Polychlorinated Dibenzo-p-dioxins And Furans Research Articles

Development and application of an efficient GC-HRMS method for the determination of PBDD/Fs in flue gas and fly ash samples

Polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) are emerging trace persistent organic pollutants (POPs) whose toxicity is comparable to or even greater than that of their chlorinated analogs, polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). However, the analysis of PBDD/Fs is particularly challenging due to the potential interference of polybrominated diphenyl ethers (PBDEs) and their pyrolytic property. In order to enhance the analysis efficiency, a time and solvent saving purification method, which was capable of effectively eliminating the interference from PBDEs, was developed for the analysis of PBDD/Fs. To improve the sensitivity of the analytical method, instrumental conditions such as inlet temperature, initial carrier gas flow rate, ion source temperature, and electron impact energy were optimized. Under the optimal conditions, the instrumental detection limit of PBDD/Fs ranged from 0.02 to 0.4 pg/μL. The recoveries of PBDD/Fs in spiked samples ranged from 79.7 % to 118 % (mean: 101 %), with an RSD value range of 2.6 %–10 % (mean: 6.0 %). The developed method was successfully applied for analyzing PBDD/Fs in four flue gas samples and two fly ash samples. The concentrations of ∑14PBDD/Fs were 2.92–7.57 ng/Nm3 and 0.042–8.78 ng/kg, respectively, in the flue gas and fly ash samples. Overall, this method greatly improved the efficiency and sensitivity for the analysis of PBDD/Fs, and it is expected to become an effective tool for the precise monitoring of PBDD/Fs.

E-waste in the environment: Unveiling the sources, carcinogenic links, and sustainable management strategies

E-waste refers to the electrical and electronic equipment discarded without the intent of reuse or at the end of its functional lifespan. In 2022, approximately 62 billion kg of e-waste, equivalent to 7.8 kg per capita, was generated globally. With an alarming annual growth of approximately 2 million metric tonnes, e-waste production may exceed 82 billion kg by 2030. Improper disposal of e-waste can be detrimental to human health and the entire biosphere. E-waste encompasses a wide range of materials, including heavy metals, Polychlorinated Biphenyls (PCBs), Per- and Polyfluoroalkyl Substances (PFAS), Polycyclic Aromatic Hydrocarbons (PAHs), Polychlorinated Dibenzo-dioxins and -furans (PCDD/Fs), Polybrominated Diphenyl Ethers (PBDEs), and radioactive elements. E-waste, when disposed inappropriately can directly contaminate the aquatic and terrestrial environment, leading to human exposure through ingestion, inhalation, dermal absorption, and trans-placental transfer. These detrimental contaminants can directly enter the human body from the environment and may fuel carcinogenesis by modulating cell cycle proteins, redox homeostasis, and mutations. Heavy metals such as cadmium, mercury, arsenic, lead, chromium, and nickel, along with organic pollutants like PAHs, PCBs, PBDEs, PFAS, and radioactive elements, play a crucial role in inducing malignancy. Effective collection, sorting, proper recycling, and appropriate disposal techniques are essential to reduce environmental contamination with e-waste-derived chemicals. Hence, this comprehensive review aims to unravel the global environmental burden of e-waste and its links to carcinogenesis in humans. Furthermore, it provides an inclusive discussion on potential treatment approaches to minimize environmental e-waste contamination.

Biochars from chlorine-rich feedstock are low in polychlorinated dioxins, furans and biphenyls

