Dioxin and Related Compound Detection: Perspectives for Optical Monitoring.

Dioxins and related compounds are environmental xenobiotics that are dangerous to human life, due to the accumulation and persistence in the environment and in the food chain. Cancer, reproductive and developmental issues, and damage to the immune system and endocrine system are only a few examples of the impact of such substances in everyday life. For these reasons, it is fundamental to detect and monitor these molecules in biological samples. The consolidated technique for analytical evaluation is gas chromatography combined with high-resolution mass spectrometry. Nowadays, the development of mid-infrared optical components like broadband laser sources, optical frequency combs, high performance Fourier-transform infrared spectroscopy, and plasmonic sensors open the way to new techniques for detection and real time monitoring of these organic pollutants in gaseous or liquid phase, with sufficient sensitivity and selectivity, and in short time periods. In this review, we report the latest techniques for the detection of dioxins, furans and related compounds based on optical and spectroscopic methods, looking at future perspectives.

Atmospheric concentrations and potential sources of dioxin-like contaminants to Acadia National Park.

Acadia National Park (ANP) is located on Mt. Desert Island, ME on the U.S. Atlantic coast. ANP is routinely a top-ten most popular National Park with over four million visits in 2022. The overall contribution and negative effects of long-range atmospheric transport and local sources of dioxin-like contaminants endangering natural and wildlife resources is unknown. Dioxin-like (DL) contaminants polychlorinated dibenzo-p-dioxins (∑PCDD) and polychlorinated dibenzofurans (∑PCDF), non-ortho coplanar PCBs (∑CP4), and polychlorinated naphthalenes (∑PCNs) were measured at the McFarland Hill air monitoring station (44.37°N, 68.26°W). On a mass/volume basis, total PCNs averaged 90.9 % (788 fg/m3) of DL contaminants measured annually, with 92.9 % of the collected total in the vapor-phase. Alternatively, total dioxin/furans (∑PCDD/Fs) represented 71.6 % of the total toxic equivalence (∑TEQ) (1.018 fg-TEQ/m3), with 69.7 % in the particulate-phase. Maximum concentrations measured for individual sampling events for ∑PCDD/F, ∑CP4, and ∑PCN were 159 (winter), 139 (summer), and 2100 (autumn), fg/m3 respectively. Whereas the maximum ∑TEQ concentrations for individual sampling events for ∑PCDD/F, ∑CP4, and ∑PCN were 2.8 (autumn), 0.38 (summer), and 0.71 (autumn), fg-TEQ/m3 respectively. Pearson correlations were calculated for ∑PCDD/Fs and ∑PCN particulate/vapor-phase air concentrations and PM2.5 wood smoke "indicator" species. The most significant correlations were observed in autumn for particulate-phase ∑PCDD/Fs suggesting a relationship between visitation-generated combustion sources (campfires and/or waste burning) or climate-change mediated forest fires. Significant Clausius-Clapeyron (C-C) correlations observed for particulate-phase ∑PCDDs (r2 = 0.567) as ambient temperatures decreased suggests a connection between localized domestic heating sources or visitor-based burning of wood/trash resources. Alternatively, highly significant C-C vapor-phase ∑CP4-PCBs correlations (r2 = 0.815) implies that the majority of ∑CP4-PCB loading to ANP is from long-range atmospheric transport processes. Based on these findings, Acadia National Park should be classified as a remote site with minor depositional impacts from ∑PCDD/Fs, ∑CP4-PCBs, and ∑PCN atmospheric transport or local diffuse sources.

A clean-up method for determination of multi-classes of persistent organic pollutants in sediment and biota samples with an aliquot sample.

In the present study, we developed a novel method to simultaneously detect eight classes of persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), polychlorinated naphthalenes (PCNs), organochlorine pesticides (OCPs), short-chain chlorinated paraffins (SCCPs) and Dechlorane Plus (DP), in sediment and fish tissue samples. The samples were extracted by accelerated solvent extraction (ASE) system, and the extracts were purified and fractionated into fraction1 and fraction2 with multi-layer silica gel column, followed by further fractionation using a basic alumina column (fraction1) and a Florisil column (fraction2), respectively. Finally, fractions were analyzed with different chromatographic columns and different detectors according to the properties of a chemical compound. The limit of detection for eight classes of POPs ranged from 1 to 30 pg/gdw in fish tissue samples, and from 1 to 33 pg/gdw in sediment samples, except for SCCPs (from 5.6 to 7.6 ng/g in fish tissue samples, and from 1.2 to 8.3 ng/gdw in sediment samples). The recoveries of eight classes of POPs spiked in fish tissue and sediment samples ranged from 43% to 120%, and from 45% to 115%, respectively. The relative standard deviation (RSD) was less than 25%. The accuracy of method was satisfactorily demonstrated by analysis of standard reference materials NIST SRM 1649b and WMF-01. In addition, the newly developed method was successfully applied for analysis of sediment and fish samples collected from the Baiyangdian Lake.

Occurrence and spatial distribution of chemical contaminants in edible fish species collected from UK and proximate marine waters.

