Plant and Soil

, Volume 311, Issue 1–2, pp 211–234 | Cite as

Quantification of N2O fluxes from soil–plant systems may be biased by the applied gas chromatograph methodology

  • Xunhua ZhengEmail author
  • Baoling Mei
  • Yinghong Wang
  • Baohua Xie
  • Yuesi Wang
  • Haibo Dong
  • Hui Xu
  • Guanxiong Chen
  • Zucong Cai
  • Jin Yue
  • Jiangxin Gu
  • Fang Su
  • Jianwen Zou
  • Jianguo Zhu
Regular Article


With regard to measuring nitrous oxide (N2O) emissions from biological sources, there are three most widely adopted methods that use gas chromatograph with an electron capture detector (GC–ECD). They use: (a) nitrogen (N2) as the carrier gas (DN); (b) ascarite as a carbon dioxide (CO2) trap with DN (DN-Ascarite); and (c) a mixture gas of argon and methane as the carrier (AM). Additional methods that use either a mixture of argon and methane (or of CO2 and N2) as a make-up gas with the carrier nitrogen or soda lime (or ascarite) as a CO2 trap with the carrier helium have also been adopted in a few studies. To test the hypothesis that the use of DN sometimes considerably biases measurements of N2O emissions from plants, soils or soil–plant systems, experiments were conducted involving DN, AM and DN-Ascarite. When using DN, a significant relationship appeared between CO2 concentrations and the apparent N2O concentrations in air samples. The use of DN led to significantly overestimated N2O emissions from detached fresh plants in static chamber enclosures. Meanwhile, comparably lower emissions were found when using either the DN-Ascarite or AM methods. When an N2O flux (from a soil or a soil–plant system), measured by DN in combination with sampling from the enclosure of a static opaque chamber, was greater than 200 μg N m−2 h−1, no significant difference was found between DN and DN-Ascarite. When the DN-measured fluxes were within the ranges of <−30, −30–0, 0–30, 30–100 and 100–200 μg N m−2 h−1, significant differences that amounted to −72, −22, 5, 38 and 64 μg N m−2 h−1, respectively, appeared in comparison to DN-Ascarite. As a result, the DN measurements in rice–wheat and vegetable fields overestimated both annual total N2O emissions (by 7–62%, p < 0.05) and direct emission factors for applied nitrogen (by 6–65%). These results suggest the necessity of reassessing the available data determined from DN measurements before they are applied to inventory estimation. Further studies are required to explore appropriate approaches for the necessary reassessment. Our results also imply that the DN method should not be adopted for measuring N2O emissions from weak sources (e.g., with intensities less than 200 μg N m−2 h−1). In addition, we especially do not recommend the use of DN to simultaneously measure N2O and CO2 with the same ECD.


Nitrous oxide Emissions Gas chromatography Carrier gas Soil Plant Inventory 



Gas chromatograph equipped with an electron capture detector.


A GC–ECD method that uses pure N2 alone as the carrier gas but does not introduce a high-concentration make-up gas with an electronegative group/atom or with an ionization potential lower than that of N2 (such as carbon dioxide or methane) into the detector while allowing carbon dioxide (CO2) in the air samples to enter the detector.


Different from the DN method only in that an ascarite (a type of sodium-hydroxide-coated silica) filter column is connected to the beginning of the separation column. As a result of this ascarite filter, CO2 and water vapor in the air samples cannot enter the detector.


A GC–ECD method that uses an argon–methane mixture instead of pure N2 as the carrier gas while having the same GC configuration as the DN method.


A GC–ECD method that uses N2 as the carrier gas and directly introduces a mixture of methane and argon (5–10% CH4 in Ar) into the detector as a make-up gas.


A GC–ECD method that uses N2 as the carrier gas and directly introduces a mixture of CO2 and N2 into the detector as a make-up gas.


A GC–ECD method that uses He as the carrier gas, along with an ascarite (or soda lime) filter column connected to the beginning of the separation column.



