Formation and Inventory of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans and Other Byproducts along Manufacturing Processes of Chlorobenzene and Chloroethylene.

Chlorinated organic chemicals are produced and used extensively worldwide, and their risks to the biology and environment are of increasing concern. However, chlorinated byproducts [e.g., polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)] formed during the commercial manufacturing processes and present in organochlorine products are rarely reported. The knowledge on the occurrences and fate of unintentional persistent organic chemicals in the manufacturing of organochlorine chemical is necessary for accurate assessment of the risks of commercial chemicals and their production. Here, PCDD/Fs were tracked throughout chlorobenzene and chloroethylene production processes (from raw materials to final products) by target analysis. Other byproducts that can further transform into PCDD/Fs were also identified by performing non-target screening. As a result, the PCDD/F concentrations were mostly the highest in bottom residues, and the octachlorinated congeners were dominant. Alkali/water washing stages may cause the formation of oxygen-containing byproducts including PCDD/Fs and acyl-containing compounds, so more attention should be paid to these stages. PCDD/Fs were of 0.17 and 0.21-1.2 ng/mL in monochlorobenzene and chloroethylene products, respectively. Annual PCDD/F emissions (17 g toxic equivalent in 2018) during chlorobenzene and chloroethylene production were estimated using PCDD/F emission factors. The results can contribute to the improvement of PCDD/F inventories for the analyzed commercial chemicals.

Serum levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in a sample of Lebanese pregnant women: The role of dietary, anthropometric, and environmental factors.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are unintentionally produced, toxic environmental chemicals that persist for long years and bioaccumulate along the food chain, contaminating humans through diet. A particularly critical population subgroup is pregnant women given the adverse health effects on fetuses and newborns. Several anthropogenic sources of exposure to PCDD/Fs exist in Lebanon. Therefore, the aim of the present cross-sectional study is to measure the levels of PCDD/Fs in a sample of pregnant women in Lebanon and to explore potential associated factors. In this study, we measured serum concentrations of seven dioxins and ten furans, among 423 pregnant women recruited at delivery, using gas chromatography MS/MS. Among 269 participants, maternal sociodemographic information was collected including vicinity to landfills, incineration, pesticide use, industrial activity, and smoking. Anthropometric data were registered regarding pre-pregnancy body mass index (BMI), pre-pregnancy weight loss from restrictive diet, and gestational weight gain. Intake of major food groups generally related to PCDD/Fs was reported (fish, red meat, poultry, and dairy). Bivariate and multivariate analyses were performed to identify associations. PCDD/Fs were detected in 0 to 56.1% of the sample. Geometric mean concentrations were 75.5 (2.35) pg/g lipid and 2.25 (1.39) TEQ2005 pg/g lipid for total dioxins, and 2.66 (1.76) pg/g lipid and 0.34 (1.78) TEQ2005 pg/g lipid for total furans. Levels were relatively lower than levels previously observed in France, Germany, Mexico, Ghana, and Japan. Red meat consumption was the most consistently associated factor with a 2.38-2.57 fold increase in PCDD/F levels. Pre-pregnancy weight loss showed inverse associations with PCDD/F congeners. Vicinity to illegal incineration was also associated with a 2.32-2.43 fold increase in PCDD/F levels. In conclusion, results showed the importance of dietary, anthropometric, and environmental factors in the present sample's exposure to PCDD/Fs, in a region that contains anthropogenic sources of contamination.

Transfer of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs) from oral exposure into cow's milk - Part I: state of knowledge and uncertainties.

Polychlorinated dibenzo-para-dioxins (PCDDs) and dibenzofurans (PCDFs) (collectively and colloquially referred to as 'dioxins') as well as polychlorinated biphenyls (PCBs) are persistent and ubiquitous environmental contaminants that may unintentionally enter and accumulate along the food chain. Owing to their chronic toxic effects in humans and bioaccumulative properties, their presence in feed and food requires particular attention. One important exposure pathway for consumers is consumption of milk and dairy products. Their transfer from feed to milk has been studied for the past 50 years to quantify the uptake and elimination kinetics. We extracted transfer parameters (transfer rate, transfer factor, biotransfer factor and elimination half-lives) in a machine-readable format from seventy-six primary and twenty-nine secondary literature items. Kinetic data for some toxicologically relevant dioxin congeners and the elimination half-lives of dioxin-like PCBs are still not available. A well-defined selection of transfer parameters from literature was statistically analysed and shown to display high variability. To understand this variability, we discuss the data with an emphasis on influencing factors, such as experimental conditions, cow performance parameters and metabolic state. While no universal interpretation could be derived, a tendency for increased transfer into milk is apparently connected to an increase in milk yield and milk fat yield as well as during times of body fat mobilisation, for example during the negative energy balance after calving. Over the past decades, milk yield has increased to over 40 kg/d during high lactation, so more research is needed on how this impacts feed to food transfer for PCDD/Fs and PCBs.

