References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-10-21439-2010

Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China

Fang

Y. T.

¹ ² Koba

² Wang

X. M.

³ Wen

D. Z.

¹ Li

¹ Takebayashi

² Liu

X. Y.

² Yoh

South China Botanical Garden, Chinese Academy of Sciences, Guangzhou 510650, China

Tokyo University of Agriculture and Technology, Tokyo 183 8509, Japan

School of Environmental Sciences and Engineering, Sun Yat-Sen University, \newline Guangzhou 501275, China

08 09 2010

10 9 21439 21474

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-discuss.net/10/21439/2010/acpd-10-21439-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/10/21439/2010/acpd-10-21439-2010.pdf

Nitric acid (HNO3) or nitrate (NO3−) is the dominant sink for reactive nitrogen oxides (NOx = NO + NO2) in the atmosphere. In many Chinese cities, HNO3 is becoming a significant contributor to acid deposition. In the present study, we used the denitrifier method to measure nitrogen (N) and oxygen (O) isotopic composition of NO3− in 113 precipitation samples collected from Guangzhou City in southern China over a two-year period (2008 and 2009). We attempted to better understand the spatial and seasonal variability of atmospheric NOx sources and the NO3− formation pathways in this N-polluted city in the Pearl River Delta region. The δ15N values of NO3− (versus air N2) ranged from −4.9 to +10.1&permil;, and averaged +3.9&permil; in 2008 and +3.3&permil; in 2009. Positive δ15N values were observed throughout the year, indicating the anthropogenic contribution of NOx emissions, particularly from coal combustion. Different seasonal patterns of δ15N-NO3− were observed between 2008 and 2009, which might reflect different human activities associated with the global financial crisis and the intensive preparations for the 16th Asian Games. Nitrate δ18O values (versus Vienna Standard Mean Ocean Water) varied from +33.4 to +86.5&permil; (average +65.0&permil; and +67.0&permil; in 2008 and 2009, respectively), a range being lower than those reported for high altitude and polar areas. Several δ18O values were observed lower than the expected minimum of 50&permil; at our study site. This was likely caused by the reaction of NO with peroxy radicals; peroxy radicals can compete with O3 to convert NO to NO2, thereby donate O atoms with much lower δ18O value than that of O3 to atmospheric NO3−. Our results highlight that the influence of human activities on atmospheric chemistry can be recorded by the N and O isotopic composition of atmospheric NO3− in a N-polluted city.

References 1

Aber, J. D., McDowell, W., Nadelhoffer, K., Magill, A., Berntson, G., Kamakea, M., McNulty, S., Currie, W., Rustad, L., and Fernandez, I.: Nitrogen saturation in temperate forest ecosystems – hypothesis revisited, BioScience, 48, 921–934, 1998.

Alexander, B., Hastings, M. G., Allman, D. J., Dachs J., Thornton J. A., and Kunasek, S. A.: Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition ($\Delta^17$O) of atmospheric nitrate, Atmos. Chem. Phys., 9, 5043–5056, doi:10.5194/acp-9-5043-2009, 2009.

Ammann, M., Siegwolf, R., Pichlmayer, F., Suter M., Saurer, M., and Brunold, C.: Estimating the uptake of traffic-derived NO2 from N-15 abundance in Norway spruce needles, Oecologia, 118(2), 124–131, 1999.

Baker, A. R., Westin, K., Kelly, S. D., Voss, M., Streu, P., and Cape, J. N.: Dry and wet deposition of nutrients from the tropical Atlantic atmosphere: Links to primary productivity and nitrogen fixation, Deep Sea Res., Part I, 54, 1704–1720, 2007.

Calvert, J. G., Lazrus, A., Kok, G. L., Heikes, B. G., Walega, J. G., Lind, J., and Cantrell, C. A.: Chemical mechanisms of acid generation in the troposphere, Nature, 317, 27–35, 1985.

Cao, Y. Z., Wang, S. Y., Zhang, G.,Luo, J. Y., and Lu, S. Y.: Chemical characteristic and source assessment of wet precipitation at Mountain Baiyun, Guangzhou, (in Chinese with English abstract), The Administ. Tech. Environ. Monit., 21(6), 20–23, 2009.

