposed Br-to-Cl transformation. Quantum chemical calculations are employed to discuss the principle of regioselectivity in the Br-to-Cl transformation, clarifying the priority of the position for electrophilic chlorination. Additionally, the concentration of PCDD/Fs formed from 1,2-DiBBz is 1.6 μg/kg, comparable to that of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) (2.4 μg/kg), highlighting the potential of brominated organic pollutants as precursors for PCDD/Fs formation. This study provides three potential pathways for PCDD/Fs formation from Br-precursors, establishing a theoretical foundation for elucidating the formation mechanism of PXDD/Fs in the coexistence of Cl and Br.

Accumulation Patterns of Polychlorinated Dibenzo-p-Dioxins, Dibenzofurans and Dioxin-like Polychlorinated Biphenyls in Sediments of the South-Eastern Baltic Sea

The current research paper presents the results of the first regional assessment of sediment contamination by dioxins (polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs)) in the south-eastern part of the Baltic Sea (Lithuanian and Polish marine areas) during the periods of 2014 and 2019–2020. In total, 143 surface and core sediment samples were taken of existing offshore dredged-soil-disposal sites in the area of the former shipyard in the Port of Gdynia (Poland), as well as in a profile from the nearshore to the deeps of the Gdansk basin, following the natural pattern of sediment migration in the region. The obtained results indicated wide variation in both the total content of the investigated compounds as well as the profiles of congeners, indicating the likely sources of their origin. Based on the obtained concentration characteristic profiles of the congeners, we determined the amount of dioxins and the likely sources of their origin in the Gdansk Basin. The profiles showed elevated contents of octa- and hepta-chlorodibenzodioxins (OCDD and HpCDD) in the sediments, while the fractions of most other toxic congeners were considerably lower. The domination of OCDF in the spectrum of the studied PCDFs suggests the possible contribution of industrial processes. The obtained results have filled the gaps in our knowledge while providing a perfect background for more detailed discussions concerning the accumulation of dioxins in surface sediments from the south-eastern part of the Baltic Sea.

Co-incineration of medical waste in municipal solid waste incineration increased emission of chlorine/brominated organic pollutants

Co-incineration of medical waste (MW) in municipal solid waste incinerators (MSWIs) is a crucial disposal method for emergency disposal of MW and the management of MW in small and medium-sized towns. This study aims to analyze and compare the levels and distribution patterns of chlorine/brominated dioxins and their precursors in fly ash from MSWIs and medical waste incinerators (MWIs) while also focusing on identifying the new pollution concerns that may arise from the co-incineration of municipal solid waste (MSW) mixed with MW (MSW/MW). The concentration of chlorobenzene (CBzs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in fly ash from co-incineration of MSW/MW are 887.4, 134.4 and 27.6 μg/kg, respectively, which are 5.1, 2.0 and 2.9 times higher than that from MSWIs. The levels of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) are about three orders of magnitude lower than that of PCDD/Fs. For the fly ash from MSWIs, the predominant PCDD/Fs congener is OCDD, which prefers synthesis and adsorption on fine-grained fly ash. For fly ash from MWIs, the major PCDD/Fs congeners are 1, 2, 3, 4, 6,7, 8-HpCDF, and OCDF, which prefer synthesis and adsorption on coarse-grained fly ash. Correlation analysis exhibited that both 1,2,3-TriCBz and 1,2,4-TriCBz in fly ash have a markedly linear correlation with PCDD/Fs and PCBs, but PBDD/Fs shows a poor negative correlation with PCDD/Fs.

Pilot-tests of the coal-fired power plant indirect coupling with multi-source organic solid waste incineration technology

The production of organic solid waste is increasing as the development of society. However, the investment of waste incineration power plant is very high and the thermal efficiency is very low. At the same time, the load of coal-fired power plant is suppressed due to the carbon neutralization policy. Therefore, using the existed coal-fired power plant to co-process the organic solid waste is a feasible method. In this paper, a coal-fired power plant indirect coupling with waste incineration technology based on flue gas circulation was proposed and studied on a 100 kW pilot-test bench. In this technology, the polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) was reduced by a three stages controlling method, which adopts the blending of multi-source organic wastes, high-temperature decomposition and selective catalytic reduction (SCR) catalyst decomposition, simultaneously. The effects of waste incineration coupling, replacement ratio of coal, and flue gas circulation on the combustion and pollutant emission characteristics of the system were studied. The experimental results indicate that the waste incineration coupling has minor influence on the temperature distribution and the toxicity of fly ash of the coal-fired furnace. The NO, HCl, and PCDD/Fs concentrations of flue gas of coal-fired furnace generally decrease as the replacement ratio of coal increases, while the SO2 concentration increases. With the help of three stages controlling method or the flue gas circulation, the PCDDFs concentration of the flue gas of coal-fired furnace can be much lower than 0.1 TEQ ng/Nm3.

