Flux between soil and atmosphere, vertical concentration profiles in soil, and turnover of nitric oxide: 1. Measurements on a model soil core

A stainless steel soil corer which was filled with homogenized soil was used to measure the flux (J) of NO between soil and atmosphere and the vertical profile of the NO mixing ratios (m) in the soil atmosphere, both as function of the NO mixing ratio (mm _a ) in the atmosphere of the headspace. The NO emission flux decreased linearly with increasing NO mixing ratio and turned into a deposition flux after passage of the compensation point (m _c) at about 400 ppbv NO. Almost the same compensation point was obtained when the turnover of NO was measured in flask-incubated soil samples as function of the NO mixing ratio. The flux (J) of NO at the soil-atmosphere interface was calculated from the production rate (P) of NO and the NO uptake rate constant (k) that were measured in these flask-incubated soil samples using the diffusion model of Galbally and Johansson (1989). The calculated fluxes agreed within <15% with those actually measured. The vertical profiles of NO were fitted to an exponential function and analyzed by Fick's first law of diffusion. The shape of the profiles indicated a net production of NO in the upper 10 cm soil layer when the atmospheric NO mixing ratio was below the compensation point and in a net consumption of NO when the atmospheric NO mixing ratio was above the compensation point. In soil layers below 10 cm depth, the turnover of NO resulted in compensation of production and consumption rates. Measurement of the actual diffusion coefficient using SF₆ showed that gas transport in the soil core was not only due to molecular diffusion but in addition due to a bidirectional gas flow. The experimentally determined diffusion coefficient was smaller than that computed from soil porosities, but resulted together with the additional transport term in NO fluxes that were close (< ±15%) to those measured. This is the first comprehensive study of NO concentration profiles and turnover rates in soil providing a theoretical basis for modelling NO fluxes at the soil-atmosphere interface.     

A study to explain the emission of nitric oxide from a marsh soil

In the period 18–21 September 1989, soil NO emission was studied at Halvergate Marshes, Norfolk (U.K.) within the framework of the BIATEX-LOVENOX joint field experiment. Using a dynamic chamber technique, 186 measurements at four plots were performed showing a net NO flux of 7.2–14.6×10^–12 kgN m^–2 s^–1. Soil samples from a soil profile (1.0 m) at a representative site and from the uppermost layer (0.1 m) of each of the four plots were sent to the laboratory for (a) detailed physical and chemical soil analysis, (b) determination of NO production rates, NO uptake rate constants, and NO compensation mixing ratios, and (c) characterization of the microbial processes involved. A diffusive model (Galbally and Johansson, 1989) was applied to the laboratory results to infer NO fluxes of the individual soil samples. When we compared these fluxes with those measured in the field, we found agreement within a factor 2–4. Furthermore, laboratory studies showed, that NO was produced and consumed only in the upper soil layer (0–0.1 m depth) and that the NO production and consumption activities observed in the Halvergate marsh soil were most probably due to the anaerobic metabolism of denitrifying bacteria operating in anaerobic microniches within the generally aerobic soil.     

Field measurements of NO and NO2 emissions from fertilized and unfertilized soils

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 g N m^-2 h^-1 for NO and 3 g 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 g N m^-2 h^-1 for NO₂ and 8 g 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.     

