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.

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.

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.

Dietary intake of metals, metalloids, and persistent organic pollutants in Spanish pregnant women. ECLIPSES study.

OBJECTIVE: This study aimed to describe dietary intake and important dietary sources to pollutants as well as to identify maternal socio-economic and lifestyle factors associated with high intake during pregnancy in women residing in a Mediterranean city with heavy industrial activity. METHODS: Dietary intake during pregnancy of As, InAs, Cd, MeHg, Pb, PCDD/Fs, DL-PCBs, and NDL-PCBs in 701 pregnant women participating in the longitudinal ECLIPSES study was calculated based on a 45-item food-frequency questionnaire and a database of pollutants in food of the Catalan Food Safety Agency. Details on socio-economic, lifestyle, and anthropometric variables were also collected. RESULTS: The mean dietary intake of pollutants per day and the food group that contributed the most (%) was: 286.51 µg of As (71.27% from white fish), 4.14 µg of InAs (70.16% from cereals-tubers), 6.27 µg of Cd (47.51% from seafood), 5.00 µg of MeHg (52.88% from blue fish), 3.32 µg of Pb (30.15% from cereals-tubers), 9.93 pg of PCDD/Fs (from many food categories), 18.39 pg of DL-PCBs (59.74% from blue fish) and 181.00 ng of NDL-PCBs (44.58% from blue fish). Adjusted multivariate analysis revealed that older age was associated with high As intake, higher educational level was related to low InAs, Cd, and DL-PCBs intake, and alcohol use and smoking were linked with high Pb intake. CONCLUSION: The dietary intake of pollutants including As and DL-PCBs among pregnant women exceeds or almost reaches the EFSA safety threshold. These findings support the urgent need for local governments to pay special attention to this situation and develop specific prevention strategies for this vulnerable group.

Identification and verification of PCDD/Fs indicators from four typical large-scale municipal solid waste incinerations with large sample size in China.

Monitoring PCDD/Fs emissions from municipal solid waste incinerations (MSWIs) is of paramount importance, yet it can be time-consuming and labor-intensive. Predictive models offer an alternative approach for estimating their levels. However, robust models specific to PCDD/Fs were lacking. In this study, we collected 190 PCDD/Fs samples from 4 large-scale MSWIs in China, with the average PCDD/Fs levels and TEQ levels of 0.987 ng/m3 and 0.030 ng TEQ/m3, respectively. We developed and evaluated predictive models, including traditional statistical methods, e.g., linear regression (LR) as well as machine learning models such as back propagation-artificial neural networks (BP ANN) and random forest (RF). Correlation analysis identified 2,3,4,7,8-PeCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF were better indicator congeners for PCDD/Fs estimation (R2 > 0.9, p < 0.001). The predictive results favored the RF model, exhibiting a high R2 value and low root mean square error (RMSE) and mean absolute error (MAE). Additionally, the RF model showed excellent prediction ability during external validation, with low absolute relative error (ARE) of 10.9 %-12.6 % for the three indicator congeners in the normal PCDD/F TEQ levels group (<0.1 ng TEQ/m3) and slightly higher ARE values (13.8 %-17.9 %) for the high PCDD/F TEQ levels group (>0.1 ng TEQ/m3). In conclusion, our findings strongly support the RF model's effectiveness in predicting PCDD/Fs TEQ emission from MSWIs.

Development of a field-deployable analytical workflow for determining current status and indicative human health risks at a historic dl-POPs hotspot.

