YAO Ziwei ( 姚子伟 ) WANG Zhen ( 王震 ) National Marine Environmental Monitoring Center 国家海洋环境监测中心 Feb. 24, 2010 Xiamen, China Second Yellow Sea Regional Science Conference

Atmospheric deposition of Chemicals Atmospheric deposition is an important way of some chemicals into the marine. Atmospheric deposition For example,  heavy metals,  nutrients  semi-volatile organic pollutants.

China Marine Environmental Quality Communique In 2007 and 2008, China Marine Environmental Quality Communique issued the results of the nutrient concentrations for five monitor stations. To date, scarce data on the atmospheric deposition of typical pollutants in the north Yellow Sea were reported. Atmospheric deposition  Swedish monitoring of POPs  The New Jersey Atmospheric Deposition Network (NJADN)  Great Lakes integrated atmospheric deposition network  Arctic Monitoring and Assessment Programme

(i) Estimate the importance of atmospheric deposition of these pollutants to the north Yellow Sea surface waters; (ii) Quantify current concentrations and deposition fluxes of the pollutants; (iii) Assess their spatial and seasonal trends. Objects of the study

 Nutrients  Heavy metals  Polycyclic aromatic hydrocarbons (PAHs)  Nutrients  Heavy metals  Polycyclic aromatic hydrocarbons (PAHs) No.itemsanalysis methods 01TSPgravimetric analysis 02nitrateion chromatography 03nitriteion chromatography 04ammoniumion chromatography 05phosphateion chromatography 06Cu, Pb, Zn, Cd, Featomic absorption 07Hgcold atomic absorption 08PAHs*GC/MS *PAHs include 15 compounds (abbreviation in parentheses): naphthalene (Nap), acenaphthene (Ace), fluorine (Fl), phenanthrene (Phe), anthracene (An), fluoranthene (Flu), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Chr), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenzo(a,h)anthracene (DbA), benzo(ghi)perylene (BghiP) and indeno(1,2,3-cd)pyrene (InP). Target analytes and analysis methods Target analytes

Location of three stations 3 Stations ：  S1-Laohutan (38º51´N, 121º41´E)  S2-Xiaomai Island (36º03´N, 120º25´E)  S3-Zhangzi Island (39º01´N, 122º43´E)

老虎滩 (38º51´N, 121º41´E), Laohutan, is located at the marine environmental monitor station of Dalian, where is an important monitor station of the north Yellow Sea. Laohutan

小麦岛 (36º03´N, 120º25´E), Xiaomai Island, is located at the marine environmental monitor station of Qingdao, where is another important monitor station of the Yellow Sea. Xiaomai Island

獐子岛 (39º01´N, 122º43´E), Zhangzi Island, is far away from the city. The station is considered as a background observation station. Zhangzi Island

Air samples (24 hours) were collected using modified high volume air samplers. Quartz fiber filters (QFFs) were used to capture particles and polyurethane foam plugs (PUFs) were used to concentrate the gas phase pollutants. Particle samples collection

Wet-only integrating precipitation samplers were employed to collect integrated precipitation samples in a stainless steel funnel. It can automatically collect the rain samples when it is raining. Rain collection equipment

This study was commenced from October The data presented here were the results from October 2008 to September Samples of TSP were collected every two weeks, and samples for PAHs are collected once per month. Precipitation samples were collected only when it is raining. Sampling duration

Mean and standard deviation (SD) of nitrate, ammonium salt, phosphate and nitrite in particle samples collected from the three sites (μg/m 3 ) Nutrients Zhangzi IslandLaohutanXiaomai Island MeanSDMeanSDMeanSD Nitrate Ammonium salt Phosphate Nitrite Total Nutrients The total nutrients at Laohutan is the highest (32.9 μg/m 3 ), followed by Xiaomai Island (29.1 μg/m 3 ) and Zhangzi Island (16.6 μg/m 3 ).

Proportion of four nutrients in samples of all three sites The results indicate that nitrate and ammonium salt are two main components of nutrients in the north Yellow Sea. Nutrients

Obvious trends were not observed at all three sites. The results may be due to the complexity of the sources. Time trends of nitrate concentration for the three sites Nutrients Nitrate and ammonium salt in the atmosphere largely derive from oxidation of NOx that are emitted from fossil fuel combustion. Moreover, nitrogen from sewage, industrial effluent and fertilizers are also important sources of nutrients into the atmosphere.

a d/w: the ratios of dry deposition fluxes to wet deposition fluxes Dry and wet deposition fluxes of nutrients at the three sites (mg/(m 2 y)) Nutrients The ratios of dry/wet deposition of nitrate, phosphate and nitrite were lower than 1, indicating their dry deposition fluxes were lower than wet deposition. The results confirmed that wet deposition of nitrate played an important role on the input of nutrients into the north Yellow Sea.

