Long-range Transport Potential Research Articles

Dissolved Organophosphate Esters and Polybrominated Diphenyl Ethers in Remote Marine Environments: Arctic Surface Water Distributions and Net Transport through Fram Strait.

Organophosphate esters (OPEs) have been found in remote environments at unexpectedly high concentrations, but very few measurements of OPE concentrations in seawater are available, and none are available in subsurface seawater. In this study, passive polyethylene samplers (PEs) deployed on deep-water moorings in the Fram Strait and in surface waters of Canadian Arctic lakes and coastal sites were analyzed for a suite of common OPEs. Total OPEs ( ∑11OPE) at deep-water sites were dominated by chlorinated OPEs, and ranged from 6.3 to 440 pg/L. Concentrations were similar in eastern and western Fram Strait. Chlorinated OPEs were also dominant in Canadian Arctic surface waters (mean concentration ranged from < DL to 4400 pg/L), while nonhalogenated alkyl/aryl-substituted OPEs remained low (1.3-55 pg/L), possibly due to the greater long-range transport potential of chlorinated OPEs. Polybrominated diphenyl ethers (PBDEs) were found at much lower concentrations than OPEs (<DL-14 pg/L). Surface-water concentrations of tris(2-chloroethyl) phosphate (TCEP) and tris(1,3-dichloroisopropyl) phosphate (TDCIPP) were similar for both active and passive sampling approaches. Several OPEs were estimated to be undergoing net transport out of the Arctic, ranging from 17 kg/yr for ethylhexyldiphenylphosphate (EHDPP) to 3400 kg/yr for tris (2-chloroisopropyl) phosphate (TCIPP). This study highlights the importance of OPEs as poorly understood contaminants present at unexpectedly high concentrations in remote marine environments.

Estimation of physicochemical properties of 2-ethylhexyl-4-methoxycinnamate (EHMC) degradation products and their toxicological evaluation

The organic UV filters, commonly used in personal protection products, are of concern because of their potential risk to aquatic ecosystems and living organisms. One of UV filters is ethylhexyl-4-methoxycinnamate (EHMC) acid. Studies have shown that, in the presence of oxidizing and chlorinating factors, EHMC forms a series of products with different properties than the substrate. In this study, the toxicities of EHMC and its transformation/degradation products formed under the influence of NaOCl/UV and H2O2/UV systems in the water medium were tested using Microtox® bioassay and by observation of mortality of juvenile crustaceans Daphnia magna and Artemia Salina. We have observed that oxidation and chlorination products of EHMC show significantly higher toxicity than EHMC alone. The toxicity of chemicals is related to their physicochemical characteristic such as lipophilicity and substituent groups. With the increase in lipophilicity of products, expressed as log KOW, the toxicity (EC50) increases. On the basis of physicochemical properties such as vapour pressure (VP), solubility (S), octanol-water partition coefficient (KOW), bioconcentration factor (BCF) and half-lives, the overall persistence (POV) and long-range transport potential (LRTP) of all the products and EHMC were calculated. It was shown that the most persistent and traveling on the long distances in environment are methoxyphenol chloroderivatives, then methoxybenzene chloroderivatives, EHMC chloroderivatives, methoxybenzaldehyde chloroderivatives and methoxycinnamate acid chloroderivatives. These compounds are also characterised by high toxicity.

Atmospheric organochlorine pesticides and polychlorinated biphenyls in urban areas of Nepal: spatial variation, sources, temporal trends, and long-range transport potential

