2Π Chemical characteristics of precipitation in regional representative sites 4. 3 High2altitude water in clouds and fogs 5 Formation mechan

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1 21 2Π PROGRESS IN CHEMISTRY Vol. 21 No. 2Π3 Mar., ( ), : ;,;SO 4 NO 3 NH + 4 Ca 2 +, ; ;; : X517 : A : X(2009) 02Π Research Progress in Precipitation Chemistry in China Wang Wenxing 3 Xu Pengju ( Environment Research Institute, Shandong University, Jinan , China) Abstract The acid rain area in China is one of the three main acid rain areas in the world, next to Europe and North America. Most acid deposition investigations have been concerned with precipitation chemistry in China. results for precipitation chemistry of China obtained by Chinese and foreign researchers are overviewed in this paper. Major conclusions are : High H + concentrations of precipitation have occurred in South and South Western China which have become areas with the highest acidity of precipitation in the world ; The pollution of precipitation in China is still sulfur type with a trend to sulfuric2nitrous mixed type ; Concentrations of dominant anions(so 4 (NH 4 + The and NO 3 ) and cations and Ca 2 + ) in precipitation are much higher than that in Europe and North America ; The high acidity and ionic concentration in precipitation at alpine sites and cloud water in eastern and southern China indicates that upper air has been polluted seriously ; Characteristics of precipitation chemistry in different areas of China and the origins of acid rain formation have been discussed ; Finally, future research is suggested. Key words precipitation chemistry ; China ; acid rain ; emissions Contents 1 Introduction 2 Geographical distributions and trends of precipitation acidity in china 2. 1 Precipitation acidity 2. 2 Trends of precipitation acidity 3 Ground precipitation chemistry 3. 1 Precipitation acidity and water2soluble ion concentrations 3. 2 Organic components in precipitation 3. 3 Heavy metals in precipitation 3. 4 Ground fogs 4 Chemistry of high altitude precipitation and cloud water 4. 1 Precipitation chemistry at mountains : e2mail com China Academic Journal Electronic Publishing House. All rights reserved.

2 2Π Chemical characteristics of precipitation in regional representative sites 4. 3 High2altitude water in clouds and fogs 5 Formation mechanisms of acid rain 5. 1 Emission trends of acidic precipitation related pollutants in China 5. 2 Mechanisms of chemical transformations 5. 3 Interactions between precipitation and aerosol and other pollutants 6 Future research on precipitation chemistry in China 1, 7811 %N %O 2 Ar Ne Kr Xe CO 2 O 3 CH 4 CO NH 3 SO 2 NO x [1 ],,,,,,,,,ph < 516,,, 1840s, Robert Angus Smith, 1872 Air and Rain : the Beginnings of a Chemical Climatology SO 4 3,, acid rain, [2 ], 1950s,,, [3 ] 1970s, ( EMEP :www. emep. int,nadp : http :ΠΠnadp. sws. uiuc. edu) 1990s ( EANET:www. eanet. cc) 1970s, [4 ],1982 [5 ],1989 [6 ],,, ,,,,(pH < 415), 1 ph, Fig. 1 Isopleths of annual mean ph of precipitation in China, 2006,2006 : (1), 1994 (2) China Academic Journal Electronic Publishing House. All rights reserved.

3 268 21, 2006, 1994,,,,2006,,,,,1,, ph,, [7 9 ] ph, ,pH [10 ], 2005 ph [11,12 ] 2005,, [13 ] ph , ,, ph [14,15 ], ph [16,17 ] ph, [18 ] 2002, ph 510 [19 ] ph 5, ph, [20 ] ,, ph [21 ] ph 4121,,2000 [22 ] ph 2000,2006 ph 5129 [23 ] 2000 ph, [24 ] [25 ],, ph 8136, ,1990s ph 810, ph, [26 ] ph 3 Fig. 2 Trends of annual mean ph of precipitation, acid rain frequency and severe acid rain frequency in China ( ), :1980s 1990s,1990s 21 [6 ] 2002,,,2006 ( 2), ph, 2,, SO 2 NO x NH 3 3, EANET,, , China Academic Journal Electronic Publishing House. All rights reserved.