Chlorinated aromatic hydrocarbons like polychlorinated dibenzo-p-dioxins and -furans (PCDD/F) and polychlorinated biphenyls (PCB) are omnipresent in the environment due to historic production, use, and (unintended) release. Nowadays, their emission and maximum concentration in environmental compartments is strictly regulated. During biochar production, PCDD/F and PCB may be formed and retained on the solid pyrolysis product. Industrial biochars certified, e.g., under the European Biochar Certificate (EBC), exhibit concentrations that were always well below threshold values for soil application and even animal feed. However, this has not been sufficiently tested for chlorine (Cl) rich organic material such as marine biomass or polyvinyl chloride (PVC) contaminated feedstock. Here, we analyzed PCDD/F and PCB contamination in biochars produced at different temperatures from different biomasses with comparatively high Cl contents in the range from 0.2 % to 3.8 % (w/w, seagrass, two types of saltwater macroalgae, tobacco stalks, and PVC contaminated wood). All of the biochars produced showed PCDD/F and PCB contents well below the applicable threshold values given by the EBC (< 20 ng TEQ kg−1 for PCDD/F and < 2×105 ng kg−1 for PCB). The EBC thresholds were undershot by a minimum of factor 1.5 for PCDD/F (mostly factor 20) and by a minimum of factor 90 for PCB. Between 1 and 27 ppb of feedstock Cl were transformed to Cl bound in PCDD/F and PCB in the biochars. No consistent correlation between biomass Cl contents and contents of PCDD/F and PCB were found but higher Cl contents in the feedstock led to a more diverse PCDD/F congener pattern in the biochars. Pyrolysis of PVC-amended wood resulted in consistently higher contamination of PCDD/F and PCB in the biochars compared to pyrolysis of the other biomasses, potentially due to differences in Cl speciation in the feedstocks i.e., Cl in PVC is already covalently bound to an organic carbon backbone. A high contamination in PCDD/F and PCB in biochar was intentionally triggered by separation of pyrogas and biochar in the reactor at < 300 °C to promote condensation of contaminants on the solid product. Between 20 % and 80 % of feedstock Cl was released via the pyrogas, i.e., neutralization of HCl in burnt pyrogas might be necessary when pyrolyzing Cl-rich feedstock in industrial biochar production. Our results indicate that biochars produced from Cl-rich feedstocks with proper biochar production process control are conform with European certification guidelines for PCDD/F and PCB contamination. The results open the opportunity to exploit and valorize so far non-used marine or otherwise Cl enriched biomasses for the production of biochar and carbon sinks.

Temporal trends (1972-2017) and spatial differences of persistent halogenated aromatic hydrocarbons in osprey eggs in Finland.

Time trends and regional differences of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), DDTs, polybrominated biphenyls (PBBs) and polybrominated diphenylethers (BDEs) were studied in unhatched osprey eggs collected by bird ringers in 1972-2017 from four areas in Finland. Two study areas were from Baltic Sea, Northern Quark and Finnish Archipelago Sea, while the two others were inland lake areas, eutrophicated Lake Vanajanselkä affected by industrial emissions, and Pristine SW Lake Area. The highest concentrations of most compound groups were in Lake Vanajanselkä consistent with high emissions, the predominance of bream as a prey, and higher concentrations in bream compared to other prey fish. Concentrations of all chlorinated compounds decreased significantly in all study areas. Average annual decreases were ∑PCDD/F 2.3-4.9%, ∑PCB 2.2-4.2%, ∑PCN 2.6-7.0% and ∑DDT 7.1-9.5%, primarily in line with decreased levels in prey fish. From 1972 PBBs and BDEs increased significantly until 1990s declining rapidly thereafter. PCDD/F congener profile was dominated by 2,3,4,7,8-PeCDF, except in Lake Vanajanselkä by 1,2,3,6,7,8-HxCDD. PCB congener profile was dominated by PCB 153 in all study areas, followed by PCB 180 and PCB 138. Among dioxin-like compounds PCBs contributed 82%, PCDDs 14% and PCDFs 4% to toxic equivalent quantity (∑TEQ). PCB 126 contributed most to ∑TEQ, followed by 1,2,3,7,8-PeCDD. BDE 47 being the dominant BDE congener, followed by BDE 100. ∑DDT concentrations were relatively similar across all study areas, with DDE contributing about 90%. Productivity of chicks per active nest was significantly decreased in Lake Vanajanselkä, and the likely explanation is embryotoxicity of dioxin-like compounds. It is plausible that dioxin-like compounds influenced embryonic survival among highly exposed ospreys prior to 2010, especially in Lake Vanajanselkä and Northern Quark. However, decreased survival due to DDE-induced eggshell thinning seems unlikely after 1985, and BDE levels were below those potentially causing adverse effects.