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.

Polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs) contamination in sediments and fish from Msimbazi River in Dar es Salam, Tanzania: patterns, sources, and their exposure to humans.

Results of a two-dimensional gas chromatograph time of flight mass spectroscopy (GCXGC-TOFMS) determination of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDF) in sediments and catfish samples collected from the Msimbazi River are presented here. Samples were extracted using USEPA Method 1613. PCDD/Fs congeners in sediments ranged from 2.0 to 393.0 and 0.7 to 654.8 pg/g in the dry and wet seasons, respectively. 1,2,3,4,7,8,9-HepCDF was detected at the highest concentration, but all were lower than the USA action level of 1000 pg/g. Toxicity for each of the sampling points ranged from 19.7 to 36.5, with a mean concentration of 27.0 pg WHO 2005-TEQ g-1 in the dry season and 2.0 to 38.7 with a mean concentration of 20.7 pg WHO 2005-TEQ g-1 in the wet season. Analysis of variance (ANOVA) showed that there was no significant difference between PCDD/Fs TEQ during the dry and wet seasons (p = 0.08; α = 0.05). The highest TEQ value was estimated at Jangwani in the wet season. Toxicity of PCDD/Fs in catfish collected from the Msimbazi River ranged from 9.3 to 145.2, with a mean of 61.2 pg WHO2005-TEQg-1. Tetrachlorodibenzo dioxin (2, 3, 7, and 8-TCDD) was detected in all fish samples and ranged from 3.5 to 12.7 with a mean of 8.1 pg/g. The concentration of TCDD in fish exceeded the Agency for Toxic Substance and Diseases Registry MRL, thus posing a probable high risk to people whose dietary requirements depend on fish from the Msimbazi River.

Persistent organic pollutants (PCBs and PCDD/Fs), PAHs, and plasticizers in spices, herbs, and tea - A review of chromatographic methods from the last decade (2010-2020).

Edible and highly demanded plant-derived products such as herbs, spices, and tea may be subjected to exogenous contamination of well-known chemical hazards such as persistent organic pollutants (POPs), and emerging ones such as plasticizers, affecting negatively the safety of these food commodities. This fact has led to the increasing analysis of exogenous compounds including priority POPs such as polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs), as well as highly persistent polycyclic aromatic hydrocarbons (PAHs). Currently, plasticizer residues are also considered an emerging issue because of the extensive use in food packaging and potential migration into foodstuffs. In this review, the studies published from 2010 to 2020 were discussed, including the main extraction methods applied for these contaminants from herbs, spices, and tea, and it was revealed the trend toward the use of less solvent-consuming and time-effective methods. Chromatographic methods were also described, which were mainly combined with detection techniques such as classical or mass spectrometry (MS) detection. Finally, a comprehensive overview of the occurrence of these selected exogenous compounds was presented in the studied matrices, showing that their monitoring should be further investigated to ensure food safety of highly consumed condiments and tea.

PCDD/Fs and PBDD/Fs in sediments from the river encompassing Guiyu, a typical e-waste recycling zone of China.

