Abstract
Field measurements of NO and NO2 emissions from soils have been performed in Finthen near Mainz (F.R.G.) and in Utrera near Seville (Spain). The applied method employed a flow box coupled with a chemiluminescent NO x detector allowing the determination of minimum flux rates of 2 μg N m-2 h-1 for NO and 3 μg m-2 h-1 for NO2.
The NO and NO2 flux rates were found to be strongly dependent on soil surface temperatures and showed strong daily variations with maximum values during the early afternoon and minimum values during the early morning. Between the daily variation patterns of NO and NO2, there was a time lag of about 2 h which seem to be due to the different physico-chemical properties of NO and NO2. The apparent activation energy of NO emission calculated from the Arrhenius equation ranged between 44 and 103 kJ per mole. The NO and NO2 emission rates were positively correlated with soil moisture in the upper soil layer.
The measurements carried out in August in Finthen clearly indicate the establishment of NO and NO2 equilibrium mixing ratios which appeared to be on the order of 20 ppbv for NO and 10 ppbv for NO2. The soil acted as a net sink for ambient air NO and NO2 mixing ratios higher than the equilibrium values and a net source for NO and NO2 mixing ratios lower than the equilibrium values. This behaviour as well as the observation of equilibrium mixing ratios clearly indicate that NO and NO2 are formed and destroyed concurrently in the soil.
Average flux rates measured on bare unfertilized soils were about 10 μg N m-2 h-1 for NO2 and 8 μg N m-2 h-1 for NO. The NO and NO2 flux rates were significantly reduced on plant covered soil plots. In some cases, the flux rates of both gases became negative indicating that the vegetation may act as a sink for atmospheric NO and NO2.
Application of mineral fertilizers increased the NO and NO2 emission rates. Highest emission rates were observed for urea followed by NH4Cl, NH4NO3 and NaNO3. The fertilizer loss rates ranged from 0.1% for NaNO3 to 5.4% for urea. Vegetation cover substantially reduced the fertilizer loss rate.
The total NO x emission from soil is estimated to be 11 Tg N yr-1. This figure is an upper limit and includes the emission of 7 Tg N yr-1 from natural unfertilized soils, 2 Tg N yr-1 from fertilized soils as well as 2 Tg N yr-1 from animal excreta. Despite its speculative character, this estimation indicates that NO x emission by soil is important for tropospheric chemistry especially in remote areas where the NO x production by other sources is comparatively small.
Similar content being viewed by others
References
Böttger, A., Ehhalt, D. M., and Gravenhorst, G., 1980, Atmosphärische Kreisläufe von Stickoxiden und Ammoniak, Jül-1558 pp. 1–97, Institut für Chemie 3, Kernforschungsanlage Jülich, 2. Auflage.
BremnerJ. M. and BlackmerA. M., 1981, Terrestrial nitrification as a source of atmospheric nitrous oxide, in C. C.Delwiche (ed.), Denitrification, Nitrification and Atmospheric Nitrous Oxide, John Wiley, New York, pp. 151–170.
ChengM. M. and BremnerJ. M., 1965, Gaseous forms of nitrogen, in C. A.Black (ed.), Methods of Soil Analysis, Vol. 2, Am. Soc. Agronom. Inc., Madison, pp. 1287–1323.
ConradR., SeilerW., and BunseG., 1983, Factors influencing the loss of fertilizer nitrogen into the atmosphere as N2O, J. Geophys. Res. 88, 6709–6718.
CrutzenP. J., 1983, Atmospheric interactions-homogeneous gas phase reactions of C, N, and S containing compounds, in B.Bolin and R. B.Cook (eds.), The Major Biochemical Cycles and Their Interactions, SCOPE 21, John Wiley, Chichester.
DelanyA. C., DickersonR. R., MelchiorF. L., and WartburgA. F., 1982, Modification of a commercial NO x detector for high sensitivity, Rev. Sci. Instr. 53, 1899–1902.
DommerguesY., 1977, Biologie du sol, Presses Universitaires de France, Paris.
EhhaltD. M. and DrummondJ. W., 1982, The tropospheric cycle of NO x , in H. W.Georgii and W.Jaeschke (eds.), Chemistry of the Unpolluted and Polluted Troposphere, D. Reidel, Dordrecht, pp. 219–251.
