ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-13-1675-2013 Spatial distribution and temporal variations of atmospheric sulfur deposition in Northern China: insights into the potential acidification risks Pan Y. P. 1 Wang Y. S. 1 Tang G. Q. 1 Wu D. 1 State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry (LAPC), Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029, China 08 02 2013 13 3 1675 1688 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/13/1675/2013/acp-13-1675-2013.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/13/1675/2013/acp-13-1675-2013.pdf

Atmospheric sulfur (S) deposition via precipitation, particles and gases was investigated at ten sites in Northern China. Measurements were performed continuously between December 2007 and November 2010. The total S deposition flux in the target area ranged from 35.0 to 100.7 kg S ha<sup>−1</sup> yr<sup>−1</sup>, noticeably higher than the values documented in Europe, North America, and East Asia. The ten-site, 3-yr average total S deposition was 64.8 kg S ha<sup>−1</sup> yr<sup>−1</sup>, with 68% attributed to dry deposition (mainly SO<sub>2</sub>) and the rest to wet deposition. Consequently, the spatial distribution of the total flux was consistent to that of dry deposition, that is, higher values were observed at industrial and urban sites than at agricultural and rural sites. However, the seasonal variation in the total S deposition was not obvious across the entire year because of opposite seasonal trends in wet and dry deposition. It was found that the wet deposition, without significant spatial and interannual differences, was influenced by the volume of precipitation, the air-column concentrations of S compounds and in-cloud scavenging. Similar to the wet deposition, the dry-deposited sulfate was also less dependent on the surface concentration. Nevertheless, the regional differences in SO<sub>2</sub> dry deposition were mostly explained by the ambient concentration, which is closely associated with local emissions. As expected, the spatial pattern of total S deposition resembled that of the emission inventory, indicating the dramatic anthropogenic imprints on the regional S budget. Although at most of the study sites the "acid equivalents" deposition of S was comparable to that of nitrogen (N), the importance of S in the acidification risks was more pronounced at the industrial sites. The ten-site, 3-yr mean total "acid equivalents" deposition of S and N was estimated to be 8.4 (range: 4.2–11.6) keq ha<sup>−1</sup> yr<sup>−1</sup>, which exceeds the critical loads for natural ecosystems in Northern China. Taking these findings and our previous studies together, a multi-pollutant perspective and joint mitigation strategies to abate SO<sub>2</sub> and NH<sub>3</sub> simultaneously in the target area are recommended to protect natural ecosystems from excess acid deposition.

