Pergamon

PII:

S1352--2310(96)00104-5

Atmospheric Environment Vol. 30, No. 22, pp. 3741-3755, 1996 Copyright 1996 Elsevier Science Ltd Printed in Great Britain. All rights reserved 1352-2310/96 $15.00 + 0.00

A EUROPEAN INVENTORY OF SOIL NITRIC OXIDE EMISSIONS AND THE EFFECT OF THESE EMISSIONS ON THE PHOTOCHEMICAL FORMATION OF OZONE
ANDREAS STOHL,* ERIC WlLLIAMS,t GERHARD WOTAWA* and HELGA KROMP-KOLB* *Institute of Meteorology and Physics, University for Agriculture, Forestry and Renewable Natural Resources, TiirkenschanzstraBe 18, 1185 Wien, Austria; and fAeronomy Laboratory, National Atmospheric and Oceanic Administration, 325 Broadway, Boulder, CO 80303, U.S.A. (First received 18 Auoust 1995 and in final form 13 March 1996) Abstract--An inventory of soil nitric oxide (NO) emissionsfor Europe was developed.The emission of NO was parameterized using empirical relationships with type of landuse, fertilization rate of agricultural areas and soil temperature. For the year 1994,it was estimated that annual soil NO emissionsin the inventoried area amounted to 535 kt NO-N yr- 1,i.e. 8% of the emissionsfrom combustion processes. On a hot summer day, this fraction increased to 27%. The uncertainty of these emissionestimates, however, is high. They are accurate only within a factor of three to four. As the major fraction (in summer 81%) of the emissionscame from arable ]and, soil NO emissions have to be considered as largely anthropogenic. Large regional differences existed in the soil NO emission rates with the highest emission rates found in southern and western Europe, intermediate rates in eastern Europe and the lowest rates in Scandinavia and northern Russia. The effect of the soil NO emissionson the photochemical formation of ozone (03) was investigated with a one-dimensional photochemical model. When soil NO emissions were considered in the model simulations, computed mean daily maximum 0 3 concentrations over Europe from June to August 1994 were 4 ppb (uncertainty range: 1.4-9.6 ppb) higher than without these emissions.Reductions of pyrogenic NO~ emissions were less efficientin reducing O3 concentrations when soil NO emissions were taken into account. Copyright 1996 Elsevier Science Ltd Key word index: Nitric oxide, nitrogen oxides, soil NO emissions, emission inventory, ozone formation, photochemisl:ry.

1. INTRODUCTION Elevated concentrations of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs) cause the photochemical production of 03 under meteorological conditions conducive to photochemistry. In rural areas, NOx concentrations are much lower than in urban areas, whereas VOC concentrations can be relatively high. This is due to the longer residence time of some VOCs in the atmosphere in comparison with NOx and to the substantial contribution of biogenic VOC emissions to total VOC emissions. Therefo~.'e, photochemical 03 production in rural areas is generally NO~-limited (National Research Council, 1992). This implies that in rural areas 03 concentrations are much more sensitive to changes in NOx emissions than to changes in VOC emissions. Thus, for developing strategies to reduce current rural 03 levels it is critical to have reliable estimates of the sources of NO~ in rural areas. The major source of NOx are emissions from combustion processes. In recent studies, however, it was found that emissions of NO from microbial processes

in soils may be a significant source of NOx in rural areas (e.g. Galbally and Roy, 1978; Williams et al., 1992b; Valente and Thornton, 1993). Although most authors report only on soil emissions of NO, a few studies also indicate significant NO2 emission rates (e.g. Slemr and Seiler, 1984), but this could be the result of the reaction of NO with 03 in the top soil layer that produces NOz before NO can escape to the atmosphere (Delany et al., 1986). In soils, NO is produced by nitrification, the oxidation of NH~ to NO~ and NO3, and denitrification, the anaerobic reduction of N O r and NO3 to gaseous NO, N 2 0 or N2 (Williams et al., 1992b). Several environmental factors control the activity of the microorganisms responsible for these processes and thus the production rate of NO. In addition, some of these factors also modify the physical and chemical parameters that regulate the transport of NO through the soil and its subsequent exchange with the atmosphere. The most important controlling factors for soil NO emissions are soil nitrogen availability, soil temperature and soil water content, but many other factors, for instance, plowing (Sanhueza et al., 1994),

3741

3742

A. STOHL et al. a two-layer approximation where a shallow slab of soil (in our case 5 cm) is bounded below by a thick constant-temperature slab. Given an initial condition, the temporal development of the soil temperature T can be determined by the prognostic equation
dT Q +
2~

influence the emissions. The great spatial and temporal variability of the controlling factors causes an extremely high variability of the NO emissions that in turn makes it very difficult to estimate them on larger spatial and temporal scales (Shepherd et al., 1991). All of the few existing countrywide to global emission estimates were based directly on point measurements (e.g. Skiba et al., 1992; Williams et al., 1992a; Yienger and Levy, 1995), sometimes taking the variability of soil temperature, fertilization rates and other factors into account to extrapolate point measurements undertaken during specific environmental conditions to the whole year and to larger areas. Although models were developed to simulate soil NO emissions explicitly (e.g. Remde et al., 1993), their applications are still limited to single case studies done under well-controlled conditions. In this study, we attempt to combine landuse data, meteorological data and information on nitrogen fertilization rates to create an inventory of NO emissions from soils in Europe. In a further step, we examine the impact of these emissions on the photochemical production of 03 and peroxyacetyl nitrate (PAN) by means of a simple one-dimensional photochemical model. The effect of soil NO emissions on the 03 levels for different reduction scenarios of pyrogenic NOx emissions is demonstrated.