Statistical comparison for assessing agreement between two mass spectrometric methods for the analysis of polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs) in contaminated soils

A gas chromatography coupled to high-resolution mass spectrometry (GC-HR/MS) has been used as the standard method for the quantification of polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs), which are regulated at screening and action levels in the environment. However, several alternative methods have been attempted due to the disadvantage of its high cost. Although a gas chromatography with triple quadrupole mass spectrometry (GC-QqQ-MS/MS) has been used in a wide variety of sample matrices, showing that they are interchangeable, there has been a lack of comprehensive studies on statistical agreement with GC-HR/MS. In this study, a pairwise comparison of the total concentrations of PCDDs/Fs in 90 soil field samples obtained by two mass spectrometric methods was performed using the Passing-Bablok (P&B) regression and Bland-Altman (B&A) analysis for the method comparison. According to the result of the B&A analysis, the concentration range of PCDDs/Fs was between 98.2 and 1760 pg/g showed good agreement between two methods at the 95 % confidence level (CL). Although there was a large discrepancy between the two methods in the low concentrations (<16.5 pg/g of PCDDs/Fs), this result was similar to the P&B regression analysis. As the verification results by B&A and P&B regression analysis, the interchangeable concentration range between the two methods was confirmed to be adequate for the monitoring of PCDDs/Fs regulating levels in soils.

Molecular mechanisms of environmental pollutant-induced cartilage damage: from developmental disorders to osteoarthritis.

The objective of the present study was to review the molecular mechanisms of the adverse effects of environmental pollutants on chondrocytes and extracellular matrix (ECM). Existing data demonstrate that both heavy metals, including cadmium (Cd), lead (Pb), and arsenic (As), as well as organic pollutants, including polychlorinated dioxins and furans (PCDD/Fs) and polychlorinated biphenyls (PCB), bisphenol A, phthalates, polycyclic aromatic hydrocarbons (PAH), pesticides, and certain other organic pollutants that target cartilage ontogeny and functioning. Overall, environmental pollutants reduce chondrocyte viability through the induction apoptosis, senescence, and inflammatory response, resulting in cell death and impaired ECM production. The effects of organic pollutants on chondrocyte development and viability were shown to be mediated by binding to the aryl hydrocarbon receptor (AhR) signaling and modulation of non-coding RNA expression. Adverse effects of pollutant exposures were observed in articular and growth plate chondrocytes. These mechanisms also damage chondrocyte precursors and subsequently hinder cartilage development. In addition, pollutant exposure was shown to impair chondrogenesis by inhibiting the expression of Sox9 and other regulators. Along with altered Runx2 signaling, these effects also contribute to impaired chondrocyte hypertrophy and chondrocyte-to-osteoblast trans-differentiation, resulting in altered endochondral ossification. Several organic pollutants including PCDD/Fs, PCBs and PAHs, were shown to induce transgenerational adverse effects on cartilage development and the resulting skeletal deformities. Despite of epidemiological evidence linking human environmental pollutant exposure to osteoarthritis or other cartilage pathologies, the data on the molecular mechanisms of adverse effects of environmental pollutant exposure on cartilage tissue were obtained from studies in laboratory rodents, fish, or cell cultures and should be carefully extrapolated to humans, although they clearly demonstrate that cartilage should be considered a putative target for environmental pollutant toxicity.

Polychlorinated dibenzodioxins/furans and dioxin-like polychlorinated biphenyls in fish and crustaceans of a recreationally fished estuary, following targeted remediation

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) are a suite of harmful chemicals (hereafter collectively referred to as ‘dioxins’), and their emission into aquatic habitats leads to persistent contamination of sediments, aquatic food-webs, and seafoods. Quantifying contaminant levels in seafood species is important for the ongoing management of exposure risk by fishers, particularly after any remediation actions. We present dioxin concentrations in four seafood species (Yellowfin Bream Acanthopagrus australis, Sea Mullet Mugil cephalus, Eastern School Prawn Metapenaeus macleayi, and Eastern King Prawn Penaeus plebejus) in a recreationally fished estuary, in relation to a contaminated site that has undergone a remediation process, partially removing contaminated sediments (Homebush Bay, Port Jackson, New South Wales, Australia). Dioxin concentrations in these species were measured before (2005/6) and after (2015/16) remediation at a range of locations in and around the remediated site. Dioxin concentrations and congener profiles differed substantially among taxa, and concentrations were frequently higher than Australian screening criteria. The two prawn species showed evidence of a decline in dioxin concentrations after remediation, but the fish species only showed a declining dioxin concentration with distance from the contaminated site (not between periods). There were some minor changes in the congener profile for some species following remediation. While there was evidence for greatly reduced dioxin concentrations in prawn species following remediation, the complex patterns for fish were likely affected by environmental changes, species-specific and temporal changes in lipid content, and animal movement patterns. Future monitoring may aid interpretation of the patterns and modelling of exposure risk associated with seafood consumption into the future.