Carrillo, J. H., Hastings, M. G., Sigman, D. M., and Huebert, B. J.: Atmospheric deposition of inorganic and organic nitrogen and base cations in Hawaii, Global Biogeochem. Cy., 16(4), 1076, doi:10.1029/2002GB001892, 2002.

Casciotti, K. L., Böhlke, J. K., McIlvin, M. R., Mroczkowski, S. J., and Hannon, J. E.: Oxygen isotopes in nitrite: Analysis, calibration, and equilibration, Anal. Chem., 79(6), 2427–2436, 2007.

Casciotti, K. L., Sigman, D. M., Hastings M. G., Böhlke, J. K., and Hilkert, A.: Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method, Anal. Chem., 74(19), 4905–4912, doi:10.1021/ac020113w, 2002.

Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website (http://ready.arl.noaa.gov/HYSPLIT.php), NOAA Air Resources Laboratory, Silver Spring, MD, USA, 2010.

Ehhalt, D., Prather, M., Dentener, F., Derwent, R., Dlugokencky, E., Holland, E., Isaksen, I., Katima, J., Kirchhoff, V., Matson, P., Midgley, P., and Wang, M.: Atmospheric chemistry and greenhouse gases. In Climate Change 2001: \textitThe Scientific Basis. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Houghton, J. T., Ding, Y., Griggs, D. J., Noguer, M., van der Linden, P. J., Dai, K., Maskell, K., Johnson, C. A., Cambridge University Press, New York, USA, 2001.

Elliott, E. M., Kendall, C., Boyer, E. W., Burns, D. A., Lear, G. G., Golden, H. E., Harlin, K., Bytnerowicz, A., Butler, T. J., and Glatz, R.: Dual nitrate isotopes in dry deposition: Utility for partitioning NOx source contributions to landscape nitrogen deposition, J. Geophys. Res., 114, G04020, doi:10.1029/2008JG000889, 2009.

Elliott, E. M., Kendall, C., Wankel, S. D., Burns, D. A., Boyer, E. W., Harlin, K., Bain, D. J., and Butler, T. J.: Nitrogen isotopes as indicators of NOx source contributions to atmospheric nitrate deposition across the midwestern and northeastern United States, Environ. Sci. Technol., 41(22), 7661–7667, 2007.

Fang, Y. T., Gundersen, P., Zhu, W. X., Mo, J. M.: Input and output of dissolved organic and inorganic nitrogen in subtropical forests of South China under high air pollution, Biogeosciences, 5, 339–352, doi:10.5194/bg-5-339-2008, 2008.

Freyer, H. D.: Seasonal variation of $^15$N/$^14$N ratios in atmospheric nitrate species, Tellus, Ser. B, 43, 30–44, 1991.

Freyer, H.: Seasonal trend of NH$_4^+$ and NO$_3^-$ nitrogen isotope composition in rain collected at Julich, Germany, Tellus, 30(1), 83–92, 1978.

Fukuzaki, N. and Hayasaka, H.: Seasonal variations of nitrogen isotopic ratios of ammonium and nitrate in precipitations collected in the Yahiko–Kakuda mountain area in Niigata Prefecture, Japan, Water Air Soil Pollut., 203, 391–397, 2009.

Galloway, J. N., Dentener, F. J., Capone, D. G., Boyer, E. W., Howarth, R. W., Seitzinger, S. P., Asner, G. P., Cleveland, C. C., Green, P. A., Holland, E. A., Karl, D. M., Michaels, A. F., Porter, J. H., Townsend, A. R., and Vorosmarty, C. J.: Nitrogen cycles: Past, present, and future, Biogeochemistry, 70, 153–226, doi:10.5194/bg-70-153-2004, 2004.

Galloway, J. N., Townsend, A. R., Erisman, J. W., Bekunda, M., Cai, Z., Freney, J. R., Martinelli, L. A., Seitzinger, S. P., and Sutton, M. A.: Transformation of the nitrogen cycle: recent trends, questions, and potential solutions, Science, 320, 889–892, 2008.