Severe pollution of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) and their brominated analogues (PBDD/Fs) was frequently reported for the waters located near unregulated e-waste recycling areas. However, the migrations of these high-level dioxins via waterways and their potential threats to the lower reaches were seldom investigated. In this study, we analyzed PCDD/Fs and PBDD/Fs in 27 surficial sediments collected from the Lian River encompassing the Guiyu, China e-waste recycling zone, and investigated their distributions, sources, migration behaviors and risks. Both PCDD/Fs and PBDD/Fs in these sediments exhibited a spatial trend of Guiyu > Guiyu downriver > Guiyu upriver, illustrating that the Guiyu e-waste recycling activities were the uppermost dioxin contributors in this watershed. Sediments from different Guiyu villages demonstrated big gaps in PCDD/F concentrations and congener compositions, and the reason was attributed to the diverse e-waste recycling activities practiced in these villages. Sediments near the e-waste open-burning areas demonstrated extremely high PCDD/F concentrations and unique PCDD/F profiles featured by low-chlorinated PCDFs (tetra- to hexa-), which is quite different from the OCDD-dominant PCDD/F profile found in most of the Lian River sediments. The geographical distributions of PCDD/F concentrations and profiles illustrate that the substantial amount of PCDD/Fs in Guiyu sediments were mainly retained in local and vicinal water bodies. The principal component analysis (PCA) results further confirm that the high-level PCDD/Fs in Guiyu sediments exhibited quite limited translocations downstream and therefore exerted little influences on the lower reaches. Pentachlorophenol use in history, ceramic industry and vehicle exhaust were diagnosed as the major PCDD/F sources for most sediments of the Lian River. Total toxicity equivalent quantities (TEQs) of 70% of the Lian River sediments surpassed the high-risk limit specified for mammalian life by the U.S.EPA (25 pg TEQ g-1), and most of these sediments were from Guiyu and its near downstream, which merit continuous attention and necessary remediation measures.

Characterizing the emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) from electric arc furnaces during steel-making.

The amount of steel produced using electric arc furnaces (EAFs) has been increasing in recent years. In this study, stack gases from EAFs in steelmaking plants were analyzed to determine if they are also dominant sources of polybrominated dibenzo-p-dioxin and dibenzofuran (PBDD/F) emissions in China. Isotope dilution high-resolution gas chromatography high-resolution mass spectrometry for qualitative and quantitative analysis of PBDD/F congeners revealed that the mean PBDD/F mass concentrations were 271.1-9467.8 pg Nm-3 for the preheating stages (PS) of three EAF plants and that the corresponding toxic equivalents (TEQs) were 10.8-971.2 pg TEQ Nm-3. The PBDD/F mass concentration from the smelting stage (SS) at plant E3 was 261.9 pg Nm-3 (4.5 pg TEQ Nm-3). The PBDD/F emission factors (EF) during the preheating stage for the three plants were 0.0356-1.51 µg TEQ t-1, and the EF was 0.0359 µg TEQ t-1 during the E3 smelting stage. PBDD/Fs were found to contribute 2.39-67.85% to the total mass and 2.84-57.68% to the total dioxin TEQ. These wide fluctuations were caused by differences in the composition of feeding materials and the working temperature of bag filters. Overall, the results indicate that PBDD/F emissions from EAF steelmaking should receive increased attention. The PBDD/F congener patterns among the three EAF plants were variable, possibly because of differences in raw materials. The results presented herein will facilitate assessment of the contribution of EAFs to total PBDD/F emissions in China and investigations of PBDD/F emissions at different stages of steelmaking processes using EAFs.

Occurrence, Human Exposure, and Risk Assessment of Polybrominated Dibenzo-p-Dioxins and Dibenzofurans, Polychlorinated Naphthalenes, and Metals in Atmosphere Around Industrial Parks in Jiangsu, China.

Air samples were collected around industrial parks in Jiangsu, China, to allow the concentrations, profiles, and risk assessment of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polychlorinated naphthalenes (PCNs), and metals to be investigated. The concentrations of ΣPBDD/Fs and ΣPCNs were 1324.26-2080.98 fg/m3 (11.35-42.57 fg I-TEQ/m3) and 10,404.9-29,322.9 fg/m3 (1.32-7.19 fg I-TEQ/ m3), respectively. The highest concentration of ΣPBDD/Fs and ΣPCNs were observed at site C. PBDD/Fs were mainly dominated by PBDFs. The main contributor to the ΣPBDD/Fs in all samples was 1,2,3,4,6,7,8-HpBDF, which accounted for 25.75%-39.4%. For PCNs, the predominating homologues were tetra-, tri- and penta-CNs, which contributed 30.7%-43.3%, 24.7%-31.0%, and 10.6%-21.6%, respectively. As for metals, the pollution of As, Mn, Cr, and Ni in most samples exceeded National Ambient Air Quality Standards of China. Assessing the risk of inhalation exposure showed that there were potential carcinogenic risks to local residents.