Long-term implications of municipal solid waste (MSW) classification on emissions of PCDD/Fs and other pollutants: Five-year field study in a full-scale MSW incinerator in southern China

Understanding how municipal solid waste (MSW) classification influences the physiochemical properties and incineration emission characteristics of MSW is imperative for sustainable waste management. To investigate how long-term changes in the composition and physical properties of MSW resulting from MSW classification affect the emissions of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and multiple flue gas pollutants, a five-year experiment (2018–2022) was conducted in a full-scale MSW incinerator in Shenzhen City, China. After MSW classification, the food waste in MSW was substantially reduced while the paper, textile, and wood components were notably increased. MSW classification also remarkably decreased the water and chlorine contents of MSW while concomitantly increasing the wet-based calorific value, sulfur content, and nitrogen content. Consequently, the PCDD/Fs emissions declined from 106.7 ng I-TEQ/t MSW in 2018 to 26.0 ng I-TEQ/t MSW in 2022. Moreover, a process-tracing experiment demonstrated noticeable decreases in PCDD/F synthesis in the post-combustion area, with mass-reduction efficiencies of 23.6 %–95.4 %. In a correlation analysis, the PCDD/F emissions were significantly positively correlated with food waste, water content, and chlorine and negatively correlated with the wet-based calorific value and nitrogen content. Furthermore, MSW classification reduced the emissions of conventional flue gas pollutants (SO2, CO, and HCl) and multiple heavy metals (total sum of Sb, As, Pb, Cr, Co, Cu, Mn, and Ni). In summary, the long-term study demonstrated that MSW classification can feasibly separate incombustible waste, improve combustion quality, and reduce pollutant emissions from sources. These findings offer practical guidance for promoting MSW classification.

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.

A decrease in serum dihydrotestosterone levels in 9-year-old Vietnamese children from a dioxin exposure area.

Dioxin is an environmental pollutant as well as an endocrine disruptor in humans. Our longitudinal study wants to clarify the relationship between dioxin exposure and endocrine disorders in children living in the Vietnamese dioxin hotspot. Seventeen congeners of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzo-furans (PCDDs/PCDFs) in maternal breast milk and seven serum steroid hormones in children of 43 and 46 mothers and their 9-year-old children from the non-exposure and the hotspot areas were measured, respectively. The steroid metabolic enzyme ratios were calculated based on the hormone level ratio. Most dioxin/furan congeners and toxic equivalents (TEQs) levels were significantly higher in the hotspot than in the non-exposure area, except for 2,4,7,8-TeCDF. The height and weight of girls from the hotspot area were substantially lower and inversely correlated with dioxin congener levels/total TEQs level dioxin. The dihydrotestosterone (DHT) levels in the hotspot were markedly lower than those in non-exposed in both genders. The cortisol concentrations were significantly higher in the hotspot than those from the non-exposure area only in the girls. The DHT/testosterone ratios that exhibited the 5α- or 5β-reductase activity declined by 50% in the hotspot area for both genders. The DHT levels showed strong inverse correlations with almost the PCDDs/PCDFs congeners and total TEQs dioxin in breast milk. This finding suggests that dioxin exposure in maternal breast milk might impact children's endocrine system until 9 years old, especially on the DHT biosynthesis.

Persistent Halogenated Organic Pollutants in Deep-Water-Deposited Particulates from South China Sea.

