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Concept: Persistent organic pollutant

169

Temporal trends of Persistent Organic Pollutants (POPs) measured in Arctic air are essential in understanding long-range transport to remote regions and to evaluate the effectiveness of national and international chemical control initiatives, such as the Stockholm Convention (SC) on POPs. Long-term air monitoring of POPs is conducted under the Arctic Monitoring and Assessment Programme (AMAP) at four Arctic stations: Alert, Canada; Stórhöfði, Iceland; Zeppelin, Svalbard; and Pallas, Finland, since the 1990s using high volume air samplers. Temporal trends observed for POPs in Arctic air are summarized in this study. Most POPs listed for control under the SC, e.g. polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethanes (DDTs) and chlordanes, are declining slowly in Arctic air, reflecting the reduction of primary emissions during the last two decades and increasing importance of secondary emissions. Slow declining trends also signifies their persistence and slow degradation under the Arctic environment, such that they are still detectable after being banned for decades in many countries. Some POPs, e.g. hexachlorobenzene (HCB) and lighter PCBs, showed increasing trends at specific locations, which may be attributable to warming in the region and continued primary emissions at source. Polybrominated diphenyl ethers (PBDEs) do not decline in air at Canada’s Alert station but are declining in European Arctic air, which may be due to influence of local sources at Alert and the much higher historical usage of PBDEs in North America. Arctic air samples are screened for chemicals of emerging concern to provide information regarding their environmental persistence (P) and long-range transport potential (LRTP), which are important criteria for classification as a POP under SC. The AMAP network provides consistent and comparable air monitoring data of POPs for trend development and acts as a bridge between national monitoring programs and SC’s Global Monitoring Plan (GMP).

Concepts: Canada, Norway, Persistent organic pollutant, Arctic Ocean, Polychlorinated biphenyl, Persistent organic pollutants, Biphenyl, Polychlorinated dibenzodioxins

136

Here we report a low-cost synthetic approach for the direct fabrication of large-area Au nanourchin arrays on indium tin oxide (ITO) via a facile galvanic-cell-reaction-driven deposition in an aqueous solution of chloroauric acid and poly(vinyl pyrrolidone) (PVP). The homogeneous Au nanourchins are composed of abundant sharp nanotips, which can served as nanoantennas and increase the local electromagnetic field enhancement dramatically. Finite element theoretical calculations confirm the strong electromagnetic field can be created around the sharp nanotips and located in the nanogaps between adjacent tips of the Au nanourchins. In addition, the interparticle nanogaps between the neighboring Au nanourchins may create additional hotspots, which can induce the higher electromagnetic field intensity. By using rhodamine 6G as a test molecule, the large-area Au nanourchin arrays on ITO exhibit active, uniform, and reproducible surface-enhanced Raman scattering (SERS) effect. To trial their practical application, the Au nanourchin arrays are utilized as SERS substrates to detect 3,3’,4,4’-tetrachlorobiphenyl (PCB-77) one congener of polychlorinated biphenyls (PCBs) as a notorious class of persistent organic pollutants. The characteristic Raman peaks can be still identified when the concentration of PCB-77 is down to 5 × 10−6 M.

Concepts: Photon, Concentration, Chemistry, Indium tin oxide, Indium(III) oxide, Persistent organic pollutant, Polychlorinated biphenyl, Polychlorinated dibenzodioxins

29

It has been speculated that marine microplastics may cause negative effects on benthic marine organisms and increase bioaccumulation of persistent organic pollutants (POPs). Here, we provide the first controlled study of plastic effects on benthic organisms including transfer of POPs. The effects of polystyrene (PS) microplastic on survival, activity, and bodyweight as well as the transfer of 19 polychlorinated biphenyls (PCBs), were assessed in bioassays with Arenicola marina (L.). PS was pre-equilibrated in natively contaminated sediment. A positive relation was observed between microplastic concentration in the sediment and both uptake of plastic particles and weight loss by A. marina. Furthermore, a reduction in feeding activity was observed at a PS dose of 7.4% dry weight (DW). A low PS dose of 0.074% increased bioaccumulation of PCBs by a factor 1.1 - 3.6, an effect that was significant for ΣPCBs and several individual congeners. At higher doses, bioaccumulation decreased compared to the low dose, which however, was only significant for PCB105. PS has statistically significant effects on the organisms' fitness and bioaccumulation, but the magnitude of the effects was not high. This may be different for sites with different plastic concentrations, or plastics with a higher affinity for POPs.