Abstract. The study of persistent organic pollutants (POPs) in low-latitude tropical and subtropical urban cities is necessary to assess their local and global impacts on ecosystems and human health. Despite studies on levels of POPs in water, soils, and sediments, analysis of the distribution patterns, seasonality, and sources of POPs in urban regions of Nepal remain limited. Polyurethane foam (PUF)-based passive air samplers were deployed in three major cities in Nepal: Kathmandu (the capital city), Pokhara, and Hetauda (agricultural cities). Dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) were the dominant organochlorine pesticides in the atmosphere at all sites. The average concentrations of POPs were ∑ DDTs, 8.7–1.0 × 103 pg m−3; ∑ HCHs, 5.3–3.3 × 103 pg m−3; HCB, 5.8–3.4 × 102 pg m−3; ∑ endosulfan, BDL–51 pg m−3; and ∑ 6PCBs, 1.4–47 pg m−3. Isomer and metabolite ratio analyses suggested that the concentrations present were from both new and historical applications of the POPs. Vegetable production sites and their market places appeared to be the major DDT and HCH source areas. Higher atmospheric concentrations of DDT and HCH occurred during the pre-monsoon and monsoon seasons, and winter, respectively, closely associated with their local application for soil preparation and vegetable spraying. The estimated travel distances of the POPs (HCB, α-HCH, γ-HCH, and p, p′-DDT) under the Nepalese tropical climate were all above 1000 km, suggesting that high precipitation levels in the tropical climate were not enough to scavenge the POPs and that Nepal could be an important source region for POPs. Due to their close proximity and cold trapping (driven by low temperatures), the high Himalayas and the Tibetan Plateau are likely the key receptors of POPs emitted in Nepal. These results add to the information available on POPs from tropical developing countries.

An Analysis of the Situation of Persistent Organic Pollutants in Ukraine (by the Example of Odessa)

Persistent organic pollutants (POPs) are chemicals of global concern due to their ability to bio-magnify and bio-accumulate in ecosystems, persistence in the environment, potential for long-range transport, as well as their significant negative effects on human health and the environment. Ukraine is a part of Stockholm Convention on Persistent Organic Pollutants witch control the environmental pollution by these substances on international level. That is why Ukraine must take measures to regulate production of persistent organic pollutants accordingly to requirements of the Convention. Purpose. The full analyses of the current state of the POPs problem in Ukraine, by the example of Odessa in the following areas: analysis of the legislative framework and monitoring system of POPs; estimation of the use of equipment containing PCBs; identification of sources of unintentional formation of POPs, calculation of POPs production volumes using the most modern European methods; identification of priority sources of POPs release into the environment; general conclusions on the situation with POPs in Ukraine. Results. Conclusions regarding the legislative framework and monitoring system of the POPs in Ukraine were made, for the first time the volumes of unintentional formation of POPs in Odessa were calculated, the main sources of unintentional formation of these substances were established and ranked, the full analyses and general conclusions on the situation with POPs in Ukraine were made. Conclusions. In Ukraine, there is no separate legislative framework and monitoring system for POPs, which does not meet the requirements of the Stockholm Convention. The basic sources of unintentional formation of POPs are established in the work, such as: burning of organic fuel, construction, waste dumps, sewerage, smoking cigarettes, crematoria and smokehouses. The main source of PCDD/F into the environment is the dump of solid household waste in landfills, and the main source of PCB and HCB is the incineration of organic fuels by stationary sources. The existing methods do not give an opportunity to fully assess the negative impact of POPs on the environment.

Modification of Hexachlorobenzene to Molecules with Lower Long-Range Transport Potentials Using 3D-QSAR Models with a Full Factor Experimental Design.

In this study, the hexachlorobenzene molecule was modified by three-dimensional quantitative structure-activity relationship (3D-QSAR) models and a full factor experimental design to obtain new hexachlorobenzene molecules with low migration ability. The 3D-QSAR models (comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA)) were constructed by SYBLY-X 2.0 software, using experimental data of octanol-air partition coefficients (KOA) for 12 chlorobenzenes (CBs) congeners as the dependent variable, and the structural parameters of CBs as independent variables, respectively. A target molecule (hexachlorobenzene; HCB: its long-distance migration capability leads to pollution of the marine environment in Antarctic and Arctic) was modified using the 3D-QSAR contour maps associated with resolution V of the 210-3 full-factorial experimental design method, and 11 modified HCB molecules were produced with a single chlorine atom (-Cl2) and three chlorine atoms (-Cl1, -Cl3, and -Cl5) replaced with electropositive groups (-COOH, -CN, -CF3, -COF, -NO2, -F, -CHF2, -ONO2, and -SiF3) to increase the logKOA. The new molecules had essentially similar biological enrichment functions and toxicities as HCB but were found to be more easily degraded. A 2D-QSAR model and molecular docking technology indicated that both dipole moments and highest occupied orbital energies of the substituents markedly affected migration and degradation of the new molecules. The abilities of the compounds to undergo long distance migration were assessed. The modified HCB molecules (i.e. 2-CN-HCB, 2-CF3-HCB, 1-F-3-COOH-5-NO2-HCB, 1-NO2-3-CN-5-CHF2-HCB and 1-CN-3-F-5-NO2-HCB) moved from a long-range transport potential of the modified molecules to a relatively low mobility class, and the transport potentials of the remaining modified HCB molecules (i.e. 2-COOH-HCB, 2-COF-HCB, 1-COF-3-ONO2-5-NO2-HCB, 1-F-3-CN-5-SiF3-HCB, 1-F-3-COOH-5-SiF3-HCB and 1-CN-3-SiF3-5-ONO2-HCB) also significantly decreased. These results provide a basic theoretical basis for designing environmentally benign molecules based on HCB.