POP data are limited in the marine environment; thus, this study aimed to investigate background persistent organic pollutant (POP) levels in oceanic deep-water-deposited particulates in the South China Sea (SCS). Six POPs, including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DL-PCBs), polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs), polychlorinated diphenyl ethers (PCDEs), and polybrominated biphenyls (PBBs), were investigated in eight pooled samples from the SCS from 20 September 2013 to 23 March 2014 and 15 April 2014 to 24 October 2014 at depths of 2000 m and 3500 m. PBDEs were the most predominant compounds, with the highest mean Σ14PBDE of 125 ± 114 ng/g dry weight (d.w.), followed by Σ17PCDD/F, Σ12PBDD/F, and Σ12DL-PCB (275 ± 1930, 253 ± 216, and 116 ± 166 pg/g d.w., respectively). Most PBDD/F, PBB, and PCDE congeners were below the detection limits. PCDDs had the highest toxic equivalency (TEQ), followed by PBDDs and DL-PCBs. Among the six POPs, PBDEs were the major components of the marine-deposited particles, regarding both concentrations and mass fluxes. Compared to 3500 m, PBDE levels were higher at a depth of 2000 m. PBDE mass fluxes were 20.9 and 14.2 ng/m2/day or 68.2 and 75.9 ng/m2/year at deep-water 2000 and 3500 m, respectively. This study first investigated POP levels in oceanic deep-water-deposited particles from existing global data.

Field study on variation characteristics of PCDD/Fs and flue gas particles along MSW incinerator

Wet scrubber systems (WSSs) are commonly used for effective flue gas cleaning by removing acid gases and dust. To determine the influence of a WSS on polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and flue gas particles, a field study was carried out in a full-scale municipal solid waste (MSW) incinerator (850 t/d). Phase-separated samples at four flue gas sampling points and two scrubbing solution sampling points were collected for PCDD/F analysis. Two particle samples at the WSS inlet and outlet were simultaneously obtained for TEM-EDS analysis. The memory effect inside the WSS apparently elevated the PCDD/F I-TEQ concentration from 0.0056 to 0.0088 ng I-TEQ Nm−3 by increasing the mass concentrations of 17 congeners. A PCDD/F flux chart was established to interpret the adsorption/desorption mechanism of PCDD/Fs inside the WSS that showed apparent desorption from scrubbing solution. The potential interaction relationship between PCDD/F and flue gas particles were also observed, that was, the desorbed PCDD/Fs from scrubbing solution might be adsorbed by flue gas particles again and therefore enhanced the concentration of solid-phase PCDD/Fs from 0.0236 to 0.0411 ng Nm−3. Furthermore, TEM-EDS analysis indicated that the WSS could evidently remove some soluble particles and reduce the particle size. And the variation in morphology, elemental composition, and distribution of flue gas particles were observed during the scrubbing process. This study systematically analyzed the memory effect of PCDD/Fs and firstly investigated the specific impact of WSS on flue gas particles, thereby improving the comprehensive understanding of WSS applications.

Serum levels of PCDDs, PCDFs and dl-PCBs in general population residing far and near from an urban waste treatment plant under construction in Gipuzkoa, Basque Country (Spain)

This research focused on investigating the basal serum concentrations of polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the general population residing in two urban-industrial zones near and far from an energy recovery plant under construction in Gipuzkoa, Basque Country (Spain). The study used a cross-sectional design and included 227 participants who were randomly selected from municipal censuses in both areas. The participants were stratified based on age (ranging from 18 to 70 years) and sex. Serum samples were collected from the participants and analysed following the established protocol to measure the concentrations of PCDD/Fs and dl-PCBs. The study used multiple linear regression models to assess the impact of various sociodemographic variables, lifestyle factors, reproductive history, and diet on the variability of the measured compounds in the participants' serum. The median total toxicity equivalent (TEQ) in serum, was 10.58 pg WHO-TEQ2005 g-1 lipid. Serum PCDD levels were lower in the population residing in the “far” zone than the “near” zone. Age was positively associated with both PCDD/F and dl-PCB levels, indicating that older participants had higher concentrations of these compounds in their serum. This finding might be attributed to cumulative exposure over time. In terms of sex differences, women exhibited lower levels of dl-PCBs compared to men. Among lifestyle factors, smokers showed lower levels of dl-PCBs compared to non-smokers. Furthermore, daily alcohol consumption was significantly associated with higher serum levels of these compounds, with daily drinkers showing higher levels than non-drinkers. Consumption of local poultry was associated with significantly higher serum levels and oil consumption with low levels of PCDD/Fs.