This study was jointly supported by the National Natural Science Foundation of China, the Chinese Academy of Sciences, and the European Union (grant numbers: 40425010, 40331014, KZCX2-yw-204, KZCX3-SW-440, NitroEurope IP 017841). We sincerely thank Mr. Guangren Liu, Prof. Wen Zhang, Dr. Zaixing Zhou, Dr. Shenghui Han, Mr. Gang Liu, Prof. Yong Han, Mr. Huajun Tong, Ms. Rui Wang, Mr. Jia Deng and Mr. Zhisheng Yao for their substantial assistance.


  1. Arah JRM, Crichton IJ, Smith KA, Clayton H, Skiba U (1994) Automated gas chromatographic analysis system for micrometeorological measurements of trace gas fluxes. J Geophys Res 99:16593–16598CrossRefGoogle Scholar
  2. Breuer L, Papen H, Butterbach-Bahl K (2000) N2O emission from tropical forest soils of Australia. J Geophys Res 105:26353–26367CrossRefGoogle Scholar
  3. Butterbach-Bahl K, Gasche R, Breuer L, Papen H (1997) Fluxes of NO and N2O from temperate forest soils: impact of forest type, N deposition and of liming on the NO and N2O emissions. Nutr Cycl Agroecosys 48:79–90CrossRefGoogle Scholar
  4. Chen GX, Shang SH, Yu KW, Yu AD, Wu J, Wang YJ (1990) Investigation on the emission of N2O by plant. Chinese J Appl Ecol 1:94–96 (in Chinese)Google Scholar
  5. Chen GX, Huang GH, Shang SH, Li N, Wu J, Yu KW, Xu H, Wang YJ, Li L (1992) Measurement of N2O emission from soil, plants and soil–plant systems. In Ghazi A (ed) Proceedings of CEC and P. R. China workshop of contribution to global change. Biosphere atmosphere interactions. Brussels Belgium pp 109–114Google Scholar
  6. Chen X, Shen SM, Zhang L, Wu J, Wang XQ (1995) A preliminary research on the effect of nitrogen and phosphorus supply on N2O emission by crops. Chinese J Appl Ecol 6:104–105 (in Chinese)Google Scholar
  7. Chen X, Cabrera ML, Zhang L, Wu J, Shi Y, Yu WT, Shen SM (2002) Nitrous oxide emission from upland crops and crop–soil systems in northeastern China. Nutr Cycl Agroecosys 62:241–247CrossRefGoogle Scholar
  8. Chen GX, Xu H, Zhang Y, Zhang XJ, Li Y, Shi RJ, Yu KW, Zhang XD (2003) Plant: a potential source of the atmospheric N2O. Quaternary Sci 23:504–511 (in Chinese)Google Scholar
  9. Clough TJ, Bertram JE, Sherlock RR, Leonard RL, Nowicki BL (2006) Comparison of measured and EF-5-r-derived N2O fluxes from a spring-fed river. Global Change Biol 12:352–363CrossRefGoogle Scholar
  10. Ding WX, Cai Y, Cai ZC, Yagi K, Zheng XH (2007) Nitrous oxide emissions from an intensively cultivated maize–wheat rotation soil in the North China Plain. Sci Total Environ 373:501–511PubMedCrossRefGoogle Scholar
  11. Du R, Lu DR, Wang GC (2006) Diurnal, seasonal, and inter-annual variations of N2O fluxes from native semi-arid grassland soils of Inner Mongolia. Soil Biol Biochem 38:3474–3482CrossRefGoogle Scholar
  12. Flessa H, Dörsch P, Beese F (1995) Seasonal variation of N2O and CH4 fluxes in differently managed arable soils in southern Germany. J Geophys Res 100:23115–23124CrossRefGoogle Scholar
  13. Gu JX, Zheng XH, Wang YS, Ding WX, Zhu B, Chen X, Wang YY, Zhao ZC, Shi Y, Zhu JG (2007) Regulatory effects of soil properties on background N2O emissions from agricultural soils in China. Plant Soil 295:53–65CrossRefGoogle Scholar
  14. Hadi A, Inubushi K, Purnomo E, Razie E, Yamakawa K, Tsuruta H (2000) Effect of land-use changes on nitrous oxide emission from tropical peatlands. Chemosphere Global Change Sci 2:347–358CrossRefGoogle Scholar