 References Aherne, J. and Farrell, E. P.: Deposition of sulphur, nitrogen and acidity in precipitation over Ireland: chemistry, spatial distribution and long-term trends, Atmos. Environ., 36, 1379–1389, http://dx.doi.org/10.1016/S1352-2310(01)00507-6doi:10.1016/S1352-2310(01)00507-6, 2002. Ayers, G. P. and Yeung, K. K.: Acid deposition in Hong Kong, Atmos. Environ., 30, 1581–1587, http://dx.doi.org/10.1016/1352-2310(95)00454-8doi:10.1016/1352-2310(95)00454-8, 1996. Ayers, G. P., Peng, L. C., Fook, L. S., Kong, C. W., Gillett, R. W., and Manins, P. C.: Atmospheric concentrations and deposition of oxidised sulfur and nitrogen species at Petaling Jaya, Malaysia, 1993–1998, Tellus. B, 52, 60–73, http://dx.doi.org/10.1034/j.1600-0889.2000.00043.xdoi:10.1034/j.1600-0889.2000.00043.x, 2000. Balestrini, R., Galli, L., and Tartari, G.: Wet and dry atmospheric deposition at prealpine and alpine sites in northern Italy, Atmos. Environ., 34, 1455–1470, http://dx.doi.org/10.1016/s1352-2310(99)00404-5doi:10.1016/s1352-2310(99)00404-5, 2000. Brook, J. R., Zhang, L., Li, Y., and Johnson, D.: Description and evaluation of a model of deposition velocities for routine estimates of dry deposition over North America. Part II: review of past measurements and model results, Atmos. Environ., 33, 5053–5070, http://dx.doi.org/10.1016/s1352-2310(99)00251-4doi:10.1016/s1352-2310(99)00251-4, 1999. Byun, D. W. and Ching, J. K. S.: Science algorithms of the EPA Models-3 community multiscale air quality (CMAQ) modeling system; Report EPA/600/R-99/030, US Environmental Protection Agency: Research Triangle Park, NC, USA, 1999. Costabile, F., Bertoni, G., Desantis, F., Wang, F., Weimin, H., Fenglei, L., and Allegrini, I.: A preliminary assessment of major air pollutants in the city of Suzhou, China, Atmos. Environ., 40, 6380–6395, http://dx.doi.org/10.1016/j.atmosenv.2006.05.056doi:10.1016/j.atmosenv.2006.05.056, 2006. Driscoll, C. T., Lawrence, G. B., Bulger, A. J., Butler, T. J., Cronan, C. S., Eagar, C., Lambert, K. F., Likens, G. E., Stoddard, J. L., and Weathers, K. C.: Acidic deposition in the northeastern United States: sources and inputs, ecosystem effects, and management strategies, Biosciences, 51, 180–198, http://dx.doi.org/10.1641/0006-3568(2001)051[0180:ADITNU]2.0.CO;2doi:10.1641/0006-3568(2001)051[0180:ADITNU]2.0.CO;2, 2001. Endo, T., Yagoh, H., Sato, K., Matsuda, K., Hayashi, K., Noguchi, I., and Sawada, K.: Regional characteristics of dry deposition of sulfur and nitrogen compounds at EANET sites in Japan from 2003 to 2008, Atmos. Environ., 45, 1259–1267 http://dx.doi.org/10.1016/j.atmosenv.2010.12.003doi:10.1016/j.atmosenv.2010.12.003, 2010. Fang, Y. T., Koba, K., Wang, X. M., Wen, D. Z., Li, J., Takebayashi, Y., Liu, X. Y., and Yoh, M.: Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in Southern China, Atmos. Chem. Phys., 11, 1313–1325, http://dx.doi.org/10.5194/acp-11-1313-2011doi:10.5194/acp-11-1313-2011, 2011. Feliciano, M. S., Pio, C. A., and Vermeulen, A. T.: Evaluation of SO<sub>2</sub> dry deposition over short vegetation in Portugal, Atmos. Environ., 35, 3633–3643, http://dx.doi.org/10.1016/s1352-2310(00)00539-2doi:10.1016/s1352-2310(00)00539-2, 2001. Flechard, C. R., Nemitz, E., Smith, R. I., Fowler, D., Vermeulen, A. T., Bleeker, A., Erisman, J. W., Simpson, D., Zhang, L., and Tang, Y. S.: Dry deposition of reactive