4 2Π3 269 SO 4 NO 3,Ca 2 + NH + 4, 2004 ph 5152,SO 4 NO eq L eq L 1, SO 4 NO 3 NH + 4,SO 4 ΠNO 3 (TSP),,pH [8,27 ] 2004 ph 4141, ( 5152 ), SO 4 eq L 1 ) NO 3 ( (7212 eq L 1 ) [9 ],NH 4 + Ca % [28 ] [29 ] ph 6146, 2 SO 4,NO 3, NH + 4 Ca 2 +,,, Xu [30 ] ph, ph 6186,SO eq L 1, NO 3 24 eq L 1, [25 ], ph 8136, ,,, SO 4 NO 3,1980s,SO 4 NO 3,pH 220km ph 6138, NH 3,NO 3 NH 4 +, NO 3 SO 4 [31 ] ,, NO 3 SO 4 NH + 4 [26 ] 2002 ph ,2003 ph , 2004 ph , [32 ] 2005, [33 ] ph 4149, , ph 2195, SO 4 NO eq L eq L 1, SO 4 Π NO 3,, [18 ] Tu [34 ] ,pH 2000,2003 5, SO 4 NO eq L eq L 1,SO 4,NO 3,2003 SO 4 ΠNO 3 6, Ca ph 5,3 SO 4 NO eq L eq L 1, NO x [35 ] Zhang [36 ] 2004, ph 4154,SO 4 NO eq L eq L 1,SO 4 NO % 9919 % %, %,SO 4 NO eq L eq L 1 2,SO 4 ΠNO 3 6,,Cl, [37 ] Zhang [38 ] ph, ph ,, NH NO 3 NO 2 PO 4 SiO , [39 ] ph 4137, 85 %, 2 SO 4 ΠNO ,,SO 4 Ca 2 +,NO 3 NH 4 +,, [14,16,17,40 ] [41 ] China Academic Journal Electronic Publishing House. All rights reserved.

5 270 21, ph < 516,, Wai [42 ], , SO 4,Ca 2 + NH 4 +, [20 ],, [43 ] 2002 ph 5138, 4131,, [44 ] [45 ] , 2, SO 4 SO 4 Π NO 3,Ca 2 + ΠSO ph 4102,9810 %, SO 4 ΠNO 3, [22 ],, SO 2 NO x 1Π2 [52 ],SO 4 NO 3,Ca 2 +,, NH + 4,, SO 4 NO 3,,, H + [53 ], Zhang [54 ] 15,, (DON),DON 111mol L 1,DON 68 %,, [46,47 ] Mu [55 ], ( COS), COS ng L 1,,, 312,,,,, [48 ],, [49 ] ,, (4162 eq L 1 ) (4160 eq L 1 ) (1117 eq L 1 ),2 %, [50,51 ] , (total organic carbon, TOC) eq L 1,7,510 %, ( < 1 %) eq L eq L 1,5 % 8 %,,,,, (DOC) 319mg L 1, 3016 %,ph 5, DOC ph, ph [40 ] %, 2312 %,, ( ) 10 6 ( ) 10 6 ( ) 10 6,,3Π Belviso (PAHs), PAHs [56 ] 2004,PAHs 2 157ng L 1,Phen,Fl Py Flur,3 (PFOS) ( PFOA),, Liu [57 ] PFOS PFOA, 210ng L 1 316ng L 1,, PFOS PFOA China Academic Journal Electronic Publishing House. All rights reserved.

6 2Π3 271,,,, POPs,, 313,,,, Tang [58 ] , 51471g L 1,,, Hg CO, 01939, PM 10,, Guo [59 ] 2006,5 4915g L g m 2, 0125ng L g m , 33ng L 1, 39g m 2 [60 ] [61 ] 2006 Zn (70141)g L 1 Fe (10175)g L 1 Al (17192)g L 1 Mn (11181)g L 1,As Pb,,, Liu [62 ] Cu Pb Cd Zn, ;Cu Cd Zn,Pb,, [63 ] Cu Cd Zn,Pb Cu Pb Cd Zn 14169mg m mg m mg m mg m 2,Liu [62 ] Hg Hg,, Hg, Hg, Hg 314,,, [64 ] km,,SO 4,SO 4 eq L 1 ) NO 3 (1 434 (122 eq L 1 ), ph (6135) [65 ], ph 6 7,SO 4 (608 eq L 1 ),NO 3 (24 eq L 1 ) [66 ] 1991, ph , ,SO 4, Ca 2 + NH 4 +,Ca 2 +,> > ;1991, Liu [67 ] , ph ,pH, SO 4 NO eq L eq L 1, [68 ] ph , F,, [69 ] ph ,5163, S cm 1 2,SO 4 ΠNO , ph ; [70 ] ph 5171, (810S cm 1 ) 418, China Academic Journal Electronic Publishing House. All rights reserved.

