<?xml version="1.0" encoding="utf-8" standalone="no"?>
<!DOCTYPE article SYSTEM "http://www.biogeosciences.net/inc/bg/copernicus.dtd">
<article language="en">
	<journal>
		<journal_title>Biogeosciences</journal_title>
		<journal_url>www.biogeosciences.net</journal_url>
		<issn>1726-4170</issn>
		<eissn>1726-4189</eissn>
		<volume_number>5</volume_number>
		<issue_number>5</issue_number>
		<publication_year>2008</publication_year>
	</journal>
	<doi>10.5194/bg-5-1215-2008</doi>
	<article_url>http://www.biogeosciences.net/5/1215/2008/</article_url>
	<abstract_html>http://www.biogeosciences.net/5/1215/2008/bg-5-1215-2008.html</abstract_html>
	<fulltext_pdf>http://www.biogeosciences.net/5/1215/2008/bg-5-1215-2008.pdf</fulltext_pdf>
	<start_page>1215</start_page>
	<end_page>1226</end_page>
	<publication_date>2008-09-02</publication_date>
	<article_title content_type="html">Groundwater N&lt;sub&gt;2&lt;/sub&gt;O emission factors of nitrate-contaminated aquifers as derived from denitrification progress and N&lt;sub&gt;2&lt;/sub&gt;O accumulation</article_title>
	<authors>
		<author numeration="1" affiliations="1">
			<name>D. Weymann</name>
		</author>
		<author numeration="2" affiliations="1">
			<name>R. Well</name>
			<email>rwell@gwdg.de</email>
		</author>
		<author numeration="3" affiliations="1">
			<name>H. Flessa</name>
		</author>
		<author numeration="4" affiliations="2">
			<name>C. von der Heide</name>
		</author>
		<author numeration="5" affiliations="3">
			<name>M. Deurer</name>
		</author>
		<author numeration="6" affiliations="4">
			<name>K. Meyer</name>
		</author>
		<author numeration="7" affiliations="5">
			<name>C. Konrad</name>
		</author>
		<author numeration="8" affiliations="5">
			<name>W. Walther</name>
		</author>
	</authors>
	<affiliations>
		<affiliation numeration="1" content_type="html">Soil Science of Temperate and Boreal Ecosystems, Büsgen-Institute, University of Göttingen, Büsgenweg 2, 37077 Göttingen, Germany</affiliation>
		<affiliation numeration="2" content_type="html">Institute for Soil Science, University of Hannover, Herrenhäuser Str. 2, 30419 Hannover, Germany</affiliation>
		<affiliation numeration="3" content_type="html">HortResearch, Tennent Drive, Palmerston North, 4474, New Zealand</affiliation>
		<affiliation numeration="4" content_type="html">Geries Ingenieure, Büro für Standorterkundung, Kirchberg 12, 37130 Gleichen, Germany</affiliation>
		<affiliation numeration="5" content_type="html">Institute for Groundwater Management, Dresden University of Technology, 01062 Dresden, Germany</affiliation>
	</affiliations>
	<abstract content_type="html">We investigated the dynamics of denitrification and nitrous oxide
(N&lt;sub&gt;2&lt;/sub&gt;O) accumulation in 4 nitrate (NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;)
contaminated denitrifying sand and gravel aquifers of northern Germany
(Fuhrberg, Sulingen, Thülsfelde and Göttingen) to quantify their
potential N&lt;sub&gt;2&lt;/sub&gt;O emission and to evaluate existing concepts of
N&lt;sub&gt;2&lt;/sub&gt;O emission factors. Excess N&lt;sub&gt;2&lt;/sub&gt; &amp;ndash; N&lt;sub&gt;2&lt;/sub&gt; produced by denitrification – was determined by using the argon
(Ar) concentration in groundwater as a natural inert tracer, assuming that
this noble gas functions as a stable component and does not change during
denitrification. Furthermore, initial NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt; concentrations
(NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt; that enters the groundwater) were derived from
excess N&lt;sub&gt;2&lt;/sub&gt; and actual NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt; concentrations in
groundwater in order to determine potential indirect N&lt;sub&gt;2&lt;/sub&gt;O
emissions as a function of the N input. Median concentrations of
N&lt;sub&gt;2&lt;/sub&gt;O and excess N&lt;sub&gt;2&lt;/sub&gt; ranged from 3 to 89 μg N L&lt;sup&gt;&amp;minus;1&lt;/sup&gt;
 and from 3 to 10 mg N L&lt;sup&gt;&amp;minus;1&lt;/sup&gt;, respectively.