Distribution of PAHs, PCBs, and PCDD/Fs in products from full-scale relevant pyrolysis of diverse contaminated organic waste

Biomass pyrolysis is the anoxic thermal conversion of biomass into a carbon rich, porous solid, often called biochar. This could be a better waste management alternative for contaminated organic wastes than incineration, due to the useful properties of biochar and potential for carbon sequestration. There are, however, concerns about the potential formation/destruction of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). Six organic wastes, including digested sewage sludges, wood wastes, and food waste reject, were pyrolyzed (500–800°C) in a full-scale relevant unit (1–5 kg biochar hr−1). Removal efficiencies for PCBs and PCDD/Fs were > 99% in the produced biochars. Biochar PAH-content (2.7–118 mgkg−1) was not significantly correlated to feedstock or temperature. PAHs (2563–8285 mgkg−1), PCBs (22–113 µgkg−1), and PCDD/Fs (1.8–50 ngTEQ kg−1) accumulated in the pyrolysis condensate, making this a hazardous waste best handled as a fuel for high temperature combustion. Emission concentrations for PAHs (0.22–421 µgNm−3) and PCDD/Fs (≤2.7 pgTEQ Nm−3) were mainly associated with particles and were below the European Union’s waste incineration thresholds. Emission factors ranged from 0.0002 to 78 mg tonne−1 biochar for PAHs and 0.002–0.45 µgTEQ tonne−1 biochar for PCDD/Fs. PCDD/F-formation was negligible during high temperature (≥500 °C) biomass pyrolysis (69–90% net loss)

The Role of Sediment Records in Environmental Forensic Studies: Two Examples from Italy of Research Approaches Developed to Address Responsibilities and Management Options

The coupling of scientific evidence from sediment cores with historical information represents an effective way to reconstruct and quantify recent anthropogenic impacts in transitional and marine-coastal areas. These are both key points pertaining to studies that aim at establishing the responsibility for envi ronmental pollution. Good practices for the selection of sampling sites and specific survey techniques are fundamental to understand pollution histories and dynamics, together with reliable dating methods and analytical procedures. In addition, a certain degree of flexibility and willingness to explore different research pathways is necessary, particularly when unexpected questions arise from scientific data or from requests posed by authorities in charge of preliminary investigations or court debates. In this paper, two different study cases are reviewed, and the approaches developed to tackle with specific issues are presented. Its main purpose is both to explain study paths undertaken to answer challenging scientific-legal questions and to provide examples for developing countries that present similar risks of uncontrolled industrialization. Results were used in preliminary investigations or court debates for the attribution of responsibility for environmental pollution to past or present industrial managements. In addition, they were fundamental for other studies aiming at implementing models that simulate the fate and distribution of contaminants and human exposure. In the Augusta Harbor, an integrated approach merged archive information, bathymetry, and high-resolution seismic profiles with the results of an independent tracer (hexachlorobenzene, HCB). This approach helped attribute the presence of high surficial Hg concentrations to resuspension and redistribution of deep sediments caused by dredging and maritime traffic and not to active outfalls. In the Venice Lagoon, an extensive literature search supported analytical results for the correct identification of industrial processes responsible for the contamination by polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in the canals of the Porto Marghera Industrial Area. In addition, sedimentary profiles of PCDD/Fs in local salt marshes (“barene”) recorded well the events relative to the industrial development and management of the area reported by historical documents, confirming their potential for this kind of investigation.