PCDD/F and DL-PCB exposure among residents upwind and downwind of municipal solid waste incinerators and source identification

Understanding the environmental and human impacts associated with polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) exposure from municipal solid waste incinerators (MSWIs) is challenging because information on ambient and dietary exposure levels, spatial characteristics, and potential exposure routes is limited. In this study, 20 households from two villages located on the upwind and downwind sides of a MSWI were selected to characterize the concentration and spatial distribution of PCDD/F and DL-PCB compounds in ambient and food samples, such as dust, air, soil, chicken, egg, and rice samples. The source of exposure was identified using congener profiles and principal component analysis. Overall, the dust and rice samples had the highest and lowest mean dioxin concentrations, respectively. Significant differences were observed (p < 0.01) in PCDD/F concentrations in chicken samples and DL-PCB concentrations in rice and air samples between the upwind and downwind villages. The exposure assessment indicated that the primary risk source was dietary exposure, especially from eggs, which had a PCDD/F toxic equivalency (TEQ) range of 0.31–14.38 pg TEQ/kg body weight (bw)/day, leading to adults in one household and children in two households exceeding the World Health Organization-defined threshold of 4 pg TEQ/kg bw/day. Chicken was the main contributor to the differences between upwind and downwind exposure. Based on the established congener profiles, the exposure routes of PCDD/Fs and DL-PCBs from the environment to food to humans were clarified.

Spatiotemporal bioavailability of PCDD/Fs and dl-PCBs in wild mussels from the Portuguese Atlantic coast

This study aimed to assess the spatiotemporal bioavailability of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in wild adult mussels, Mytilus galloprovincialis, collected along the Portuguese Atlantic coast between 2009 and 2020. The work is part of a national environmental monitoring program. The purpose was to evaluate the dioxins’ temporal trends, the human and ecological risks, and the correlation between mussels’ location and the main pollutant sources in Portugal. The levels and congener patterns of the most toxicity-relevant 17 PCDD/Fs and 12 dl-PCBs were determined, with the dl-PCBs dominant. The sum of Σ17PCDD/Fs and Σ12dl-PCBs values ranged from 2.0 to 4.0 ng WHO-TEQ kg−1, (wet weight basis), below the limits established by the European Commission for contamination in fish and fishery products (6.5 ng per kg−1). The study included five years – 2009, 2010, 2016, 2018 and 2020 –, allowing to verify the impact of European Directive 2013/39/UE against the pollution of water in Portugal; it was observed that dioxin levels in mussels diminished over the time. Statistical analysis allowed verification of different spatial trends of dl-PCB profiles along the Portuguese Atlantic coast. The mono-ortho dl-PCB pentachlorinated congener IUPAC #118 prevailed in 2009 and 2018 in all sampling sites, and it was predominant in 2010, 2016 and 2020, followed by the congeners IUPAC #105, #156 and #167. The IUPAC #167, #169 and #123 were the most abundant hexachlorinated congeners, and the IUPAC #77 the most abundant tetrachlorinated congener. This work emphasises the importance of monitoring dioxins and mapping the congeners in Atlantic coastal ecosystems, to contribute to their elimination.

Formation and distribution of dioxins in agglomerated products and emitted dust during iron ore sintering

This study investigated the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in sintered products and emitted dust samples. Four types of iron ores were used in this study and tested in a sinter pot grate. The PCDD/F analysis showed that the PCDD concentrations (0.175–1.415, pg/g, 0.028–0.087 pg WHO-TEQ/g) were higher than the PCDFs (0.105–0.327 pg/g, 0.006–0.032 pg WHO-TEQ/g) in sinter. In dust samples, three of the four test experiments showed PCDDs < PCDFs in their measured concentrations. Although PCDD/F concentrations were different in sinter and dust samples, the PCBs presented similar behavior in both solid samples. The PCB analysis (pg WHO-TEQ/g) showed that non-ortho PCBs were higher in concentration than the mono-ortho PCBs. The statistical analysis showed significant correlations between low chlorinated PCDD/F congeners and high chlorinated PCDD/F congeners, as well as strong correlations between non-ortho PCBs and mono-ortho PCBs in both sinter and dust samples. However, the dust samples presented stronger and more positive correlations among the PCDD/F and PCB congeners in comparison to corresponding data in sinter samples. The differences in PCDD/F profiles and correlation matrix in sinter and dust samples suggest the dioxin formation during sintering undergos different mechanisms in the sinter and dust samples.