Concepts: Plastic, Persistent organic pollutant, Polychlorinated biphenyl, Persistent organic pollutants, Biomagnification, PCB Congener List, Biphenyl, Polychlorinated dibenzodioxins

28

Maternal exposure to polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) may result in adverse health effects in their children. In Japan in 1968, an accidental human exposure to rice oil contaminated with PCDDs, PCDFs, and PCBs, led to the development of Yusho disease. Yusho mothers delivered descendants with low birth weights and hyperpigmented skin and mucosa, which are characteristic of fetal Yusho disease (FYD). The Yusho cohort was used to evaluate the effect of maternal exposure to PCDDs, PCDFs, and PCBs on the development of FYD. Blood samples, obtained from 64 Yusho mothers (117 descendants: 10 with FYD and 107 without FYD), were analyzed for congeners of seven PCDDs, 10 PCDFs, and four coplanar PCBs. We investigated the association between the maternal estimated blood levels of dioxins at delivery and the risk of fetal Yusho disease. We also studied the differences in dioxin blood levels in 24 mother-descendant pairs (5 with FYD and 19 without FYD). The estimated levels of total PCDD TEQ, total PCDF TEQ, total coplanar PCB TEQ, and total TEQ in the maternal blood at delivery were associated with significantly increased risk of FYD. The odds ratios, which present the risk of FYD for a 10-fold increase in blood dioxin, were largest for 1,2,3,6,7,8-HexaCDD (odds ratio=28.6, 95% confidence interval=1.67-489.9, p=0.02). The levels of 1,2,3,6,7,8-HexaCDD in both the Yusho mothers and their descendants with FYD were higher than the levels in those without FYD. These findings suggest that 1,2,3,6,7,8-HexaCDD is the most important causative congener for the development of FYD.

Concepts: Persistent organic pollutant, Polychlorinated biphenyl, PCB Congener List, Biphenyl, Polychlorinated dibenzodioxins, Chloracne, Aryl hydrocarbon receptor, Low birth weight paradox

28

A fast, simple and efficient technique based on matrix solid phase dispersion has been presented for extraction and clean-up of some chlorinated pesticides and derivative products; α-BHC, β-BHC, γ-BHC, δ-BHC, heptachlor, aldrin, dieldrin, endrin, endosulfan 1, endosulfan 2, 4,4'-DDT, 4,4'-DDE, 4,4'-DDD, heptachlor epoxide, endrin aldehyde, endosulfan sulfate. Box-Behnken response surface methodology was employed for optimization of the extraction efficiency. As the optimized procedure, 0.5g of dried and sieved soil samples were mixed with 2.0g of 10% C18 in silica (w/w) as dispersant and after transferring into the extraction tube they were extracted with 8mL of dichloromethane-n-hexane (1:1, v/v). Gas chromatography with electron capture detector was used for selective and sensitive determination of the analytes. Recoveries for the extraction of the proposed analytes were calculated and were satisfying (more than 75%), except for endrin aldehyde (59%) and endosulfan sulfate (62%). Also the method was linear over the calibration range (R(2)>0.991) and the quantitative results were reasonably reproducible and sensitive (LODs ranged between 0.3 and 1.8ngg(-1)).

Concepts: Fundamental physics concepts, Gas chromatography, Persistent organic pollutant, Insecticide, Organochloride insecticides, Dieldrin, Electron capture detector, Hexachlorocyclopentadiene

27

A new method for rapid determination of 73 target organic environmental contaminants including 18 polychlorinated biphenyls, 16 organochlorinated pesticides, 14 brominated flame retardants and 25 polycyclic aromatic hydrocarbons in fish and fish feed using gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-MS/MS) was developed and validated. GC-MS/MS in electron ionization mode was shown to be a powerful tool for the (ultra)trace analysis of multiclass environmental contaminants in complex matrices, providing measurements with high selectivity and sensitivity. Another positive aspect characterizing the newly developed method is a substantial simplification of the sample preparation, which was achieved by an ethyl acetate QuEChERS (quick, easy, cheap, effective, rugged and safe) based extraction followed by silica minicolumn clean-up. With use of this sample preparation approach the sample laboratory throughput was increased not only because six samples may be prepared in approximately 1 h, but also because all the above-mentioned groups of contaminants can be determined in a single GC-MS/MS run. Under the optimized conditions, the recoveries of all target analytes in both matrices were within the range from 70 to 120 % and the repeatabilities were 20 % or less. The method quantification limits were in the range from 0.005 to 1 μg kg(-1) and from 0.05 to 10 μg kg(-1) for fish muscle tissue and fish feed, respectively. The developed method was successfully applied to the determination of halogenated persistent organic pollutants and polycyclic aromatic hydrocarbons in fish and fish feed samples.

Concepts: Mass spectrometry, Polycyclic aromatic hydrocarbon, Benzene, Flame retardant, Persistent organic pollutant, Polychlorinated biphenyl, Soil contamination, Brominated flame retardant

27

A series of graphene/TiO2 composites were fabricated using a single-step nonionic surfactant strategy combined with the solvothermal treatment technique. Their phase structure, morphology, porosity, optical absorption property, as well as composition and structure, were characterized. The as-prepared composites were successfully applied to degrade aqueous persistent organic pollutants (POPs) such as rhodamine B, aldicarb, and norfloxacin in simulated sunlight (λ>320nm) and visible light (λ>400nm) irradiation. The degradation mechanism and kinetics of aqueous POPs were studied in detail. The mineralization of aqueous POPs and the recyclability of the composites were also tested in the same condition.