Feasibility of gas chromatography-atmospheric pressure photoionization-high-resolution mass spectrometry for the analysis of polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in environmental and feed samples.

In this work, the suitability of atmospheric pressure photoionization (APPI) has been assessed for the determination of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) by gas chromatography-high-resolution mass spectrometry (GC-HRMS). The APPI of target compounds has been tested in both positive and negative ion modes. Under positive ion mode, the analytes generated the molecular ion, which was favoured using dopants that promote charge exchange gas-phase reactions (i.e., benzene), while in negative ion mode, the ion [M-Cl+O]- for PCDFs and dl-PCBs were mainly formed, providing the best results using benzene and diethyl ether as dopants, respectively. Concerning PCDDs, highly chlorinated congeners were mainly ionized by means of the [M-Cl]- ion, whereas [M-Cl+O2]- was the base peak for tetraCDD and [M-Cl+O]- for penta- and hexaCDDs. Method quality parameters, in accordance with the current EU Regulation guidelines for food and feed analysis, showed the good performance of the two GC-APPI-HRMS (Orbitrap) methods since they provided high detection capability (low fg levels), good linearity, and satisfactory precision (RSD% < 9%). In addition, the GC-APPI-HRMS (Orbitrap) methods were validated by analysing selected environmental and feed samples and the results were compared to those obtained using conventional GC-EI-HRMS, demonstrating the good performance in the analysis of the target compounds. Hence, the GC-APPI-HRMS technique can be proposed as alternative to the conventional methods for the determination of PCDD/Fs and dl-PCBs in environmental and feed matrices.

Atmospheric bulk deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the vicinity of MSWI in Shanghai, China.

Atmospheric bulk deposition samples were gathered month by month throughout a year at two sites in vicinity of a MSWI in Shanghai, to carry out an investigation on the atmospheric bulk deposition fluxes and seasonal variations of polychlorinated dibenzo-p-dioxinsand dibenzofurans (PCDD/Fs). The atmospheric bulk deposition fluxes of PCDD/Fs ranged from 23.5 to 560 pg m-2·d-1 (1.01-23.9 pg WHO-TEQ·m-2·d-1), with an average value of 136 pg m-2·d-1 (5.08 pg WHO-TEQ·m-2·d-1) in the Vicinity of the MSWI in Shanghai. The measured concentrations were well compared with those from urban or industrial sites in other regions in China and abroad. The seasonal trend of atmospheric bulk deposition fluxes of PCDD/Fs throughout a year exhibited as high levels in summer, moderate levels in winter, and low levels in spring and autumn. The principal component analysis (PCA) indicated not only the MSWI, but also vehicle emission was the indispensable source of PCDD/Fs in the vicinity of the MSWI, especially for the urban areas. The positive matrix factorization (PMF) apportioned 5 source categories: MSWI, diesel vehicles, atmosphere background, industrial combustion and un-leaded gas vehicles, accounting for 43.3%, 38.1%, 6.89%, 6.19% and 5.50% in average, respectively of PCDD/Fs in atmospheric bulk deposition in the vicinity of the MSWI in Shanghai, China.

Emission characteristics of polychlorinated, polybrominated and mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, PBDD/Fs, and PBCDD/Fs) from waste incineration and metallurgical processes in China.

Typical thermal processes are common sources of polychlorinated, polybrominated and mixed polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, PBDD/Fs, and PBCDD/Fs); however, very few reports have investigated their coemission. To clarify the emission characteristics of these DD/Fs, two municipal waste incinerators (MWIs), three hazardous waste incinerators (HWIs), one cement kiln coprocessing municipal waste incinerator (CMWI), one secondary copper smelter (SCu), and one iron and steel sintering smelter (ISS) in China were investigated. In total, 17 congeners of PCDD/Fs, 14 congeners of PBDD/Fs, and 12 congeners of PBCDDs in stack flue gases from these thermal processes were analyzed using a high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS) in this study. PCDD/Fs, PBDD/Fs and PBCDD/Fs were detectable in all samples, with total concentrations of 911-5.15 × 103 pg/Nm3 (80.2-414 pg TEQ/Nm3). The concentrations of each DD/F were similar within the same type of facility and varied among different types of facilities. The contributions of PBDD/Fs and PBCDD/Fs to the total concentrations exceeded that of PCDD/Fs in some cases, such as in HWIs and SCu. In general, the ∑Cl4-7 CDFs and ∑Cl7-8 CDDs, 1,2,3,4,6,7,8-HpBDF, and 1-B-2,3,7,8-TeCDD and 2-B-1,3,7,8-TeCDD were the dominant congeners in the PCDD/F, PBDD/F, and PBCDD/F mass concentrations, respectively. Several other congeners present at low mass concentrations, such as 1,2,3,4,7,8-HxBDF, have potential as major contributors to the TEQs due to their high toxic equivalency factors. These results reveal the necessity of synergistically inhibiting the occurrences of PCDD/Fs, PBDD/Fs, and PBCDD/Fs from these sources and provide valuable information for use in the source identification of these pollutants in the environment.

