Time trends of persistent organic pollutants (POPs) and Chemicals of Emerging Arctic Concern (CEAC) in Arctic air from 25 years of monitoring.

The long-term time trends of atmospheric pollutants at eight Arctic monitoring stations are reported. The work was conducted under the Arctic Monitoring and Assessment Programme (AMAP) of the Arctic Council. The monitoring stations were: Alert, Canada; Zeppelin, Svalbard; Stórhöfði, Iceland; Pallas, Finland; Andøya, Norway; Villum Research Station, Greenland; Tiksi and Amderma, Russia. Persistent organic pollutants (POPs) such as α- and γ-hexachlorocyclohexane (HCH), polychlorinated biphenyls (PCBs), α-endosulfan, chlordane, dichlorodiphenyltrichloroethane (DDT) and polybrominated diphenyl ethers (PBDEs) showed declining trends in air at all stations. However, hexachlorobenzene (HCB), one of the initial twelve POPs listed in the Stockholm Convention in 2004, showed either increasing or non-changing trends at the stations. Many POPs demonstrated seasonality but the patterns were not consistent among the chemicals and stations. Some chemicals showed winter minimum and summer maximum concentrations at one station but not another, and vice versa. The ratios of chlordane isomers and DDT species showed that they were aged residues. Time trends of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were showing decreasing concentrations at Alert, Zeppelin and Andøya. The Chemicals of Emerging Arctic Concern (CEAC) were either showing stable or increasing trends. These include methoxychlor, perfluorohexane sulfonic acid (PFHxS), 6:2 fluorotelomer alcohol, and C9-C11 perfluorocarboxylic acids (PFCAs). We have demonstrated the importance of monitoring CEAC before they are being regulated because model calculations to predict their transport mechanisms and fate cannot be made due to the lack of emission inventories. We should maintain long-term monitoring programmes with consistent data quality in order to evaluate the effectiveness of chemical control efforts taken by countries worldwide.

Polycyclic Aromatic Hydrocarbons Not Declining in Arctic Air Despite Global Emission Reduction.

Two decades of atmospheric measurements of polycyclic aromatic hydrocarbons (PAHs) were conducted at three Arctic sites, i.e., Alert, Canada; Zeppelin, Svalbard; and Pallas, Finland. PAH concentrations decrease with increasing latitude in the order of Pallas > Zeppelin > Alert. Forest fire was identified as an important contributing source. Three representative PAHs, phenanthrene (PHE), pyrene (PYR), and benzo[ a]pyrene (BaP) were selected for the assessment of their long-term trends. Significant decline of these PAHs was not observed contradicting the expected decline due to PAH emission reductions. A global 3-D transport model was employed to simulate the concentrations of these three PAHs at the three sites. The model predicted that warming in the Arctic would cause the air concentrations of PHE and PYR to increase in the Arctic atmosphere, while that of BaP, which tends to be particle-bound, is less affected by temperature. The expected decline due to the reduction of global PAH emissions is offset by the increment of volatilization caused by warming. This work shows that this phenomenon may affect the environmental occurrence of other anthropogenic substances, such as more volatile flame retardants and pesticides.

Retrospective analysis of "new" flame retardants in the global atmosphere under the GAPS Network.

A retrospective analysis was conducted on air samples that were collected in 2005 under the Global Atmospheric Passive Sampling (GAPS) Network around the time period when the Stockholm Convention on Persistent Organic Pollutants came into force. Results are presented for several new flame retardants, including hexabromocyclododecane (HBCD), which was recently listed under the Convention (2013). These results represent the first global-scale distributions in air for these compounds. The targeted compounds are shown to have unique global distributions in air, which highlights the challenges in understanding the sources and environmental fate of each chemical, and ultimately in their assessments as persistent organic pollutants. The study also demonstrates the feasibility of using the PUF disk passive air sampler to study these new flame retardants in air, many of which exist entirely in the particle-phase as demonstrated in this study using a KOA-based partitioning model.

Temporal trends of Persistent Organic Pollutants (POPs) in arctic air: 20 years of monitoring under the Arctic Monitoring and Assessment Programme (AMAP).

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).

Organophosphate flame retardants and organosiloxanes in predatory freshwater fish from locations across Canada.

