Organophosphorus compounds (OPs) being applied as flame retardants and plasticizers were investigated in airborne particles over the Pacific, Indian, Arctic, and Southern Ocean. Samples taken during two polar expeditions in 2010/11, one from East Asia to the high Arctic (CHINARE 4) and another from East Asia toward the Indian Ocean to the Antarctic (CHINARE 27), were analyzed for three halogenated OPs (tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCPP) and tris(1,3-dichloro-2-isopropyl) phosphate (TDCP)), four alkylated OPs (tri-n-butyl phosphate (TnBP), tri-iso-butyl phosphate (TiBP), tris(2-butoxyethyl)phosphate (TBEP), and tris(2-ethylhexyl) phosphate (TEHP)), and triphenyl phosphate (TPhP). The sum of the eight investigated OPs ranged from 230 to 2900 pg m(-3) and from 120 to 1700 pg m(-3) during CHINARE 4 and CHINARE 27, respectively. TCEP and TCPP were the predominating compounds, both over the Asian seas as well as in the polar regions, with concentrations from 19 to 2000 pg m(-3) and 22 to 620 pg m(-3), respectively. Elevated concentrations were observed in proximity to the Asian continent enhanced by continental air masses. They decreased sharply toward the open oceans where they remained relatively stable. This paper shows the first occurrence of OPs over the global oceans proving that they undergo long-range atmospheric transport over the global oceans toward the Arctic and Antarctica.
Marine boundary layer air and seawater samples taken during a polar expedition cruise from East China Sea to the Arctic were analyzed in order to compare the occurrence, distribution, and fate of the banned polybrominated diphenyl ethers (PBDEs) with their brominated alternatives as well as the chlorinated Dechloranes. The sum of PBDEs (∑10PBDEs) in the atmosphere ranged from 0.07 to 8.1 pg m–3 with BDE–209 being the dominating congener and from not detected (n.d.) to 0.6 pg L–1 in seawater. Alternate brominated flame retardants (BFRs), especially hexabromobenzene (HBB), (2,3–dibromopropyl–2,4,6–tribromophenyl ether (DPTE), pentabromotoluene (PBT), 2–ethylhexyl 2,3,4,5–tetrabromobenzoate (EHTBB), bis–(2–ethylhexyl)–tetrabromophthalate (TBPH), were detected in higher concentrations than PBDEs, even in the high Arctic (0.6 to 15.4 pg m–3 for sum of alternate BFRs), indicating the change of PBDEs toward alternate BFRs in the environmental predominance. In addition, Dechlorane Plus (DP) as well as Dechlorane 602, 603, and 604 were detected both in the atmosphere and in seawater. The highest concentrations as well as the highest compound variability were observed in East Asian samples suggesting the Asian continent as source of these compounds in the marine environment. The air–seawater exchange indicates strong deposition, especially of alternate BFRs, as well as dry particle–bound deposition of BDE–209 into the ocean.
Surface seawater and marine boundary layer air samples were collected on the ice-breaker R/V Xuelong (Snow Dragon) from the East China Sea to the high Arctic (33.23À84.5°N) in July to September 2010 and have been analyzed for six current-use pesticides (CUPs): trifluralin, endosulfan, chlorothalonil, chlorpyrifos, dacthal, and dicofol. In all oceanic air samples, the six CUPs were detected, showing highest level (>100 pg/m 3 ) in the Sea of Japan. Gaseous CUPs basically decreased from East Asia (between 36.6 and 45.1°N) toward Bering and Chukchi Seas. The dissolved CUPs in ocean water ranged widely from
Perfluoroalkyl compounds (PFCs) were determined in 22 surface water samples (39-76°N) and three sea ice core and snow samples (77-87°N) collected from North Pacific to the Arctic Ocean during the fourth Chinese Arctic Expedition in 2010. Geographically, the average concentration of ∑PFC in surface water samples were 560 ± 170 pg L(-1) for the Northwest Pacific Ocean, 500 ± 170 pg L(-1) for the Arctic Ocean, and 340 ± 130 pg L(-1) for the Bering Sea, respectively. The perfluoroalkyl carboxylates (PFCAs) were the dominant PFC class in the water samples, however, the spatial pattern of PFCs varied. The C(5), C(7) and C(8) PFCAs (i.e., perfluoropentanoate (PFPA), perfluoroheptanoate (PFHpA), and perfluorooctanoate (PFOA)) were the dominant PFCs in the Northwest Pacific Ocean while in the Bering Sea the PFPA dominated. The changing in the pattern and concentrations in Pacific Ocean indicate that the PFCs in surface water were influenced by sources from the East-Asian (such as Japan and China) and North American coast, and dilution effect during their transport to the Arctic. The presence of PFCs in the snow and ice core samples indicates an atmospheric deposition of PFCs in the Arctic. The elevated PFC concentration in the Arctic Ocean shows that the ice melting had an impact on the PFC levels and distribution. In addition, the C(4) and C(5) PFCAs (i.e., perfluorobutanoate (PFBA), PFPA) became the dominant PFCs in the Arctic Ocean indicating that PFBA is a marker for sea ice melting as the source of exposure.
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