Goodale, C. L., Thomas, S. A., Fredriksen, G., Elliott, E. M., Flinn, K. M., Butler, T. J., and Walter, M. T.: Unusual seasonal patterns and inferred processes of nitrogen retention in forested headwaters of the Upper Susquehanna River, Biogeochemistry, 93, 197–218, doi:10.5194/bg-93-197-2009, 2009.

Gundersen, P., Emmett, A., Kjønaas, O. J., Koopmans, C. J., and Tietema, A.: Impact of nitrogen deposition on nitrogen cycling in forest: a synthesis of NITREX data, For. Ecol. Manag. 101, 37–55, 1998.

Hastings, M. G., Sigman, D. M., and Lipschultz, F.: Isotopic evidence for source changes of nitrate in rain at Bermuda, J. Geophys. Res., 108(D24), 4790, doi:10.1029/2003JD003789, 2003.

Hastings, M. G., Steig, E. J., and Sigman, D. M.: Seasonal variations in N and O isotopes of nitrate in snow at Summit, Greenland: Implications for the study of nitrate in snow and ice cores, J. Geophys. Res., 109, D20306, doi:10.1029/2004JD004991, 2004.

Heaton, T. H. E., Wynn, P., and Tye, A. M.: Low $^15$N/$^14$N ratios for nitrate in snow in the High Arctic (79 degrees N), Atmos. Environ., 38, 5611–5621, 2004.

Heaton, T. H. E.: $^15$N/$^14$N ratios of NOx from vehicle engines and coal-fired power stations, Tellus, Ser. B, 42, 304–307, 1990.

Hoering, T.: The isotopic composition of the ammonia and the nitrate ion in rain, Geochim. Cosmochim. Acta, 12(1–2), 97–102, 1957.

Hua, W., Chen, Z. M., Jie, C. Y., Kondo, Y., Hofzumahaus, A., Takegawa, N., Chang, C. C., Lu, K. D., Miyazaki, Y., Kita, K., Wang, H. L., Zhang, Y. H., and Hu, M.: Atmospheric hydrogen peroxide and organic hydroperoxides during PRIDE-PRD'06, China: their concentration, formation mechanism and contribution to secondary aerosols, Atmos. Chem. Phys., 8, 6755–6773, doi:10.5194/acp-8-6755-2008, 2008.

Huang, D. Y., Xu, Y. G., Peng, P. A., Zhang, H. H., and Lan, J. B.: Chemical composition and seasonal variation of acid deposition in Guangzhou, South China: Comparison with precipitation in other major Chinese cities, Environ. Pollut., 157, 35–41, 2009.

Jarvis, J. C., Steig, E. J., Hastings, M. G., and Kunasek, S. A.: Influence of local photochemistry on isotopes of nitrate in Greenland snow, Geophys. Res. Lett., 35, L21804, doi:10.1029/2008GL035551, 2008.

Kendall, C., Elliott, E. M., and Wankel, S. D.: Tracing anthropogenic inputs of nitrogen to ecosystem, in: Stable Isotopes in Ecology and Environmental Science, edited by: Lajtha, K. and Michener, R. H., 2nd edition, Wiley-Blackwell Scientific Publication 375–449, 2007.

Kiga, T., Yoshikawa K., Tsunogai, U., Okitsu, S., and Narukawa, K.: Evaluation of NOx formation in pulverized coal firing by use of nitrogen isotope ratios, paper presented at International Joint Power Generation Conference, Am. Soc. Mech. Eng., Miami Beach, FL, USA, 23–26 July, 2000.

Koba, K., Fang, Y. T., Mo, J.M., Zhang, W., Lu, X. K., Liu, L., Zhang, T., Takebayashi, Y., Toyoda, S., and Yoshida, N.: $^15$N natural abundance in a nitrogen-saturated subtropical forest in southern China: Does a nitrogen-saturated forest lose $^14$N preferentially? Ecosystems, under review, 2010.

Kurata, H.: Nitrogen isotope composition in atmospheric deposition – annual, seasonal and regional variation. Master's thesis, Tokyo University of Agriculture and Technology, Fuchu, Tokyo, 2002.

Li, D. J. and Wang, X. X.: Nitrogen isotopic signature of soil-released nitric oxide (NO) after fertilizer application, Atmos. Environ., 42, 4747–4754, 2008.