Assessment of PCDD/Fs formation and emission characteristics at a municipal solid waste incinerator for one year

Municipal solid waste incineration (MSWI) has become a predominant emission source of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). Research focusing on the impact of operating conditions, environmental changes, and operating time on the generation and emissions of PCDD/Fs has not been resolved. To this end, this study tracked and investigated the PCDD/Fs and 17 congener emissions of a typical grate incinerator (800 t/d) continuously for one year. Results showed that the PCDD/Fs concentration at the boiler outlet, stack inlet, and bag filter, including normal and abnormal operation conditions, ranges from 2.11E-02–41.86 ng I-TEQ/Nm3, 7.00E-04–6.76 ng I-TEQ/Nm3, and 1.12–2.90E+03 ng I-TEQ/Nm3, respectively. The 2,3,4,7,8-P5CDF has the highest contribution in all samples, in which a proportion of TEQ ranged from 30 % to 77.73 %. Moreover, by applying the correlation analysis between PCDD/Fs and operating parameters, the emission characteristic is mainly affected by incinerators and boilers during the normal period, and it is affected by the whole MSWI process under abnormal conditions. In addition, the PCDD/Fs emission from the MSWI plant gradually increases from spring to winter. This study is beneficial for supporting the control of PCDD/Fs emission reduction and assisting the operators to optimize the relevant operating parameters of the MSWI plant to achieve a stable and up-to-substandard emissions during the operation period.

Footprints in compositions, PCDD/Fs and heavy metals in medical waste fly ash: Large-scale evidence from 17 medical waste thermochemical disposal facilities across China.

Chemical compositions, polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) profiles and heavy metals (HMs) leachability of medical waste fly ash (MWFA) from 17 thermochemical treatment facilities in eight Chinese provinces were first investigated. Large-scale and extended monitoring revealed high chloride and Zn contents and similar PCDD/Fs congener profiles in MWFA. Particularly, the PCDD/Fs and HMs concentrations implied greater toxicity than that observed for municipal solid waste incinerator fly ash (MSWIFA). The maximum international toxic equivalent value of PCDD/Fs in MWFA was 40 times that of MSWIFA, and the leaching concentrations of Zn and Hg were 15 and 4 times those of MSWIFA, respectively. Notably, MWFA characteristics suggest the possibility of recycling and sustainable disposal solutions owing to the high Cl and Zn content with good recovery instead of landfill disposal. Similarities in chemical composition, PCDD/Fs homolog distribution, and water-solubility of chloride salts allows co-processing of MWFA and MSWIFA via water-washing detoxification and thermal treatment, such as that used in cement kilns. This study supplements existing literature on the characteristics and risk management of MWFA.

Formation of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in the electrochemical oxidation of polluted waters with pharmaceuticals used against COVID-19

The COVID-19 pandemic has produced a huge impact on our lives, increasing the consumption of certain pharmaceuticals, and with this, contributing to the intensification of their presence in wastewater and in the environment. This situation demands the implementation of efficient remediation technologies, among them, electrochemical oxidation (ELOX) is one the most applied. This work studies the application of ELOX with the aim of eliminate pharmaceuticals used in the fight against COVID-19, assessing its degradation rate, as well as the risk of formation of toxic trace by-products, such as unintentional POPs like polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). To this end, model solutions containing 10 mg L-1 of dexamethasone (DEX), paracetamol (PAR), amoxicillin (AMX), and sertraline (STR) with two different electrolytes (NaCl and Na2SO4) have been evaluated. However, electrochemical systems that contain chloride ions in solution together with PCDD/Fs precursor molecules may lead to the formation of these highly toxic by-products. So, PCDD/Fs were quantified under conditions of complete degradation of the drugs. Furthermore, the presence of PCDD/Fs precursors such as chlorophenols was determined, as well as the role of Cl-, Cl• and SO4•− radicals in the formation of the by-products and PCDD/Fs. The maximum measured concentration of PCDD/Fs was around 2700 pg L-1 for the amoxicillin case in NaCl medium. The obtained results emphasise the importance of not underestimating the potential formation of these highly toxic trace by-products, in addition to the correct selection of oxidation processes and operation variables, in order to avoid final higher toxicity in the medium.

Polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and furans in imported canned fish in Nigeria and risk assessment

ABSTRACT Concentrations of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) were measured in imported canned fish such as mackerel, sardine and tuna to evaluate the risk relating to human consumption of these products. Gas chromatography-mass spectrometry (GC/MS) was used to evaluate the concentrations of PCBs and PCDD/Fs in the samples. The 28 PCB concentrations in the canned mackerel, tuna and sardine ranged from 0.33 to 9.48 ng g −1, <LOQ to 8.8 ng g−1 and <LOQ to 15.1 ng g−1, respectively, while the 14 PCDD/Fs concentrations varied from 0.06 to 4.70 ng g−1 for mackerel, 0.72 to 9.43 ng g−1 for tuna and not detected to 22.0 ng g −1 for sardines. Health risk analysis suggests that ingestion of these samples could lead to adverse non-carcinogenic and carcinogenic risks over a lifetime.

Multi-omics responses in tree swallow (Tachycineta bicolor) nestlings from the Maumee Area of Concern, Maumee River, Ohio

A multi-omics approach was utilized to identify altered biological responses and functions, and to prioritize contaminants to assess the risks of chemical mixtures in the Maumee Area of Concern (AOC), Maumee River, OH, USA. The Maumee AOC is designated by the United States Environmental Protection Agency as having significant beneficial use impairments, including degradation of fish and wildlife populations, bird or animal deformities or reproduction problems, and loss of fish and wildlife habitat. Tree swallow (Tachycineta bicolor) nestlings were collected at five sites along the Maumee River, which included wastewater treatment plants (WWTPs) and industrial land-use sites. Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo p dioxins and furans (PCDD/Fs), and chlorinated pesticide concentrations were elevated in Maumee tree swallows, relative to a remote reference site, Star Lake, WI, USA. Liver tissue was utilized for non-targeted transcriptome and targeted metabolome evaluation. A significantly differentially expressed gene cluster related to a downregulation in cell growth and cell cycle regulation was identified when comparing all Maumee River sites with the reference site. There was an upregulation of lipogenesis genes, such as PPAR signaling (HMGCS2, SLC22A5), biosynthesis of unsaturated fatty acids (FASN, SCD, ELOVL2, and FADS2), and higher lipogenesis related metabolites, such as docosapentaenoic acid (DPA), docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and arachidonic acid (AA) at two industrial land-use sites, Ironhead and Maumee, relative to WWTP sites (Perrysburg and SideCut), and the reference site. Toledo Water, in the vicinity of the other two industrial sites and also adjacent to a WWTP, showed a mix of signals between industrial land-use and WWTP land-use. PAHs, oxychlordane, and PBDEs were determined to be the most likely causes of the differentiation in biological responses, including de novo lipogenesis and biosynthesis of unsaturated fatty acids.

Determination of polychlorinated dibenzo-p-dioxins and furans in food samples by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) and comparison with gas chromatography-high resolution mass spectrometry (GC-HRMS)

Although gas chromatography–triple quadrupole mass spectrometry (GC-MS/MS) has been applied to the determination of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in various food samples, there is insufficient evidence to evaluate its equivalence with gas chromatography–high resolution mass spectrometry (HRMS). In the present study, two GC-MS/MS instruments with different ion sources (advanced electron ionization [EI] and atmospheric pressure chemical ionization [APCI]) were evaluated for detecting trace levels of PCDD/Fs in various foods. GC-EI-MS/MS and GC-APCI-MS/MS showed good linear relationships for 17 PCDD/Fs (0.01–200 ng/mL, R2 > 0.999), and the relative standard deviations of the relative response factors were 3–18%. The limit of quantitation range of the PCDD/Fs was 0.005–0.101 ng/mL with GC-APCI-MS/MS and 0.006–0.201 ng/mL with GC-EI-MS/MS. The capabilities of the GC-MS/MS methods were evaluated for determination of PCDD/Fs in reference materials and real food samples. Statistical analyses showed that the toxic equivalents (TEQs) were comparable to those obtained with GC-HRMS, and the methods had good sensitivity, repeatability, and reproducibility. No difference was found between the results from the GC-MS/MS techniques and GC-HRMS when the PCDD/Fs concentrations were greater than 10−2 pg/g. The results suggest that when the total TEQ is greater than 0.57 pg TEQ/g (lipid weight) or 0.052 pg TEQ/g (wet weight), GC-MS/MS techniques could be used as a complementary approach to GC-HRMS. Both GC-EI-MS/MS and GC-APCI-MS/MS have similar sensitivity, selectivity, and stability to HRMS and could be used as confirmation methods for the analysis of trace PCDD/Fs in animal foods.