  15. Hakata M, Takahashi M, Zumft W, Sakamoto A, Morikawa H (2003) Conversion of the nitrate nitrogen and nitrogen dioxide to nitrous oxides in plants. Acta Biotechnol 23:249–257CrossRefGoogle Scholar
  16. Helfritch DJ, Somerville NJ, R&D RCC (1993) Pulsed corona discharge for hydrogen sulfide decomposition. IEEE T Ind Appl 29:882–886CrossRefGoogle Scholar
  17. Henrich M, Haselwandter K (1997) Denitrification and gaseous nitrogen losses from an acid spruce forest soil. Soil Biol Biochem 29:1529–1537CrossRefGoogle Scholar
  18. Holst J, Liu CY, Brüggemann N, Butterbach-Bahl K, Zheng XH, Wang YS, Han SH, Yao ZS, Yue J, Han XG (2007) Microbial N turnover and N-Oxide (N2O/NO/NO2) fluxes in semi-arid grassland of Inner Mongolia. Ecosystems 10:623–634CrossRefGoogle Scholar
  19. Huang GH, Chen GX, Xu H (1992) Investigation on emission of nitrous oxide by aseptic soybean plant. J Integr Plant Biol (former Acta Botanica Sinica) 34:835–839 (in Chinese)Google Scholar
  20. IPCC (2006) Guidelines for national greenhouse gas inventories. IGES, HayamaGoogle Scholar
  21. IPCC (2007) In: Solomon S, Qin D, Manning M, Chen Z, Marquis M, Averyt KB, Tignor M, Miller HL (eds) Climate change 2007: the physical science basis, contribution of working group I to the fourth assessment report of the intergovernmental panel on climate change. Cambridge University Press, CambridgeGoogle Scholar
  22. Kester RA, Meijer ME, Libochant JA, de Boer W, Laanbroek HJ (1997) contribution of nitrification and denitrification to the NO and N2O emissions of an acid forest soil, a river sediment and a fertilized grassland soil. Soil Biol Biochem 29:1655–1664CrossRefGoogle Scholar
  23. Kiese R, Hewett B, Graham A, Butterbach-Bahl K (2003) Seasonal variability of N2O emissions and CH4 uptake by tropical rainforest soils of Queensland, Australia. Global Biogeochem Cy 17:GB1043CrossRefGoogle Scholar
  24. Laville P, Jambert C, Cellier P, Delmas R (1999) Nitrous oxide fluxes from a fertilized maize crop using micrometeorological and chamber methods. Agric For Meteorol 96:19–38CrossRefGoogle Scholar
  25. Lee NS, Hsieh YZ, Paisley RF, Morris MD (1988) Surface-enhanced Raman spectroscopy of the catecholamine neurotransmitters and related compounds. Anal Chem 60:442–446PubMedCrossRefGoogle Scholar
  26. Li N, Chen GX (1993) N2O emission by plants and influence of fertilization. Chinese J Appl Ecol 4:295–298 (in Chinese)Google Scholar
  27. Li YY, Yang Y, Zhang XD, Chen GX (2004) Effects of illumination, carbon source and reducing power on N2O emission from maize and soybean seedlings. Chinese J Appl Ecol 15:1851–1854 (In Chinese)Google Scholar
  28. Loftfield NS, Brumme R, Beese F (1992) Automated monitoring of nitrous oxide and carbon dioxide fluxes from forest soils. Soil Sci Soc Am J 56:1147–1150Google Scholar
  29. Loftfield N, Flessa H, Beese F, Augustin J (1997) Automated gas chromatographic system for rapid analysis of the atmospheric trace gases methane, carbon dioxide, and nitrous oxide. J Environ Qual 26:560–564CrossRefGoogle Scholar
  30. Ludowise P, Blackwell M, Chen Y (1996) Perturbation of electronic potentials by femtosecond pulses—time resolved photoelectron spectroscopic study of NO multiphoton ionization. Chem Phys Lett 258:530–539CrossRefGoogle Scholar
  31. Maljanen M, Liikanen A, Silvola J, Martikainen PJ (2003) Measuring N2O emissions from organic soils by closed chamber or soil/snow N2O gradient methods. Eur J Soil Sci 54:625–631CrossRefGoogle Scholar