Dioxin-like POPs in national samples from global monitoring plan projects (2017–2019)

The global monitoring plan (GMP) established under the Stockholm Convention on Persistent Organic Pollutants (POPs) had defined ambient air, human milk or blood, and water as core matrices to be analyzed and assessed for spatial and temporal distribution. Within projects coordinated by the United Nations Environment Programme (UNEP), developing countries were offered to have other matrices analyzed for dioxin-like POPs (dl-POPs) in experienced laboratories. Subsequently, 185 samples from 27 countries located in Africa, Asia, and Latin America were collected during 2018–2019 and analyzed for polychlorinated dibenzodioxins (PCDD), dibenzofurans (PCDF), and biphenyls (PCB). Using the WHO2005 toxic equivalency approach (TEQ), the amounts of dl-POPs found were low (<1 pg TEQ/g); however, singular samples had higher values; e.g., egg from Morocco, fish from Argentina or Tunisia; soil and sediment samples. Results showed that the matrix, abiotic or biota, had more impact on the TEQ pattern than the geographic location. Independent of the location and across all samples, dl-PCB in (shell)fish and beef samples had a contribution of 75% to the total TEQ; milk (63%), chicken (52%), and butter (50.2%) more than 50%. Sediment (57% and 32%) and soil (40% and 36%)) samples were dominated by PCDD and PCDF, respectively; therein, dl-PCB had shares of 11% and 24%. Egg samples (N = 27) did not follow the general biota pattern and had 21% of the TEQ from the PCDD, 45% from PCDF, and 34% from dl-PCB; thus, indicating that abiotic matrices such as soil or other material may have an impact.

Kinetics of PCDD/Fs from feed to cow milk and its implications for food safety

Guideline levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in feed and food have been separately recommended for the official food safety control around the world. However, less is considered about the transfer effect of PCDD/Fs from feed to food, and consequently possible human exposure risk. In this study, different controlled feeding experiments (E1 group: 4.92 pg TEQ/g in feed, E2 group: 0.61 pg TEQ/g in feed) were conducted on dairy cow (Chinese Holstein breed) to evaluate kinetics of PCDD/Fs from feed to milk and blood. Even though the PCDD/F level in feed in E2 was satisfied with the EU Regulation (No 277/2012), the TEQ levels in milk and tissues exceeded the European Union maximum level (EU ML) after approximately one-week exposure. The dynamic variation in milk during the initial 20-day exposure was successfully described by a first-order kinetic model. The levels at the plateau period showed a significant linear relationship (p < 0.01, R2 = 0.98) against the intake amounts from feed. Based on modeling, a maximum content was obtained at approximately 0.33 pg TEQ/g in cow feed with 12 % moisture to ensure the milk and meat safety under the current regulatory requirements of EU for cow-origin food. After the cease of exposure, the PCDD/F levels in milk declined below the EU ML within 40 days, while those in meat were still higher than the EU ML over 160 days. In serum, PCDD/Fs detected in E1 showed a similar dynamic variation during the exposure period. Regarding congener profile, higher-chlorinated congeners tended to transfer from feed to feces, whereas lower ones were preferably transferred into milk, which required specific concern about the metabolic effect of PCDD/Fs in large mammals. This study revealed a necessity for re-evaluation of official regulation on pollutants in cow feed and cow-origin food in terms of biotransfer and bioaccumulation.

Influence of transition metal catalysts on the decomposition product distribution of PCBs and PCDD/Fs

In this study, reliable and stable polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) generation systems were used to investigate catalyst performance. The distribution characteristics of PCBs and PCDD/Fs after reaction were evaluated under different simulated flue gas conditions using NiO- and MnO2-loaded γ-Al2O3 and ZSM-5 catalysts. The results showed that the active metal of the catalyst affected mainly the decomposition efficiency, the substrate type affected the distribution characteristics of PCBs, and both the active metal and substrate type jointly determined the fingerprint distribution characteristics of PCBs. Moreover, there was an apparent marginal effect of the active metal loading on the same catalyst and the decomposition efficiency of the pollutants. In the temperature range of 100–350 °C, temperature variation had little effect on the removal efficiency of PCBs, but the gas–solid phase distribution characteristics of the pollutants changed significantly, and large amounts of di- and tri-CBs were generated in the products at 200 °C. A small amount of water generated hydrogen via the water–gas shift reaction at medium temperature, which promoted the hydro-dechlorination reaction of the chlorinated organics. However, excess water in the substrate gas competes with the pollutants for adsorption sites and reduces the reaction activity of the catalyst.

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.