The first German total diet study (BfR MEAL Study) confirms highest levels of dioxins and dioxin-like polychlorinated biphenyls in foods of animal origin.

The first German Total Diet Study, called the BfR MEAL Study, generated a comprehensive dataset of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in foods representative for the consumption habits in households in Germany. PCDD/Fs and dl-PCBs are persistent organic pollutants. Dietary intake is considered to be the most relevant exposure pathway for humans. Levels were examined in 300 foods that were prepared as typically consumed by the population in Germany. Highest PCDD/F and dl-PCB levels were detected in animal-based foods such as fish, butter, dairy products, liver, and meat. The comparison of conventionally and organically produced foods revealed a trend to slightly higher contents in organically produced foods. Sampling discriminated by region and season showed no major differences. Analysed occurrence data will improve future dietary exposure and food safety assessments in Germany.

Dehalobium species implicated in 2,3,7,8-tetrachlorodibenzo-p-dioxin dechlorination in the contaminated sediments of Sydney Harbour Estuary

Polychlorinated dibenzo-p-dioxins and furans (PCDD/F) are some of the most environmentally recalcitrant and toxic compounds. They occur naturally and as by-products of anthropogenic activity. Sydney Harbour Estuary (Sydney, Australia), is heavily contaminated with PCDD/F. Analysis of sediment cores revealed that the contamination source area in Homebush Bay continues to have one of the highest levels of PCDD/F contamination in the world (5207 pg WHO-TEQ g−1) with >50% of the toxicity attributed to 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), the most toxic PCDD/F congener. Comparison of congener profiles at the contamination source area with surrounding bays and historical data provided evidence for the attenuation of 2,3,7,8-TCDD and other congeners at the source area. This finding was supported by the detection of di-, mono- and unchlorinated dibenzo-p-dioxin. Microbial community analysis of sediments by 16S rRNA amplicon sequencing revealed an abundance of lineages from the class Dehalococcoidia (up to 15% of the community), including the genus Dehalobium (up to 0.5%). Anaerobic seawater enrichment cultures using perchloroethene as more biologically available growth substrate enriched the Dehalobium population by more than six-fold. The enrichment culture then proved capable of reductively dechlorinating 2,3,7,8-TCDD to 2,3,7-TriCDD and octachlorodibenzo-p-dibenzodioxin (OCDD) to hepta and hexa congeners. This work is the first to show microbial reductive dehalogenation of 2,3,7,8-TCDD with a bacterium from outside the Dehalococcoides genus, and one of only a few that demonstrates PCDD/F dechlorination in a marine environment.

Heavy metals, PAHs and POPs in recycled polyethylene samples of agricultural, post-commercial, post-industrial and post-consumer origin

In the present work, recycled polyethylene (LDPE) samples of agricultural, post-commercial, post-industrial and post-consumer origin were selected and analysed. The analysis comprised the determination of different contaminants such as metals, polycyclic aromatic hydrocarbons (PAHs), dioxin-like biphenyl polychlorides (PCBs), and polychlorinated-dibenzo-p-dioxins and furans (PCDD/Fs). A comparison with one sample of virgin plastic (unrecycled) was performed. The study aimed at stressing the importance of this type of analysis in recycled plastics. Indeed, such an examination will determine the material’s final destination, and the possible origin of the pollutants analysed is investigated. Black post-industrial and post-consumer samples presented the highest concentration of PCBs and PCDD/Fs, attaining a maximum value of 2.40 pg WHO-TEQ/g, while the least toxic sample (post-commercial) presented a toxicity of 0.38 pg WHO-TEQ/g. PAHs content was also much higher in black samples, reaching 514.41 ng/g, while the lowest concentrations were obtained for the post-commercial plastic sample, which did not exceed 38.98 ng/g. The higher PAHs concentrations in the black samples were related to the carbon black content of the black samples, which was 2.00% for black post-industrial sample and 1.51% for post-consumer sample. The PCDD/Fs congener profile observed in almost all samples was very similar to the profile found in the literature on urban air samples, indicating that the plastic is mainly influenced by the environment. The presence of some metals (mainly copper) showed a slight correlation with PCDD/Fs content. The pollutants analysed were found to be significantly reduced during the cleaning processes that are generally carried out in recycling companies.

