Polychlorinated Dibenzo-p-dioxins And Furans Research Articles

Optimizing removal of arsenic, chromium, copper, pentachlorophenol and polychlorodibenzo-dioxins/furans from the 1–4 mm fraction of polluted soil using an attrition process

ABSTRACTThe objective of this study was to evaluate, at a pilot scale, the performance of an attrition process for removing As, Cr, Cu, pentachlorophenol (PCP) and polychlorodibenzodioxins and furans (PCDDF) from a 1-4 mm soil fraction. A Box-Behnken experimental design was utilized to evaluate the influence of several parameters (temperature, surfactant concentration and pulp density) and to optimize the main operating parameters of this attrition process. According to the results, the concentration of surfactant (cocamidopropylbetaine-BW) was the main parameter influencing both PCP and PCDDF removal from the 1-4 mm soil fraction by attrition. The behavior of each 2,3,7,8-PCDD/F congener during the attrition process was studied. The results indicated that the concentration of surfactant had a significant and positive effect on the removal of almost all of the dioxin and furan. The removal of 56%, 55%, 50%, 67% and 62% of the contaminants were obtained for As, Cr, Cu, PCP and PCDDF, respectively, using the optimized conditions ([BW]= 2% (w.w−1), T = 25°C and PD = 40% (w.w−1)). These results showed that attrition in the presence of a surfactant can be efficiently used to remediate the coarse fractions of soil contaminated by As, Cr, Cu, PCP and PCDDF.

Effect of pyrolysis temperature on potential toxicity of biochar if applied to the environment

Biochars have increasingly been used as adsorbents for organic and inorganic contaminants in soils. However, during the carbonization process of pyrolysis, contaminants, including polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dioxins and furans (PCDD/DF) can be generated. In this study, biochars made from sawdust, were prepared at various temperatures ranging from 250 to 700 °C. The Microtox® and rat hepatoma cell line H4IIE-luc assays were used to characterize the general toxic and effects, mediated through the aryl hydrocarbon receptor (AhR), or dioxin-like potencies of organic extracts of biochars. The greatest total concentrations of PAHs (8.6 × 102 μg kg−1) and PCDD/DF (6.1 × 102 pg g−1) were found in biochar generated at 400 °C and 300 °C, respectively. Results of the H4IIE-luc assay, which gives total concentrations of 2,3,7,8-TCDD equivalents (TEQH4IIE-luc), indicated that total potencies of aryl hydrocarbon receptor (AhR) agonists were in decreasing order: 300 °C > 250 °C > 400 °C > 500 °C > 700 °C. The 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQchem) calculated as the sum of products of 16 PAHs and 17 PCDD/DF congers multiplied by their respective relative potencies (RePs) was less than that of TEQH4IIE-luc determined by use of the bioanalytical method, with the H4IIE-luc assay, which measures the total dioxin-like potency of a mixtures. The ratio of TEQchem/TEQH4IIE-luc was in the range of 0.7%–3.8%. Thus, a rather small proportion of the AhR-mediated potencies extracted from biochars were identified by instrumental analyses. Results of the Microtox test showed similar tendencies as those of the H4IIE-luc test, and a linear correlation between EC50 of Microtox test and EC20 of H4IIE-luc test was found. The results demonstrated that biochars produced at higher pyrolysis temperatures (>400 °C) were less toxic and had lower potencies of AhR-mediated effects, which may be more suitable for soil application.

Concentrations and spatial patterns of organic contaminants in tree swallow (Tachycineta bicolor) eggs at United States and binational Great Lakes Areas of Concern, 2010-2015.