Persistent organic pollutant emission via dust deposition throughout Pakistan: Spatial patterns, regional cycling and their implication for human health risks

In the current study, Persistent Organic Pollutants (POPs) in outdoor dustfall was monitored for the first time along the Indus river system of Pakistan. Among the studied OCPs (ng/g, dry weight), DDTs (0.16–62) were the predominant contaminants identified in deposited dust followed by HCHs (0.1–10.2), HCB (0.09–7.4) and chlordanes (0.1–2.8). The indicative diagnostic ratio for DDTs and HCHs suggested recent emission of DDTs as well as historical emission of both chemicals in regions where they were used for crop protection and malarial control. The levels of ∑31PCBs (ng/g, dry weight) in dust ranged from 0.95–125, and compositional profiles suggested arochlor-1248, -1254 commercial mixtures as source. A few exceptions were samples from urban areas that reflected the use of aroclor-1260, and-1262 and/or unintentional leakage from several industrial processes. The WHO05-TEQ values for dioxin-like PCBs (with major contributions of PCB-126) were found to be 0.07–34.5 (median; 1.87) pg TEQg−1dw for all the studied samples. Correlation analysis identified that DDTs, HCHs, HCB and PCBs were significantly associated (r=90; p<0.01) with dusts collected in proximity to urban centers with widespread anthropogenic activities in these areas. A few cases where high levels of POPs from remote mountain highlands were detected, point to the potential for long range transport of these chemicals. Human risk assessment analysis of contaminated dust showed that DDTs and PCBs are major constituent chemicals of concern with regard to the development of cancer in children, with ingestion being the main route of exposure of dust-borne DDTs (0.12–1.03×10−6) and PCBs (0.86–12.43×10−6).

Occurrence, Loading, and Exposure of Atmospheric Particle-Bound POPs at the African and European Edges of the Western Mediterranean Sea.

A comparative study for 62 toxic chemicals based on the simultaneous monthly collection of aerosol samples during 2015-2016 in two coastal cities at both the African (Bizerte, Tunisia) and European (Marseille, France) edges of the Western Mediterranean basin is presented. Legacy polychlorinated biphenyls (∑18PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (∑17PCDD/Fs) show generally higher median levels at the African edge (2.1 and 0.2 pg m-3, respectively) compared to the European coastal site (1.0 and 0.08 pg m-3, respectively). Contrarily, the "emerging" polybrominated diphenyl ethers' (∑27PBDEs) median concentrations were higher in Marseille (∼9.0 pg m-3) compared to Bizerte (∼6.0 pg m-3). Different past usages and current emission patterns were found at both edges of the Western Mediterranean, most probably linked to the respective different regulatory frameworks for toxic chemicals. Our results indicate that the total organic carbon (TOC) and/or the elemental carbon (EC) contents in the atmospheric aerosol may have a stronger effect than the total suspended particle (TSP) content as a whole on the spatial-temporal variability and the long-range atmospheric transport potential of the studied POPs. A "jumping" of the PBDE local atmospheric stocks from the Northwestern European Mediterranean edge to the Northwestern African coast seems to be possible under favorable conditions at present. While a higher PBDE median loading is estimated for the Marseille area (∼550 ng m-2 y-1) compared to Bizerte (∼400 ng m-2 y-1), the median PCB and PCDD/F dry deposition fluxes were higher at the African site, resulting in a 3-fold higher toxic equivalent (TEQ) loading of dioxin-like pollutants (400 pg TEQ m-2 y-1) compared to Marseille (∼140 pg TEQ m-2 y-1), with potential implications for aquatic organisms. However, the inhalation exposure assessment points to a minimum risk for human health at both sites.