  32. Matsunaga FM, Watanabe K (1967) Ionization potential and absorption coefficient of COS. J Chem Phys 46:4457–4459CrossRefGoogle Scholar
  33. Mosier AR, Mack L (1980) Gas chromatographic system for precise, rapid analysis of nitrous oxide. Soil Sci Soc Am J 44:1121–1123Google Scholar
  34. Nishimura S, Sawamoto T, Akiyama H, Sudo S, Yagi K (2004) Methane and nitrous oxide emissions from a paddy field with Japanese conventional water management and fertilizer application. Global Biogeochem Cy 18:GB2017CrossRefGoogle Scholar
  35. Nykänen H, Alm J, Lang K, Silvola J, Martikainen PJ (1995) Emissions of CH4, N2O and CO2 from a virgin fen and a fen drained for grassland in Finland. J Biogeogr 22:351–357CrossRefGoogle Scholar
  36. Phuoc TX (2000) Laser spark ignition: experimental determination of laser-induced breakdown thresholds of combustion gases. Opt Commun 175:419–423CrossRefGoogle Scholar
  37. Pihlatie M, Ambus P, Rinne J, Pilegaard K, Vesala T (2005) Plant-mediated nitrous oxide emissions from beech (Fagus sylvatica) leaves. New Phytol 168:93–98PubMedCrossRefGoogle Scholar
  38. Purbopuspito J, Veldkamp E, Brumme R, Murdiyarso D (2006) Trace gas fluxes and nitrogen cycling along an elevation sequence of tropical montane forest in Central Sulawesi, Indonesia. Global Biogeochem Cy 20:GB3010CrossRefGoogle Scholar
  39. Regina K, Syväsalo E, Hannukkala A, Esala M (2004) Fluxes of N2O from farmed peat soils in Finland. Eur J Soil Sci 55:591–599CrossRefGoogle Scholar
  40. Sanper A, Jönsson P, Watson JB, Burnett K (1995) Harmonic generation beyond the saturation intensity in helium. Phys Rev A 51:3148–3153CrossRefGoogle Scholar
  41. Ševčík J (1977) Nitrogen-n-pentane mixture as a purging gas for electron capture detectors. Chromatographia 10:601–603CrossRefGoogle Scholar
  42. Smart DR, Bloom AJ (2001) Wheat leaves emit nitrous oxide during nitrate assimilation. PNAS 98:7875–7878PubMedCrossRefGoogle Scholar
  43. Stapelfeldt H, Sakai H, Constant E, Corkum PB (1997) Deflection of neutral molecules using the Nonresonant Dipole Force. Phys Rev Lett 79:2787–2790CrossRefGoogle Scholar
  44. Stearns SD, Wentworth WE (1996) Gas sampling apparatus including a sealed chamber cooperative with a separate detector chamber. US Patent: 5,528,150Google Scholar
  45. Stehfest E, Bouwman L (2006) N2O and NO emission from agricultural fields and soils under natural vegetation: summarizing available measurement data and modeling of global annual emissions. Nutr Cycl Agroecosys 74:207–228CrossRefGoogle Scholar
  46. Tanner SD, Baranova VI (1999) A dynamic reaction cell for inductively coupled plasma mass spectrometry (ICP-DRC-MS). II. Reduction of interferences produced within the cell. J Am Soc Mass Spectrom 10:1083–1094CrossRefGoogle Scholar
  47. Teepe R, Vor A, Beese F, Ludwig B (2004) Emissions of N2O from soils during cycles of freezing and thawing and the effects of soil water, texture and duration of freezing. Eur J Soil Sci 55:357–365CrossRefGoogle Scholar
  48. van Bochove E, Prévost D, Pelletier F (2000) Effects of freeze–thaw and soil structure on nitrous oxide produced in a clay soil. Soil Sci Soc Am J 64:1638–1643Google Scholar
  49. Wang YS, Wang YH (2003) Quick measurement of CH4, CO2 and N2O emissions from a short-plant ecosystem. Adv Atmos Sci 20:842–844CrossRefGoogle Scholar