Tree swallows, Tachycineta bicolor, were sampled across the Great Lakes basin in 2010 through 2015 to provide a system-wide assessment of current exposure to organic contaminants. The results provide information identified as critical by regulators to assess the "bird or animal deformity or reproductive problems" beneficial use impairment. Eggs were collected from 69 sites across all 5 Great Lakes, including 27 Areas of Concern (AOCs), some with multiple sites, and 10 sites not listed as an AOC. Concentrations of organic contaminants in eggs were quantified and compared with background and reproductive effect thresholds. Approximately 30% of AOCs had geometric mean concentrations of total polychlorinated biphenyls (PCBs) at or below average background exposure (0.34 μg/g wet wt). Exposure to polybrominated diphenyl ethers (PBDEs) was minimal, and only 3 of 27 AOCs and 1 non-AOC had geometric mean concentrations that exceeded background for tree swallows (96 ng/g wet wt). Concentrations of both PCBs and PBDEs were 10 to 20 times below the lower limit associated with impaired hatching success. In contrast, geometric mean concentrations of polychlorinated dibenzo-p-dioxin and furan (PCDD-F) toxic equivalents (TEQs) at the Saginaw River and Bay AOC and Midland, Michigan, USA (a non-AOC site), exceeded the lower limit for hatching effects (181 pg/g PCDD-F TEQs). The rest of the sites had geometric mean concentrations of PCDD-F TEQs below background levels (87 pg/g PCDD-F TEQs). Other organic contaminants, including p,p'-dichlorodiphenyldichloroethylene, mirex, heptachlor, and chlordane, were at or below background or adverse effect concentrations. Environ Toxicol Chem 2016;35:3071-3092. Published 2016 Wiley Periodicals Inc on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

A four-year survey in the farming region of Chile, occurrence and human exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans, and dioxin -like polychlorinated biphenyls in different raw meats

For the first time in South America, a four-year survey (2011–2014) was conducted to assess the occurrence of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in different raw meats (bovine, pork, ovine, chicken, and turkey) sampled from ten of the fifteen regions of Chile. When expressed as pg World Health Organization Toxic Equivalent (WHO-TEQ2005)g−1 fat, the highest PCDD/F values for each species were 0.54 (bovine-2012), 0.27 (pork-2013), 0.23 (ovine-2011), 0.61 (chickens-2013), and 0.34 (turkey-2012). The highest mean dl-PCBs levels were 0.18 (bovine-2011), 0.05 (pork-2014), 0.13 (ovine-2011), 0.1 (chicken-2014), and 0.21 (turkey-2013). Penta- and tetra-chlorinated congeners dominated PCDD/F WHO-TEQ2005 profiles during the survey, while PCB 126 dominated dl-PCBs profiles. Statistically significant interspecies differences were found. Dietary intake was also estimated, and the highest total PCDD/F and dl-PCBs values, found in poultry meat, were 0.09pgWHO-TEQ2005kg−1bwd−1 (2013) for adults and 0.36pgWHO-TEQ2005kg−1bwd−1 (2013) for children. The concentrations and dietary intakes for the studied compounds in raw meat were below international and national maximum permitted limits.

Low temperature destruction of PCDD/Fs over V2O5-CeO2/TiO2 catalyst with ozone.

Catalytic destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans) over V2O5-CeO2/TiO2 catalyst was investigated at a low temperature range of 140-180°C, in the absence and presence of ozone (200ppm). Nano-TiO2 support was used to prepare the catalyst by step impregnation method. A stable PCDD/Fs-generating system was established to support the catalytic destruction tests. In the presence of ozone alone, destruction efficiencies of PCDD/Fs are between 32.2 and 43.1% with temperature increasing from 140 to 180°C. The activity of V2O5-CeO2/TiO2 catalyst alone on PCDD/Fs destruction is also studied. The increase of temperature from 140 to 180°C enhances the activity of catalyst with destruction efficiencies increasing from 54.7 to 73.4%. However, ozone addition greatly enhances the catalytic activity of V2O5-CeO2/TiO2 catalyst on PCDD/Fs decomposition. At 180°C, the destruction efficiency of PCDD/Fs achieved with V2O5-CeO2/TiO2 catalyst and ozone is above 86.0%. It indicates that the combined use of ozone and catalyst reduces the reaction temperature of PCDD/Fs oxidation and offers a new method to destroy PCDD/Fs with high destruction efficiency at a low temperature. Furthermore, the destruction efficiencies of 17 toxic PCDD/F congeners, achieved with ozone alone, catalyst alone, and catalyst/ozone are analyzed.