Liang, J. Y., Horowitz, L. W., Jacob, D. J., Wang, Y., Fiore, A. M., Logan, J. A., Gardner, G. M., and Munger, J. W.: Seasonal budgets of reactive nitrogen species and ozone over the United States, and export fluxes to the global atmosphere, J. Geophys. Res., 103(D11), 13435–13450, doi:10.1029/97JD03126, 1998.

Liu, J. F., Song, Z. G., and Xu, T.: Study on ionic composition of rainwater at Guangzhou and the primary factors of rainwater acidity, Environ. Sci., 27(10), 1998–2002, 2006.

Liu, J. Q., Keene, W. C., and Wu, G. P.: Study of precipitation background value in Lijiang, China, China Environ. Sci. 13, 246–251, 1993.

Liu, Y., Shao, M., Lu, S. H., Chang, C. C., Wang, J. L., and Chen, G.: Volatile organic compound (VOC) measurements in the Pearl River Delta (PRD) region, China, Atmos. Chem. Phys., 8, 1531–1545, doi:10.5194/acp-8-1531-2008, 2008.

Michalski, G., Scott, Z., Kabiling, M., and Thiemens, M. H.: First measurements and modeling of $\Delta^17$O in atmospheric nitrate, Geophys. Res. Lett., 30(16), 1870, doi:10.1029/2003GL017015, 2003.

Moore, H.: The isotopic composition of ammonia, nitrogen dioxide, and nitrate in the atmosphere, Atmos. Environ., 11, 1239–1243, 1977.

Morin, S., Savarino, J., Frey, M. M., Domine, F., Jacobi, H. W., Kaleschke, L., and Martins, J. M. F.: Comprehensive isotopic composition of atmospheric nitrate in the Atlantic Ocean boundary layer from 65°S to 79° N, J. Geophys. Res., 114, D05303, doi:10.1029/2008JD010696, 2009.

Morin, S., Savarino, J., Frey, M. M., Yan, N., Bekki, S., Bottenheim, J. W., and Martins, J. M. F.: Tracing the origin and fate of NOx in the arctic atmosphere using stable isotopes in nitrate, Science, 322(5902), 730–732, 2008.

Pearson, J., Wells, D. M., Seller, K. J., Bennett, A., Soares, A., Woodall, J., and Ingrouille, M. J.: Traffic exposure increases natural $^15$N and heavy metal concentrations in mosses, New Phytol., 147, 317–326, 2000.

Quan, W. Z., Feng, S. Y., and Lu, X. A.: Current status and tendency of acid rain in Guangzhou City, Shanghai, (in Chinese), Environ. Sci., 11(1), 20–23, 1992.

Russell, K. M., Galloway, J. N., Macko, S. A., Moody, J. L., and Scudlark, J. R.; Sources of nitrogen in wet deposition to the Chesapeake Bay region, Atmos. Environ., 32, 2453–2465, 1998.

Savarino, J., Kaiser, J., Morin, S., Sigman, D. M., and Thiemens, M. H.: Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica, Atmos. Chem. Phys., 7(8), 1925–1945, doi:10.5194/acp-7-1925-2007, 2007.

Shao, M, Zhang, Y. H., Zeng, L. M., Tang, X. Y., Zhang, J., Zhong, L. J., and Wang, B. G.: Ground-level ozone in the Pearl River Delta and the roles of VOC and NOx in its production, J. Environ. Manag., 90(1), 512–518, 2009.

Sigman, D. M., Casciotti, K. L., Andreani, M., Barford, C., Galanter, M., and Böhlke, J. K.: A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater, Anal. Chem., 73(17), 4145–4153, 2001.

Tian, H. Z., Hao, J. M., Lu, Y. Q., and Zhu, T. L.: Inventories and distribution characteristics of NOx emissions in China, (in Chinese with English abstract), China Environ. Sci., 21(6), 493-497, 2001.

Tobari, Y., Koba, K., Fukushima, K., Tokuchi, N., Ohte, N., Tateno, R., Toyoda, S., Yoshioka, T., and Yoshida, N.: Contribution of atmospheric nitrate to stream-water nitrate in Japanese coniferous forests revealed by oxygen isotope ratio of nitrate, Rapid Commun. Mass. Spectrom. 24, 91281–1286, 2010.