[TM-

T] - a[T-

T~],

(2)

2. A EUROPEAN INVENTORY OF SOIL NITRIC OXIDE EMISSIONS

2.1. M e t h o d and database The method used in this paper to develop a European inventory for NO emissions from soils is based on the work of Williams et al. (1992a) who established an inventory for the United States. They parameterized the soil N O emission with two variables, namely soil temperature and landuse class. Soil temperature is an important controlling element because it can influence biological reaction rates and soil gas diffusion rates. On the basis of previous measurements with the enclosure technique (Williams et al., 1987, 1988; Williams and Fehsenfeld, 1991) Williams et al. (1992a) established the functional dependence R = A exp[(0.071 _+ 0.007)T] (1)

where R is the NO emission rate ( n g N m - 2 s - 1 ) , A a factor associated with the landuse class (ng N m - 2 s - 1) and T the soil temperature (C). Williams et al. (1992a) computed soil temperatures with a linear functional dependence on air temperatures for which they had climatological data available. In this study we used hourly soil temperatures that we computed from data from more than 500 synoptic stations in Europe with the force-restore method described in Stull (1988). This method is

where Q is the net radiation calculated with the meteorological preprocessor O M L (Olesen and Brown, 1988), a boundary layer model based on routine meteorological observations, C is the heat capacity of the soil per unit area, ~ is the period of the daily cycle (86,400 s), TM is the temperature of the lower slab, Ta is the air temperature and a is a form of conductivity between the ground and the air. Through equation (2) the temperature of the top slab responds to the net radiative forcing, to conduction from the deeper slab and to turbulent heat transport with the air. We compared soil temperatures computed with equation (2) with measurements of soil temperatures at 2 cm depth at a grass-covered site in Vienna and found a good correspondence (Fig. 1). The computed maximum temperatures for bare soils were probably somewhat lower than actual values giving a conservative estimate for the NO emission rate. Although a more simple approach would have been sufficient for computing average emission rates, an accurate description of soil temperature behavior was essential for modeling the effect of soil NO emissions on photochemistry. Soil temperature peaks earlier during the day than air temperature because it responds fast to solar radiation, whereas the air temperature maximum lags the radiation maximum by several hours. Thus, the daily maximum NO emission takes place at a time when the solar radiation and hence the potential for 03 formation is greatest. Equation (1) was based on data that had been measured between 5 and 35C and thus the temperature range was truncated at 35C. However, the lower temperature range for which equation (1) was applied, was extended to 0C. As emission rates at these temperatures are low, the uncertainty introduced by this extension is small. For soil temperatures below 0C or snow-covered ground, the emission rate was set to zero, although there exists experimental evidence that NO emissions can even penetrate through a snow pack (Stocker et al., 1995). The soil temperatures in the grid cells of our landuse inventory were calculated using linear interpolation of the soil temperatures at the closest three synoptic stations. Subsequently, the soil temperatures were roughly corrected for the effect of altitude, assuming a dry adiabatic lapse rate. It would have been physically more correct to apply the correction to the air temperatures. This, however, would have required to run the soil temperature model for each grid cell of the landuse inventory and not only for the synoptic stations as we did.

Soil nitric oxide emissions

3743

353025Ud 2015 10 5 0
IIIIm

l'O

1'5

2'0

2'5

3'0

3'5

M O D E L E D S O I L T E M P E R A T U R E [C] Fig. 1. Comparison of hourly values of soil temperatures measured at 2 cm depth at a grass-covered site in Vienna with soil temperatures computed using the force restore method from January to October 1994.The lines are the linear regression curve fit through the data, and the ideal relationship. The observed mean temperature was 14.7C,the calculated mean temperature was 14.4C.The correlation coefficientwas 0.98.

Table 1. The landuse classes, their fraction of the total inventoried area (%) and their associated A factors Landuse category Grassland Arable land Permanent crops Forests Inland water Urban areas Others Area (%) 15.6 26.1 2.1 30.2 1.8 1.2 23.0 A (ng N m- 2s 0.70 See text 0.70 0.05 0.00 0.05 0.40
1)

The A factors in equation (1) depend on the type of landuse. We used the recently published database of van de Velde et al. (1994) for information on landuse. It has a resolution of 10 min and contains the area fractions of seven landuse classes (Table 1). Each class was attributed an individual A factor (see Table 1), except for the category "arable land". Emissions from agricultural areas depend on fertilization. Shepherd et al. (1991) and Skiba et al. (1992) reported linear relationships between NO emission rates and the amount of nitrogen fertilizer applied. Therefore, we used the empirical relationship A = 0.05 F, (3)

with F being the amount of nitrogen fertilizer applied and given in kg N h a - 1yr- 1, independent of the type of fertilizer. Fertilizer usage varies considerably in Europe. We calculated the fertilization amounts and the associated A factor for each country from country statistics on total nitrogen fertilizer consumption in

1992/93 and total arable land in 1993 that were published by the Food and Agriculture Association (FAO, 1994a, b). Dividing the fertilizer consumption by the area of arable land yielded the fertilization rates presented in Table 2. As in Williams et al. (1992a), these A factors were used throughout the growing season from May to August. During the rest of the year, A for arable land was set to 0.5. Valente and Thornton (1993) also reported an exponential dependence of NO emissions from corn, forest and pasture on temperature, but the increase of the emission rates with temperature was steeper than that given by Williams et al. (1992a). For corn, their relationship gave almost the same emission rates as Williams and coworkers formula at high temperatures, but significantly smaller emission rates at low temperatures. On the other hand, their emission rates from forest soits were higher than those of Williams et al. (1992a) and they found very high values for pasture. Stocker et al. (1993) used the eddy correlation technique to measure fluxes of NO2 and NOr at 6 m height at the same grassland site as Williams and Fehsenfeld (1991). Their fluxes corresponded to NO emission rates that were only slightly lower than those of Williams and coworkers. The agreement was very good, taking into account that the soil temperatures inside the enclosures of Williams and Fehsenfeld (1991) were probably somewhat higher than those outside of the enclosures. In addition, eddy correlation measurements integrate over a larger spatial scale than enclosure measurements and thus the results of the two methods are not directly comparable. The finding of this good correspondence is important,