Box and whisker plot of Cu, Pb, Zn, Cd, Fe and Hg Heavy metals

Dry and wet deposition fluxes of six metals at the three sites (mg/(m 2 y)) The total (dry + wet) deposition fluxes of Cu, Pb and Hg at Xiaomai Island are the highest, while those of Zn and Fe at Laohutan are the highest. These indicate that Xiaomai Island and Laohutan, where is located near the urban area, is suffered heavy pollution with metals.

Annual precipitation and dry particle deposition fluxes (mg/(m 2 y)) of trace metals from other atmospheric deposition studies  Compared to the deposition fluxes in the other areas of the world, the fluxes are higher in the north Yellow Sea.  Higher deposition fluxes were due to higher concentrations of the target metals in the atmosphere, which are originated certainly from anthropogenic activities. Heavy metals

Relative contributions of precipitation and dry particle deposition to the total deposition fluxes of metals  The patterns of relative wet and dry deposition were similar at all three sites.  For Cu, Pb, Fe and Zn, more than 60% of the total atmospheric deposition was due to dry deposition.  However, more than 60% of the total deposition of Hg was due to wet deposition. Heavy metals Zhangzi IslandLaohutan Xiaomai Island

Box and whisker plot of PAHs at Zhangzi Island, Laohutan and Xiaomai Island for samples collected from October 2008 to September 2009  The highest PAH concentrations are measured at the most highly urban sites, Xiaomai Island.  Midrange concentrations are measured in Laohutan.  The lowest concentrations are found at Zhangzi Island far away from the mainland. PAHs

Distribution of particle and gas PAHs at the three sites Although the average concentrations vary spatially across the north Yellow Sea, the average PAH profiles at all sites are similar, indicating that while the source strength is different at each site, the mix of sources is similar. PAHs The proportions of the gas phase PAHs to the total PAHs (gas + particle) are 62%, 81% and 54% for Zhangzi Island, Laohutan and Xiaomai Island, respectively. The results indicate that the gas phase PAHs are the main component of atmospheric PAHs in the north Yellow Sea.

The higher concentrations were observed from November to April. In the north Yellow Sea, the residential heating period in winter lasts from mid November to the end of March of the next year, for which more coal are consumed to meet the heating demand. Time trends of ΣPAHs at Zhangzi Island, Laohutan and Xiaomai Island PAHs

Total deposition fluxes of PAHs at the three sites Annual average Σ15PAH total atmospheric deposition fluxes (gas + particle) range from to ng/(m 2 d). The order of highest to lowest fluxes follows the trend Xiaomai Island, Laohutan and Zhangzi Island. The particle deposition fluxes of PAHs at the three sites were lower than the gas deposition fluxes. PAHs

 Compared to other regions, PAHs deposition fluxes of the north Yellow Sea were higher slightly. For example, in New Jersey, annual average PAH total deposition fluxes ranged from 1479 to ng/(m 2 d). The results may be due to the following factors: 1) more coal, oil and wood were combusted due to a large number of population and rapid economic development; 2) low combustion efficiency of fossil fuels; 3) more total suspended particulate in the atmosphere. PAHs

Based on the findings of the study, some suggestions for management to reduce the emissions of the target pollutants into marine atmosphere are presented as follows: Suggestions for management For nutrients:  Reduce the use amounts and improve the efficiency of fertilizer in agriculture, and prevent the loss of fertilizer;  Cut the consumption and improve the combustion efficiency of fossil fuels;  Treatment the municipal wastewater and animal waste properly;

For heavy metals  Cut the emission of the industrial dust and vehicle exhaust;  Control the total suspended particles of the region;  Cut the consumption of coal and control the emission of industrial waste gas; For PAHs  Cut the consumption and improve the combustion efficiency of fossil fuels;  Abate the incomplete combustion of waste;  Reduce the discharge of vehicle exhaust;  Reduce the combustion of wood in rural areas; Suggestions for management

Thanks! 谢 谢！