Tsunogai, U., Komatsu, D. D., Daita, S., Kazemi, G. A., Nakagawa, F., Noguchi, I., and Zhang, J.: Tracing the fate of atmospheric nitrate deposited onto a forest ecosystem in Eastern Asia using $\Delta^17$O. Atmos. Chem. Phys. 10, 1809–1820, 2010.

Vitousek, P. M., Aber, J. D., Howarth, R. W., Likens, G. E., Matson, P. A., Schindler, D. W., Schlesinger, W. H., and Tilman, D. G.: Human alteration of the global nitrogen cycle: Sources and consequences, Ecol. Appl., 7, 737–750, 1997.

Wang, H. K., Fu, L. X., Zhou, Y., Du, X., and Ge, W. H.: Trends in vehicular emissions in China's mega cities from 1995 to 2005, Environ. Pollut., 158, 394–400, 2010.

Wang, T., Poon, C. N., Kwok, Y. H., and Li, Y. S.: Characterizing the temporal variability and emission patterns of polluting plumes in the Pearl River Delta of China, Atmos. Environ. 37, 3539–3550, 2003.

Wang, Y., McElroy, M. B., Martin, R. V., Streets, D. G., Zhang, Q., and Fu, T. M.: Seasonal variability of NOx emissions over east China constrained by satellite observations: Implications for combustion and microbial sources, J. Geophys. Res., 112, D06301, doi:10.1029/2006JD007538, 2007.

Wankel, S. D., Chen, Y., Kendall, C., Post, A. F., and Paytan, A.: Sources of aerosol nitrate to the Gulf of Aqaba: Evidence from $\delta^15$N and $\delta^18$O of nitrate and trace metal chemistry, Mar. Chem., 120(1–4), 90–99, 2010.

Widory, D.: Nitrogen isotopes: Tracers of origin and processes affecting PM10 in the atmosphere of Paris. Atmos. Environ., 41, 2382–2390, 2007.

Wu, J. H., Nishijima, Y., and Satake, H.: Seasonal variation of $\delta^15$N of nitrate ion found in precipitation at Toyama, Chikyukagaku Geochemistry, 42(1), 1–11, 2008.

Xiao H. Y. and Liu, C. Q.: Sources of nitrogen and sulfur in wet deposition at Guiyang, southwest China, Atmos. Environ. 36, 5121–5130, 2002.

Ye, S. D., Liu, J. J., and Wu, R. H.: Analysis on the chemical characteristics and variation tendency of precipitation in Guangzhou City, Acta Scientiarum Naturalium Universitatis Sunyatseni, (in Chinese with English abstract), 47(suppl.), 43–47, 2008.

Yeatman, S. G., Spokes, L. J., Dennis, P. F., and Jickells, T. D.: Comparison of aerosol nitrogen isotopic composition at two polluted coastal sites, Atmos. Environ., 35, 1307–1320, 2001.

Zhang, Y. H., Su, H., Zhong, L. J., Cheng, Y. F., Xiang, Y. R., Wang, J. L., Gao, D. F., Shao, M., Fan, S. J., and Liu, S. C.: Regional ozone pollution and observation-based approach for analyzing ozone–precursor relationship during the PRIDE-PRD2004 campaign, Atmos. Environ., 42(25), 6203–6218, 2008a.

Zhang, Y., Liu, X. J., Fangmeier, A., Goulding, K. T. W., and Zhang, F. S.: Nitrogen inputs and isotopes in precipitation in the North China Plain, Atmos. Environ., 42, 1436–1448, 2008b.

Zhao, Y., Duan, L., Xing, J., Larssen T., Nielsen C. P., and Hao J. M.: Soil acidification in China: Is controlling SO2 emissions enough?, Environ. Sci. Tech., 43(21), 8021–8026, 2009.

Zheng, J. Y., Zhang, L. J., Che, W. W., Zheng, Z. Y., and Yin, S. S.: A highly resolved temporal and spatial air pollutant emission inventory for the Pearl River Delta region, China and its uncertainty assessment, Atmos. Environ., 43, 5112–5122, 2009.