Reaction progress (RP) of denitrification was determined as the ratio
between products (N&lt;sub&gt;2&lt;/sub&gt;O-N + excess N&lt;sub&gt;2&lt;/sub&gt;) and
starting material (initial NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt; concentration) of the
process, characterizing the different stages of denitrification.
N&lt;sub&gt;2&lt;/sub&gt;O concentrations were lowest at RP close to 0 and RP close
to 1 but relatively high at a RP between 0.2 and 0.6. For the first time, we
report groundwater N&lt;sub&gt;2&lt;/sub&gt;O emission factors consisting of the
ratio between N&lt;sub&gt;2&lt;/sub&gt;O-N and initial NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;-N
concentrations (EF1). In addition, we determined a groundwater emission
factor (EF2) using a previous concept consisting of the ratio
between N&lt;sub&gt;2&lt;/sub&gt;O-N and actual NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;-N
concentrations. Depending on RP, EF(1) resulted in smaller values
compared to EF(2), demonstrating (i) the relevance of
NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt; consumption and consequently (ii) the need
to take initial NO&lt;sup&gt;&amp;minus;&lt;/sup&gt;&lt;sub&gt;3&lt;/sub&gt;-N concentrations into account. In
general, both evaluated emission factors were highly variable within and
among the aquifers. The site medians ranged between 0.00043–0.00438 for
EF(1) and 0.00092–0.01801 for EF(2), respectively. For the aquifers of
Fuhrberg and Sulingen, we found EF(1) median values which are close to the
2006 IPCC default value of 0.0025. In contrast, we determined significant
lower EF values for the aquifers of Thülsfelde and Göttingen.
Summing the results up, our study supports the substantial downward
revision of the IPCC default EF5-g from 0.015 (1997) to 0.0025 (2006).</abstract>
	<references>
		<reference numeration="1" content_type="text"> Aeschbach-Hertig, W., Beyerle, U., Holocher, J., Peeters, F., and Kipfer, R.: Excess air in groundwater as a potential indicator of past environmental changes, in: Study of Environmental Change using Isotope Techniques, IAEA, Vienna, Austria, C&amp;S Papers Series 13/P, 174–183, 2002. </reference>
		<reference numeration="2" content_type="text"> Almeida, J. S., Reis, M. A. M., and Carrondo M. J. T.: A unifying kinetic model of denitrification, J. Theor. Biol., 186, 241–249, 1997. </reference>
		<reference numeration="3" content_type="text"> Blackmer, A. M. and Bremner, J. M.: Inhibitory effect of nitrate on reduction of nitrous oxide to molecular nitrogen by soil microorganisms, Soil Biol. Biochem., 10, 187–191, 1978. </reference>
		<reference numeration="4" content_type="text"> Blicher-Mathiesen, G., McCarty G. W., and Nielsen, C. P.: Denitrification and degassing in groundwater estimated from dissolved nitrogen and argon, J. Hydrol., 208, 16–24, 1998. </reference>
		<reference numeration="5" content_type="text"> Blicher-Mathiesen, G. and Hoffmann, C. C.: Denitrification as a sink for dissolved nitrous oxide in a freshwater riparian fen, J. Environ. Qual., 28, 257–262, 1999. </reference>
		<reference numeration="6" content_type="text"> Böhlke, J. K.: Groundwater recharge and agricultural contamination, Hydrogeol. J., 10, 153–179, 2002. </reference>
		<reference numeration="7" content_type="text"> Böhlke, J. K. and Denver J. M.: Combined use of groundwater dating, chemical and isotopic analyses to resolve the history and fate of nitrate contamination in two agricultural watersheds, Atlantic Coastal Plain, Maryland, Water Resour. Res., 31, 2319–2339, 1995. </reference>
		<reference numeration="8" content_type="text"> Böttcher, J., Strebel, O., and Duijnisveld, W. H. M.: Vertikale \mboxStoffkonzentrationsprofile im Grundwasser eines Lockergesteins-Aquifers und deren Interpretation (Beispiel Fuhrberger Feld), Z. dt. Geol. Ges., 136, 543–552, 1985. </reference>
		<reference numeration="9" content_type="text"> Böttcher, J., Strebel, O., Voerkelius, S., and Schmidt, H. L.: Using isotope fractionation of nitrate-nitrogen and nitrate-oxygen for evaluation of microbial denitrification in a sandy aquifer, J. Hydrol., 114, 413–424, 1990. </reference>