Characteristics of turnover of carbonyl sulfide in four different soils

Release and uptake of carbonyl sulfide (OCS) were measured at 25°C in samples of three forest soils (BL, BW, PBE) and one soil from a rape field (RA). The soil samples were flushed with a constant flow of either air (oxic conditions) or nitrogen (anoxic conditions) containing defined concentrations of OCS. A cryogenic trapping technique with liquid argon (-186 °C) was used to collect gas samples for analysis in a gas chromatograph equipped with a flame-photometric detector. The dependence of net OCS fluxes between soil and atmosphere could be described by a simple model of simultaneous OCS production and OCS uptake. By using this model, production rates (P), uptake rate constants (k) and compensation concentrations (m _c ) of OCS could be determined as function of the soil type and the incubation conditions. Under oxic conditions, OCS production (P) and uptake were observed in all soils tested. However, the compensation concentrations (<166 ng l^-1; 1 ng OCS l^-1=0.41 ppbv) that were calculated from the model were high relative to the ambient OCS concentration (ca. 0.5 ppbv). The production rates (0.16–1.9 ng h^-1 g^-1 dw) that were actually measured when flushing the soil samples with air containing zero OCS were smaller than those (17–114 ng h^-1 g^-1 dw) calculated from the model. This observation was explained by two different concepts: one assuming the existence of a threshold concentration (m _t ) below which OCS was no longer consumed in the soil; the other assuming the existence of two different OCS consumption processes, of which only the process active at elevated OCS concentrations was covered by the experiments. The latter concept allowed the estimation of OCS compensation concentrations that were partially low enough to allow the uptake of atmospheric OCS by soil. Both OCS production and uptake in PBE soil were dependent on soil temperature (optimum 20 °C) indicating a microbial process. However, both production and consumption of OCS were not consistently inhibited by sterilization of the soil, suggesting that they were not exclusively due to microbiological processes. Under anoxic conditions, OCS was also produced, but was not consumed except in one soil (RA). Production of OCS in the soils was stimulated after addition of thiocyanate, but not thiourea, thiosulfate, thioglycolate, tetrathionate, sulfate, elemental sulfur, cysteine and methionine.     

Calculations of the temperature dependence of the NO2 photodissociation coefficient in the atmosphere

The photodissociation coefficient, J _NO2 of NO₂ in the atmosphere was calculated at 235 and 298 K using the measured temperature dependences of the absorption cross-sections and quantum yields. These calculations gave a ratio J _NO2(298 K)/J _NO2(235 K)=1.155±0.010 which is only weakly dependent on altitude, surface albedo and solar zenith angle.     

Sensitivity of PBL model predictions to model design and uncertainties in environmental inputs

A simple time-dependent one-dimensional model of the planetary boundary layer (PBL) is described and used to examine the degree to which model design decisions affect model output variables. The model's sensitivity to changes in the environmental conditions is also explored. Averages of the surface fluxes, near-ground wind speeds and other PBL properties from 48 h simulations are compared to control runs. The model-calculated surface fluxes are most sensitive, in decreasing order of importance, to the vertical grid spacing, the form of closure between the surface temperature and the atmosphere, the use of vertical diffusivity smoothing, the choice of maximum time step and choice of turbulence closure scheme. These fluxes are relatively insensitive to mixing-length scaling or choice of implicit time step weighting factor. Sensitivity to changes in soil type exceeds any of the design criteria tested. The modeled fluxes are moderately sensitive to small variations in the horizontal pressure gradient, to unsteadiness in the geostrophic wind and to variations in surface roughness. They are relatively insensitive to uncertainties in local vertical velocities and small (25%) variations applied separately to soil thermal diffusivity or heat capacity. The sensitivity of the average PBL depth (Z _i ) to model and environmental changes are similar to those of surface fluxes except thatZ _i is more sensitive to changes in mixing length, albedo and imposed vertical velocity then are the surface fluxes.     

Available energy and energy balance closure at four coniferous forest sites across Europe