Typical persistent organic pollutants (POPs) in sediments from the Yellow and East China Seas and adjacent coastal areas, China

Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), short-chain chlorinated paraffins (SCCPs), polybrominated diphenyl ethers (PBDEs) and perfluoroalky chemicals (PFCs) are five kinds of typical persistent organic pollutants (POPs), which can be transported from emission sources to marine environments via many pathways, including riverine inputs, surface runoff of contaminated soils and atmospheric deposition. Due to their hydrophobicity and lipophilicity, they are preferentially adsorbed onto particles with higher organic contents and finally buried in marine sediments, which are generally regarded as one of the major sinks of POPs. Once absorbed by organisms, they are more easily accumulated in tissues with higher lipid contents. Meanwhile, under certain weather and environmental conditions, POPs adsorbed on sediments can be re-released to aquatic environments, leading to secondary pollution of water systems. POPs are of environmental persistence, bioaccumulation and biomagnification in biota and long-range transport potential, and thus may cause seriously adverse effects on marine ecosystems after they entered into marine environments. These effects are important to the safety of marine system. The present review mainly summarizes the pollution characteristics of the above POPs in sediments from the Yellow and East China Seas and adjacent coastal areas, China. In addition, their potential sources, mechanisms for migration from the land to the sea, as well as the ecological risk assessment for some of these POPs, are also reviewed. Future researches urgently needed are proposed.

Screening-level exposure-based prioritization to identify potential POPs, vPvBs and planetary boundary threats among Arctic contaminants

Abstract A report that reviews Arctic contaminants that are not currently regulated as persistent organic pollutants (POPs) under international treaties was recently published by the Arctic Monitoring and Assessment Programme (AMAP). We evaluated 464 individual chemicals mentioned in the AMAP report according to hazard profiles for POPs, very persistent and very bioaccumulative (vPvB) chemicals, and two novel and distinct hazard profiles we derived from the planetary boundary threat framework. The two planetary boundary threat profiles assign high priority to chemicals that will be mobile and poorly reversible environmental contaminants. Utilizing persistence as a proxy for poor reversibility, we defined two exposure-based hazard profiles; airborne persistent contaminants (APCs) and waterborne persistent contaminants (WPCs) that are potential planetary boundary threats. We used in silico estimates of physicochemical properties and multimedia models to calculate hazard metrics for persistence, bioaccumulation and long-range transport potential, then we synthesized this information into four exposure-based hazard scores of the potential of each AMAP chemical to fit each of the POP, vPvB, APC and WPC exposure-based hazard profiles. As an alternative to adopting a “bright line” score that represented cause for concern, we scored the AMAP chemicals by benchmarking against a reference set of 148 known and relatively well-studied contaminants and expressed their exposure-based hazard scores as percentile ranks against the scores of the reference set chemicals. Our results show that scores in the four exposure-based hazard profiles provide complementary information about the potential environmental exposure-based hazards of the AMAP chemicals. Our POP, vPvB, APC and WPC exposure-based hazard scores identify high priority chemicals for further study from among the AMAP contaminants.

Assessment of long-range transport potential of polychlorinated Naphthalenes based on three-dimensional QSAR models.