This paper introduces an integrated workflow that effectively evaluates environmental and health risks of dioxin-like Persistent Organic Pollutants (dl-POPs) at industrial hotspot regions. The developments of validated, cost effective and user-friendly analytical strategies which can be field deployable are quintessential for routine monitoring of dl-POPs, particularly in developing countries. This study addresses the lacunae by enabling an exclusive gas chromatography triple quadrupole mass spectrometer based analytical workflow substituting conventional magnetic sector high resolution mass spectrometer technique and validated the methodology as per the European Union regulation 644/2017. The viable monitoring utility of the methodology for predicting enviro-food-health nexus was field-tested by analyzing fish and sediment samples from the Eloor-Edayar industrial belt, a solitary POPs hotspot in India. The profiles of congeners indicate that dl-POPs were formed through precursor pathways, suggesting the potential release of chlorinated precursor species from surrounding industrial area as the root cause. Fish samples from hotspots were observed to have 8 times higher levels of polychlorinated dibenzo-p-dioxin/furans (PCDD/Fs) and 30 times higher levels of polychlorinated biphenyls (PCBs) than the control sites. A strong statistically significant (p < 0.05) positive correlation was observed between dl-POPs levels in fish and sediment samples at the study site and the Biota sediment accumulation factors for PCDD/Fs and dl-PCBs ranged from 0.019 to 0.092 and 0.004 to 0.671 respectively. The estimated weekly intake from fish consumption in the study region was observed to be 3 to 24 times higher than the maximum levels set by the European food safety authority (2 pgTEQ kg-1bwweek-1). Hence, the periodic surveillance of dl-POPs employing user friendly/validated confirmatory tools stands highly imperative to safeguard human health and environment. Keywords: Dioxin and PCBs, GC-MS/MS, POPs Hotspot, Biota-sediment accumulation factor, Correlation analysis, Health risk assessment.

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.

Occurrence and carcinogenic potential of airborne PBDD/Fs and PCDD/Fs around a large-scale municipal solid waste incinerator: A long-term passive air sampling study.

Municipal solid waste incinerator (MSWI) not only is deemed one of the uppermost sources of polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), but also produces substantial amount of polybrominated dibenzo-p-dioxins/furans (PBDD/Fs) owing to the existence of brominated flame retardants (BFRs) in the waste. So far, however, PBDD/Fs in the vicinal environments of MSWI and their associated risks remain rarely studied. Based on a one-year passive air sampling (PAS) scheme, we investigated airborne PBDD/Fs and PCDD/Fs around a large-scale MSWI that has been operated for multi-years. Both the concentrations of PBDD/Fs and PCDD/Fs showed spatially decreasing trends with the distance away from the MSWI, confirming the influence of the MSWI on the dioxin levels in its ambient air. But its influence on PBDD/Fs was less because PBDD/Fs exhibit lower volatility and therefore lower gaseous concentrations than PCDD/Fs. Compared to the existing global data of airborne PCDD/Fs and PBDD/Fs, our data of the MSWI vicinity were at medium levels, despite PAS samples only represent the concentrations of gaseous dioxins in theory. The seasonal data suggest that meteorological conditions exerted apparent influences over the concentrations and sources of airborne dioxins around the MSWI. As for PCDD/Fs, the MSWI was diagnosed as their uppermost source, followed by local traffic and volatilization/deposition. Whereas the top three PBDD/F sources were related to PBDEs, bromophenol/bromobenzene, and traffic vehicles, respectively. The bioassay-derived TEQs based on the aryl hydrocarbon receptor activation of airborne dioxins around the MSWI were one or two orders of magnitudes higher than their concentration-based TEQs, and the corresponding carcinogenic risks at some MSWI-vicinal sites exceeded the acceptable threshold proposed by the U. S. EPA (10-6 âˆ¼ 10-4) and deserve continuous attention.

Global survey of dioxin- and thyroid hormone-like activities in consumer products and toys.