The available energy (AE), driving the turbulent fluxes of sensible heat and latent heat at the earth surface, was estimated at four partly complex coniferous forest sites across Europe (Tharandt, Germany; Ritten/Renon, Italy; Wetzstein, Germany; Norunda, Sweden). Existing data of net radiation were used as well as storage change rates calculated from temperature and humidity measurements to finally calculate the AE of all forest sites with uncertainty bounds. Data of the advection experiments MORE II (Tharandt) and ADVEX (Renon, Wetzstein, Norunda) served as the main basis. On-site data for referencing and cross-checking of the available energy were limited. Applied cross checks for net radiation (modelling, referencing to nearby stations and ratio of net radiation to global radiation) did not reveal relevant uncertainties. Heat storage of sensible heat J _H, latent heat J _E, heat storage of biomass J _veg and heat storage due to photosynthesis J _C were of minor importance during day but of some importance during night, where J _veg turned out to be the most important one. Comparisons of calculated storage terms (J _E, J _H) at different towers of one site showed good agreement indicating that storage change calculated at a single point is representative for the whole canopy at sites with moderate heterogeneity. The uncertainty in AE was assessed on the basis of literature values and the results of the applied cross checks for net radiation. The absolute mean uncertainty of AE was estimated to be between 41 and 52 W m^?2 (10–11 W m^?2 for the sum of the storage terms J and soil heat flux G) during mid-day (approximately 12% of AE). At night, the absolute mean uncertainty of AE varied from 20 to about 30 W m^?2 (approximately 6 W m^?2 for J plus G) resulting in large relative uncertainties as AE itself is small. An inspection of the energy balance showed an improvement of closure when storage terms were included and that the imbalance cannot be attributed to the uncertainties in AE alone.     

Emission of nitric oxide from soils and termite nests in a Trachypogon savanna of the Orinoco basin

Nitric oxide fluxes from soils in the Trachypogon savanna of the Orinoco basin were determined during the dry season using the static chamber method. The emission from dry soils fluctuated from 0.4 to 3 ng N m^–2 s^–1 and increased up to 25 ng N m^–2 s^–1 after moderate watering or light rain-falls (1 to 5 mm). The mean emission values are up to 6 times lower than one observed earlier at the Chaguaramas site, but up to 10 times higher than one recorded at the Guri site, indicating an important spatial variability in NO fluxes of the Venezuelan savanna region. The changes observed after the addition of nitrogen to the soil, in the form of ammonium and/or nitrate, indicate a high denitrification potential in this acidic soil. Burning of the surface vegetation produced an increase by a factor of 10 in the emission rate of NO, but the effect was relatively short in time, about 5 days. It was estimated for the savanna region that burning increases the total NO soil emission during the dry season by 15% compared to the unburnt case. Soils with termite nests emit 10 times more NO than soil without nests, but the contribution from this source is less than 2% of the total savanna soil flux.     

A photoelectric detector for the measurement of photolysis frequencies of ozone and other atmospheric molecules

Photoelectric detectors for the measurement of photolysis frequencies of different trace gases in the atmosphere are described. They exhibit uniform response characteristics over one hemisphere (2 sr) and wavelength characteristics closely matched to those of the photolysis frequencies J _O1D, J _NO2, and J _NO3, respectively. Absolute calibration of the J _O1D detector was performed by chemical actinometry with an accuracy of ±16 percent. Simultaneous measurements of J _NO2 and J _O1D are presented.     

Profiles and simulated exchange of H2O,O3, NO2 between the atmosphere and the HartX Scots pine plantation

Summary Vertical profiles of H₂O, CO₂, O₃, NO and NO₂ were measured during the Hartheim Experiment (HartX) to develop and calibrate a multi-layer resistance model to estimate deposition and emission of the cited gaseous species. The meteorological and gas concentration data were obtained with a 30 m high telescopic mast with 7 gas inlets located at 5 m intervals and meteorological sensors at 5, 15 and 30 m above ground; a complete gas profile was obtained every 9 min 20 s. Measured profiles were influenced by several exchange processes, namely evapotranspiration, dewfall, assimilation of CO₂ in the tree crowns, soil respiration, deposition of NO₂ and O₃ to the soil and advection of NO_x from the nearby highway. Surprisingly, no decrease in O₃ concentration was observed in the crown layer during daytime, probably due to the relatively low density of foliage elements and strong turbulent mixing.The advantage of measuring in-canopy profiles is that turbulent exchange coefficients need not be estimated as a prerequisite to obtaining vertical flux estimates. In recent years, flux-gradient relationships in canopies have been subject to many criticisms. If fluxes are calculated at several heights considering only the transfers between the turbulent air and the interacting surfaces at a certain height, and those fluxes are then integrated vertically in a subsequent step, then exchange estimates (deposition or emission) can be obtained independent of turbulent exchange conditions.Typical estimated deposition velocities calculated for a 3-day period are between 4 and 10 mm/s for NO₂ and about 4–9 mm/s for O₃ (day and night values respectively). This leads to deposition rates of about 20–40 ng N/m²s for NO₂ and about 30–40 mg O₃/m² deposited daily under the conditions encountered during HartX. Sensitivity tests done with the best available and most realistic values for model parametrization have shown that sensitivity is large with respect to the soil and cuticula resistances as well as for gas-phase ozone destruction and that more research is required to describe the effectiveness of cuticula and soil in modifying sink characteristics for NO₂ and O₃.With 12 Figures     