Development of new transition metal oxide catalysts for the destruction of PCDD/Fs

Various transition metal oxide and vanadium-containing multi-metallic oxide catalysts were developed for the destruction of PCDD/Fs (polychlorinated dibenzo-p-dioxins and furans). A stable PCDD/Fs generating system was installed to support the catalytic destruction tests in this study. Nano-titania supported vanadium catalyst (VOx/TiO2) showed the highest activity, followed by CeOx, MnOx, WOx and finally MoOx. Multi-metallic oxide catalysts, prepared by doping WOx, MoOx, MnOx and CeOx into VOx/TiO2 catalysts, showed different activities on the decomposition of PCDD/Fs. The highest destruction efficiency of 92.5% was observed from the destruction test over VOxCeOx/TiO2 catalyst. However, the addition of WOx and MoOx even played a negative role in multi-metallic VOx/TiO2 catalysts. Characterizations of transition metal oxides and multi-metallic VOx/TiO2 catalysts were also investigated with XRD and TPR. After the catalysts were used, the conversion from high valent metals to low valence states was observed by XPS.

Synergetic inhibition of thermochemical formation of chlorinated aromatics by sulfur and nitrogen derived from thiourea: Multielement characterizations

Nitrogen and sulfur (N/S)-containing compounds inhibit the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in thermal processes. However, few studies have examined the inhibition mechanisms of N/S-containing compounds. In the present study, we focused on thiourea [(NH2)2CS] as such a compound and investigated its inhibition effects and mechanisms. The production of PCDD/Fs, polychlorinated biphenyls (PCBs), and chlorobenzenes (CBzs) were inhibited by >99% in the model fly ash in the presence of 1.0% thiourea after heating at 300°C. Experimental results using real fly ash series were indicative of the thermal destruction of these chlorinated aromatics by thiourea. Multielement characterization using K-edge X-ray absorption fine structures of copper, chlorine, sulfur, nitrogen, and carbon revealed three possible inhibition paths, namely, (a) sulfidization of the copper catalyst to CuS, Cu2S, and CuSO4; (b) blocking the chlorination of carbon via the reaction of chlorine with N-containing compounds to generate ammonium chloride and other minor compounds; and (c) changing the carbon frame involved in attacking the carbon matrix by sulfur and nitrogen. Thus, thiourea plays a role as a sulfur and nitrogen donor to achieve multiple and synergistic inhibition of chlorinated aromatics. Our results suggest that other N/S-containing inhibitors function based on similar mechanisms.

Meeting the European Commission performance criteria for the use of triple quadrupole GC-MS/MS as a confirmatory method for PCDD/Fs and dl-PCBs in food and feed samples.

Until recently, European Union (EU) legislation required the use of high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC-HRMS) based on magnetic sector analyzers as a standard approach for confirmatory analysis of dioxins (PCDDs) and furans (PCDFs) in feed and food. However, recent technological advances in MS instruments enabled other alternative analytical techniques to meet the same analytical criteria as those requested for HRGC-HRMS. In this sense, triple quadrupoles (GC-MS/MS) can be a realistic alternative for the analysis of dioxins. In this work, the performance of GC-MS/MS technology was evaluated against the criteria demanded by the EU for confirmatory analysis of dioxins and PCBs in food and feed. Thus, the study comprises a number of parameters including chromatographic separation, limit of quantification, linearity, repeatability, and ion ratio precision. Analyses of solvent standards as well as sample extracts (inter-calibration extracts and certified reference materials) were also considered within the scope of this study. Additionally, direct comparisons of the results obtained by GC-MS/MS with those from GC-HRMS were made. The results of this work suggested that GC-MS/MS was highly sensitive and selective for confirmatory analysis of PCDD/Fs and related compounds in food and feed samples and meets all the criteria requested by the European Commission.

