Distribution characteristics and sea-to-air fluxes of volatile halocarbons in the East China Sea in autumn
LI Guan-lin1, HE Zhen1, YANG Gui-peng1,2, YUAN Da1
1. College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China;
2. Laboratory for Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071, China
The concentrations of four kinds of VHCs including CH3I, CH3Br, CHBr3 and C2Cl4 in the East China Sea were measured during the period of 19 October 2015 to 2 November 2015. Furthermore, C2Cl4 and three kinds of CFCs concentrations in the marine atmosphere were determined. The concentrations of CH3I, CH3Br, CHBr3 and C2Cl4 in the coastal waters were higher than those in the open sea. In the PN section the vertical distribution of VHCs had a common feature that the maxima appeared in the upper mixed layer. The distributions of the four kinds of VHCs were significantly influenced by the Yangtze River runoff, the Kuroshio water, biological production and anthropogenic activities. A positive correlation was found between the CH3I and chlorophyll-a (Chl-a) concentrations in the surface seawater, indicating that phytoplankton biomass might play an important role in the distribution of CH3I. Besides, a marked positive correlation among the CH3I, CH3Br and CHBr3concentrations were observed, suggesting that they might have some common sources and removal pathways. The atmospheric concentrations of the three kinds of CFCs were lower than the global averages, showed that the emissions of CFCs in China were progressively reduced. According to the analysis results of backward trajectories, the offshore terrigenous pollutant diffusion and transport were the main source of C2Cl4, CFC-11, CFC-113 and CFC-114 in the East China Sea atmosphere. The sea-to-air flux data indicated that the entire East China Sea shelf acted as a source for atmospheric CH3I, CH3Br, CHBr3 and C2Cl4 during the study period.
李冠霖, 何真, 杨桂朋, 袁达. 秋季东海挥发性卤代烃的分布和海-气通量研究[J]. 中国环境科学, 2017, 37(5): 1724-1734.
LI Guan-lin, HE Zhen, YANG Gui-peng, YUAN Da. Distribution characteristics and sea-to-air fluxes of volatile halocarbons in the East China Sea in autumn. CHINA ENVIRONMENTAL SCIENCECE, 2017, 37(5): 1724-1734.
Lovelock J E. Natural halocarbons in the air and in the sea. [J]. Nature, 1975,256(5514):193-4.
[2]
Von Glasow R, Crutzen P J. Tropospheric Halogen Chemistry [J]. Treatise on Geochemistry, 2003,4(2007):1-67.
[3]
Cincinelli A, Pieri F, Zhang Y, et al. Compound Specific Isotope Analysis (CSIA) for chlorine and bromine: A review of techniques and applications to elucidate environmental sources and processes [J]. Environmental Pollution, 2012,169(15):112-127.
[4]
Solomon S, Mills M, Heidt L E, et al. On the evaluation of ozone depletion potentials [J]. Journal of Geophysical Research Atmospheres, 1992,97(D1):825-842.
[5]
Lu X L, Yang G P, Song G S, et al. Distributions and fluxes of methyl chloride and methyl bromide in the East China Sea and the Southern Yellow Sea in autumn [J]. Marine Chemistry, 2010,118(1):75-84.
[6]
Yang G P, Xiao-Lan LU, Song G S, et al. Purge-and-Trap Gas Chromatographic Method for the Analysis of Methyl Chloride and Methyl Bromide in Seawater [J]. Chinese Journal of Analytical Chemistry, 2010,38(5):719-722.
[7]
Reifenhäuser W, Heumann K G. Determinations of methyl iodide in the Antarctic atmosphere and the south polar sea [J]. Atmospheric Environment. part A. general Topics, 1992,26(16): 2905-2912.
[8]
Parsons T R, Maita Y R, Lalli C M. A Manual of Chemical and Biological Methods of Seawater Analysis [J]. Pergamon Press, 1984.
[9]
Sundström J, Collén J, Abrahamsson K, et al. Halocarbon production and in vivo, brominating activity of Eucheuma denticulatum [J]. Phytochemistry, 1996,42(6):1527-1530.
[10]
Liu S M, Zhang J, Chen S Z, et al. Inventory of nutrient compounds in the Yellow Sea [J]. Continental Shelf Research, 2003,23(11-13):1161-1174.
[11]
Zhang J, Su J L. 2006. Nutrient dynamics of the China Seas: the Bohai Sea, Yellow Sea, East China Sea and South China Sea [C]//Robinson, A., Brink, K. (EDs.), The Sea, Press of Harvard University, USA, p. 14. Chapter 14-17.
[12]
Müller B, Berg M, Yao Z P, et al. How polluted is the Yangtze river? Water quality downstream from the Three Gorges Dam [J]. Science of the Total Environment, 2008,402(2/3):232-247.
[13]
Chiang K P, Chou Y H, Chang J, et al. Winter distribution of diatom assemblages in the East China Sea [J]. Journal of Oceanography, 2004,60(6):1053-1062.
Lobert J M, Butler J H, Montzka S A, et al. A Net Sink for Atmospheric CH3Br in the East Pacific Ocean [J]. Science, 1995,267(5200):1002-5.
[16]
Abrahamsson K, Ekdahl A, Collén J, et al. Marine algae-a source of trichloroethylene and perchloroethylene [J]. Limnology & Oceanography, 1995,40(7):1321-1326.
[17]
Allonier A S, Khalanski M, Camel V, et al. Characterization of chlorination by-products in cooling effluents of coastal nuclear power stations [J]. Marine Pollution Bulletin, 1999, 38(12):1232-1241.