Experimentally determined octanol-air partition coefficients (K OA) for 43 polychlorinated naphthalene (PCN) congeners and experimentally determined subcooled liquid vapor pressures (P L) for 17 PCN congeners were used with comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) to generate three-dimensional quantitative structure-activity relationship (3D-QSAR) models. The data were used to predict K OA values for the other 32 congeners and P L values for the other 58 congeners. The CoMFA and CoMSIA model contour maps showed that the electrostatic fields of the PCN molecules are the most important factors affecting the K OA and P L values. The long-range transport potentials of several PCN homologs were assessed using the following grading system: high mobility (MoCNs), relatively high mobility (DiCNs to TeCNs), relatively low mobility (PeCNs to HeCNs) and low mobility (HeCNs and OCN). The PCN-2 molecule was modified using the contour maps of the two models, and the results showed that introducing an electronegative R1 substituent increased the K OA value but introducing an electropositive R6 substituent decreased the P L value. PCN-2 was in the high mobility class, but introducing these substituents moved the long-range transport potentials of the modified molecules to the relatively high mobility class.

Elevated Concentrations of 4-Bromobiphenyl and 1,3,5-Tribromobenzene Found in Deep Water of Lake Geneva Based on GC×GC-ENCI-TOFMS and GC×GC-μECD.

We quantified the concentrations of two little-studied brominated pollutants, 1,3,5-tribromobenzene (TBB) and 4-bromobiphenyl (4BBP), in the deep water column and sediments of Lake Geneva. We found aqueous concentrations of 625 ± 68 pg L–1 for TBB and 668 ± 86 pg L–1 for 4BBP over a depth range of 70–191.5 m (near-bottom depth), based on duplicate measurements taken at five depths during three separate 1 month sampling periods at our sampling site near Vidy Bay. These levels of TBB and 4BBP were 1 or 2 orders of magnitude higher than the quantified aqueous concentrations of the components of the pentabrominated biphenyl ether technical mixture, which is a flame retardant product that had a high production volume in Europe before 2001. We observed statistically significant vertical concentration trends for both TBB and 2,2′,4,4′,6-pentabromobiphenyl ether in the deep water column, which indicates that transport and/or degradation processes affect these compounds. These measurements were enabled by application of a comprehensive two-dimensional gas chromatograph coupled to an electron capture negative chemical ionization time-of-flight mass spectrometer (GC×GC-ENCI-TOFMS) and to a micro-electron capture detector (GC×GC-μECD). GC×GC-ENCI-TOFMS and GC×GC-μECD were found to be >10× more sensitive toward brominated pollutants than conventional GC×GC-EI-TOFMS (with an electron impact (EI) ionization source), the latter of which had insufficient sensitivity to detect these emerging brominated pollutants in the analyzed samples. GC×GC also enabled the estimation of several environmentally relevant partitioning properties of TBB and 4BBP, further confirming previous evidence that these pollutants are bioaccumulative and have long-range transport potential.

Atmospheric oxidation of halogenated aromatics: comparative analysis of reaction mechanisms and reaction kinetics.

Atmospheric transport is the major route for global distribution of semi-volatile compounds such as halogenated aromatics as well as their major exposure route for humans. Their major atmospheric removal process is oxidation by hydroxyl radicals. There is very little information on the reaction mechanism or reaction-path dynamics of atmospheric degradation of halogenated benzenes. Furthermore, the measured reaction rate constants are missing for the range of environmentally relevant temperatures, i.e. 230-330 K. A series of recent theoretical studies have provided those valuable missing information for fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene. Their comparative analysis has provided additional and more general insight into the mechanism of those important tropospheric degradation processes as well as into the mobility, transport and atmospheric fate of halogenated aromatic systems. It was demonstrated for the first time that the addition of hydroxyl radicals to monohalogenated as well as to perhalogenated benzenes proceeds indirectly, via a prereaction complex and its formation and dynamics have been characterized including the respective transition-state. However, in fluorobenzene and chlorobenzene reactions hydroxyl radical hydrogen is pointing approximately to the center of the aromatic ring while in the case of hexafluorobenzene and hexachlorobenzene, unexpectedly, the oxygen is directed towards the center of the aromatic ring. The reliable rate constants are now available for all environmentally relevant temperatures for the tropospheric oxidation of fluorobenzene, chlorobenzene, hexafluorobenzene and hexachlorobenzene while pentachlorophenol, a well-known organic micropollutant, seems to be a major stable product of tropospheric oxidation of hexachlorobenzene. Their calculated tropospheric lifetimes show that fluorobenzene and chlorobenzene are easily removed from the atmosphere and do not have long-range transport potential while hexafluorobenzene seems to be a potential POP chemical and hexachlorobenzene is clearly a typical persistent organic pollutant.