Whole body homogenates of Lake Trout (Salvelinus namaycush) or Walleye (Sander vitreus) collected from Canadian lakes were screened for organophosphate flame retardant (OPFR) and organosiloxane compounds. Six OPFR and five siloxane compounds were detected above quantitation limits in at least one individual fish from sampled lakes. The OPFRs, tris(2-chloroethyl) phosphate (TCEP) and tris(2-butoxyethyl) phosphate (TBOEP), were most frequently quantified with concentrations ranging from <0.07 to 9.8 ng/g (ww). Levels of TBOEP were highest in fish from the Great Lakes region while TCEP was detected only in fish from the northernmost lakes in our network. Concentrations of the cyclic siloxanes, octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6), were above quantitation limits in all fish. D5 was the most abundant siloxane across all sampling locations with the highest concentrations (45-719 ng/g ww) observed in Lake Trout from the western end of Lake Ontario near the mouth of the Niagara River.

Determination of cyclic volatile methylsiloxanes in water, sediment, soil, biota, and biosolid using large-volume injection-gas chromatography-mass spectrometry.

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid-solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI-GC-MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS's associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4°C were stable within 29d; however, significant depletion of D6 (60-70%) occurred only after 3d. Whereas cVMS in sewage influent and effluent were stable at 4°C within 21d. cVMS in sediment sealed in amber glass jars at -20°C and in pentane extracts in vials at -15°C were stable during 1month under both storage conditions.

Field evaluation of a flow-through sampler for measuring pesticides and brominated flame retardants in the arctic atmosphere.

A flow-through sampler (FTS) was codeployed with a super high volume active sampler (SHV) between October 2007 and November 2008 to evaluate its ability to determine the ambient concentrations of pesticides and brominated flame retardants in the Canadian High Arctic atmosphere. Nine pesticides and eight flame retardants, including three polybrominated diphenyl ether (PBDE) replacement chemicals, were frequently detected. Atmospheric concentrations determined by the two systems showed good agreement when compared on monthly and annually integrated time scales. Pesticide concentrations were normally within a factor of 3 of each other. The FTS tended to generate higher PBDE concentrations than the SHV presumably because of the entrainment of blowing snow/ice crystals or large particles. Taking into account uncertainties in analytical bias, sample volume, and breakthrough estimations, the FTS is shown to be a reliable and cost-effective method, which derives seasonally variable concentrations of semivolatile organic trace compounds at extremely remote locations that are comparable to those obtained by conventional high volume air sampling. Moreover, the large sampling volumes captured by the FTS make it suitable for the screening of new and emerging chemicals in the remote atmosphere where concentrations are usually low.

Atmospheric concentrations of halogenated flame retardants at two remote locations: the Canadian High Arctic and the Tibetan Plateau.

Atmospheric concentrations of halogenated flame retardants (FRs) were monitored for approximately one year at two remote stations, namely Nam Co on the Tibetan Plateau and Alert in the Canadian High Arctic. BDE-47 and 99 were the dominant polybrominated diphenyl ether (PBDE) congeners at both sites. Atmospheric PBDE concentrations in Nam Co were generally lower than those at Alert. While significant seasonal variations were observed for PBDEs at Alert, the FR concentrations at Nam Co showed no significant seasonality, even though air masses originated from distinctly different regions during different seasons. This suggests that FRs in Tibet do not have regional sources, but are reflective of truly global background contamination. Three new FRs, namely 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate (EHTeBB) and bis(2-ethyl-1-hexyl)tetrabromophthalate (TBPH) were detected at relatively high concentrations at both sites. This is the first report of these FRs in the remote global atmosphere and suggests significant potential for long-range atmospheric transport.

Bias from two analytical laboratories involved in a long-term air monitoring program measuring organic pollutants in the Arctic: a quality assurance/quality control assessment.

Initiated in 1992, air monitoring of organic pollutants in the Canadian Arctic provided spatial and temporal trends in support of Canada's participation in the Stockholm Convention of Persistent Organic Pollutants. The specific analytical laboratory charged with this task was changed in 2002 while field sampling protocols remained unchanged. Three rounds of intensive comparison studies were conducted in 2004, 2005, and 2008 to assess data comparability between the two laboratories. Analysis was compared for organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in standards, blind samples of mixed standards and extracts of real air samples. Good measurement accuracy was achieved for both laboratories when standards were analyzed. Variation of measurement accuracy over time was found for some OCPs and PCBs in standards on a random and non-systematic manner. Relatively low accuracy in analyzing blind samples was likely related to the process of sample purification. Inter-laboratory measurement differences for standards (<30%) and samples (<70%) were generally less than or comparable to those reported in a previous inter-laboratory study with 21 participating laboratories. Regression analysis showed inconsistent data comparability between the two laboratories during the initial stages of the study. These inter-laboratory differences can complicate abilities to discern long-term trends of pollutants in a given sampling site. It is advisable to maintain long-term measurements with minimal changes in sample analysis.