[18]
Quack B, Wallace D W R. Air-sea flux of bromoform: Controls, rates, and implications [J]. Global Biogeochemical Cycles, 2003, 17(1):GB1004.
[19]
Zhou Y, Varner R K, Russo R S, et al. Coastal water source of short-lived halocarbons in New England [J]. Journal of Geophysical Research Atmospheres, 2005,110(D21):2935-2948.
[20]
Class T, Ballschmiter K. Chemistry of organic traces in air: VIII: Sources and distribution of bromo-and bromochloromethanes in marine air and surfacewater of the Atlantic Ocean [J]. Journal of Atmospheric Chemistry, 1988,6(1):35-46.
[21]
Nightingale P D, Malin G, Liss P S. Production of chloroform and other low molecular weight halocarbons by some species of macroalgae. Limnol Oceanogr [J]. Limnology & Oceanography, 1995,40(4):680-689.
[22]
许建平.浙江近海上升流区冬季水文结构的初步分析 [J]. 海洋学研究, 1986(3).
[23]
Biziuk M, Przyjazny A. Methods of isolation and determination of volatile organohalogen compounds in natural and treated waters [J]. Journal of Chromatography A, 1996,733(1/2):417-448.
[24]
Moore R M, Groszko W. Methyl iodide distribution in the ocean and fluxes to the atmosphere [M]//The Integration of modern Iraq/. St. Martin's Press, 1979:11163-11172.
[25]
Tokarczyk R, Moore R M. Production of volatile organohalogens by phytoplankton cultures [J]. Geophysical Research Letters, 1994,21(4):285-288.
[26]
Roy R. Short-term variability in halocarbons in relation to phytoplankton pigments in coastal waters of the central eastern Arabian Sea [J]. Estuarine Coastal & Shelf Science, 2010,88(3): 311-321.
[27]
Langanke K, Stademann R. Sources Of Short-Lived Bromocarbons In The Iberian Upwelling System [J]. Biogeosciences Discussions, 2010,8(6):1551-1564.
[28]
Liu K K, Gong G C, Lin S, et al. The Year-Round Upwelling at the Shelf Break Near the Northern Tip of Taiwan as Evidenced by Chemical Hydrography [J]. Terrestrial Atmospheric & Oceanic Sciences, 1992,3(3).
[29]
Moore R M, Groszko W. Methyl iodide distribution in the ocean and fluxes to the atmosphere [M]//The Integration of modern Iraq/. St. Martin's Press, 1979:11163-11172.
[30]
Khalil M A K, Moore R M, Harper D B, et al. Natural emissions of chlorine-containing gases: Reactive Chlorine Emissions Inventory [J]. Journal of Geophysical Research Atmospheres, 1999,104(D7):8333-8346.
[31]
Colomb A, Yassaa N, Williams J, et al. Screening volatile organic compounds (VOCs) emissions from five marine phytoplankton species by head space gas chromatography/mass spectrometry (HS-GC/MS) [J]. Journal of Environmental Monitoring, 2008,10(3):325-30.
[32]
Yokouchi Y, Akimoto H, Barrie L A, et al. Serial gas chromatographic/mass spectrometric measurements of some volatile organic compounds in the Arctic atmosphere during the 1992Polar Sunrise Experiment [J]. Journal of Geophysical Research Atmospheres, 1994,99(D12):25379-25389.
[33]
Zhang Y L, Guo H, Wang X M, et al. Emission patterns and spatiotemporal variations of halocarbons in the Pearl River Delta region, southern China [J]. Journal of Geophysical Research Atmospheres, 2010,115(D15):4447-4458.
[34]
Chan C Y, Tang J H, Li Y S, et al. Mixing ratios and sources of halocarbons in urban, semi-urban and rural sites of the Pearl River Delta, South China [J]. Atmospheric Environment, 2006, 40(38):7331-7345.
[35]
Blake N J, Blake D R, Simpson I J, et al. NMHCs and halocarbons in Asian continental outflow during the Transport and Chemical Evolution over the Pacific (TRACE-P) Field Campaign: Comparison With PEM-West B [J]. Journal of Geophysical Research Atmospheres, 2003,108(D20):1301-1336.
[36]
Singh H B, Salas L J, Stiles R E. Selected man-made halogenated chemicals in the air and oceanic environment [J]. J. Geophys. Res.; (United States), 1983,88:c6(C6):3675-3683.
[37]
Chan L Y, Chu K W. Halocarbon in the atmosphere of the industrial-related Pearl River Delta region of China [J]. Journal of Geophysical Research Atmospheres, 2007,112(D4):195-205.
[38]
Liss P S, Slater P G. Flux of Gases across the Air-Sea Interface [J]. Mantyla A.w.on the Potential Temperature in the Abyssal Pacific, 1974(5438):181-184.
[39]
Moore R M, Geen C E, Tait V K. Determination of Henry's Law constants for a suite of naturally occurring halogenated methanes in seawater [J]. Chemosphere, 1995,30(6):1183-1191.
[40]
Moore R M. The solubility of a suite of low molecular weight organochlorine compounds in seawater and implications for estimating the marine source of methyl chloride to the atmosphere [J]. Chemosphere-Global Change Science, 2000,2(1):95-99.
[41]
Liss P L, Merlivat L. The Role of Air-Sea Gas Exchange in Geochemical Cycling [J]. Nato Asi, 1986,185:113-127.
[42]
Khalil M A K, Moore R M, Harper D B, et al. Natural emissions of chlorine-containing gases: Reactive Chlorine Emissions Inventory [J]. Journal of Geophysical Research Atmospheres, 1999,104(D7):8333-8346.