3744

A. STOHL et al. Table 2. Nitrogen fertilization rates (F) for arable land in Europe (1993) used in this study (kg N ha- 1yr- 1) Country Albania Belgium + Luxembourg Czech Republic Finland Former Soviet Union Germany Hungary Italy Norway Portugal Slovak Republic Sweden U.K. F (kgNha-I yr -1 ) 26 226 47 68 37 147 26 100 124 57 47 69 203 Country Austria Bulgaria Denmark Former Yugoslavia France Greece Ireland The Netherlands Poland Romania Spain Switzerland F (kgNha-I yr -1 ) 86 56 13l 41 119 115 365 425 48 28 50 157

because it shows that a large fraction of the emitted NO is not locally deposited on plant surfaces, but actually reaches the atmosphere, at least in locations with rather sparse vegetation. The A factors and their dependence on nitrogen fertilization used in this study were essentially taken from Williams et al. (1992a), but were reduced by approximately 30% to account for the somewhat lower emission rates found by Stocker et al. (1993) for grassland and Valente and Thornton (1993) for corn. For those landuse classes for which data were lacking ("permanent crops", "urban areas", "others"), conservative estimates were made. See the discussion on the uncertainties of the inventory how these A factors were determined. The emission inventory was developed for the area 24.6 W to 41.9E and 34.9N to 72.1N which covers most of Europe. We investigated three cases: 1. The annual emissions based on meteorological data for the year 1994. 2. The summertime (June-August) emissions in 1994. 3. The daily emissions on 5 August 1994 which was one of the hottest days of the year, especially in Central Europe. The inventory of pyrogenic emissions for the year 1991, developed by the Co-Operative Programme for Monitoring and Evaluation of the Long-Range Transmission of Air Pollutants in Europe (EMEP) (Sandnes, 1993), was used for comparison. The resolution of this inventory was 150 km, but for the OECD countries it was refined to 50 km resolution using the relative emission intensities of the OECD inventory (L/ibkert and de Tilly, 1989). F o r the comparison it was assumed that the pyrogenic NO~ emissions have no annual variation, a reasonable assumption as the major pyrogenic NOx source are traffic and power plants which indeed have little annual variation. Both the pyrogenic as well as the soil emissions were appor-

tioned to individual countries using a country-code inventory with 75 km resolution. This inventory gives the country with the dominating area fraction within each grid element. Due to its coarse resolution, however, country totals must be interpreted with caution, especially for smaller countries. 2.2. R e s u l t s Over the whole inventoried area, total soil emissions were 535 kt N O - N y r - 1 (Table 3). This result is in good agreement with the global soil NOx inventory of Yienger and Levy (1995). For Europe and Russia they calculated a total emission of 740 kt NOx-N yr-1. As emission rates in Europe were much higher than in the Asian part of Russia, most of the soil emissions stems from Europe. Thus, the agreement with our total emission estimate is excellent. Figure 2 shows the annual soil NO emissions in Europe. From a visual comparison it appeared that the spatial distribution of the emission was also in good agreement with the results of Yienger and Levy (1995). Yienger and Levy (1995) accounted explicitly for the attenuation of soil emissions by vegetative canopies. We accounted for this effect only by reducing the original A factors of Williams et al. (1992a) by 30%. Probably, this reduction was sufficient to compensate for the loss through deposition on the foliage. Basically, three large areas with significantly different emission levels could be identified: 1. The lowest emission rates ( < 2 x l 0 - S k g N m -2 yr -1) were found in Scandinavia and northern Russia. This was due to "forests" being the dominant type of landuse and relatively low temperatures prevailing throughout the year. For the same reasons, emission minima were estimated for the Alps and the Pyrenees. 2. Medium emission rates (2 x 10 -5 to 1 x 10-4kg N m - 2 y r - 1) predominated in Eastern Europe. Here, summer temperatures were high, and "arable land" and "grasslands" were the dominating landuse classes.

Soil nitric oxide emissions Table 3. Comparison of the NO emissions from soils and pyrogenic sources for the year 1994, for summer 1994 (June-August), and for 5 August 1994 for individual countries. S gives the annual soil emissions (kt N yr- 1), p tile annual pyrogenic emissions (kt N yr - 1), S/P (year) their ratio (%), S/P (summer) gives the ratio (%) of soil and pyrogenic emissions during summer (June-August), and S/P (day) the ratio (%) of soil and pyrogenic emissions on 5 August 1994. The sum of the country emissions is slightly less than the total emission whiclz is mostly due to the erroneous classification of land areas as sea in the country-code inventory. Country Albania Austria Belgium Bulgaria Czech Republic: + Slovak Republic Denmark Finland France Germany Greece Hungary Iceland Ireland Italy The Netherlands Norway Poland Portugal Romania Former Soviet Union Spain Sweden Switzerland U.K. Former Yugoslavia Total S P (ktNyr-') (ktNyr-') 1.0 4.4 3.5 8.2 8.5 4.8 2.9 61.6 45.3 12.5 5.4 1.4 9.8 31.5 8.8 4.4 19.7 6.9 14.1 120.1 35.6 6.5 1.5 25.4 17.3 535.4 1.4 74.2 125.2 56.9 243.4 32.8 58.6 549.2 972.1 198.0 62.6 1.0 38.4 362.4 120.6 28.9 340.7 22.6 121.9 825.8 151.8 88.8 49.1 770.5 148.7 6437.3 S/P (year) (%) 70.2 6.0 2.8 14.4 3.5 14.8 5.0 l 1.2 4.7 6.3 8.7 135.9 25.5 8.7 7.3 15.2 5.8 30.3 11.5 14.5 23.5 7.3 3.0 3.3 11.6 8.3 S/P (summer) (%) 138.5 15.4 8.2 36.6 9.0 43.9 11.4 31.4 13.7 15.8 20.4 191.4 69.4 23.8 22.4 28.1 15.4 74.4 25.9 34.7 57.9 17.4 7.2 9.2 27.8 21.4 S/P (day) (%) 154.8 22.0 11.3 41.4 12.7 63.8 15.7 40.5 20.9 17.7 27.3 209.2 77.6 29.4 32.0 37.3 22.3 80.6 30.6 44.6 64.7 24.0 10.1 11.2 34.5 27.2