Evaluation of Long‐Range Transport Potential of Selected Brominated Flame Retardants with Measured 1‐Octanol–Air Partition Coefficients

Various alternative flame retardants are used in many countries since polybrominated diphenyl ethers (PBDEs) were classified as persistent organic pollutants (POPs). However, difficulties in the evaluation of the long‐range transport potential (LRTP) of the alternatives are related to the lack of information on their physicochemical properties, which govern their environmental fates and transport. Based on the simulation of LRTP using OECD POV and LRTP Screening Tool, five alternative brominated flame retardants (BFRs) (hexabromobenzene [HBB], 2,3,4,5,6‐pentabromotoluene [PBT], 2,3,4,5,6‐pentabromoethylbenzene [PBEB], 2‐ethylhexyl 2,3,4,5‐tetrabromobenzoate [TBB], and 1,2,4,5‐tetrabromo‐3,6‐dimethylbenzene [TBX]), and 3 PBDEs (BDE‐28, BDE‐47, and BDE‐99) were chosen to perform a refined assessment. This was done using an experimentally measured 1‐octanol–air partition coefficient (KOA) for the calculation of the air–water partition coefficient (KAW) required for the model. The four selected alternative BFRs (HBB, PBT, PBEB, TBX) have KOA values close to the in silico estimation used in the screening evaluation. On the other hand, the measured KOA value for TBB was two orders of magnitude lower than the estimated value used in the screening simulation. The refined simulation showed that characteristic travel distance (CTD) and transfer efficiency (TE) for HBB, PBT, PBEB, and TBX were greater than those for BDE‐28, whereas CTD and TE for TBB were lower than those for BDE‐28. This suggested that TBB has a lower LRTP than BDE‐28, considering the refined partition coefficients.

Global production, use, and emission volumes of short-chain chlorinated paraffins – A minimum scenario

Short-chain chlorinated paraffins (SCCPs) show high persistence, bioaccumulation potential, and toxicity (PBT properties). Consequently, restrictions on production and use have been enforced in several countries/regions. The Stockholm Convention on Persistent Organic Pollutants recognized the PBT properties and long-range transport potential of SCCPs in 2015 and is now evaluating a possible global phase-out or restrictions. In this context, it is relevant to know which countries are producing/using SCCPs and in which amounts, and which applications contribute most to their environmental emissions. To provide a first comprehensive overview, we review and integrate all publicly available data on the global production and use of both chlorinated paraffins (CPs) as a whole and specifically SCCPs. Considerable amount of data on production/use of CPs and SCCPs are missing. Based on the available data and reported emission factors, we estimate the past and current worldwide SCCP emissions from individual applications. Using the available data as a minimum scenario, we conclude: (i) SCCP production and use is increasing, with the current worldwide production volume being 165,000t/year at least, whereas the global production of total CPs exceeds 1milliont/year. (ii) The worldwide release of SCCPs from their production and use to air, surface water, and soil between 1935 and 2012 has been in the range of 1690–41,400t, 1660–105,000t, and 9460–81,000t, respectively. (iii) The SCCP manufacture and use in PVC, the use in metal working applications and sealants/adhesives, and the use in plastics and rubber contribute most to the emissions to air, surface water, and soil. Thus, the decrease in the environmental emissions of SCCPs requires reduction of SCCP use in (almost) all applications. (iv) Emissions due to the disposal of waste SCCPs cannot be accurately estimated, because relevant information is missing. Instead, we conduct a scenario analysis to provide some insights into it.