Emission levels and phase distributions of PCDD/Fs in a full-scale municipal solid waste incinerator: The impact of wet scrubber system

The emission of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from municipal solid waste (MSW) incinerations will pose serious risk to ecological environment and human health. To further understand the memory effect of wet scrubber system (WSS) on PCDD/Fs emission and phase distribution characteristics, a field study was conducted in a full-scale (850 t d−1) MSW incinerator where a WSS was newly adopted. The four exhaust flue gas samples and the two scrubbing solution samples inside WSS were separately collected for PCDD/Fs analyzing. The results indicated that the memory effect of WSS obviously enhanced the I-TEQ concentration of PCDD/Fs from 0.007 to 0.033 ng I-TEQ Nm−3 after flue gas passed through WSS, owing to increasing the total mass concentration of PCDD/Fs and the proportion of low-chlorinated congeners. The gas-phase PCDD/Fs was dominant (62.5%–88.9%) in flue gas, among which the PCDD/Fs enriched in condensed water notably contributed to nonnegligible proportions of 25.0%–67.6%. The adsorption/desorption process of PCDD/Fs was considered as one of the reasonable mechanisms of memory effect, based on the PCDD/Fs phase distribution and the congeners profile inside the WSS. Besides, the I-TEQ concentration of PCDD/Fs determined in scrubbing solution was up to 50.2 pg I-TEQ L−1, which might be a potential source to cause the enhancement of PCDD/Fs emission. This study verified the enhancement impact of WSS on PCDD/Fs emission and inspired the optimal design of WSS, i.e., choosing more suitable filling materials and timely replacing them to reduce the negative impact of memory effect, keeping WSS operated in relatively stable and consistent conditions, and safely disposing the scrubbing solution to mitigate the secondary pollution of PCDD/Fs.

An experimental simulation study of conventional waste burning practices in India for the assessment and inventorisation of PCDD/F/dl-PCB emissions

The paper reports an update to the polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) annual emission inventory of India from open burning of municipal solid wastes (MSW) through the generation of nation-specific emission factors for air (EFair) and burned residue (EFland) vectors. The MSW characteristics and modes of disposal practiced in Indian cities exhibits subtle variations from that of developed nations due to differences in food habits, living standards and climatic conditions. The annual emission calculations based on EFs from hitherto studies simulating conditions prevailing in developed countries can lead to anomalous accounting of emission levels. It is the first experimental study reported from Indian subcontinent to determine EFs of dioxins and dl-PCBs from MSW open burning by simulated combustion experiments conducted in a custom fabricated Open Burning Test Facility (OBTF) - “Burn Hut”, using real dumpsite waste samples. Iso-kinetic sampling and coning and quartering methods were employed for the sampling of air and land emissions from combustion experiments. The PCDD/F's EFair ranged from 3 to 675 μg toxicity equivalence (TEQ)/ton of waste with a geometric mean (GMair) of 67.0 μgTEQ/ton and EFland ranged from 10 to 2531 μgTEQ/ton waste (GMland – 100.0 μgTEQ/ton). The EFair and EFland of dl-PCBs ranged from 0.5 to 46 μgTEQ/ton (GMair 7.0 μgTEQ/ton) and 0.5 to 96 μgTEQ/ton of waste (GMland 6.0 μgTEQ/ton) respectively. A detailed assessment of correlations between emission and MSW composition/combustion practices were conducted along with a comparative evaluation of EFpresent vis-à-vis EFs reported elsewhere.