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

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

Distribution of PCDD/Fs and PCBs at different locations in a circulating fluidised bed municipal solid waste incinerator.

This study investigates a circulating fluidised bed (CFB) incineration plant to examine the concentrations and fingerprints of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) at five locations downstream of the post-combustion zone. Sampling encompassed both flue gas and ash, spanning from the high-temperature superheater to the outlet of the baghouse filter, thus covering a wide range of flue gas temperatures. The analysis reveals a continuous increase in PCDD/F and PCB concentrations in the flue gas from the superheater to the inlet of the air pollution control system (APCS). The maximum concentrations observed were 75.8 ng/Nm3 for PCDDs, 219 ng/Nm3 for PCDFs, and 763 ng/Nm3 for PCBs. These values represent 9.14, 11.5, and 6.37 times their respective concentrations at the outlet of the high-temperature superheater. Concurrently, the levels of PCDD/Fs and dioxin-like PCBs (dl-PCBs) in the ash steadily increased along the cooling path of the flue gas within the plant. Comparing dl-PCBs to the total amount of 209 PCB congeners, it was evident that dl-PCBs exhibited a trend more akin to that of PCDD/Fs. A robust linear correlation was observed between dl-PCBs and PCDD/Fs (R2 = 0.99, p < 0.001), surpassing that between PCBs and PCDD/Fs (R2 = 0.92, p < 0.01), suggesting that dl-PCBs share closer formation pathways with PCDD/Fs. Additionally, elemental composition analysis of fly ash samples aimed to explore potential links between fly ash characteristics and PCDD/F and PCB formation. The Cl/S ratio increased from 1.58 to 5.13 with decreasing flue gas temperature. Principal component analysis (PCA) was employed to visualise the concentrations of PCDD/Fs and PCBs in the flue gas alongside elemental contents in the fly ash. With the exception of PCBs in ash, all other PCDD/Fs and PCBs in fly ash exhibited positive correlations with both carbon (C) and chlorine (Cl). Furthermore, a positive relationship between C/Cl and PCDD/Fs-PCBs in fly ash implies that fly ash serves as the primary reaction surface for dioxin generation during low-temperature heterogeneous catalytic reactions.

Short- and medium-chain chlorinated paraffins in breast milk in Shanghai, China: Occurrence, characteristics, and risk assessment.

As novel contaminants, short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) have been of great concern in the past several years. Shanghai was one of the provinces with the largest chlorinated paraffins (CPs) emission in China; nevertheless, there is currently little information on the human exposure to SCCPs and MCCPs, particularly MCCPs. In this study, 25 breast milk samples were collected in Shanghai from 2016 to 2017. The concentrations of SCCPs and MCCPs were determined using two-dimensional gas chromatography coupled with orbitrap high-resolution mass spectrometry (GC × GC-orbitrap-HRMS) to investigate their characteristics and assess the associated health risks for breast-fed infants. Compared with the previous studies in other areas, the current study presented the higher CPs concentrations, with median concentrations of SCCPs and MCCPs up to 771 and 125 ng/g lipid weight (lw), respectively. The exposure profiles of the CPs were characterized by C10 and Cl6-7 as the predominant congeners of SCCPs, while C14 and Cl7-9 were identified as the dominant groups of MCCPs. CP-42 and CP-52 were identified as potential sources of CPs found in breast milk samples collected in Shanghai. The concentrations of MCCPs exhibited a positive correlation (p value < 0.05) with the dietary consumption of meat and poultry. No significant positive correlations were observed for SCCPs and MCCPs with polychlorinated dibenzodioxins/furans (PCDD/Fs) congeners. A preliminary exposure assessment showed that SCCPs in breast milk potentially posed high risks to the breast-fed infants in Shanghai.