Influence of trophic ecology on the accumulation of dioxins and furans (PCDD/Fs), non-ortho polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in Mediterranean gulls (Larus michahellis and L. audouinii): A three-isotope approach

The impact of pollution caused by severe anthropogenic pressure in the Mediterranean Sea, an important biodiversity hotspot, requires continuous research efforts. Sources of highly toxic chemicals such as Persistent Organic Pollutants (POPs) are misunderstood in representative Mediterranean species, which limits our capability to establish proper conservation strategies. In the present study, eggs of Audouin's and yellow-legged gulls (Larus audouinii and L. michahellis) were used to investigate the trophic sources, as measured by δ13C, δ15N, and δ34S, of legacy POPs, in particular, polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and non-ortho polychlorinated biphenyls (no-PCBs), as well as recently-regulated POPs, e.g., polybrominated diphenyl ethers (PBDEs). Special attention was paid to the usefulness of rarely-explored δ34S ratios in explaining POP exposure in wildlife, and δ34S was the isotopic ratio that best explained POP variations among gulls in most cases, thus demonstrating its usefulness for understanding POP exposure in wildlife. Significant relationships between stable isotope signatures and POP concentrations revealed increasing levels of no-PCBs and low halogenated PCDD/Fs and PBDEs in Mediterranean gulls as the consumption of marine resources increases. In contrast, highly chlorinated and brominated congeners appeared to preferentially accumulate in gulls feeding primarily on refuse from dump sites and terrestrial food webs. The use of suitable dietary tracers in the study of POPs in yellow-legged gulls revealed the importance of dump sites as a source of POPs in Mediterranean seabirds, which has not previously been reported. In contrast, the preferential accumulation through marine food webs of low chlorinated PCCD/Fs and no-PCBs, which show the highest toxic equivalents factors (TEFs), led to a significantly greater toxicological concern in Audouin's as compared to yellow-legged gulls. Audouin's gull exposure to POPs appears primarily related to the pelagic food webs commonly exploited by fisheries, highlighting the need for further research given the potential impact on human consumption.

Catalytic Decomposition of PCDD/Fs over Nano-TiO2 Based V2O5/CeO2 Catalyst at Low Temperature

ABSTRACTCatalytic decomposition of PCDD/Fs (Polychlorinated dibenzo-p-dioxins and furans) over nano-TiO2 based V2O5/CeO2 catalyst is investigated at 180°C based on a stable PCDD/Fs generating system. Step impregnation method is used to prepare the powder catalyst, and catalyst characterization is conducted by XRD and TPR. Effects of oxygen, water vapour and sulphur dioxide on PCDD/Fs destruction are studied in terms of destruction efficiency. Oxygen plays a positive role on PCDD/Fs destruction by accelerating the conversion of V4+Ox and V5+Ox, Ce3+Ox and Ce4+Ox. The destruction efficiencies of PCDD/Fs increase from 67.6% to 77.8% with oxygen contents increasing from 11 vol.% to 21 vol.%. In the absence of oxygen, PCDD/Fs can still be destroyed with destruction efficiency of 33.7% due to the lattice oxygen atoms stored by V2O5 and CeO2. Water vapour negatively affects the destruction of PCDD/Fs by competitive adsorption. On the other hand, negative destruction efficiencies of TCDD and TCDF are observed in the presence of water, and the values become lower with water vapour contents increasing. This result demonstrates water vapour facilitates the removal of Cl- present on the catalyst surface. SO2 inhibits the activity of catalyst by poisoning active sites of catalyst. With SO2 concentration increasing from 0 to 100 ppm, destruction efficiencies of PCDD/Fs significantly decrease from 67.6% to 51.9%. Finally, catalyst regeneration is also investigated at 180°C in the presence of oxygen. Most of PCDD/Fs residues in the catalyst will be destroyed, and catalyst is regenerated without PCDD/Fs contaminated.