3745

The fertilization of the "arable land", however, was moderate ( < 50 kg N h a - 1 y r - 1). 3. The highest emission rates (1 10 -4 to 8 10 -4 kg N m - 2 yr-1) were located in southern and western Europe, where the conditions were generally similar to eastern Europe, but where a high nitrogen input (up to 400 kg N ha-~ y r - 1 ) to agricultural areas was responsible for high soil N O emissions. F o r the U.K., the total emission from soils in 1994 was 25.4 kt N O N. This is in good agreement with an annual emission estimate of 13-38 kt N O - N by Skiba et al. (1992). To investigate the importance of soil emissions relative to pyrogenic emissions, the former were expressed as the fraction of the total pyrogenic emissions taken from the E M E P inventory. F o r the whole investigation area, the annual soil N O emissions were 8.3% of the annual pyrogenic NO~ emissions, but large regional differences we.re observed throughout Europe (Fig. 3), reflecting the large variability of both, pyrogenic and soil emissions. F o r individual countries (Table 3), soil N O emissions contributed between 2.8% (Belgium) and 70.2% (Albania) of the annual pyrogenic emissions. The extremely high fraction for Iceland (136%) should be interpreted with caution. N o N O flux measurements exist for the landuses typically found in Iceland. A large fraction of Icelands

landuse was classified as "others", the class with the most uncertain A factors. In summer (June-August), soil N O emission rates were much higher than the annual average emission rates. In this period, the soil N O emissions for the whole investigation area amounted to 21% of the pyrogenic NOx emissions (Table 3), but again, large regional variations were found, ranging from 7.2% for Switzerland to 139% for Albania. Even higher than the average summertime soil N O emission rates were those estimated for a hot summer day (5 August 1994) (Fig. 4). The fraction of the soil N O emissions of the pyrogenic NOx emissions, averaged over the whole investigation area, increased from 8.3% for the whole year and 21% for summer to 27% on 5 August (Table 3). For some countries, the magnitude of the soil emissions was comparable to that of the pyrogenic emissions and in all countries soil N O emissions contributed to more than 10% of the pyrogenic NOx emissions. European soil N O emissions were dominated by emissions from "arable land" that accounted for 72% of the annual soil emissions and 81% of the soil emissions in summer and on 5 August (Table 4). Similar figures were calculated by Williams et al. (1992a) for the United States. Thus, soil N O emissions are strongly influenced by agricultural activities.

3746

A. STOHL et al.

Lla

LLI

o
q

z
W

z o I"

.o

--

I
Z o tt') Z o tt'3

Z c.O

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3 a nlVfl

Soil nitric oxide emissions

DATA SET: EMTOT.yeor

3747

65"N

LIA
55ON -

0.5

0.2

5
45ON
-

0.1

0.05

iiiii!i!i ~i~
ili~i!~ : !

0.02

35ON -

I 20W

I
IOW

OE

lOE
LONGITUDE

20E

50E

40E

RATIO SOILS/PYROGENIC
Fig. 3. The ratio of annual soil NO emissions and annual pyrogenic NOx emissions. In some areas, pyrogenic NOx emissionsare zero and the ratio is thus infinte. For practical reasons, however, ratios were limited to a maximum value of 5.

2.3. Discussion of the uncertainties There were several sources of error that produced a relatively large uncertainty for the whole inventory. One error source wa.s the computation of soil temperatures. We used the same soil temperatures--which we found to agree well with measurements at a grasscovered site---for all landuse classes. For "forests", the computed temperatures were too high, especially during daytime, because forest soils are experiencing a weaker radiative fi)rcing. As the emission rates from "forests" were much smaller than those from other landuses, this effect was of minor importance for the total emission, but could be important in forested regions. On the other hand, for bare soils the daily maximum soil temperatures were probably underestimated. This was of importance for "arable land" for certain periods of the year and for the landuse class "others". Nevertheless, the uncertainty ranged within a few degrees, yielding an uncertainty for the emission rate of les.,; than 50%. The major source, of error arose from the formulation of the temperature dependence of the emissions and from the preexponential factor in equation (1) (see also Williams et al., 1992a). No measurements were available to derive preexponential factors for the land-

use classes "permanent crops", "urban areas" and "others". The area fractions of the first two classes together were only 3.3% and thus their contribution to the total emission was of minor importance. The class "urban areas" only covered city centers where most of the ground is sealed and thus a very low A factor was chosen. Recently, Thornton et al. (1996) presented measurements from Nashville that support this choice of the A factor. For "permanent crops", we took the A factor for "grasslands" which should give a minimum estimate. To define an A factor for the landuse class "others" was more difficult because of its heterogeneity. In addition, emissions from this landuse class had a larger impact as it contributed 23% of the total area. A large, but not explicitly specified fraction of class "others" are mountainous areas (rocks, ice, etc.) where hardly any emissions can be expected. Therefore, we took a factor that was only about half of that for grasslands. The landuse class "forests" covered large areas and was thus potentially important. Our A factors for "forests" were based on the measurements of Williams and Fehsenfeld (1991), although some authors reported much higher emission rates (e.g. Valente and Thornton, 1993). However, as it was not clear what

3748

A. STOHL et al.

DATA SET: EMTOT.doy

I I

65N

0.5
ILl

55NI-I--<I:: 0.2
m

0.1 45ON - 0.05 0.02 ,35ON - -

I
20W

I
10W OE IOE LONGITUDE 20E 50E 40E

RATIO SOILS/PYROGENIC
Fig. 4. Same as Fig. 3, but for the emissions on 5 August 1994.