Concepts: Photon, Light, Electromagnetic radiation, Chemistry, Persistent organic pollutant, Visible spectrum, Biomagnification

26

Exposure to persistent organic pollutants (POPs) is linked to many chronic diseases, including diabetes and cardiovascular diseases. Among several possible mechanisms are gradual glutathione depletion and mitochondrial dysfunction after chronic exposure to very low doses of POP mixtures. However, it is biologically noteworthy that glutathione status and mitochondrial function is subject to hormesis, defined broadly as mild stress-induced stimulation of cellular protective mechanisms, including increased synthesis of glutathione and promotion of mitochondrial biogenesis. Although high levels of reactive oxygen/nitrogen species (ROS) can cause cellular damage, certain levels of ROS function as signalling molecules to induce hormetic effects. Thus, similar to many other stressors generating ROS, glutathione status and mitochondrial function can be improved at higher POP doses. However, higher POP levels are dangerous despite their hormetic effects due to other adverse phenomena. Also, the persistent nature of POPs can make hormetic effects less effective in humans as hormesis may be the most active with transient stressors. Hormesis-inducing stressors should be placed into three categories for public health purposes: (1) disadvantageous: chemicals like POPs and radiation, that could harm humans by endocrine disruption, action of chemical mixtures and susceptible populations; (2) neutral: cold, heat, and gravity; and (3) advantageous: moderate exercise, phytochemical intake, and calorie restriction. Noting that regulation of POPs, while critical, has provided insufficient protection because POPs persist in human bodies and the food chain, advantageous stressors should be used by the public to mitigate glutathione depletion and mitochondrial dysfunction due to POPs.

Concepts: Medicine, Health, Mitochondrion, Antioxidant, Calorie restriction, Persistent organic pollutant, Radiation hormesis, Hormesis

25

Perfluorooctane sulfonate (PFOS) found extensive use for over 60years up until its restriction in the early 2000s, culminating in its listing under the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2009. Efforts to minimise human body burdens are hindered by uncertainty over their precise origins. While diet appears the principal source for the majority of western populations (with other pathways like dust ingestion, drinking water and inhalation also important contributors); the role played by exposure to PFOS-precursor compounds followed by in vivo metabolism to PFOS as the ultimate highly stable end-product is unclear. Such PFOS-precursor compounds include perfluorooctane sulfonamide derivates, e.g., perfluorooctane sulfonamides (FOSAs) and sulfonamidoethanols (FOSEs). Understanding the indirect contribution of such precursors to human body burdens of PFOS is important as a significant contribution from this pathway would render the margin of safety between the current exposure limits and estimates of external exposure to PFOS alone, narrower than hitherto appreciated. Estimates derived from mathematical modelling studies, put the contribution of so-called “precursor exposure” at between 10% and 40% of total PFOS body burdens. However, there are substantial uncertainties associated with such approaches. This paper reviews current understanding of human exposure to PFOS, with particular reference to recent research highlighting the potential of environmental forensics approaches based on the relative abundance and chiral signatures of branched chain PFOS isomers to provide definitive insights into the role played by “precursor exposure”.

Concepts: Chirality, Persistent organic pollutant, Persistent organic pollutants, Conformational isomerism, Isomer, Perfluorooctanesulfonic acid, Stockholm Convention on Persistent Organic Pollutants, Perfluorooctanesulfonyl fluoride

24

BACKGROUND: In the absence of current cumulative dietary exposure assessments, this analysis was conducted to estimate exposure to multiple dietary contaminants for children, who are more vulnerable to toxic exposure than adults. METHODS: We estimated exposure to multiple food contaminants based on dietary data from preschool-age children (2–4 years, n=207), school-age children (5–7 years, n=157), parents of young children (n=446), and older adults (n=149). We compared exposure estimates for eleven toxic compounds (acrylamide, arsenic, lead, mercury, chlorpyrifos, permethrin, endosulfan, dieldrin, chlordane, DDE, and dioxin) based on self-reported food frequency data by age group. To determine if cancer and non-cancer benchmark levels were exceeded, chemical levels in food were derived from publicly available databases including the Total Diet Study. RESULTS: Cancer benchmark levels were exceeded by all children (100%) for arsenic, dieldrin, DDE, and dioxins. Non-cancer benchmarks were exceeded by >95% of preschool-age children for acrylamide and by 10% of preschool-age children for mercury. Preschool-age children had significantly higher estimated intakes of 6 of 11 compounds compared to school-age children (p<0.0001 to p=0.02). Based on self-reported dietary data, the greatest exposure to pesticides from foods included in this analysis were tomatoes, peaches, apples, peppers, grapes, lettuce, broccoli, strawberries, spinach, dairy, pears, green beans, and celery. CONCLUSIONS: Dietary strategies to reduce exposure to toxic compounds for which cancer and non-cancer benchmarks are exceeded by children vary by compound. These strategies include consuming organically produced dairy and selected fruits and vegetables to reduce pesticide intake, consuming less animal foods (meat, dairy, and fish) to reduce intake of persistent organic pollutants and metals, and consuming lower quantities of chips, cereal, crackers, and other processed carbohydrate foods to reduce acrylamide intake.

Concepts: Nutrition, Pollution, Fruit, Persistent organic pollutant, Insecticide, DDT, Food safety, Polychlorinated dibenzodioxins