The occurrence of a range of regulated and emerging organic environmental contaminants was investigated in 182 samples of edible marine fish sampled mainly from UK marine regions, but extending northerly to the coast of Norway and south to the Algarve. These species (sprats, mackerel, turbot, halibut, herring, grey mullet, sea bass, grey mullet, sardines, etc.) are among those considered to be at the highest risk of contamination with regulated contaminants such as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs, dioxins), and polychlorinated biphenyls (PCBs), but the occurrence of polybrominated diphenylethers (PBDEs) and polybrominated biphenyls (PBBs) was also investigated. Sub-sets of samples (50-75) were also analysed for emerging contaminants: polychlorinated naphthalenes (PCNs), polybrominated and mixed halogenated dibenzo-p-dioxins, dibenzofurans and biphenyls (PBDD/Fs, PXDD/Fs and PXBs) and perfluoroalkyl substances (PFAS). Contaminant occurrence varied with species and location, but all measured contaminants were detected, with sprats, sea bass, sardines, mackerel, and herring showing higher tissue concentrations. The concentrations of the different contaminants in the various samples were mapped utilising the GPS coordinate data of the capture locations to visualise spatial distribution levels. In terms of catch location, fish sampled from the coasts of southern Britain, north-western France and the Irish Sea appeared to contain proportionately higher levels of some contaminants - e.g. samples from the Irish Sea tended to show higher PCN concentrations, whereas higher levels of PCBs were observed in some fish sampled off the coasts of northern France. Similarly, samples of mullet from the southeast coast of UK showed much higher concentrations of BDE-99 than the other regions. In terms of occurrence trends, PCDD/F and PCB concentrations show a modest decline over the last decade but where limited background data is available for emerging contaminants, there is no evidence of downward trends.

PCDD/F and dioxin-like PCB minimization: A 13-year experimental study along the flue gas cleaning system of a secondary aluminium refining plant.

A 13-years study shows that a careful design of the flue gas cleaning system of a full scale secondary aluminium refining plant results in a minimized and very stable emission of Polychlorinated Dibenzo-p-Dioxins (PCDD), Polychlorinated Dibenzo Furans (PCDF) and dioxin-like Polychlorinated Biphenyls (PCB). The value of equivalent toxicity of PCDD/F in the emission was definitely of an order of magnitude less than the regulation limit. In the initial flue gas cleaning system, the PCB mean fingerprint after the slow cooling of the flue gas was typical of de novo synthesis. Instead, in the presence of quenching, there was evidence that the fast cooling of flue gas prevented the PCB de novo synthesis. In fact, the PCB profile was similar to that in the air collected from the aspiration hoods for the quenching. The gas-phase and solid-phase partitioning of PCBs, before and after the fabric filters, highlights the predominant role of the vapor phase with respect to the total removal efficiency. The polycyclic aromatic hydrocarbons breakdown could be an additional de novo formation pathway even in industrial plants.

Emissions of PCDD/Fs, PBDD/Fs, dioxin like-PCBs and PAHs from a cement plant using a long-term monitoring system.

The aim of the present work was to assess the emission of different persistent organic pollutants from a cement plant over a period of one year, under normal operational conditions. Thus, a long-term sampling device was installed in the clinker kiln stack of the cement plant. The factory uses petroleum coke as primary fuel, but also alternative fuels such as solid recovered fuel (SRF), automotive shredder residue (ASR), sewage sludge, waste tires, and meat and bone meal (MBM) wastes, with an energy substitution level of about 40%. Both PCDD/Fs (together with dl-PCBs) and PBDD/Fs were continuously sampled, with a total of ten samples collected in 2-4week periods. Also, PAHs were sampled during one-week periods, in order to evaluate their emissions in three different samples. The emission levels throughout the year were much lower than the set legal limits in all substances, being <10pgI-TEQ/Nm(3) in the case of PCDD/Fs. The data obtained allowed calculation of updated emission factors for the cement sector, which were 8.5ng I-TEQ/ton clinker for PCDD/Fs and 3.2ng WHO-TEQ/ton clinker for PCBs. With respect to the congener distribution, 2,3,7,8-TCDF accounts for 60 to 68% of the total toxicity for PCDD/Fs, and in PBDD/F emissions, a clear predominance of octa-substituted species (both dioxin and furan) was found.

PCDD, PCDF, dl-PCB and organochlorine pesticides monitoring in São Paulo City using passive air sampler as part of the Global Monitoring Plan.

The persistent organic pollutants (POPs), such as organochlorine pesticides and PCBs, are ordinarily monitored in the aquatic environment or in soil in the environmental quality monitoring programs in São Paulo, Brazil. One of the core matrices proposed in the POPs Global Monitoring Plan (GMP) from the Stockholm Convention list is the ambient air, which is not a usual matrix for POPs monitoring in the country. In this study POP levels were evaluated in the air samples from an urban site in São Paulo City over five years, starting in 2010 as a capacity building project for Latin America and the Caribbean region for POP monitoring in ambient air using passive samplers. Furthermore, after the end of the Project in 2012, the monitoring continued in the same sampling site as means to improving the analytical capacity building and contribute to the GMP data. The POPs monitored were 17 congeners of 2,3,7,8 chloro-substituted PCDDs and PCDFs, dioxin-like PCBs, indicator PCBs, organochlorine pesticides and toxaphene. The results show a slight decrease in PCDD/F, dl-PCBs and indicator PCBs levels along the five years. The organochlorine pesticide endosulfan was present at its highest concentration at the beginning of the monitoring period, but it was below detection level in the last year of the monitoring. Some other organochlorine pesticides were detected close to or below quantitation limits. The compounds identified were dieldrin, chlordane, α-HCH, γ-HCH, heptachlor, heptachlor epoxide, hexachlorobenzene and DDTs. Toxaphene congeners were not detected. These results have confirmed the efficacy of passive sampling for POP monitoring and the capacity building for POP analysis and monitoring was established. However more needs to be done, including expansion of sampling sites, new POPs and studies on sampling rates to be considered in calculating the concentration of POPs in ambient air using a passive sampler.