7 272 21,, ph,,,,,,,,,,, ,, ( 1 3) 3 Fig. 3 Geographic distribution of regional representive sites, [71 73 ] ph 4161, eq L 1,,SO 4 NH + 4 Ca 2 + SO 4 NO 3 NH 4 + Ca 2 +,NH 4 +,, 1 ph ( eq L 1 ) Table 1 ph and ion concentrations in precipitation at some regional representive sites ( eq L 1 ) site duration altitudeπm ph SO 4 NO 3 Cl F NH 4 + Ca 2 + K + Na + Mg 2 + SO 4 NO total ions conc This table only shows concentrations of major ions, not includes other ion concentrations detected in the researches. 2. means not detected. ref ,Zhao [74 ] ph ,pH 6186Ca 2 + SO 4, Ca 2 + SO eq L eq L 1, eq L eq L 1, ( GEF) China Academic Journal Electronic Publishing House. All rights reserved.

8 2Π3 273 [75 ] 1997 ( 1), ph S cm 1, NH + 4 Ca 2 + SO 4 Mg 2 +, SO 4 2,SO 4 ΠNO NH 4 + Ca 2 + ph, ; NH 4 + ( eq L 1 ) Ca 2 + (80178 eq L 1 ) %, [80 ] ,pH, 4145,8716 % SO 4 ( eq L 1 ),NO 3 ( eq L 1 ),SO 4 ΠNO [81 ] m 210m 270m, ph,,so 4 Ca 2 + Ca 2 + ( IMPACTS) ,NO 3 NH + 4, [82 ] m,88 %, ph 4173, 22115S cm 1,,SO 4 (120 eq L 1 ) Ca 2 + (92 eq L 1 ), 2,SO 4 ΠNO 3, 15 [83 ] 1 500m,SO 4 NO 3, ph 5113,, SO eq L 1 5,6417 %,,, NH + 4 NO 3, SO 2 SO 4 SO 4 ( 132 eq L 1, NO 3 NH + 4 Ca 2 +, [76 ] [77,78 ] eq L 1 ) Ca 2 + ( eq L 1, 9318 eq L 1 ),SO 4 2,SO 4 ΠNO ,1993 1,,, SO 4 NO 3,,1987 ph 2 600m(SO 4 + NO 3 ),,2 600m, H + [53 ] [79 ] ,, ph 5123, 33190S cm 1, SO 4,,,, %,SO 4 ( eq L 1 ) NO 3 (14102 eq L 1 ),, 3, 1, ph 516,,,,,SO China Academic Journal Electronic Publishing House. All rights reserved.

9 SO 4, 4 5,; SO 4 NO 3, ( ) ( ) (Ca NH )Π(SO 4 + NO 3 ),Ca 2 + 2,(SO 4 + NO 3 ), Ca 2 + NH + 4, ph Cl, Ca 2 + NH 4 + SO 4 NO 3,pA i [84 ] ph,pa i SO 4 NO 3 10, pa i ph (nss2so 4 + NO 3 ) (Ca NH 4 + ) ph EANET pai ph 4 [84 ] pa i (nss2so 4, + NO 3 ), Ca 2 +,ph pai, (nss2so 4 + NO 3 ),,, 4 EANET ph pa i [84 ] Fig. 4 ph versus pai at selected EANET monitoring sites in China ( ) [84 ] 413,,,,,, [85 ] , 1985, ph > 610,, ph 510 SO 4 NH 4 + ; NH 4 +, SO 4 ΠNO 3 1 3,,,,,, [86 ] , 8013 %ph < 516,44 % ph < 415,pH %,ph %,ph, China Academic Journal Electronic Publishing House. All rights reserved.