		<reference numeration="10" content_type="text"> Cho, C. M. and Mills, J. G.: Kinetic formulation of the denitrification process in soil, Can. J. Soil. Sci., 59, 249–257, 1979. </reference>
		<reference numeration="11" content_type="text"> Clough, T. J., Sherlock, R. R., and Rolston, D. E.: A review of the movement and fate of N&lt;sub&gt;2&lt;/sub&gt;O in the subsoil, Nutr. Cycl. Agroecosys., 72, 3–11, 2005. </reference>
		<reference numeration="12" content_type="text"> Clough, T. J., Addy, K., Kellogg, D. Q., Nowicki, B. L., Gold, A. J., and Groffman, P. M.: Dynamics of nitrous oxide in groundwater at the aquatic-terrestrial interface, Global Change Biol., 13, 1528–1537, 2007. </reference>
		<reference numeration="13" content_type="text"> Crutzen, P. J.: Atmospheric chemical processes of the oxides of nitrogen, including nitrous oxide, in: Denitrification, nitrification and nitrous oxide, edited by: Delwiche, C., Wiley, New York, 17–44, 1981. </reference>
		<reference numeration="14" content_type="text"> Deurer, M., von der Heide, C., Böttcher, J., Duijnisveld, W. H. R., Weymann, D., and Well, R.: The dynamics of N&lt;sub&gt;2&lt;/sub&gt;O near the groundwater table and the transfer of N&lt;sub&gt;2&lt;/sub&gt;O into the unsaturated zone: A case study from a sandy aquifer in Germany, Catena, 72, 362–373, 2008. </reference>
		<reference numeration="15" content_type="text"> Dobbie, K. E. and Smith, K. A.: Nitrous oxide emission factors for agricultural soils in Great Britain: the impact of soil water-filled pore space and other controlling variables, Global Change Biol., 9, 204–218, 2003. </reference>
		<reference numeration="16" content_type="text"> Dunkle, S. A., Plummer, L. N., Busenberg, E., Phillips, P. J., Denver, J. M., Hamilton, P. A., Michel, R. L., and Coplen, T. B.: Chlorofluorocarbons (CCl&lt;sub&gt;3&lt;/sub&gt;F and CCl&lt;sub&gt;2&lt;/sub&gt;F$_2)$ as dating tools and hydrologic tracers in shallow ground water of the Delmava Peninsula, Atlantic Coastal Plain, United States, Water Resour. Res., 29, 3837–3860, 1993. </reference>
		<reference numeration="17" content_type="text"> Duxbury, J. M. and Mosier, A. R.: Status and issues concerning agricultural emissions of greenhouse gases, in: Agricultural dimensions of global climate change, edited by: Kaiser, H. M. and Drennen, T. E., St Lucie Press, USA, 229–258, 1993. </reference>
		<reference numeration="18" content_type="text"> Firestone, M. K., Firestone, R. B., and Tiedje, J. M.: Nitrous oxide from soil denitrification: factors controlling its biological production, Science, 208, 749–751, 1980. </reference>
		<reference numeration="19" content_type="text"> Granli, T. and Bøckman, O. C.: Nitrous oxide from agriculture, Norwegian Journal of Agricultural Sciences, 12, 128 pp., 1994. </reference>
		<reference numeration="20" content_type="text"> Green, T. C., Puckett, L. J., Böhlke, J. K., Bekins, B. A., Phillips, S. P., Kauffman, L. J., Denver, J. M., and Johnson, H. M.: Limited occurance of denitrification in four shallow aquifers in agricultural areas of the United States, J. Environ. Qual., 37, 994–1009, doi:10.2134/jeq2006.0419, 2008. </reference>
		<reference numeration="21" content_type="text"> Heaton, T. H. E. and Vogel, J. C.: Excess air in groundwater, J. Hydrol., 50, 201–216, 1981. </reference>
		<reference numeration="22" content_type="text"> Heaton, T. H. E., Talma, A. S., and Vogel, J. C.: Origin and history of nitrate in confined groundwater in the Western Kalahari, J. Hydrol., 62, 243–262, 1983. </reference>
		<reference numeration="23" content_type="text"> Hefting, M. M., Bobbink, R., and de Caluwe, H.: Nitrous oxide emission and denitrification in chronically nitrate-loaded riparian buffer zones, J. Environ. Qual., 32(4), 1194–1203, 2003. </reference>
		<reference numeration="24" content_type="text"> Hiscock, K. M., Bateman, A. S., Fukada, T., and Dennis, P. F.: The concentration and distribution of groundwater N&lt;sub&gt;2&lt;/sub&gt;O in the chalk aquifer of eastern England, in: Proceedings 3rd International Symp. on non-CO&lt;sub&gt;2&lt;/sub&gt; greenhouse gases, edited by: van Ham, J., Baede, A. P. M., Guicherit, R., and Williams-Jacobsen, J. G. F. M., Maastricht, The Netherlands, 185–190, 2002. </reference>