Emission of nitrogen oxides (NO x ) from a flooded soil fertilized with urea: Relation to other nitrogen loss processes

Emissions of nitric oxide and other odd nitrogen oxides (NO _x ) from a flooded rice field were studied after urea had been broadcast into the floodwater.The NO _x flux from the fertilized area was very low (0.2×10^-9 g N m^-2 s^-1) for the first few days after application of urea and was high (0.95×10^-9 g N m^-2 s^-1) in the subsequent period when significant nitrite and nitrate were present in the floodwater. At night, little if any NO _x was exhaled but ambient NO₂ was absorbed by the floodwater. An uptake velocity for NO₂ of 3×10^-4 m s^-1 was measured during one night. Maximum NO _x losses were observed near 1300 h when temperature and solar ultraviolet light were maximum.While the amounts of nitrogen oxides emitted are of little agronomic importance (2×10^-3 per cent of the fertilizer nitrogen was lost as NO _x during the 10-day study period), they may well be of significance as a source for some gas reactions in the atmosphere and for the global nitrogen cycle.Of the fertilizer nitrogen applied (as urea) approximately 30% was lost to the atmosphere by NH₃ volatilization, 15% by denitrification, presumably as N₂, and the remainder, less minor losses of NO and N₂O, remained in the plant/soil/water system.Now at Forestry Department, Australian National University, G.P.O. Box 4, ACT 2601, Australia.     

A Parameterization of Bowen Ratio with Respect to Soil Moisture Availability

The Bowen ratio (B) is impacted by 5 environmental elements: soil moisture availability, m, the ratio of resist-ances between atmosphere and soil pores, ra/rd, atmospheric relative humidity, h, atmospheric stability, ΔT, and environment temperature. These impacts have been investigated over diverse surfaces, including bare soil, free water surface, and vegetation covered land, using an analytical approach. It was concluded that: (a) B is not a continuous function. The singularity exists at the condition αhcb=h, occurring preferably in the following conditions: weak turbulence, stable stratified stability, dry soil, and humid air, where hcb, defined by Eq.(11) is a critical variable. The existence of a singularity makes the dependence of B on the five variables very complicated. The value of B approaches being inversely proportional to m under the conditions m≥mfc (the soil capacity) and / or ra/rd→0. The proportional coefficient changes with season and latitude with relatively high values in winter and over the poles; (b) B is nearly independent of ra/rd during the day. The impact of m on B is much larger as compared to that of ra/rd on B, (c) when h increases, the absolute value of B also increases; (d) over bare soil, when the absolute surface net radiation increases, the absolute value of B will increase. The impact of RN on B is larger at night than during the day, and (e) over plant canopy, the singularity and the dependcies of B on m, ra , and h are modified as compared to that over bare soil. Also (i) during the daytime unstable condition, m exerts an even stronger impact on B, at night, however, B changes are weak in response to the change in m; (ii) the value of B is much more sensitive in response to the changes of turbulent intensity; (iii) the B response to the variation of h over a vegetation covered area is weaker; and (iv) the singularity exists at the condition hcp=h instead of αhcb=h as over bare soil, where hcp is defined by Eq.(49). The formulas derived over bare soil also hold the same when applied to free water bodies as long as they are visualized as a special soil in which the volumetric fraction of soil pore is equal to one and are fully filled with water. Finally, the above discussions, are used to briefly study the impact on the thermally induced mesoscale circulations.     