FAO, 1982, Fertilizer Yearbooks, Food and Agriculture Organization of the United Nations, Rome.
FirestoneM. K., 1982, Biological denitrification, in Nitrogen in Agricultural Soils, Agronomy Monograph No. 22, Soil Sci, Soc. Am., Madison, pp. 289–326.
Firestone, M. K., Firestone, R. B., and Tiedje, J. G., Nitric oxide as an intermediate in denitrification: evidence from nitrogen-13 isotope exchange, Biochem. Biophys. Res. Comm. 91, 10–16.
FochtD. D. and VerstraeteW., 1977, Biochemical ecology of nitrification and denitrification, Adv. Microbiol. Ecol. 1, 135–214.
GalballyI. E. and RoyC. R., 1978, Loss of fixed nitrogen from soils by nitric oxide exhalation, Nature 275, 734–735.
GarberE. A. E. and HollocherT. C., 1982, 15N, 180 tracer studies on the activation of nitrite by denitrifying bacteria, J. Biol. Chem. 257, 8091–8097.
HahnJ. and CrutzenP. J., 1982, The role of fixed nitrogen in atmospheric photochemistry, Phil. Trans. R. Soc. Lond. B296, 521–541.
HillA. C., 1971, Vegetation: A sink for atmospheric pollutants, J. Air. Pollut. Contr. Assoc. 21, 341–346.
JohnR. T. S. and HollocherT. C., 1977, Nitrogen-15 tracer studies on the pathway of denitrification by Pseudomonas aeraginosa, J. Biol. Chem. 252, 212–218.
JudeikisM. S. and WrenA. G., 1978, Laboratory measurements of NO and NO2 depositions onto soil and ambient surfaces, Atmos. Environ. 12, 2315–2319.
KellyT. J., StedmanD. H., and KokG. L., 1979, Measurements of H2O2 and HNO3 in rural air, Geophys. Res. Lett. 6, 375–378.
KimC. M., 1973, Influence of vegetation types on the intensity of ammonia and nitrogen dioxide liberation from soil, Soil Biol. Biochem. 5, 163–166.
KnowlesR., 1981, Denitrification, in E. A.Paul and J. N.Cadd (eds.), Soil Biochemistry, Vol. 5, Marcel Dekker, New York.
LeeYin-Nan and SchwartzS. E., 1981, Evaluation of the rate of uptake of nitrogen dioxide by atmospheric and surface liquid water, J. Geophys. Res. 86, 11971–11983.
LipschultzF., ZafiriouO. C., WofsyS. C., ElroyM. B., ValoisF. W., and WatsonS. W., 1982, Production of NO and N2O by soil nitrifying bacteria, Nature 294, 641–643.
LoganJ. A., 1983, Nitrogen oxides in the troposphere: Global and regional budgets, J. Geophys. Res. 88, 10785–10807.
MakarovB. N., 1969, Release of nitrogen dioxide from the soil, Pochvovedeniye 1, 49–53.
MakarovB. N and IgnatovaV. P., 1963, Losses of nitrogen from the soil in the gaseous form, Pochvovedeniye 4, 407–413.
McKenneyD. J., ShuttleworthK. F., VriesackerJ. R., and FindlayW. I., 1982, Production and loss of nitric oxide from denitrfication in anaerobic Brookston clay, Appl. Environ. Microbiol. 43, 534–541.
MulvaneyR. L. and BremnerJ. M., 1981, Control of urea transformation in soils, in E. A.Paul and J. N.Cadd (eds.), Soil Biochemistry, Vol. 5, Marcel Dekker, New York.
NelsonD. W. and BremnerJ. M., 1970, Gaseous products of nitrite decomposition in soil, Soil. Biol. Biochem. 2, 203–215.
PattenD. K., BremnerJ. M., and BlackmerA. M., 1980, Effect of drying and air-dry storage of soils on their capacity for denitrification of nitrate, Soil. Sci. Soc. Am. J. 44, 67–70.
PayneW. J., 1981, The status of nitric oxide and nitrous oxide as intermediates in denitrification, in C. C.Delwiche (ed.), Denitrification, Nitrification and Atmospheric Nitrous Oxide, John Wiley, New York, pp. 85–103.