Potential impact on food safety and food security from persistent organic pollutants in top soil improvers on Mediterranean pasture

The organic carbon of biosolids from civil wastewater treatment plants binds persistent organic pollutants (POPs), such as polychlorodibenzo -dioxins and -furans (PCDD/Fs), dioxin and non-dioxin -like polychlorobiphenyls (DL and NDL-PCBs), polybrominated diphenyl ethers (PBDEs), and perfluorooctane sulfonic acid (PFOS). The use of such biosolids, derived digestates and composts as top soil improvers (TSIs) may transfer POPs into the food chain. We evaluated the potential carry-over of main bioavailable congeners from amended soil-to-milk of extensive farmed sheep. Such estimates were compared with regulatory limits (food security) and human intakes (food safety). The prediction model was based on farming practices, flocks soil intake, POPs toxicokinetics, and dairy products intake in children, of the Mediterranean area. TSI contamination ranged between 0.20–113ngWHO-TEQ/kg dry matter for PCDD/Fs and DL-PCBs (N=56), 3.40–616μg/kg for ∑6 NDL-PCBs (N=38), 0.06–17.2 and 0.12–22.3μg/kg for BDE no. 47 and no. 99, 0.872–89.50μg/kg for PFOS (N=27). For a 360g/head/day soil intake of a sheep with an average milk yield of 2.0kg at 6.5% of fat percentage, estimated soil quality standards supporting milk safety and security were 0.75 and 4.0ngWHO-TEQ/kg for PCDD/Fs and DL-PCBs, and 3.75 and 29.2μg/kg for ∑6 NDL-PCBs, respectively. The possibility to use low-contaminated TSIs to maximize agriculture benefits and if the case, to progressively mitigate highly contaminated soils is discussed.

Declining Dioxin Concentrations in the Rhone River Basin, France, Attest to the Effectiveness of Emissions Controls.

Emission-control policies have been implemented in Europe and North America since the 1990s for polychlorodibenzodioxins (PCDDs) and furans (PCDFs). To assess the effect of these policies on temporal trends and spatial patterns for these compounds in a large European river system, sediment cores were collected in seven depositional areas along the Rhone River in France, dated, and analyzed for PCDDs and PCDFs. Results show concentrations increase in the downstream direction and have decreased temporally at all sites during the last two decades, with an average decrease of 83% from 1992 to 2010. The time for a 50% decrease in concentrations (t1/2) averaged 6.9±2.6 and 9.1±2.9 years for the sum of measured PCDDs and PCDFs, respectively. Congener patterns are similar among cores and indicate dominance of regional atmospheric deposition and possibly weathered local sources. Local sources are clearly indicated at the most downstream site, where concentrations of the most toxic dioxin, TCDD, are about 2 orders of magnitude higher than at the other six sites. The relatively steep downward trends attest to the effects of the dioxin emissions reduction policy in Europe and suggest that risks posed to aquatic life in the Rhone River basin from dioxins and furans have been greatly reduced.

Association between levels of persistent organic pollutants in adipose tissue and cryptorchidism in early childhood: a case-control study.