Emerging technologies for in situ measurement of soil carbon

Carbon sequestration in the terrestrial biosphere is critical to mitigating the increasing anthropogenic CO₂ content of the atmosphere. However, improved efficiency of methods for soil C measurement is important to better estimate terrestrial C inventories and fluxes at a regional and global scale. Laboratory based measurement of soil C involves intensive, time consuming, and costly methodology that limits applicability for large land areas. Recently, research efforts have focused on measuring soil C in situ using a variety of methods. These methods include Laser Induced Breakdown Spectroscopy (LIBS), Inelastic Neutron Scattering (INS), near-infrared spectroscopy (NIRS), and remote sensing. Basic fundamentals of each of these in situ methods for soil C determination are presented, and the differences among the methods and their relative advantages and disadvantages are discussed.     

Effects of the soil heat flux estimates on surface energy balance closure over a semi-arid grassland

Soil heat flux is important for surface energy balance (SEB), and inaccurate estimation of soil heat flux often leads to surface energy imbalance. In this paper, by using observations of surface radiation fluxes and soil temperature gradients at a semi-arid grassland in Xilingguole, Inner Mongolia, China from June to September 2008, the characters of the SEB for the semi-arid grassland were analyzed. Firstly, monthly averaged diurnal variations of SEB components were revealed. A 30-min forward phase displacement of soil heat flux (G) observed by a fluxplate at the depth of 5-cm below the soil surface was conducted and its effect on the SEB was studied. Secondly, the surface soil heat flux (G _s) was computed by using harmonic analysis and the effect of the soil heat storage between the surface and the fluxplate on the SEB was examined. The results show that with the 30-min forward phase displacement of observed G, the slope of the ordinary linear regression (OLR) of turbulent fluxes (H+LE) against available energy (R _n-G) increased from 0.835 to 0.842, i.e., the closure ratio of SEB increased by 0.7%, yet energy imclosure of 15.8% still existed in the SEB. When G _s, instead of G was used in the SEB equation, the slope of corresponding OLR of (H+LE) against (R _n-G _s) reached 0.979, thereby the imclosure ratio of SEB was reduced to only 2.1%.     

Exchange fluxes of VOSCs between rice paddy fields and the atmosphere in the oasis <Emphasis Type="Bold">of arid area</Emphasis> in Xinjiang,China

Investigations about VOSCs (volatile organic sulfur compounds) have been received increasing attention for their significant contribution to the nonvolcanic background sulfate layer in the stratosphere and the earth’s radiation balance and as a potential tool to understand the carbon budget. In this study, COS and CS₂ were always recorded throughout the entire rice cultivation season of 2014. COS fluxes appeared as emission in non-planted soil and as uptake in planted soil, the corresponding results were obtained as 2.66 and ?2.35 pmol·m^?2·s^?1, respectively. For CS₂, both planted and non-planted paddy fields acted as sources with an emission rate of 1.02 pmol·m^?2·s^?1 and 2.40 pmol·m^?2·s^?1, respectively. COS emission or uptake rates showed a distinct seasonal variation, with the highest fluxes at the jointing-booting stage. COS and CS₂ fluxes increased with increasing N fertilizer use because of improved plant and microbial growth and activity. Plots treated with both N and S reduced COS and CS₂ fluxes slightly compared with plots with only-N treatment. Light, soil moisture or temperature showed no significant correlation with COS and CS₂ fluxes, but revealed the important impacts on the magnitude and direction of gases fluxes. The results also showed that the (available) sulfur contents in soil and roots had a certain effect on VOSCs emission or uptake. Our results highlight the significance of biotic and abiotic production and consumption processes existing in the soil.     