nitrogen to European ecosystems: a comparison of inferential models across the NitroEurope network, Atmos. Chem. Phys., 11, 2703–2728, http://dx.doi.org/10.5194/acp-11-2703-2011doi:10.5194/acp-11-2703-2011, 2011. Galloway, J. N., Likens, G. E., and Hawley, M. E.: Acid precipitation: natural versus anthropogenic components, Science, 226, 829–831, http://dx.doi.org/10.1126/science.226.4676.829doi:10.1126/science.226.4676.829, 1984. Galloway, J. N., Zhao, D. W., Xiong, J. L., and Likens, G. E.: Acid rain: China, United States, and a remote area, Science, 236, 1559–1562, http://dx.doi.org/10.1126/science.236.4808.1559doi:10.1126/science.236.4808.1559, 1987. Hao, J., Duan, L., Zhou, X., and Fu, L.: Application of a LRT model to acid rain control in China, Environ. Sci. Technol., 35, 3407–3415, http://dx.doi.org/10.1021/es001888udoi:10.1021/es001888u, 2001. Huang, K., Zhuang, G., Xu, C., Wang, Y., and Tang, A.: The chemistry of the severe acidic precipitation in Shanghai, China, Atmos. Res., 89, 149–160, http://dx.doi.org/10.1016/j.atmosres.2008.01.006doi:10.1016/j.atmosres.2008.01.006, 2008. Ichikawa, Y. and Fujita, S.: An analysis of wet deposition of sulfate using a trajectory model for East Asia, Water Air. Soil Poll., 85, 1927–1932, http://dx.doi.org/10.1007/bf01186116doi:10.1007/bf01186116, 1995. Kuribayashi, M., Ohara, T., Morino, Y., Uno, I., Kurokawa, J., and Hara, H.: Long-term trends of sulfur deposition in East Asia during 1981–2005, Atmos. Environ., 59, 461–475, http://dx.doi.org/10.1016/j.atmosenv.2012.04.060doi:10.1016/j.atmosenv.2012.04.060, 2012. Larssen, T., and Carmichael, G. R.: Acid rain and acidification in China: the importance of base cation deposition, Environ. Pollut., 110, 89–102, http://dx.doi.org/10.1016/s0269-7491(99)00279-1doi:10.1016/s0269-7491(99)00279-1, 2000. Larssen, T., Lydersen, E., Tang, D., He, Y., Gao, J., Liu, H., Duan, L., Seip, H. M., Vogt, R. D., and Mulder, J.: Acid rain in China, Environ. Sci. Technol., 40, 418–425, http://dx.doi.org/10.1021/es0626133doi:10.1021/es0626133, 2006. Larssen, T., Duan, L., and Mulder, J.: Deposition and leaching of sulfur, nitrogen and calcium in four forested catchments in China: Implications for acidification, Environ. Sci. Technol., 45, 1192–1198, http://dx.doi.org/10.1021/es103426pdoi:10.1021/es103426p, 2011. Lestari, P., Oskouie, A. K., and Noll, K. E.: Size distribution and dry deposition of particulate mass, sulfate and nitrate in an urban area, Atmos. Environ., 37, 2507–2516, http://dx.doi.org/10.1016/s1352-2310(03)00151-1doi:10.1016/s1352-2310(03)00151-1, 2003. Lin, W., Xu, X., Ma, Z., Zhao, H., Liu, X., and Wang, Y.: Characteristics and recent trends of sulfur dioxide at urban, rural, and background sites in North China: Effectiveness of control measures, J. Environ. Sci., 24, 34–49, http://dx.doi.org/10.1016/s1001-0742(11)60727-4doi:10.1016/s1001-0742(11)60727-4, 2012. Liu, X. J., Duan, L., Mo, J. M., Du, E., Shen, J. L., Lu, X. K., Zhang, Y., Zhou, X. B., He, C. E., and Zhang, F. S.: Nitrogen deposition and its ecological impact in China: An overview, Environ. Pollut., 155, 