Table 4. Contribution of the different landuse types to the soil NO emission for the year 1994, the summer 1994 (June-August) and for 5 August 1994. Values are given as % of total soil NO emissions Landuse category Grassland Arable land Permanent crops Forests Inland water Urban areas Others Year Summer (%) (%) 13.8 72.2 2.6 1.6 0.0 0.1 9.7 9.3 81.2 1.7 1.1 0.0 0.1 6.6 5 August (%) 9.1 81.4 1.6 1.2 0.0 0.1 6.6

fraction of these emissions actually penetrates the canopy (Jacob and Bakwin, 1991), we used the lower estimate, although Kaplan et al. (1988) reported that a significant fraction of the soil NO emissions penetrated even the canopy of an Amazon tropical forest. The uncertainty of the A factors for "grasslands" was already discussed by Williams et al. (1992a) and estimated to be a factor of two. A difficulty arises because managed grasslands also receive fertilization. As our landuse database allowed no distinction be-

tween managed and unmanaged grasslands, we assumed that the whole fertilizer consumption of a country is applied to "arable land". This probably gives too high emission rate estimates for "arable land" and too low estimates for "grasslands", but does not change the country total emissions, because of the linear dependence of the A factors on fertilization rates. Most important were the A factors for "arable land", because of the large contribution of emissions from this landuse class to total emissions. Williams et al. (1992a) estimated them to be accurate within a factor of two. In Europe, however, the variations in crops, agricultural techniques and fertilization levels are larger than in the United States. Thus, we estimated A to be uncertain by a factor of three. The total annual NO emissions from "arable land" amounted to 407 kt N which was approximately 4.3% of the total fertilizer consumption in the area. Shepherd et al. (1991) reported that on the bean field they studied, approximately 11% of the fertilizer-nitrogen was emitted as NO and 5% as nitrous oxide (N20) throughout half a year. These figures are high as compared to other values cited in the literature. Yienger and Levy (1995) compiled NOx loss rates integrated mostly over periods of a few weeks that ranged

Soil nitric oxide emissions Table 5. Nitrogen fertilizer loss rates as NOx. This table was originally compiled by Yienger and Levy (1995). The Yamulki et al. (1995) reference was added by the authors Reference Hutchinson and Brams (1992) Williams et al. (1992b) Valente and Thornton (1993) Shepherd et al. (1991) Slemr and Seiler (1984', Slemr and Seiler (1991) Anderson and Levine (1987) Johansson et al. (1988) Yamulki et al. (1995) Period 9 weeks 4 weeks 15 weeks 26 weeks 4 weeks 3 weeks 52 weeks 30 h 52 weeks % loss 3.2 2.8 2.5 11.0 2.7 0.064).21 0.8 0.5 0.5

3749

total VOC emissions, nearly all studies investigating photochemical pollution in Europe neglect the effect of soil NO emissions. We made a first attempt to assess the sensitivity of ozone to soil N O emissions using a photochemical model. 3.1. M o d e l description We used a one-dimensional photochemical model with eight layers and tested its sensitivity to soil N O emissions. The model is a modified version of the Lagrangian photochemical model P O P described by Stohl et al. (1995) and Wotawa et al. (1996). Here, it was used to model a non-moving column of air centered over Europe. The chemical mechanism we used is an updated version of the carbon bond mechanism (CBM-IV) first described by Gery et al. (1989). Photolysis rates required by the chemistry module were computed from solar elevation and cloud cover, reaction rates depended on temperature and reactant concentrations. Exchange of a species between the eight layers of the model was described by the diffusion equation using K-theory (Stull, 1988)
Oz \ az }

from 0.06 to 11% of the fertilizer nitrogen applied, but with most values from 2 to 3% (Table 5). Annual loss rates are likely higher than that. Significantly lower figures were recently found by Yamulki et al. (1995) for a fertilized wheat field in the U.K. They estimated that approximately 0.93% of the fertilizer nitrogen was emitted as N 2 0 and only 0.53% was emitted as NO. These results ate unusual as they indicate higher N 2 0 than NO emis,don rates. More typical is a production ratio of N O / N 2 0 of 2:1 (Bouwman, 1990). Our estimate of the fraction of the annual nitrogen fertilizer application lost as NO is lower than that of Shepherd et al. by a factor of three, but higher than that of Yamulki et al. by a factor of eight. It agrees reasonably well with the other values given in Table 5. The A factors for ;'arable land" depended on fertilization rates and thus were different for each country. Our country-code inventory had a rather rough resolution of 75 km which introduced an error that we estimate was less than 10% of the total emission, but much higher for individual, especially small, countries. A further uncertainty of the inventory resulted from the deposition of reduced and oxidized nitrogen from the atmosphere. Sandnes (1993) reported that in 1991 the annual deposition exceeded 15 kg N ha-1 in large parts of Europe and 2 5 k g N h a -1 in western and central Europe. There, both natural and agricultural areas experienced additional nitrogen input which nearly equalled the fertilization rates of some eastern European countries. From the discussion above, we estimate the uncertainty of the whole inventory to be a factor of 3-4. For the development of the A factors we excluded reports of extremely high NO emissions from our considerations, and we reduced the A factors of Williams et al. (1992a) by approximately 30%. Thus, our inventory is likely to give a conservative estimate of actual emissions.