  50. Wentworth WE, Freeman RR (1973) Measurement of atmospheric nitrous oxide using an electron capture detector in conjunction with gas chromatography. J Chromatogr 79:322–324PubMedCrossRefGoogle Scholar
  51. Werner C, Zheng XH, Tang JW, Xie BH, Liu CY, Kiese R, Butterbach-Bahl K (2006) N2O, CH4 and CO2 emissions from seasonal tropical rainforests and a rubber plantation in Southwest China. Plant Soil 289:335–353CrossRefGoogle Scholar
  52. Xu H, Huang B, Zhang XJ, Han SJ, Huang GH, Chen GX (2001) Above-ground vertical concentration profiles of nitrous oxide within coniferous–deciduous mixed forests. Chemosphere Global Change Sci 3:145–146CrossRefGoogle Scholar
  53. Xu ZJ, Zheng XH, Wang YS, Huang Y, Zhu JG, Butterbach-Bahl B (2004) Effects of elevated CO2 and N fertilization on CH4 emissions from paddy rice fields. Global Biogeochem Cy 18:GB3009CrossRefGoogle Scholar
  54. Xu ZJ, Zheng XH, Wang YS, Wang YL, Huang Y, Zhu JG (2006) Effect of free-air atmospheric CO2 enrichment on dark respiration of rice plants (Oryza sativa L.). Agr Ecosyst Environ 115:105–112CrossRefGoogle Scholar
  55. Zhang XJ (2001) N2O emission by tree and soil in a forest ecosystem. Ph.D. thesis of the Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang, pp. 77–96, (in Chinese)Google Scholar
  56. Zhang XJ, Chen GX, Xu H (2002a) N2O emission from trees under different light radiances. Chinese J Appl Ecol 13:1563–1565 (in Chinese)Google Scholar
  57. Zhang XJ, Xu H, Chen GX (2002b) N2O emission rate from trees. ACTA Phytoecol Sin 26:538–543 (in Chinese)Google Scholar
  58. Zheng XH, Wang MX, Wang YS, Shen RX, Gou J, Li J, Jin JS, Li LT (2000) Impacts of soil moisture on nitrous oxide emission from croplands: a case study on the rice-based agro-ecosystem in Southeast China. Chemosphere Global Change Sci 2:204–227CrossRefGoogle Scholar
  59. Zheng XH, Han SH, Huang Y, Wang YX, Wang MX (2004) Re-quantifying the emission factors based on field measurements and estimating the direct N2O emission from Chinese croplands. Global Biogeochem Cy 18:GB2018CrossRefGoogle Scholar
  60. Zheng XH, Zhou ZZ, Wang YS, Zhu JG, Wang YL, Yue J, Shi Y, Kobayashi K, Inubushi K, Huang Y, Han S, Xu Z, Xie B, Butterbach-Bahl K, Yang L (2006) Nitrogen-regulated effects of free-air CO2 enrichment on methane emissions from paddy rice fields. Global Change Biol 12:1717–1732CrossRefGoogle Scholar
  61. Zou JW, Huang Y, Sun WJ, Zheng XH, Wang YS (2005) Contribution of plants to N2O emissions in soil–winter wheat ecosystem: pot and field experiments. Plant Soil 269:205–211CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • Xunhua Zheng
    • 1
    Email author
  • Baoling Mei
    • 1
  • Yinghong Wang
    • 1
  • Baohua Xie
    • 1
  • Yuesi Wang
    • 1
  • Haibo Dong
    • 1
  • Hui Xu
    • 2
  • Guanxiong Chen
    • 2
  • Zucong Cai
    • 3
  • Jin Yue
    • 1
  • Jiangxin Gu
    • 1
  • Fang Su
    • 4
  • Jianwen Zou
    • 5
  • Jianguo Zhu
    • 3
  1. 1.State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry, Institute of Atmospheric PhysicsChinese Academy of SciencesBeijingChina
  2. 2.Institute of Applied EcologyChinese Academy of SciencesShenyangChina
  3. 3.Institute of Soil ScienceChinese Academy of SciencesNanjingChina
  4. 4.China Agricultural UniversityBeijingChina
  5. 5.Nanjing Agricultural UniversityNanjingChina

Personalised recommendations