10 2Π3 275 [87 ] 2003,,pH , , Cl NH + 4, [88 ] %, SO 4,NO 3 ; Ca 2 + NH + 4, NH 4 + Ca 2 +,, Ca 2 + SO 4 Mg SO 2 NO x 5 SO 2 NO 2 NH 3 Fig. 5 Trends of annual emissions of anthropogenic SO 2,,NH 3 NO 2, NH 3, soot and industrial dust 5,2002 SO 2 NO x : (1) [89,90 ] ; (2) ; (3),,, NH 3,NH 3, SO 2 NO x, 512 NH 3 SO 2 NO x,,so 2 NO x,,,,,,,, 5, ,SO 2 NO x NH ,SO 2, NO x, [91 ] ( K por,t ),,,, 2002 SO 2 NO x,, K por,t SO 2 NO x ph, ( 1), SO 2, NO x, K por,t OH 1998,, OH,,,SO China Academic Journal Electronic Publishing House. All rights reserved.

11 OH HO 2 [92 ] 2000 OH HO 2,OH HO 2 ; HNO 2 HCHO OH HO 2,OH VOCs HCHO NO 2 CO,, NO 2 [101 ] VOCs NO x,bian [102 ] PM 10 O 3 O 3 PM 10 :PM 10,O 3 PM 10 ; PM 10, O 3 [103 ],, NO x O 3 HONO HO x,hono, HONO Hao [104 ],40 % < RH < 70 %, HONOΠNO 2 RH ;RH > 70 %,HONOΠNO 2 RH Su [105 ] HONO O 3 OH, HONO NO 2 HONO, [97 ] Hao [104 ] Su [106 ] HONO,HONO BC Wang [107 ] HCl AgNO 2 HONO, HONO [108 ] HONO CS 2,355nm : CS 2 OH2HONO OH HO 2 [93 ] CS 2 NO + Quan [109 ] NH 3 SO 2 S, NH 3 (VOCs) NO x SO 4 SO 2, S,,S 10 % 30 %,,VOCs O 3,, NO x O 3,,, O 3 VOCs [94 99 ] Wang [100 ] SO 4,, SO,VOCs O 3, 2 [110,111 ] Li [112,113 ] VOCs O 3 SO 2 NO x,no x, O 3 ; NO x O 3,NO x O 3 [114 ], NO 2 N 2 O 5 NO 3 NONO, COS, COS [115 COS,He 118 ] Chen [119,120 ] COS :COS, HSCO 2 HSO 3 SO 4 CO 2,,, COS Liu [121 ] 2000, Ca2K2S, Ouyang OHO 3 OH 3 [122 ] SO 4 Cl NO 3 HSO 3 HCO 3, Cl SO 4 Yu [123 ], China Academic Journal Electronic Publishing House. All rights reserved.

12 2Π3 277, Du [124 ] (DES), DES,O 3,,, SO 2,,,SO 2 NO x,,, Lester HOOO ( HONO 2 ), SO 2 NO 2 [125,126 ], 513,,,,,3 PM 10, PM 10,1980s, PM 10 [128 ] 2002, (TSP),, TSP,,, [129 ] TSP,,,,, ph,,, PM 10 Cu,, Pb Zn Cd,Cd Zn Cu Pb,pH, [130 ] [131 ] H + H +, H +, [132 ] :,, ;, [133 ] [134 ], ph, SO 2 ph, SO 2 NO 2 PM 10 [135 ] RH > 90 %,RH < 80 % ; 80 % < RH < 90 %PM 10, SO 2,NO 2, [136 ],, Ca2K2S, 012m [127 ] , 014m PM 10, [137 ],2 011m 013m 1m 215m,, SO 2,, China Academic Journal Electronic Publishing House. All rights reserved.

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<D2BDC1C6BDA1BFB5CDB6C8DAD7CAB8DFB7E5C2DBCCB3B2CEBBE1C3FBB5A52E786C7378> 参会人员名单 Last Name 姓名公司 Tel Fax Bai 柏煜康复之家 8610 8761 4189 8610 8761 4189 Bai 白威久禧道和股权投资管理 ( 天津 ) 有限公司 8610 6506 7108 8610 6506 7108 Bao 包景明通用技术集团投资管理有限公司 8610