(4)

where C is the concentration of the species, t is the time, and K~ is the eddy diffusivity coefficient at height z above the ground. The eddy-diffusivity coefficients were calculated as layer averages according to Byun and Dennis (1995). Dry deposition velocities Vd were parameterized using the resistance method (Wesely and Hicks, 1977), with the surface resistance being calculated for each landuse class separately following the procedure of Wesely (1989). The dry deposition flux VdC served as the lower boundary condition for equation (4) as follows:
K~ a c = vdc. Oz

(5)

3. EFFECTSOF SOIL NO EMISSIONSON PHOTOOXIDANT CONCENTRATIONS Whereas biogenic VOCs have already been generally recognized as giving an important contribution to

The model had a relatively high resolution near the ground with the lowest layer extending up to 30 m above the ground. This allowed an adequate treatment of the dry deposition and emission processes. Wet deposition was calculated using the scavenging coefficients of McMahon and Denison (1979). Initial and boundary conditions for several species were taken from results of a two-dimensional global model by Isaksen and Hov (1987) and depended on latitude, altitude and time of the year. These background concentrations were advected into the model domain with a constant speed of 5 m s -1, a value typical for summer conditions in the midlatitudes. The model domain extended from 10W to 40E and from 36N to 60N. All model input data were averaged over this domain. Although it would have been interesting to investigate also much smaller modeling domains, this was not possible with the simple model

3750

A. STOHL et al. that nighttime concentrations in that box were very sensitive to the choice of the boundary-layer parameterization. NOx concentrations were considerably lower when pyrogenic NOx emissions were omitted (Fig. 5a). This was expected as it was estimated in Section 2.2 that even on a hot day soil NO emissions accounted for less than 30% of the pyrogenic NOx emissions. Nevertheless, soil emissions do have a clear effect on summertime NOx concentrations as indicated by the reduction in estimated mean daily NOx concentration when soil NO emissions were omitted. Due to the episodic nature of soil NO emissions, short-term concentration fluctuations were much larger when soil NO emissions were included. 03 concentrations were very sensitive to changes in NOx emissions (Fig. 5b) as 03 production on a regional to continental scale is NOx-limited (National Research Council, 1992). With soil NO emissions alone, 03 concentrations varied between 20 and 30 ppb. This was much less than the initial and boundary conditions for 03 used in the model runs. Advected 03 concentrations varied with altitude and season, but a typical value was 45 ppb (Isaksen and Hov, 1987). Thus, allowing for soil NO emissions only resulted in a net 03 destruction above Europe. Contrary, the other two scenarios which included the pyrogenic NOx emissions, resulted in a net 03 production. In both scenarios, mean 03 concentrations from June to August were above 50 ppb. The mean 03 concentration in the model run with pyrogenic and soil emissions was higher than in the run with pyrogenic emissions only. The average 03 concentration difference from June to August was 3.0 ppb. For the means of the daily maximum 03 concentrations this difference was 4.0 ppb. The major source of nitric acid, HNO3, is the reaction of OH with NO2. As both NO2 and OH (see Fig. 5e) concentrations increased with increasing NO~ emissions, HNO3 concentrations were very sensitive to changes in NO~ emissions (Fig. 5c). Summertime HNO3 concentrations in the scenario with both pyrogenic and soil NO~ emissions were higher than in the other two scenarios which excluded either pyrogenic or soil emissions. As HNO3 reacted very sensitive to soil NO emissions, it can possibly be used as an indicator to what extent soil NO emissions influence photochemistry. Peroxyacetyl nitrate (PAN) is formed by the reaction of the peroxyacetyl radical with NO2. It is in thermal equilibrium with its precursors and can thermally decompose, thereby recycling NO2, when temperatures are high enough. This explains the pronounced minimum of PAN concentrations in July and August (Fig. 5d). Omitting pyrogenic NOx emissions resulted in much lower P A N concentrations than in the other two scenarios. Contrary, omitting soil NO emissions had only a minor effect on PAN concentrations. Thus, P A N concentrations appear to be much more sensitive to changes in pyrogenic NOx emissions than to changes in soil NO emissions.

concept. With an advection speed of 5 m s - 1, the residence time of the air in the modeling domain was approximately 8 days. Reducing the model domain would have reduced this residence time. With such a reduction, the model results would have been too sensitive to the advected background concentrations. Meteorological input data were compiled from more than 500 synoptic and 100 radiosonde stations in Europe. These data included temperature, dew point temperature, their vertical gradients between the model layers, cloud cover, precipitation rate, sensible heat flux, friction velocity, convective velocity scale and boundary layer height. The boundary layer parameters were calculated with the O M L meteorological preprocessor (Olesen and Brown, 1988). Anthropogenic NO~ and VOC emissions were taken from the EMEP emission inventory for 1991 (Sandnes, 1993). They were temporally disaggregated using functions for the daily, weekly and yearly variations of emission strength. Carbon monoxide (CO) emissions were assumed to be five times the NOx emissions. The emissions of low- and high-level sources were assumed to take place from ground up to 100 m height and from 100 to 400 m height, respectively. Biogenic isoprene emissions from forests were calculated as functions of radiation and temperature, whereas terpene emissions depended solely on temperature (Guenther et al., 1993). NO emissions from soils were implemented as described in Section 2, but were split to 90%o NO and 10%o NO2, respectively, to account for the partial conversion of NO to NO2 by reaction with 03 that occurs in the top soil. T~e factor of this split is highly uncertain. We checked its effect on the modeled ozone concentration by calculating an additional scenario with emissions split equally between NO and NOz. In this scenario, modeled ozone concentrations, for instance, were higher by only 0.2 ppb as compared to the 90% NO and 10% NO 2 split. Thus, the uncertainty of the model results due to this split is rather low. Soil emissions were released into the lowest layer of the model which is 30 m high. The differential equations describing both physical and chemical processes were integrated together with a flexible time step assuming the quasi-steady-state approximation (QSSA) (De Leeuw, 1988). 3.2. M o d e l results We computed three NO~ emission scenarios for the period March-October 1994: 1. Pyrogenic NOx and soil NO emissions 2. Pyrogenic NOx emissions only 3. Soil NO emissions only. Figure 5 shows the time series of the daily mean concentrations of selected species in the second box (30-100 m above the ground) for the three emission scenarios. The results for the lowest box are not presented here, because Wotawa et al. (1996) have shown