Results of an international interlaboratory study on dioxin-like activities in drinking-, river surface- and wastewater using DR CALUX bioassay.

Aquatic animals and consumers of aquatic animals are exposed to increasingly complex mixtures of known and as-yet-unknown chemicals with dioxin-like toxicities in the water cycle. Effect- and cell-based bioanalysis can cover known and yet unknown dioxin and dioxin-like compounds as well as complex mixtures thereof but need to be standardized and integrated into international guidelines for environmental testing. In an international laboratory testing (ILT) following ISO/CD 24295 as standard procedure for rat cell-based DR CALUX un-spiked and spiked extracts of drinking-, surface-, and wastewater were validated to generate precision data for the development of the full ISO-standard. We found acceptable repeatability and reproducibility ranges below 36 % by DR CALUX bioassay for the tested un-spiked and spiked water of different origins. The presence of 17 PCDD/Fs and 12 dioxin-like PCBs was also confirmed by congener-specific GC-HRMS analysis. We compared the sum of dioxin-like activity levels measured by DR CALUX bioassay (expressed in 2,3,7,8-TCDD Bioanalytical Equivalents, BEQ; ISO 23196, 2022) with the obtained GC-HRMS chemical analysis results converted to toxic equivalents (TEQ; van den Berg et al., 2013).

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.

Risk ranking of chemical hazards in foods: comparison of aggregating methods using infant formula as an example.

The aim of this study was to rank several chemical hazards present in one food item, namely infant formula. We first identified the substances potentially present in infant foods according to the results of the French infant Total Diet Study and to the available scientific literature. Second, we built three criteria to rank the hazards: severity, contribution to the total exposure, and risk characterisation. Each criterion was scored using quantitative or semi-quantitative scales. Third, in order to rank the chemical hazards, two approaches of aggregation of the three criteria were deployed. On the one hand, a multi-criteria decision analysis outranking method and on the other hand a semi-quantitative risk-matrix type method. We then tested these approaches on follow-on formulae for the 7-12 months population, for which contamination data from the French infant Total Diet study were available. The results of both methods showed that the six prioritised substances are the same even if not in the exact same order (acrylamide, inorganic arsenic, furan, chromium VI, lead and PCDD/Fs) demonstrating the robustness of these approaches.

Polybrominated dibenzo-p-dioxins/furans and their chlorinated analogues in sediments from a historical hotspot for both brominated flame retardants and organochlorine pesticides.

Polybrominated dibenzo-p-dioxin/furans (PBDD/Fs) and polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) in the environment are closely related to their precursors, brominated flame retardants (BFRs) and organochlorine pesticides (OCPs). However, their change trends following the regulation of BFRs and OCPs remain incompletely characterized. Here, we examined PBDD/Fs and PCDD/Fs in sediments from a historical hotspot for both BFRs and OCPs, namely the Pearl River Delta (PRD), China. PBDD/Fs showed ubiquity in these samples but significantly lower concentrations than PCDD/Fs. Spatially, the occurrence of PBDD/Fs was positively correlated with local development levels and sediments from highly urbanized/industrialized areas showed higher and increasing PBDD/F concentrations. Polybrominated diphenyl ether (PBDE)-related products/industries were the greatest PBDD/F contributors to the PRD, followed by bromo-phenol/benzene-related products/industries. PCDD/Fs in PRD sediments showed significant positive correlations with local grain planting area, yield, and pesticide consumption. The historical use of pentachlorophenol (PCP)/PCP-Na and biomass open-burning were the leading PCDD/F sources of the PRD agricultural/rural areas, where the concentrations and toxic equivalent quantities (TEQs) of PCDD/Fs in sediments changed very little over the past decade. Anthropogenic thermal processes involved in metallurgy, waste incineration, and vehicles were the greatest PCDD/F contributors in the PRD urban/industrial areas, where the PCDD/F concentrations in sediments almost doubled over the last decade. This finding indicates the increasing PCDD/F contributions of industrial and municipal activities in the PRD, despite the implementation of strict emission standards. Over sixty percent of the samples showed TEQs that surpassed the low-risk threshold specified for mammalian life by the U.S. EPA (2.5 pg TEQ g-1) and warrant continuous attention.

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.