2251–2264, http://dx.doi.org/10.1016/j.envpol.2010.08.002doi:10.1016/j.envpol.2010.08.002, 2010. Lu, Z., Streets, D. G., Zhang, Q., Wang, S., Carmichael, G. R., Cheng, Y. F., Wei, C., Chin, M., Diehl, T., and Tan, Q.: Sulfur dioxide emissions in China and sulfur trends in East Asia since 2000, Atmos. Chem. Phys., 10, 6311–6331, http://dx.doi.org/10.5194/acp-10-6311-2010doi:10.5194/acp-10-6311-2010, 2010. Meng, Z. Y., Ding, G. A., Xu, X. B., Xu, X. D., Yu, H. Q., and Wang, S. F.: Vertical distributions of SO<sub>2</sub> and NO<sub>2</sub> in the lower atmosphere in Beijing urban areas, China, Sci. Total. Environ., 390, 456–465, http://dx.doi.org/10.1016/j.scitotenv.2007.10.012doi:10.1016/j.scitotenv.2007.10.012, 2008. Meng, Z. Y., Xu, X. B., Wang, T., Zhang, X. Y., Yu, X. L., Wang, S. F., Lin, W. L., Chen, Y. Z., Jiang, Y. A., and An, X. Q.: Ambient sulfur dioxide, nitrogen dioxide, and ammonia at ten background and rural sites in China during 2007-2008, Atmos. Environ., 44, 2625–2631, http://dx.doi.org/10.1016/j.atmosenv.2010.04.008doi:10.1016/j.atmosenv.2010.04.008, 2010. Miller, E. K., Panek, J. A., Friedland, A. J., Kadlecek, J., and Mohnen, V. A.: Atmospheric deposition to a high-elevation forest at Whiteface Mountain, New York, USA, Tellus. B, 45, 209–227, http://dx.doi.org/10.1034/j.1600-0889.1993.t01-2-00001.xdoi:10.1034/j.1600-0889.1993.t01-2-00001.x, 1993. Pan, Y. P., Wang, Y. S., Xin, J. Y., Tang, G. Q., Song, T., Wang, Y. H., Li, X. R., and Wu, F. K.: Study on dissolved organic carbon in precipitation in Northern China, Atmos. Environ., 44, 2350–2357, http://dx.doi.org/10.1016/j.atmosenv.2010.03.033doi:10.1016/j.atmosenv.2010.03.033, 2010a. Pan, Y. P., Wang, Y. S., Yang, Y. J., Wu, D., Xin, J. Y., and Fan, W. Y.: Determination of trace metals in atmospheric dry deposition with a heavy matrix of PUF by inductively coupled plasma mass spectroscopy after microwave digestion (in Chinese), Environ. Sci., 31, 553–559, 2010b. Pan, Y. P., Wang, Y. S., Tang, G. Q., and Wu, D.: Wet and dry deposition of atmospheric nitrogen at ten sites in Northern China, Atmos. Chem. Phys., 12, 6515–6535, http://dx.doi.org/10.5194/acp-12-6515-2012doi:10.5194/acp-12-6515-2012, 2012. Park, S. U. and Lee, E. H.: Long-range transport contribution to dry deposition of acid pollutants in South Korea, Atmos. Environ., 37, 3967–3980, http://dx.doi.org/10.1016/S1352-2310(03)00470-9doi:10.1016/S1352-2310(03)00470-9, 2003. Reuss, J. O., Cosby, B. J., and Wright, R. F.: Chemical processes governing soil and water acidification, Nature, 329, 27–32, http://dx.doi.org/10.1038/329027a0doi:10.1038/329027a0, 1987. Rodhe, H., Dentener, F., and Schulz, M.: The global distribution of acidifying wet deposition, Environ. Sci. Technol., 36, 4382–4388, http://dx.doi.org/10.1021/es020057gdoi:10.1021/es020057g, 2002. Sakata, M., Marumoto, K., Narukawa, M., and Asakura, K.: Regional variations in wet and dry deposition fluxes of trace elements in Japan, Atmos. Environ., 40, 521–531, http://dx.doi.org/10.1016/j.atmosenv.2005.09.066doi:10.1016/j.atmosenv.2005.09.066, 2006. Saxena, A., Kulshrestha, U. C., Kumar, N., Kumari, K. M., Prakash, S., and Srivastava, S. S.: Dry deposition of sulphate and nitrate to polypropylene surfaces in a semi-arid area of India, Atmos. Environ., 31, 2361–2366, http://dx.doi.org/10.1016/s1352-2310(97)00052-6doi:10.1016/s1352-2310(97)00052-6, 1997. Schwede, D., Zhang, L., Vet, R., and Lear, G.: An intercomparison of the deposition models used in the CASTNET and CAPMoN networks, Atmos. Environ., 45, 1337–1346 http://dx.doi.org/10.1016/j.atmosenv.2010.11.050doi:10.1016/j.atmosenv.2010.11.050, 2011. Shen, J. L., Tang, A. H., Liu, X. J., Fangmeier, A., Goulding, K. T. W., and Zhang, F. S.: High concentrations and dry deposition of reactive nitrogen species at two sites in the North China Plain, Environ. Pollut., 157, 3106–3113, http://dx.doi.org/10.1016/j.envpol.2009.05.016doi:10.1016/j.envpol.2009.05.016, 2009. Shimadera, H., Kondo, A., Shrestha, K. L., Kaga, A., and Inoue, Y.: Annual sulfur deposition through fog, wet and dry deposition in the Kinki Region of Japan, Atmos. Environ., 45, 6299–6308, http://dx.doi.org/10.1016/j.atmosenv.2011.08.055doi:10.1016/j.atmosenv.2011.08.055, 2012. Sickles, J. E., Shadwick, D. S., Kilaru, J. V., and Grimm, J. W.: Errors in representing regional acid deposition with spatially sparse monitoring: Case studies of the eastern US using model predictions, Atmos. Environ., 43, 2855–2861, http://dx.doi.org/10.1016/j.atmosenv.2009.03.018doi:10.1016/j.atmosenv.2009.03.018, 2009. Sun, M., Wang, Y., Wang, T., Fan, S., Wang, W., Li, P., Guo, J., and Li, Y.: Cloud and the corresponding precipitation chemistry in south China: Water-soluble components and pollution transport, J. Geophys. Res., 115, D22303, http://dx.doi.org/10.1029/2010JD014315doi:10.1029/2010JD014315, 2010. Sun, Y.: Chemical composition and mass closure of particulate matter in Beijing, Tianjin and Hebei megacities, Northern China, Ms. thesis, Capital Normal University, Beijing, 69 pp., 2011. Sun, Y., Wang, Y., and Zhang, C.: Measurement of the vertical profile of atmospheric SO<sub>2</sub> during the heating period in Beijing on days of high air pollution, Atmos. Environ., 43, 468–472, http://dx.doi.org/10.1016/j.atmosenv.2008.09.057doi:10.1016/j.atmosenv.2008.09.057, 2009. Tang, J., Xu, X. B., Ba, J., and Wang, S. F.: Trends of the precipitation acidity over China during 1992–2006, Chinese. Sci. Bull., 55, 1800–1807, http://dx.doi.org/10.1007/s11434-009-3618-1doi:10.1007/s11434-009-3618-1, 2010. Tsai, J. L., Chen, C. L., Tsuang, B. J., Kuo, P. H., Tseng, K. H., Hsu, T. F., Sheu, B. H., Liu, C. P., and Hsueh, M. T.: Observation of SO<sub>2</sub> dry deposition velocity at a high elevation flux tower over an evergreen broadleaf forest in Central Taiwan, Atmos. Environ., 44, 1011–1019, http://dx.doi.org/10.1016/j.atmosenv.2009.12.022doi:10.1016/j.atmosenv.2009.12.022, 2010. Tsai, Y. I., Hsieh, L. Y., Kuo, S. C., Chen, C. L., and Wu, P. L.: Seasonal and rainfall-type variations in inorganic ions and dicarboxylic acids and acidity of wet deposition samples collected from subtropical East Asia, Atmos. Environ., 45, 3535–3547, http://dx.doi.org/10.1016/j.atmosenv.2011.04.001doi:10.1016/j.atmosenv.2011.04.001, 2011. Wai, K. M., Tanner, P. A., and