		<reference numeration="25" content_type="text"> Hiscock, K. M., Bateman, A. S., Mühlherr, I. H., Fukada, T., and Dennis, P. F.: Indirect emissions of nitrous oxide from regional aquifers in the United Kingdom, Environ. Sci. Technol., 37, 3507–3512, 2003. </reference>
		<reference numeration="26" content_type="text"> Holocher, J., Peeters, F., Aeschbach-Hertig, W., Hofer, M., Brennwald, M., Kinzelbach, W., and Kipfer, R.: Experimental investigations on the formation of excess air in quasi-saturated porous media, Geoch. Cosm. Acta, 66, 4103–4117, 2002. </reference>
		<reference numeration="27" content_type="text"> Höll, B. S., Jungkunst, H. F., Fiedler, S., and Stahr, K.: Indirect nitrous oxide emission from a nitrogen saturated spruce forest and general accuracy of the IPCC methodology, Atmos. Environ., 39, 5959–5970, 2005. </reference>
		<reference numeration="28" content_type="text"> Kölle, W., Strebel, O., and Böttcher, J.: Formation of sulfate by microbial denitrification in a reducing aquifer, Water Supply, 3, 35–40, 1985. </reference>
		<reference numeration="29" content_type="text"> International Panel on Climate Change: Revised 1996 IPCC guidelines for national greenhouse gas inventories, Reference manual, Vol. 3, Organisation for Economic Cooperation and Development, Paris, 1997. </reference>
		<reference numeration="30" content_type="text"> International Panel on Climate Change: 2006 IPCC guidelines for national greenhouse gas inventories, Prepared by the National Greenhouse Gas Inventories Programme, edited by: Egglestone H. S., Buendia L., Miwa, K., Ngara T., and Tanabe, K., IGES, Japan, 2006. </reference>
		<reference numeration="31" content_type="text"> Konrad, C.: Methoden zur Bestimmung des Umsatzes von Stickstoff, dargestellt für drei pleistozäne Grundwasserleiter Norddeutschlands, PhD thesis, Dresden Univ. of Techn., Germany, 157 pp., 2007. </reference>
		<reference numeration="32" content_type="text"> McMahon, P. B., Bruce, B. W., Becker, M. F., Pope, L. M., and Dennehy, K. F.: Occurrence of nitrous oxide in the Central High Plains Aquifer, 1999, Environ. Sci. Technol., 34, 4873–4877, 2000. </reference>
		<reference numeration="33" content_type="text"> Mölders, N., Jankov, M., and Kramm, G.: Application of Gaussian error propagation principles for theoretical assessment of model uncertainty in simulated soil processes caused by thermal and hydraulic parameters, J. Hydromet., 6, 1045–1062, 2005. </reference>
		<reference numeration="34" content_type="text"> Mookherji, S., McCarty, G. W., and Angier, J. T.: Dissolved gas analysis for assessing the fate of nitrate in wetlands, J. American Wat. Res. Ass., 39(2), 381–387, 2003. </reference>
		<reference numeration="35" content_type="text"> Mosier, A., Kroeze, C., Nevison, C., Oenema, O., Seitzinger, S., and van Cleemput, O.: Closing the global N&lt;sub&gt;2&lt;/sub&gt;O budget: Nitrous oxide emissions through the agricultural nitrogen cycle. OECD/IPCC/IEA Phase II: development of IPCC guidelines for national greenhouse gas inventory methodology, Nutr. Cycl. Agroecosys., 52, 225–248, 1998. </reference>
		<reference numeration="36" content_type="text"> Nevison, C.: Review of the IPCC methodology for estimating nitrous oxide emissions associated with agricutural leaching and runoff, Chemosphere, 2, 493–500, 2000. </reference>
		<reference numeration="37" content_type="text"> Pätsch, M.: Analyse des Nitratumsatzes und dessen Heterogenität im quartären Grundwasserleiter des Wasserwerkes Thülsfelde – Berücksichtigung bei der Modellierung des Transportes, PhD thesis, Dresden Univ. of Techn., Germany, 223 pp., 2006. </reference>
		<reference numeration="38" content_type="text"> Reay, D. S., Smith, K. A., and Edwards, A. C.: Nitrous oxide emission from agricultural drainage waters, Global Change Biol., 9, 195-203, 2003. </reference>