Screening for perfluoroalkyl acids in consumer products, building materials and wastes

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a large group of important chemical compounds with unique and useful physico-chemical properties, widely produced and used in many applications. However, due to the toxicity, bioaccumulation and long-range transport potential of certain PFASs, they are of significant concern to scientists and policy makers. To assess human exposure to PFASs, it is necessary to understand the concentrations of these emerging contaminants in our environment, and particularly environments where urban population spend most of their time, i.e. buildings and vehicles.A total of 126 samples of building materials, consumer products, car interior materials and wastes were therefore analyzed for their content of key PFASs - 15 perfluoroalkyl acids (PFAAs). At least one of the target PFAAs was detected in 88% of all samples. The highest concentration of Σ15PFAAs was found in textile materials (77.61 μg kg−1), as expected, since specific PFAAs are known to be used for textile treatment during processing. Surprisingly, PFAAs were also detected in all analyzed composite wood building materials, which were dominated by perfluoroalkyl carboxylic acids with 5–8 carbons in the chain (Σ4PFCAs up to 32.9 μg kg−1). These materials are currently widely used for building refurbishment, and this is the first study to find evidence of the presence of specific PFASs in composite wood materials. Thus, in addition to consumer products treated with PFASs, materials used in the construction of houses, schools and office buildings may also play an important role in human exposure to PFASs.

Organophosphate Esters in Canadian Arctic Air: Occurrence, Levels and Trends.

Fourteen organophosphate esters (OPEs) were measured in the filter fraction of 117 active air samples from yearly ship-based sampling campaigns (2007-2013) and two land-based stations in the Canadian Arctic, to assess trends and long-range transport potential of OPEs. Four OPEs were detected in up to 97% of the samples, seven in 50% or less of the samples, and three were not detected. Median concentrations of ∑OPEs were 237 and 50 pg m(-3) for ship- and land-based samples, respectively. Individual median concentrations ranged from below detection to 119 pg m(-3) for ethanol, 2-chloro-, phosphate (3:1) (TCEP). High concentrations of up to 2340 pg m(-3) were observed for Tri-n-butyl phosphate (TnBP) at a land-based sampling location in Resolute Bay from 2012, whereas it was only detected in one ship-based sample at a concentration below 100 pg m(-3). Concentrations of halogenated OPEs seemed to be driven by river discharge from the Nelson and Churchill Rivers (Manitoba) and Churchill River and Lake Melville (Newfoundland and Labrador). In contrast, nonhalogenated OPE concentrations appeared to have diffuse sources or local sources close to the land-based sampling stations. Triphenyl phosphate (TPhP) showed an apparent temporal trend with a doubling-time of 11 months (p = 0.044). The results emphasize the increasing relevance of halogenated and nonhalogenated OPEs as contaminants in the Arctic.

Influence of long-range atmospheric transportation (LRAT) on mono-to octa-chlorinated PCDD/Fs levels and distributions in soil around Qinghai Lake, China

Long-range atmospheric transportation (LRAT) of persistent organic pollutants followed by their deposition in cold, arid regions is of wide concern. This problem occurs at Qinghai Lake in the northeastern Tibetan Plateau, a sparsely populated area with extreme weather conditions and little current or historical anthropogenic pollution. The concentrations and distribution patterns of the mono-to octa-chlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) congeners in surface soil samples collected from around Qinghai Lake were quantified. Concentration differences between low-(mono-to tri-) chlorinated PCDD/Fs and high-(tetra-to octa-) chlorinated PCDD/Fs were measured. High PCDD/F levels were detected, with total concentrations of 15,108 ± 6323 pg/g for the 27 PCDD/F congeners and 15,104 ± 6324 pg/g for the low-chlorinated PCDD/Fs. The concentrations of 17 2,3,7,8-substituted PCDD/Fs were only 3.1 ± 4.4 pg/g and the corresponding international toxicity equivalency (I-TEQ) was 0.11 ± 0.22 pg I-TEQ/g. Given their higher vapor pressures and lower boiling points, low-chlorinated PCDD/Fs, were predominantly gaseous, whereas high-chlorinated PCDD/Fs were predominantly solid, indicating that there is a higher potential for long-range transport of low-chlorinated PCDD/Fs. Overall, because of their high LRAT potential, low-chlorinated PCDD/Fs may pose a greater risk to local ecosystems in cold, remote areas than high-chlorinated PCDD/Fs.

Nationwide Distribution of Per- and Polyfluoroalkyl Substances in Outdoor Dust in Mainland China From Eastern to Western Areas.