Soil nitric oxide emissions

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3752

A. STOHL et al. In Europe, the aim is to decrease anthropogenic VOC and NOx emissions in order to reduce ambient 03 levels (e.g. Simpson and Styve, 1992). Therefore, the relative contribution of soil NO emissions to the total NOx emissions will increase. We examined the effect of a 50% reduction of pyrogenic NOx emissions on the 03 concentrations. This was investigated for two scenarios, first with pyrogenic and our best estimate of the soil emissions, and second, with pyrogenic emissions only. The difference between the 03 concentrations in these two scenario simulations allowed to assess the influence of the soil NO emissions on the effectivity of pyrogenic NO~ emission reductions. The results of these scenario simulations are summarized in Table 7. It can easily be seen that a significant reduction of the 03 concentrations was achieved when pyrogenic NOx emissions were reduced by 50%. This reduction, however, was less successful when the soil NO emissions were taken into account. With soil emissions accounted for, a 50% pyrogenic NOx emission reduction decreased the mean daily maximum 03 concentration from June to August by 9.5 ppb. With soil emissions omitted, the respective value was 11.6 ppb. After the pyrogenic emission reduction, mean daily maximum O 3 concentrations were 6.1 ppb higher when soil NO emissions were accounted for than when soil emissions were omitted. A 50% reduction of pyrogenic NO~ emissions is likely to influence the initial and advected concentrations of NOx and 03 in the background atmosphere.

OH radical concentrations increased with increasing NO~ concentrations (Fig. 5e), because polluted air provides additional radical sources (Cox, 1988), such as the reaction HONO + hv --, OH + NO. The effect of soil NO emissions on the OH concentrations is, however, moderate. In Section 2.3 we estimated that our inventory of soil NO emissions was uncertain by a factor of three to four. To investigate the effect of this uncertainty on the model results, we repeated the scenario calculations discussed above, but decreased/increased the soil NO emissions by a factor of three. Table 6 summarizes the results of these scenario simulations for 03. Accounting for pyrogenic emissions only resulted in a mean daily maximum 03 concentration of 59.4 ppb. Accounting additionally for 33, 100 and 300% of our best estimate of the soil NO emissions, increased this value by 1.4, 4.0 and 9.6 ppb, respectively. Thus, with the estimated uncertainty of the emission estimates, the importance of soil NO emissions ranged from a relatively small to a major contribution to the photochemical 03 formation. For the scenarios with 33, 100 and 300% of our best estimate of the soil emissions only, without pyrogenic N O x emissions, the modeled mean daily maximum 03 concentrations were 20.4, 29.3 and 47.7 ppb, respectively. The first two values indicated Oa destruction over the continent, while the last value indicated a balanced 03 budget. It equalled approximately the background concentration advected into the model domain.

Table 6. Mean and mean daily maximum 03 concentrations from June to August 1994 for the three scenarios discussed in the text (pyrogenicNOx emissions only, soil NO emissions only, pyrogenic NOx and soil NO emissions).The soil NO emissions were varied from 33% to 300% of the best emission estimate to account for the uncertainty of the inventory Scenario Pyrogenic emissions only Pyrogenic + 33% soil emissions Pyrogenic + 100% soil emissions Pyrogenic + 300% soil emissions 33% soil emissions only 100% soil emissions only 300% soil emissions only Mean 03 (ppb) 52.0 53.2 55.0 58.8 18.6 26.4 41.7 Mean daily maximum 03 (ppb) 59.4 60.8 63.4 69.0 20.4 29.3 47.7

Table 7. Mean and mean daily maximum 03 concentrations from June to August 1994 for the scenarios with 100 and 50% of the pyrogenic emissions,with soil NO emissionsaccounted for and soil NO emissions omitted and with and without background concentrations changed for NO2 and 03. For further specifications of the model runs, refer to the main text Mean 03 (ppb) 55.0 52.0 47.4 42.5 46.1 41.1 Mean daily maximum O3 (ppb) 63.4 59.4 53.9 47.8 52.5 46.3

Scenario 100% pyrogenic + soil 100% pyrogenic 50% pyrogenic + soil 50% pyrogenic 50% pyrogenic + soil + changed background concentrations 50% pyrogenic + changed background concentrations

Soil nitric oxide emissions

3753

It is not possible to give any exact estimate on how the background concentrations respond to emission reductions in Europe (and possibly also in other areas). It is likely, however, that Oa concentrations will be slightly lowered. NOx concentrations probably respond stronger. To illustrate the sensitivity of the model results on the background concentrations, we reduced them by 10% for O3 and by 20% for NO2. The results of these scenarios are also given in Table 7. Mean daily maximum 03 concentrations were approximately 1.5 ppb lower than in the scenarios with unchanged background concentrations. Thus, the model was moderately sensitive to changes in the background concentrations. The difference in the 03 concentrations between the simulations with and without soil emissions was 6.2 ppb, very similar to the results for the unchanged background concentrations (6.1 ppb) Thus, the result that soil NO emissions make pyrogenic emission reductions less efficient was unaffected by the exact choice of the background concentrations.

4. DISCUSSION AND CONCLUSIONS

We developed an NO emission inventory for Europe and found that soil N O emissions can be a significant source of atmospheric NOx in Europe. According to our best estimates, soils contributed to approximately 8% of the an:aual pyrogenic NOx emissions in 1994, and to 27% of the pyrogenic NO~ emissions on a hot summer day. We found, however, large regional differences. In some countries, soil NO emissions contributed to less than 3% of the annual pyrogenic NOx emissions, and to only about 10% of the emissions on a hot summer day. Contrary, in other countries soil NO emissions were nearly as high as or even exceeded the pyrogenic NOx emissions on a hot summer day. Large uncertainties in the soil NO emission inventory remain. We estimated the inventory to be accurate only within a factor of three to four. With this large uncertainty, the significance of soil N O emissions remains unclear, although we have demonstrated their possibly large contribution to total NOx emissions. To overcome the uncertainties of the emission estimates, additional measurements are required. There is a general lack of European measurements that was already noted by Yienger and Levy (1995). Therefore, our emission inventory was mostly based on nonEuropean measurements. European soil NO emission measurements for many types of soils and under different surface conditions, and for varying levels of fertilization are necessary to provide a more reliable database for emissio:a estimates. Especially, the influence of soil water co~atent on the emissions should be better characterized. From previous measurements, it is not yet clear what fraction of the soil N O emissions are deposited on the foliage and what fraction actually enters the