		<reference numeration="39" content_type="text"> Reay, D. S., Smith, K. A., Edwards, A. C., Hiscock, K. M., Dong, L. F., and Nedwell, D. B.: Indirect nitrous oxide emissions: revised emission factors, Environ. Sci., 2(2–3), 153–158, 2005. </reference>
		<reference numeration="40" content_type="text"> Ronen, D., Magaritz, M., and Almon, E.: Contaminated aquifers are a forgotten component of the global N&lt;sub&gt;2&lt;/sub&gt;O budget, Nature, 335, 57–59, 1988. </reference>
		<reference numeration="41" content_type="text"> Ross, S. M.: Overview of the hydrochemistry and solute processes in British wetlands, in: Hydrology and hydrochemistry of British wetlands, edited by: Hughes, J. M. R. and Heathwaite, A. L., Wiley, New York, 133–182, 1995. </reference>
		<reference numeration="42" content_type="text"> Sawamoto, T., Nakajima, Y., Kasuya, M., Tsuruta, H., and Yagi, K.: Evaluation of emission factors for indirect N&lt;sub&gt;2&lt;/sub&gt;O emission due to nitrogen leaching in agro-ecosystems, Geophys. Res. Let., 32(3), L03403, doi:10.1029/2004GL021625, 2005. </reference>
		<reference numeration="43" content_type="text"> Schlie, P.: Hydrogeologie des Grundwasserwerkes Stegemühle in Göttingen, PhD thesis, university of Göttingen, Germany, 137 pp., 1989. </reference>
		<reference numeration="44" content_type="text"> Stevens, R. J., Laughlin, R. J., and Malone, J. P.: Soil pH affects the processes reducing nitrate to nitrous oxide and di-nitrogen, Soil Biol. Biochem., 30, 1119–1126, 1998. </reference>
		<reference numeration="45" content_type="text"> Strebel, O., Böttcher J., and Duijnisveld W. H. M.: Ermittlung von Stoffeinträgen und deren Verbleib im Grundwasserleiter eines norddeutschen Wassergewinnungsgebietes, Texte 46/93, Umweltbundesamt, Berlin, 1993. </reference>
		<reference numeration="46" content_type="text"> Vogel, J. C., Talma, A. S., and Heaton, T. H. E.: Gaseous nitrogen as evidence for denitrification in groundwater, J. Hydrol., 50, 191–200, 1981. </reference>
		<reference numeration="47" content_type="text"> Walther, W.: Diffuser Stoffeintrag in Böden und Gewässer, Teubner BG, Stuttgart, Germany, 1999. </reference>
		<reference numeration="48" content_type="text"> Walther, W., Pätsch M., Weller D., Reinstorf F., Harms E., and Kersebaum C.: Nutrient loads on a Northern German sandy aquifer, reduction processes, their distribution and management tools, in: New approaches to characterising Groundwater Flow, XXXI, IAH Congress, Munich, Germany, 10–14 September 2001. </reference>
		<reference numeration="49" content_type="text"> Weiss, R. F.: The solubility of nitrogen, oxygen and argon in water and sea water, Deep Sea Res., 17, 721–735, 1970. </reference>
		<reference numeration="50" content_type="text"> Weiss, R. F.: The solubility of helium and neon in water and sea water, J. Chem. Eng. Data, 16, 235–241, 1971. </reference>
		<reference numeration="51" content_type="text"> Weiss, R. F. and Price, B. A.: Nitrous oxide solubility in water and sea water, Mar. Chem., 8, 347–359, 1980. </reference>
		<reference numeration="52" content_type="text"> Well, R. and Myrold, D. D.: Laboratory evaluation of a new method for in situ measurement of denitrification in water-saturated soils, Soil Biol. Biochem., 31, 1109–1119, 1999. </reference>
		<reference numeration="53" content_type="text"> Well, R., Augustin, J., Meyer, K., and Myrold, D.D.: Comparison of field and laboratory measurement of denitrification and N&lt;sub&gt;2&lt;/sub&gt;O production in the saturated zone of hydromorphic soils, Soil Biol. Biochem., 35, 783–799, 2003. </reference>
		<reference numeration="54" content_type="text"> Well, R., Weymann, D., and Flessa, H.: Recent research progress on the significance of aquatic systems for indirect agricultural N&lt;sub&gt;2&lt;/sub&gt;O emissions, Environ. Sci., 2(2–3), 143–151, 2005a. </reference>
		<reference numeration="55" content_type="text"> Well, R., Flessa, H., Jaradat, F., Toyoda, S., and Yoshida, N.: Measurement of isotopomer signatures of N&lt;sub&gt;2&lt;/sub&gt;O in groundwater, J. Geophys. Res.-Bio., 110, G02006, doi:10.1029/2005JG000044, 2005b. </reference>
	</references>
</article>