BackgroundCongenital cryptorchidism, i.e. failure of the testicular descent to the bottom of the scrotum, is a common birth defect. The evidence from epidemiological, wildlife, and animal studies suggests that exposure to mixtures of endocrine disrupting chemicals during fetal development may play a role in its pathogenesis. We aimed to assess the association between cryptorchidism and prenatal exposure to polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), and polybrominated diphenyl ethers (PBDEs).MethodsWe conducted a case–control study consisting of 44 cryptorchid cases, and 38 controls operated for inguinal hernia, umbilical hernia, or hydrocele at the Turku University Hospital or Rigshospitalet, Copenhagen in 2002–2006. During the operation a subcutaneous adipose tissue biopsy was taken. Samples were analysed for 37 PCBs, 17 PCDD/Fs and 14 PBDEs by gas chromatography-high-resolution mass spectrometry. Chemical concentrations were adjusted for postnatal variation introduced by differences in duration of breastfeeding, age at the operation, and country of origin with a multiple linear regression. Association between adjusted and unadjusted chemical concentrations and the risk of cryptorchidism were analysed with logistic regression to get an estimate for odds ratio (OR) of cryptorchidism per multiplication of chemical concentrations with ca. 2.71 (Napier’s constant).ResultsTotal-TEq i.e. the WHO-recommended 2,3,7,8-TCDD equivalent quantity of 17 dioxins and 12 dioxin-like PCBs and sum of PCDD/Fs were positively associated with cryptorchidism [OR 3.21 (95 % CI 1.29–9.09), OR 3.69 (95 % CI 1.45–10.9), respectively], when adjusting for country of origin, the duration the child was breastfed, and age at operation. The association between the sum of PCBs and cryptorchidism was close to significant [OR 1.92 (95 % CI 0.98–4.01)], whereas the association between the sum of PBDEs and cryptorchidism was not [OR 0.86 (95 % CI 0.47–1.54)]. There were no associations between unadjusted chemical concentrations and the risk of cryptorchidism.ConclusionsPrenatal exposure to PCDD/Fs and PCDD/F-like PCBs may be associated with increased risk for cryptorchidism. Our finding does not exclude the possibility of an association between the exposure to PBDEs and cryptorchidism.Electronic supplementary materialThe online version of this article (doi:10.1186/s12940-015-0065-0) contains supplementary material, which is available to authorized users.

Oceanic Sink and Biogeochemical Controls on the Accumulation of Polychlorinated Dibenzo-p-dioxins, Dibenzofurans, and Biphenyls in Plankton.

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were measured in plankton samples from the Atlantic, Pacific, and Indian Oceans collected during the Malaspina circumnavigation cruise. The concentrations of PCDD/Fs and dl-PCBs in plankton averaged 14 and 240 pg gdw(-1), respectively, but concentrations were highly variable. The global distribution of PCDD/Fs and dl-PCBs was not driven by proximity to continents but significantly correlated with plankton biomass, with higher plankton phase PCDD/F and dl-PCB concentrations at lower biomass. These trends are consistent with the interactions between atmospheric deposition, biomass dilution, and settling fluxes of organic matter in the water column (biological pump), as key processes driving POPs plankton phase concentrations in the global oceans. The application of a model of the air-water-plankton diffusive exchange reproduces in part the influence of biomass on plankton phase concentrations and suggests future modeling priorities. The estimated oceanic sink (Atlantic, Pacific, and Indian Oceans) due to settling fluxes of organic matter bound PCDD/Fs and dl-PCBs is of 400 and 10,500 kg y(-1), respectively. The atmospheric inputs due to gross diffusive absorption and dry deposition are nearly 3 and 10 times larger for PCDD/Fs and dl-PCBs, respectively, than the oceanic sink. These observations suggest that the coupling of atmospheric deposition with water column cycling supports and drives the accumulation of dl-PCBs and PCDD/Fs in plankton from the global oligotrophic oceans.

Microbial dechlorination of polychlorinated biphenyls, dibenzo-p-dioxins, and -furans at the Portland Harbor Superfund site, Oregon, USA.

The Portland Harbor (Oregon, USA) has been declared a "Superfund" site because it is impacted by a variety of contaminants, including polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs). Using data collected in the remedial investigation, concentrations of PCBs and PCDD/Fs in sediment and water were examined using positive matrix factorization to look for evidence that PCBs and PCDD/Fs are dechlorinated by anaerobic bacteria. This process has long been known to occur in sediments. Recently, it has been recognized that PCB and PCDD/F dechlorination may also occur in other anaerobic environments, such as in landfills, sewers, and groundwater. The results indicate that a factor related to the dechlorination of PCBs and PCDD/Fs was present in the water but not in the sediment. Spatial patterns in dechlorination products suggest that they come primarily from groundwater. Dechlorination products comprise 22% of the PCBs in the water. The Portland Harbor therefore represents the third major US watershed in which PCBs appear to undergo dechlorination in an environment other than sediment, suggesting that the microbial dechlorination of PCBs and PCDD/Fs is more common than previously assumed. In addition, the Portland Harbor is impacted by PCBs generated inadvertently during the production of pigments, such as PCB 11, which alone exceeded the 64 pg/L federal water quality standard for the sum of PCBs in two of 120 whole water samples.