PratherR. J., MiyamotS., and BohrH. L., 1973, Sorption of nitrogen dioxide by calcareous soils, Soil Sci. Soc. Am. Proc. 37, 860–863.
PratherR. J. and MiyamotoS., 1974, Nitric oxide sorption by calcareous soils. III: Effects of temperature and lack of oxygen on capacity and rate, Soil Sci. Soc. Am. Proc. 38, 582–585.
RogersH. H., CampbellJ. C., and VolkR. J., 1979, Nitrogen-15 dioxide tuptake and incorporation by Phaseolus vulgaris (L.), Science 206, 333–335.
SchmidtE. L., 1982, Nitrification in soil, in Nitrogen in Agricultural Soils, Agronomy Monograph No. 22, Soil Sci. Soc. Am., Madison, pp. 253–288.
SehmelG. A., 1980, Particle and gas dry deposition: A review, Atmos. Environ. 14, 983–1011.
Seiler, W., 1978, Influence of the biosphere on the atmospheric CO and H2 cycles, in W. Krumbein (ed.), Environmental Biogeochemistry and Geomicrobiology, Vol. 3, Ann Arbor Science, pp. 773–810.
SeilerW. and ConradR., 1982, Field measurements of natural and fertilizer-induced N2O release rates from soils, J. Air Pollut. Control. Assoc. 31, 767–772.
ShetterR. E., StedmanD. H., and WestD. H., 1983, The NO/NO2/O3 photo-stationary state in Claremont, California, J. Air Pollut. Control Assoc. 33, 212–214.
SlemrF., ConradR., and SeilerW., 1984, Field measurements of fertilizer-induced N2O emission in a subtropical region (Andalusia, Spain), J. Atmos. Chem., 1, 159–169.
Slemr, F., Seiler, W., and Dickerson, R. R. (to appear), Field measurements of NO x emissions by soils: 1. Flow-through box method, Atmos. Environ.
SmithC. J. and ChalkP. M., 1979, Factors affecting the determination of nitric oxide and nitrogen dioxide evolution from soil, Soil Sci. 128, 327–330.
SmithC. J. and ChalkP. M., 1980a, Fixation and loss of nitrogen during transformations of nitrite in soils, Soil Sci. Soc. Am. J. 44, 288–291.
SmithC. J. and ChalkP. M., 1980b, Gaseous nitrogen evolution during nitrification of ammonia fertilizer and nitrite transformations in soils, Soil Sci. Soc. Am. J. 44, 277–282.
StedmanD. M., 1976, A flow independent procedure for the gas phase titration of an ozone source, J. Air Pollut. Control Assoc. 26, 62.
Stedman, D. M. and Shetter, R. E., 1983, The global budget of atmospheric nitrogen species, in S. E. Schwartz (ed.), Trace Atmospheric Constituents, Adv. Environ. Sci. Technol., Vol. 12, pp. 411–454.
SteenW. C. and StojanovicB. J., 1971, Nitric oxide volatilization from a calcareous soil and model aqueous solutions, Soil Sci. Soc. Am. Proc. 35, 277–282.
StephenH. and StephenT., 1963, Solubilities of Inorganic and Organic Compounds, Vol. 1, Part 1, Pergamon Press, Oxford, p. 330.
TaylorS. A. and JacksonR. D., 1965, Temperature, in C. A.Black (ed.), Methods of Soil Analysis, Vol. 1, Am. Soc. Agronomy Inc., Madison, pp. 331–344.
WeselyM. L., EastmanJ. A., StedmanD. M., and Jalvac, 1982, An eddy-correlation measurement of NO2 flux to vegetation and comparison to O3 flux, Atmos. Environ. 16, 815–820.
WinerA. M., PetersJ. W., SmithJ. P., and PittsJ. N., 1974, Response of commercial chemiluminescent NO−NO2 analyzers to other nitrogen containing compounds, Environ. Sci. Tech. 8, 1118–1121.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Slemr, F., Seiler, W. Field measurements of NO and NO2 emissions from fertilized and unfertilized soils. J Atmos Chem 2, 1–24 (1984). https://doi.org/10.1007/BF00127260
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF00127260