From eastern to western areas, per- and polyfluoroalkyl substances (PFASs) were detected at substantial levels in the outdoor dust across mainland China. Urban samples generally showed higher levels compared with those of rural samples. Compared with neutral PFASs, ionizable PFASs (C4-C12 perfluoroalkyl carboxylic acids and C4/C8 perfluoroalkyl sulfonic acids) were more abundant, with the highest total concentration up to 1.6 × 10(2) ng/g and perfluorooctanoic acid (PFOA) being a predominant analogue. Fluorotelomer alcohols (FTOHs) and polyfluoroalkyl phosphoric acid diesters (DiPAPs) were both detected in most samples with total concentrations of 0.12-32 and 0.030-20 ng/g, respectively. Perfluorooctane sulfonamidoethanols/sulfonamides (FOSE/As) were detected at low frequencies (<30%). In addition to partitioning to organic moiety, specific adsorption onto mineral particles can be important for PFASs to bind onto outdoor dust, especially for short-chain ionizable PFASs. The eastern plain areas were characterized by a higher contribution of long-chain ionizable PFASs; whereas the western high plateau areas were characterized by the dominating contribution of short-chain analogues. The difference suggests that the long-range atmospheric transport potential of PFASs from source regions to the inland is probably limited by the increase in altitude, and different sources from adjacent regions may influence the western border area of China.

PCBs in the Arctic atmosphere: determining important driving forces using a global atmospheric transport model

Abstract. We present a spatially and temporally resolved global atmospheric polychlorinated biphenyl (PCB) model, driven by meteorological data, that is skilled at simulating mean atmospheric PCB concentrations and seasonal cycles in the Northern Hemisphere midlatitudes and mean Arctic concentrations. However, the model does not capture the observed Arctic summer maximum in atmospheric PCBs. We use the model to estimate global budgets for seven PCB congeners, and we demonstrate that congeners that deposit more readily show lower potential for long-range transport, consistent with a recently described "differential removal hypothesis" regarding the hemispheric transport of PCBs. Using sensitivity simulations to assess processes within, outside, or transport to the Arctic, we examine the influence of climate- and emissions-driven processes on Arctic concentrations and their effect on improving the simulated Arctic seasonal cycle. We find evidence that processes occurring outside the Arctic have a greater influence on Arctic atmospheric PCB levels than processes that occur within the Arctic. Our simulations suggest that re-emissions from sea ice melting or from the Arctic Ocean during summer would have to be unrealistically high in order to capture observed temporal trends of PCBs in the Arctic atmosphere. We conclude that midlatitude processes are likely to have a greater effect on the Arctic under global change scenarios than re-emissions within the Arctic.

Persistent organic pollutant levels and the importance of source proximity in Baltic and Svalbard breeding common eiders

The distance to sources and the long-range transport potential of persistent organic pollutants (POPs) are important in understanding the impact of anthropogenic pollution on natural seabird populations. The present study documented blood concentrations of POPs in the Baltic Sea (Tvärminne, Finland) population of common eiders (Somateria mollissima) in 2009 and in 2011 and compared the concentrations with the presumably less exposed Arctic population in Svalbard (Kongsfjorden, Norway). The Baltic population had 26, 10, and 5 times greater concentrations of hexachlorocyclohexane, polychlorinated biphenyls, and p,p'-dichlorodiphenyldichloroethylene than the Svalbard population. Unexpectedly, concentrations of chlordanes were higher in Svalbard eiders, whereas concentrations of hexachlorobenzenes (HCBs) did not differ between the 2 populations. Although the similar HCB levels may partly be explained by the high transport potential of HCBs, unknown factors may have been more important than distance to sources and long-range transport potential for the chlordanes. One plausible explanation may be that the fasting-related redistribution of POPs from fat to blood was greater throughout the incubation in Arctic eiders, causing them to have higher blood levels of these POPs at the end of incubation. The blood concentrations of POPs in Baltic eiders were higher than documented in any other eider population and were comparable to levels in seabirds feeding at higher trophic positions in the food chain. Environ Toxicol Chem 2016;35:1526-1533. © 2015 SETAC.