Eddy correlation measurements of CO2, latent heat,and sensible heat fluxes over a crop surface

Eddy correlation equipment was used to measure mass and energy fluxes over a soybean crop. A rapid response CO₂ sensor, a drag anemometer, a Lyman-alpha hygrometer and a fine wire thermocouple were used to sense the fluctuating quantities.Diurnal fluxes of sensible heat, latent heat and CO₂ were calculated from these data. Energy budget closure was obtained by summing the sensible and latent heat fluxes determined by eddy correlation which balanced the sum of net radiation and soil heat flux. Peak daytime CO₂ fluxes were near 1.0 mg m^–2 (ground area) s^–1.The eddy correlation technique was also employed in this study to measure nocturnal CO₂ fluxes caused by respiration from plants, soil, and roots. These CO₂ fluxes ranged from - 0.1 to - 0.25 mg m^–2s^–1.From the data collected over mature soybeans, a relationship between CO₂ flux and photosynthetically active radiation (PAR) was developed. The crop did not appear to be light-saturated at PAR flux densities < 1800 Ei m^–2 s^–1. The light compensation point was found to be about 160 Ei m^–2 s^–1.Published as Paper No. 7402, Journal Series, Nebraska Agricultural Experiment Station. The work reported here was conducted under Nebraska Agricultural Experiment Station Project 27-003 and Regional Research Project 11–33.Post-doctoral Research Associate, Professor and Professor, respectively. Center for Agricultural Meteorology and Climatology, Institute of Agriculture and Natural Resources, University of Nebraska, Lincoln, NE 68583-0728.     

Intercomparison of NO,NO2 and HNO3 measurements with photochemical theory

The simultaneous measurements of NO, NO₂ and HNO_A mixing‐ratio profiles carried out on the Stratoprobe balloon flight of 22 July 1974 have been simulated with a time‐dependent model using the measured temperature and ozone profiles. The calculated ratios of NO/NO₂, HNO₃/NO₂ using currently accepted photochemistry are consistent with the measured ratios within the experimental errors of the measurements. The measured NO₂/NO ratio is almost a factor of two smaller than predicted, although the discrepancy is still within the experimental errors. A remarkable proportionality in the NO₂ and O₃ profiles has been noted and is unexplained. A time‐dependent simulation has been employed to convert the measurements into diurnally‐averaged profiles suitable for intercomparison with two‐dimensional stratospheric models and a comparison with constituent profiles from Prinn et al. (1975) is carried out as an example. The NO_V mixing ratio, formed from the sum of the NO, NO₂ and HNO₂ measurements is similar to the NO_V mixing ratio from several one‐ and two‐dimensional models used to predict the effects of SST's on the ozone layer. The odd nitrogen mixing ratio is roughly constant from 20 to 35 km at 11 ppbv.     

A modified profile method for determining the vertical fluxes of NO,NO2, ozone,and HNO3 in the atmospheric surface layer

A modified profile method for determining the vertical deposition (or/and exhalation) fluxes of NO, NO₂, ozone, and HNO₃ in the atmospheric surface layer is presented. This method is based on the generally accepted micrometeorological ideas of the transfer of momentum, sensible heat and matter near the Earth's surface and the chemical reactions among these trace gases. The analysis (aerodynamic profile method) includes a detailed determination of the micrometeorological quantities (such as the friction velocity, the fluxes of sensible and latent heat, the roughness length and the zero plane displacement), and of the height-invariant fluxes of the composed chemically conservative trace gases with group concentrations c ₁=[NO]+[NO₂]+[HNO₃], c ₂=[NO₂]+[O₃]+3/2·[HNO₃], and c ₃=[NO]–[O₃]–1/2·[HNO₃]. The fluxes of the individual species are finally determined by the numerical solution of a system of coupled nonlinear ordinary differential equations for the concentrations of ozone and HNO₃ (decoding method). The parameterization of the fluxes is based on the flux-gradient relationships in the turbulent region of the atmospheric surface layer. The model requires only the vertical profile data of wind velocity, temperature and humidity and concentrations of NO, NO₂, ozone, and HNO₃.The method has been applied to vertical profile data obtained at Jülich (September 1984) and collected in the BIATEX joint field experiment LOVENOX (Halvergate, U.K., September 1989).     