Temporal trends in the levels of polychlorinated dioxins, -furans, -biphenyls and polybrominated diethyl ethers in bank voles in Northern Finland

Dioxin-like chemicals and brominated flame retardants are ubiquitous in the environment, despite the introduction of international prohibitions and restrictions. These chemicals do not remain in the vicinity of their source, instead they can be transported over long distances, in fact even to pristine areas in the northern latitudes. However, there have been rather few time series experiments monitoring the trends in the levels of chlorinated and brominated forms of these chemicals in the environment. In this study, the concentrations of polychlorinated dibenzo-p-dioxins and -furans (PCDDs/Fs), polychlorinated biphenyls (PCBs) and polybrominated diethyl ethers (PBDEs) were measured in the liver and muscle of bank voles (Myodes glareolus) caught in a remote area in Finnish Lapland during 1986–2007. Five time points were selected: years 1986, 1992, 1998, 2003 and 2007. The levels of PCDDs/Fs and PCBs declined from 1986 until 2003 in both females and males, but tended to increase again in 2007. The peak levels of the most abundant PBDE congeners (PBDEs 47, 99, 100 and 153) were measured in 1998 and 2003. These results reveal that the levels of dioxin-like chemicals remain high also in rural areas in Lapland, whereas the concentrations of brominated flame retardants decreased and follow the current restriction prohibitions.

Chemical conversion pathways and kinetic modeling for the OH-initiated reaction of triclosan in gas-phase.

As a widely used antimicrobial additive in daily consumption, attention has been paid to the degradation and conversion of triclosan for a long time. The quantum chemistry calculation and the canonical variational transition state theory are employed to investigate the mechanism and kinetic property. Besides addition and abstraction, oxidation pathways and further conversion pathways are also considered. The OH radicals could degrade triclosan to phenols, aldehydes, and other easily degradable substances. The conversion mechanisms of triclosan to the polychlorinated dibenzopdioxin and furan (PCDD/Fs) and polychlorinated biphenyls (PCBs) are clearly illustrated and the toxicity would be strengthened in such pathways. Single radical and diradical pathways are compared to study the conversion mechanism of dichlorodibenzo dioxin (DCDD). Furthermore, thermochemistry is discussed in detail. Kinetic property is calculated and the consequent ratio of kadd/ktotal and kabs/ktotal at 298.15 K are 0.955 and 0.045, respectively. Thus, the OH radical addition reactions are predominant, the substitute position of OH radical on triclosan is very important to generate PCDD and furan, and biradical is also a vital intermediate to produce dioxin.

Contrasting effects of sulfur dioxide on cupric oxide and chloride during thermochemical formation of chlorinated aromatics.

Sulfur dioxide (SO2) gas has been reported to be an inhibitor of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) formation in fly ash. However, other research has suggested little or no inhibitory effect of SO2 gas. Although these studies focused on reactions between SO2 gas and gas-phase chlorine (Cl) species, no attention was paid to thermochemical gas-solid reactions. In this study, we found contrasting effects of SO2 gas depending on the chemical form of copper (CuO vs CuCl2) with a solid-phase inorganic Cl source (KCl). Chlorinated aromatics (PCDD/Fs, polychlorinated biphenyls, and chlorobenzenes) increased and decreased in model fly ash containing CuO + KCl and CuCl2 + KCl, respectively, with increased SO2 injection. According to in situ Cu K-edge and S K-edge X-ray absorption spectroscopy, Cl gas and CuCl2 were generated and then promoted the formation of highly chlorinated aromatics after thermochemical reactions of SO2 gas with the solid-phase CuO + KCl system. In contrast, the decrease in aromatic-Cls in a CuCl2 + KCl system with SO2 gas was caused mainly by the partial sulfation of the Cu. The chemical form of Cu (especially the oxide/chloride ratio) may be a critical factor in controlling the formation of chlorinated aromatics using SO2 gas.