Tam, C. W. F.: 2-year study of chemical composition of bulk deposition in a south China coastal city: Comparison with east Asian cities, Environ. Sci. Technol., 39, 6542–6547, http://dx.doi.org/10.1021/es048897ddoi:10.1021/es048897d, 2005. Wang, T. J., Zhang, Y., Zhang, M., Hu, Z. Y., Xu, C. K., and Zhao, Y. W.: Atmoshperic sulfur deposition and the sulfur nutrition of crops at an agricututral site in Jiangxi province of China, Tellus. B, 55, 893–900, http://dx.doi.org/10.1046/j.1435-6935.2003.00076.xdoi:10.1046/j.1435-6935.2003.00076.x, 2003. Wang, Y., Yu, W., Pan, Y., and Wu, D.: Acid neutralization of precipitation in Northern China, J. Air. Waste. Manage., 62, 204–211, http://dx.doi.org/10.1080/10473289.2011.640761doi:10.1080/10473289.2011.640761, 2012. Wesely, M. L. and Hicks, B. B.: A review of the current status of knowledge on dry deposition, Atmos. Environ., 34, 2261–2282, http://dx.doi.org/10.1016/s1352-2310(99)00467-7doi:10.1016/s1352-2310(99)00467-7, 2000. Wiegand, F., Pereira, F. N., and Teixeira, E. C.: Study on wet scavenging of atmospheric pollutants in south Brazil, Atmos. Environ., 45, 4770–4776, http://dx.doi.org/10.1016/j.atmosenv.2010.02.020doi:10.1016/j.atmosenv.2010.02.020, 2011. Wyers, G. P. and Duyzer, J. H.: Micrometeorological measurement of the dry deposition flux of sulphate and nitrate aerosols to coniferous forest, Atmos. Environ., 31, 333–343, http://dx.doi.org/10.1016/S1352-2310(96)00188-4doi:10.1016/S1352-2310(96)00188-4, 1997. Yang, F., Tan, J., Shi, Z. B., Cai, Y., He, K., Ma, Y., Duan, F., Okuda, T., Tanaka, S., and Chen, G.: Five-year record of atmospheric precipitation chemistry in urban Beijing, China, Atmos. Chem. Phys., 12, 2025–2035, http://dx.doi.org/10.5194/acp-12-2025-2012doi:10.5194/acp-12-2025-2012, 2012a. Yang, Y., Ji, C., Ma, W., Wang, S., Wang, S., Han, W., Mohammat, A., Robinson, D., and Smith, P.: Significant soil acidification across Northern China's grasslands during 1980s–2000s, Global. Change. Biol., 18, 2292–2300, http://dx.doi.org/10.1111/j.1365-2486.2012.02694.xdoi:10.1111/j.1365-2486.2012.02694.x, 2012b. Zhang, Q., Streets, D. G., Carmichael, G. R., He, K. B., Huo, H., Kannari, A., Klimont, Z., Park, I. S., Reddy, S., and Fu, J. S.: Asian emissions in 2006 for the NASA INTEX-B mission, Atmos. Chem. Phys., 9, 5131–5153, http://dx.doi.org/10.5194/acp-9-5131-2009doi:10.5194/acp-9-5131-2009, 2009. Zhang, X., Van Geffen, J., Liao, H., Zhang, P., and Lou, S.: Spatiotemporal variations of tropospheric SO2 over China by SCIAMACHY observations during 2004–2009, Atmos. Environ., 60, 238-246, http://dx.doi.org/10.1016/j.atmosenv.2012.06.009doi:10.1016/j.atmosenv.2012.06.009, 2012. Zhao, D., Xiong, J., Xu, Y., and Chan, W. H.: Acid rain in southwestern China, Atmos. Environ., 22, 349-358, http://dx.doi.org/10.1016/0004-6981(88)90040-6doi:10.1016/0004-6981(88)90040-6, 1988. Zhao, Y., Duan, L., Xing, J., Larssen, T., Nielsen, C. P., and Hao, J.: Soil acidification in China: Is controlling SO<sub>2</sub> emissions enough?, Environ. Sci. Technol., 43, 8021–8026, http://dx.doi.org/10.1021/es901430ndoi:10.1021/es901430n, 2009.