atmosphere (Jacob and Bakwin, 1991). To answer this question, flux measurements using micrometeorological techniques (e.g. eddy correlation measurements) concurrently with enclosure measurements are needed. The difference between the vertical fluxes of oxidized nitrogen compounds found with those two methods must be caused by deposition onto the ground and onto the foliage. We have tried to take these current uncertainties into account by using low estimates of the emission fluxes for "forests", the landuse class for which deposition is most important, and by considering the results of eddy correlation measurements of Stocker et al. (1993) that lead to a 30% reduction of the A factors originally published by Williams et al. (1992a). However, because of a general lack of combined micrometeorological and enclosure measurements, our results may be an upper estimate of the emissions that actually reach the atmosphere and take part in photochemical 03 formation. Nevertheless, our emission estimates agreed excellently with those of Yienger and Levy (1995), who explicitly accounted for the attenuation of soil NO emissions by vegetative canopies. The effect of soil NO emissions on 03 concentrations was investigated using a simple one-dimensional model covering most of Europe. It was found that soil emissions, which are currently neglected in most other photochemical models, can have a significant effect on 03 concentrations. Adding our best estimate of these emissions to the pyrogenic NOx emissions resulted in a 4 ppb increase of mean daily maximum 03 concentrations from June to August 1994. With an estimated uncertainty of a factor three for the emission estimate, this increase ranged between 1.4 and 9.6 ppb. While the lower emission estimate gives a relatively small contribution to photochemical 03 formation, the upper estimate is very significant. Soil NO emissions may gain even more in importance if current pyrogenic emissions of NOx will be reduced in the future. Although a 50% decrease of pyrogenic emissions reduced summertime 03 levels significantly, both with soil emissions accounted for and with soil emissions omitted, the modeled 03 concentrations were higher by more than 6 ppb when our best estimate of soil NO emissions was accounted for. The overall effect of soil NO emissions on the European 03 concentration level may actually even be stronger than the model simulations presented here suggest. Sillman et al. (1990) and Jacob et al. (1993) have shown that an NOx molecule in an urban area or a power plant plume is less efficient in producing 03 than an NOx molecule under the low-NOx conditions typical for rural areas. In our box model calculations, all emissions were artificially dispersed over Europe and were thus equally efficient in producing 03. In reality, however, pyrogenic emissions are concentrated in urban areas, power plant plumes and along major roads, whereas soil emissions are more widespread. Thus, the artificial dispersion in our model is less justified for pyrogenic emissions than for

3754

A. STOHL et al. results for the whole year and the summer period are available. The author's electronic mail address is "andreas.stohl@zamg.ac.at".
Acknowledgements--Thanks are due to H. R. Olesen for providing us with the OML meteorological preprocessor. We thank H. Veldkamp from RIVM for sending us the European Land Use Database version 1.0. Thanks are due to F.A.A.M. de Leeuw and J, Beck for their help in photochemical modeling a few years ago and for de Leeuw's comments on the paper. We also thank two anonymous referees for their excellent reviews that helped a lot in revising the paper.
REFERENCES

soil emissions. Therefore, our model probably overemphasized the efficiency of pyrogenic emissions in producing 0 3 . It would be very interesting to investigate the effect of soil N O emissions on the 0 3 concentrations with a more complex model which overcomes the deficiencies of our one-dimensional model and which can account for the large regional differences in the emission rates. Large regional differences also exist in the concentration ratios of VOC and NOx. In some areas of Europe with low VOC/NOx ratios 0 3 formation is mostly limited by VOCs. There, soil N O emissions may have little effect on the photochemical 0 3 formation. O n the other hand, in regions with high VOC/NOx ratios and NOx limitation of the 0 3 formation, soil N O emissions may be especially effective in producing 03. VOC limited areas are mostly found in western Europe, while 0 3 formation in the rest of Europe is limited by NOx. Thus, it is possible that, although soil N O emission rates are highest in western Europe, their effect on 0 3 formation is strongest in eastern Europe. It is, however, under discussion whether 0 3 formation in rural areas of western Europe really is VOC limited, as indicated, for instance, by the E M E P model (Simpson, 1995). VOC limitation on a larger scale could also be an artifact of the coarse resolution of most European-scale models. In reality, VOC limitation might exist only in the plumes of major cities (Neftel and Staffelbach, 1995), whereas rural areas might generally be NOx limited. In that case, the effect of soil N O emissions on 0 3 formation might be strongest in western Europe. A problem that will arise with more complex photochemical models that are validated against measurements is how to capture adequately the large spatial and temporal variability of Soil N O emissions. This high variability can only partly be captured by the relationship with soil temperature, but to a large part must be attributed to other factors. For instance, wetting of a dry soil can result in N O emission bursts (Slemr and Seiler, 1984; Williams et al., 1992b), flooding of a soil modifies N O emissions (Galbally et al., 1987), the timing of fertilizer application has a large influence on N O emissions (Shepherd et al., 1991), a growing vegetation cover reduces the emissions due to deposition on the foliage (Slemr and Seiler, 1984) and high ambient N O levels above a compensation point may hinder soil emissions (Kim et al., 1994). It is not yet clear how this episodic behavior is to be modeled adequately, although an attempt was made by Yienger and Levy (1995). Yamulki et al. (1995) reported that in a wheat field approximately 82% of the annual N O emission occurred in the spring, shortly after fertilization. If such behavior is typical, soil N O emissions could help to explain the springtime 0 3 maximum often observed in more remote locations of Europe. Requests for the soil N O emission inventory are welcome and may be directed to the authors. The

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