Congener profiles and source-wise phase partitioning analysis of PCDDs/Fs and PCBs in Gyeonggi-do ambient air, South Korea.

The atmospheric concentrations and gas–particle partitioning of polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs) and polychlorinated biphenyls (PCBs) were investigated at two sites (Suwon and Ansan) in Gyeonggi-do, a heavily industrialized area of Korea, during the year 2010. The sum level (Σ17) of PCDDs/Fs and dioxin-like PCBs (dl-PCBs) in the ambient air at Suwon and Ansan ranged from 0.04 to 0.30 pg-TEQ·m−3 (geometric mean: 0.09 pg-TEQ·m−3) and 0.17 to 0.63 pg-TEQ·m−3 (geometric mean: 0.36 pg-TEQ·m−3), respectively. Moreover, the geometric mean concentrations of Σ180 PCBs at Suwon and Ansan were 233.6 pg·m−3 and 274.2 pg·m−3, respectively, and di-chlorinated biphenyls and tri-chlorinated biphenyls were the predominant homologs. Among the PCB congeners, 3,3'-dichlorobiphenyl (PCB-11) was the dominant species at both sites during all sampling periods, comprising up to 15.1% of Σ180 PCBs at Ansan and 24.6% at Suwon. We evaluated their gas-to-particle equilibriums by conducting regression between the particle–gas partition coefficient Kp (m3·ug−1) and the corresponding subcooled liquid vapor pressure (PL°). The slope (m) values for log–log plots of Kp vs. PL° were steeper in industrial areas owing to local source proximity. Moreover, owing to enhanced emissions from combustion-related sources at low temperatures, PCDD/Fs exhibited the largest deviation from the regression line of the particle–gas partition coefficient. Incinerators were found to be the primary emission source of atmospheric PCDDs/Fs, whereas re-evaporation from pre-existing environmental loads (e.g., storage areas or spilled soil and water bodies) was the dominant source for PCBs.

The influence of low level pre- and perinatal exposure to PCDD/Fs, PCBs, and lead on attention performance and attention-related behavior among German school-aged children: results from the Duisburg Birth Cohort Study.

Prenatal exposure to polychlorinated biphenyls (PCBs) and lead are thought to be risk factors for attention-deficit hyperactivity disorder (ADHD), whereas the prenatal influence of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs) on attention performance has been less studied. Within the Duisburg Birth Cohort Study, we investigated low-level exposure to these compounds in relation to children's attention. We measured blood levels of PCDD/Fs, PCBs and lead from pregnant mothers (32(nd) week of pregnancy) and PCDD/Fs and PCBs in breast milk (2 weeks after delivery). The attention of school-aged children (N=117) was investigated with a computer-based test battery of attention performance (KITAP) and a parent rating questionnaire of behaviors related to ADHD (FBB-ADHS). Influences of the exposure on attention were analyzed by multiple regression analyses. Increasing prenatal PCDD/F and PCB concentrations were significantly (p<0.05) associated with a higher number of omission errors in the subtest Divided Attention (47% and 42%; 95% confidence intervals (95%-CI): 1.08-2.00 and 1.07-1.89, respectively). Prenatal lead concentrations had few significant associations with attention performance (e.g., a 23% higher number of omission errors in the subtest Distractibility; 95%-CI: 1.00-1.51), whereas ADHD-related behavior (questionnaire based) was increased with increasing lead exposure (Overall-ADHD: 9%; 95%-CI: 1.01-1.17). ADHD-related behavior was negatively associated with prenatal PCDD/F or PCB exposures (e.g., for PCB exposure: -10%; 95%-CI: 0.82-0.99). Pre- and perinatal PCDD/F and PCB exposure may have subtle influences on attention performance in healthy children at low environmental levels, while behavior changes are negatively associated. Furthermore, we provide additional evidence for the impact of prenatal lead exposure on attention deficits.