BACKGROUND: Children and consumers are exposed to increasingly complex mixtures of known and as-yet-unknown toxic chemicals from toys and products. However traditional chemical analysis methods only evaluate a small number of chemicals at a time thereby restricting consumer awareness of the full range of potentially harmful chemicals in products. METHODS: We used high-throughput effect-based non-animal methods to investigate exposures to complex chemical mixtures of several kinds of brominated flame retardants (BFRs) for their dioxin- and thyroid hormone-like activities in various kinds of consumer products and toys from 26 different countries, on four continents (Africa, America, Asia and Europe) in combination with chemical analysis of various polybrominated flame retardants (BFRs) and their impurities (such as polyhalogenated PCDD/Fs and PBDD/Fs). RESULTS: We found high levels of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in toys and now, for the first time, also in consumer products that are manufactured from black plastics containing certain brominated flame retardants (BFRs). The presence of PBDD/PBDFs as well as other BFRs in various black plastic materials from additional countries as well as additional kinds of consumer products as confirmed by effect-based in vitro reporter gene DR CALUX and TTR-TRß CALUX assays as well as congener-specific chemical analysis. We compared total Toxicity Equivalent (TEQ) levels of PBDD/F-TEQs analysed by chemical analysis to by CALUX bioassay measured Biological equivalence (BEQ) concentrations (for further info see at ISO 23196, ISO, 2022). In the case of TBBPA, both chemical and TTR-TRß CALUX analysis measure direct the amount of TBBPA. Finally, the daily ingestion of 2,3,7,8-TCDD equivalents from PBDD/Fs-contaminated plastic toys by child mouthing habits have been related to our earlier study (Budin et al., 2020). CONCLUSIONS: Interaction of children with such contaminated plastics may significantly contribute to the daily uptake of dioxin- and thyroid hormone transport disrupting-like compounds. Effect-based bioassays for dioxin- and thyroid hormone-like activities are relevant to pick-out such complex mixtures of known and yet unknown (and therefore not regulated) substances for safer and more sustainable plastics. Low POPs Content Levels and other mechanisms set under the Basel and Stockholm Conventions are set far too high to prevent a significant flow of BFRs and PBDD/Fs into consumer products.

Influence of different loads on PCDD/F removal by SCR during municipal solid waste incineration.

This study was conducted on a full-scale (500 t/d) municipal solid waste incinerator (MSWI), investigating the influence of different loads on the emission of polychlorinated dibenzodioxins and polychlorinated dibenzofurans (PCDD/Fs) and their removal by selective catalytic reduction (SCR) system. The total concentration of PCDD/Fs at the SCR inlet under 100% load was higher than that under 80% load. The changing loads caused different distribution characteristics of PCDD/Fs at the SCR inlet, and the dominant congeners changed from high-chlorinated PCDDs (80% load) to low-chlorinated PCDFs (100% load). Moreover, the increased load enhanced the removal efficiency of PCDD/Fs by SCR from 17.3% to 64.2%, which was influenced by the inlet PCDD/F distribution and the moisture content. The high-chlorinated PCDD/Fs with the more stable structure were more difficult to be deteriorated and the high moisture content can weaken the catalytic activity of SCR catalysts. Correlation analysis was used to study the relationship between major air pollutants and PCDD/F emissions. The results showed that HCl positively correlated with PCDD/F emission concentrations, while NOx and SO2 negatively correlated. The results of this study can provide a reference for MSWI to operate properly under variable loads.

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.

The transfer of environmental contaminants (Brominated and Chlorinated dioxins and biphenyls, PBDEs, HBCDDs, PCNs and PFAS) from recycled materials used for bedding to the eggs and tissues of chickens.

Some types of poultry bedding made from recycled materials have been reported to contain environmental contaminants such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins), polychlorinated biphenyls (PCBs) brominated flame retardants (BFRs) polychlorinated naphthalenes (PCNs), polybrominated dioxins (PBDD/Fs), perfluoroalkyl substances (PFAS), etc. In one of the first studies of its kind, the uptake of these contaminants by chicken muscle tissue, liver, and eggs from three types of recycled, commercially available bedding material was simultaneously investigated using conventional husbandry to raise day old chickens to maturity. A weight of evidence analysis showed that PCBs, polybrominated diphenylethers (PBDEs), PCDD/Fs, PCNs and PFAS displayed the highest potential for uptake which varied depending on the type of bedding material used. During the first three to four months of laying, an increasing trend was observed in the concentrations of ΣTEQ (summed toxic equivalence of PCDD/Fs, PCBs, PBDD/Fs, PCNs and polybrominated biphenyls), NDL-PCBs and PBDEs in the eggs of chickens raised on shredded cardboard. Further analysis using bio-transfer factors (BTFs) when egg production reached a steady state, revealed that some PCB congeners (PCBs 28, 81, 138, 153 and 180) irrespective of molecular configuration or chlorine number, showed the highest tendency for uptake. Conversely, BTFs for PBDEs showed good correlation with bromine number, increasing to a maximum value for BDE-209. This relationship was reversed for PCDFs (and to some extent for PCDDs) with tetra- and penta- chlorinated congeners showing a greater tendency for selective uptake. The overall patterns were consistent, although some variability in BTF values was observed between tested materials which may relate to differences in bioavailability. The results indicate a potentially overlooked source of food chain contamination as other livestock products (cow's milk, lamb, beef, duck, etc.) could be similarly impacted.