Field measurements of emission of nitric oxide from fertilized and unfertilized forest soils in Sweden

Application of nitrate fertilizers on two types of forest soils led to a marked increase in the NO emission rate indicating a large potential for NO production in these soils. The largest fluxes on the fertilized plots were up to 60 ng NO–N m^–2 s^–1. About 0.35% of the applied nitrogen was lost as NO within about 14 days after fertilization. The fluxes from the unfertilized forest soils were in the range 0.1 to 0.8 ng NO–N m^–2 s^–1 with a median value of 0.3 ng NO–N m^–2 s^–1. If this value, obtained during June and August to September, is representative for the growing season (150 days), it corresponds to an annual emission of 0.04 kg NO–N ha^–1. This is about 30% of the value obtained for an unfertilized agricultural soil. Because of the large areas occupied by forests in Sweden the flux of NO from forest soils represents a significant contribution to the total flux of NO from soils in Sweden.Earlier observations of equilibrium concentrations for NO have been verified. These were found to range from 0.2 to 2 ppbv for an unfertilized forest soil and up to 170 ppbv for a fertilized soil. At the rural site in Sweden where these measurements were performed the ambient concentrations where found to be less than this equilibrium concentration, and consequently there was generally a net emission of NO.There are still large uncertainties about the global flux of NO from soils. Using direct measurements on three different types of ecosystems and estimates based on a qualitative discussion for the remaining land areas, a global natural source for NO of the order of 1 Tg N a^–1 was obtained. If 0.35% of the total annual production of fertilizer nitrogen is lost as NO, fertilization of soils may contribute with 20% to the natural flux from soils.     

Effects of Irrigation on Nitrous Oxide, Methane and Carbon Dioxide Fluxes in an Inner Mongolian Steppe

Increased precipitation during the vegetation periods was observed in and further predicted for Inner Mongolia. The changes in the associated soil moisture may affect the biosphere-atmosphere exchange of greenhouse gases. Therefore, we set up an irrigation experiment with one watered （W） and one unwatered plot （UW） at a winter-grazed Leymus chinensis-steppe site in the Xilin River catchment, Inner Mongolia. UW only received the natural precipitation of 2005 （129 mm）, whereas W was additionally watered after the precipitation data of 1998 （in total 427 mm）. In the 3-hour resolution, we determined nitrous oxide （N20）, methane （CH4） and carbon dioxide （CO2） fluxes at both plots between May and September 2005, using a fully automated, chamber-based measuring system. N20 fluxes in the steppe were very low, with mean emissions （±s.e.） of 0.9-4-0.5 and 0.7-4-0.5 μg N m^-2 h^-1 at W and UW, respectively. The steppe soil always served as a CH4 sink, with mean fluxes of -24.1-4-3.9 and -31.1-4- 5.3 μg C m^-2 h^-1 at W and UW. Nighttime mean CO2 emissions were 82.6±8.7 and 26.3±1.7 mg C m^-2 h^-1 at W and UW, respectively, coinciding with an almost doubled aboveground plant biomass at W. Our results indicate that the ecosystem CO2 respiration responded sensitively to increased water input during the vegetation period, whereas the effects on CH4 and N2O fluxes were weak, most likely due to the high evapotranspiration and the lack of substrate for N2O producing processes. Based on our results, we hypothesize that with the gradual increase of summertime precipitation in Inner Mongolia, ecosystem CO2 respiration will be enhanced and CH4 uptake by the steppe soils will be lightly inhibited.