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.

Particle and gas phase sampling of PCDD/Fs and dl-PCBs by activated carbon fiber and GC/MS analysis.

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), and polychlorobiphenyls (PCBs) are semi-volatile compounds and can be partitioned in the atmosphere between the gas and particulate phase, due to their physicochemical properties. For this reason, the reference standard methods for air sampling include a quartz fiber filter (QFF) for the particulate and a polyurethane foam (PUF) cartridge for the vapor phase, and it is the classical and most popular sampling method in the air. Despite the presence of the two adsorbing media, this method cannot be used for the study of the gas-particulate distribution, but only for a total quantification. This study presents the results and the performance aim to validate an activated carbon fiber (ACF) filter for the sampling of PCDD/Fs and dioxin-like PCBs (dl-PCBs) using laboratory and field tests. The specificity, precision, and accuracy of the ACF in relation to the QFF + PUF were evaluated through the isotopic dilution technique, the recovery rates, and the standard deviations. Then the ACF performance was assessed on real samples, in a naturally contaminated area, through parallel sampling with the reference method (QFF + PUF). The QA/QC was defined according to the standard methods ISO 16000-13 and -14 and EPA TO4A and 9A. Data confirmed that ACF meets the requirements for the quantification of native POPs compounds in atmospheric and indoor samples. In addition, ACF provided accuracy and precision comparable to those offered by standard reference methods using QFF + PUF, but with significant savings in terms of time and costs.

PCDD/Fs in indoor environments of residential communities around a municipal solid waste incineration plant in East China: Occurrence, sources, and cancer risks.

Prolonged exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) can pose several adverse outcomes on human health. However, there is limited information on public health associated with indoor PCDD/F exposure in residential environments. Here, we examined PCDD/F concentrations in indoor air and indoor dust samples obtained from households near a municipal solid waste incineration (MSWI) plant. Our measurements revealed that the toxic equivalent (TEQ) concentrations of PCDD/Fs in indoor air ranged from 0.01 to 0.05 pg TEQ/m3, which were below intervention thresholds (0.6 pg TEQ/m3). Additionally, the TEQ concentrations of PCDD/Fs in indoor dust ranged from 0.30 to 11.56 ng TEQ/kg. Higher PCDD/F levels were found in household dust in the town of Taopu compared to those in the town of Changzheng. Principal component analysis (PCA) of PCDD/Fs suggested that waste incineration was the primary source of PCDD/Fs in indoor air, whereas PCDD/Fs in indoor dust came from multiple sources. The results of the health risk assessment showed the carcinogenic risk due to indoor PCDD/F exposure was higher for adults than for nursery children and primary school children. The carcinogenic risks of PCDD/Fs for age groups residing near the MSWI plant were all less than the risk threshold (10-5). Our findings will help to better understand the levels of PCDD/F exposure among urban populations living in residential communities around the MSWI plant and to formulate corresponding control measures to reduce probabilistic risk implications.

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.

Occurrence and congener profiles of dioxins (PCDDs), furans (PCDFs) and polychlorinated biphenyls (PCBs) in ovine and caprine milk samples collected in a very polluted site in Central Italy.

Concentrations of 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs) and 18 polychlorinated biphenyls (PCBs), including 12 dioxin-like (DL-PCBs) and 6 non-dioxin-like PCBs (NDL-PCBs) were measured in 16 ovine and caprine milk samples collected in the territory of Bussi sul Tirino, central Italy, a Site of National Interest (SNI) due to its high and widespread environmental pollution. All the analyzed samples were compliant with the maximum levels fixed by Commission Regulation (EU) 1259/2011 for the content of PCDD/Fs and the sum of PCDD/Fs and DL-PCBs. In two cases, contamination levels of the sum of PCDD/Fs and DL-PCBs were higher than the action levels fixed by EU Recommendation 663/2014. The statistical analysis, performed by Principal Component Analysis (PCA), revealed that the differences in contamination profiles of the different milk samples were independent of the distance of the farms from the Bussi illegal landfill but likely related to local emission sources influencing the exposure to POPs of studied animals.

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.