The interfacial mass transfer resistances of the ozone dry deposition over the field soil of Taichung County in Taiwan

This study aims to design a dry deposition chamber and to measure ozone depletion over the Taichung field soil. This study seeks to verify the phenomena by an experimental and mathematical model. It is demonstrated that interfacial mass transfer resistances of ozone dry deposition involve reactive resistance (R(sr)) and kinetic resistance (R(sk)). It reveals the chemical reaction (O3 + NO --> NO2) to produce the reactive resistance, and verifies that the interfacial mass transfer resistances depend on nitrogen oxide emission and soil temperature. It shows that the interfacial mass transfer resistances are reduced with increasing soil temperature (T(S)). The model profiles are smaller than the observed data within a relative error of 15%. The reactive resistance decreases exponentially with increasing soil temperature; R(sr)(-1) (cm x sec(-1)) = 0.0001 exp (0.1455T(S)). The kinetic resistance decreases linearly with increasing soil temperature; R(sk)(-1)(cm x sec(-1)) = 0.0108T(S) + 1.4012. This model is more accurate with higher soil temperature and larger ozone concentration. Results are consistent with thermodynamics and reaction kinetics. Ozone dry deposition over agricultural soil causes conversion of nitrogen oxide (NO) to nitrogen dioxide (NO2).     

Deposition of nitrogen-containing compounds to an extensively managed grassland in central Switzerland

During four intensive observation periods in 1992 and 1993, dry deposition of nitrogen dioxide (NO(2)) and ammonia (NH(3)), and wet deposition of nitrogen (N) were determined. The measurements were carried out in a small, extensively managed litter meadow surrounded by intensively managed agricultural land. Dry deposition of NH(3) was estimated by the gradient method, whereas eddy correlation was used for NO(2). Rates of dry deposition of total nitrate (= nitric acid (HNO(3)) + nitrate (NO(3)(-))), total nitrite (= nitrous acid (HONO) + nitrite (NO(2)(-))) and aerosol-bound ammonium (NH(4)(+)) were estimated using deposition velocities from the literature and measured concentrations. Both wet N deposition and the vertical NH(3) gradient were measured on a weekly basis during one year. Dry deposition was between 15 and 25 kg N ha(-1) y(-1), and net wet deposition was about 9.0 kg N ha(-1) y(-1). Daily average NO(2) deposition velocity varied from 0.11 to 0.24 cm s(-1). Deposition velocity of NH(3), was between 0.13 and 1.4 cm s(-1), and a compensation point between 3 and 6 ppbV NH(3) (ppb = 10(-9)) was found. Between 60 and 70% of dry deposition originated from NH(3) emitted by farms in the neighbourhood. It is concluded that total N deposition is exceeding the critical load for litter meadows, is highly correlated to local NH(3) emissions, and that NH(3) is of utmost importance with respect to possible strategies to reduce N deposition in rural regions.     

Nitric oxide and nitrous oxide emission from Hungarian forest soils; linked with atmospheric N-deposition

Studies of forest nitrogen (N) budgets generally measure inputs from the atmosphere in wet and dry deposition and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of N oxides from forest soils is an important, and often overlooked, component of an ecosystem N budget. During 1 year (2002–03), emissions of nitric oxide (NO) and nitrous oxide (N₂O) were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N₂O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 μg N m⁻² h⁻¹, and for N₂O were 15 and 20 μg N m⁻² h⁻¹, for spruce and oak soils, respectively. Due to the relatively high soil water content, and low C/N ratio in soil, denitrification processes dominate, resulting in an order of magnitude greater N₂O emission rate compared to NO. The previously determined N balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry+wet) atmospheric N-deposition to the soil was 1.42 and 1.59 g N m⁻² yr⁻¹ for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 g N m⁻² yr⁻¹. Thus, about 10–13% of N compounds deposited to the soil, mostly as and , were transformed in the soil and emitted back to the atmosphere, mostly as greenhouse gas (N₂O).     

Fluxes of oxidised and reduced nitrogen above a mixed coniferous forest exposed to various nitrogen emission sources

Concentrations of nitrogen gases (NH(3), NO(2), NO, HONO and HNO(3)) and particles (pNH(4) and pNO(3)) were measured over a mixed coniferous forest impacted by high nitrogen loads. Nitrogen dioxide (NO(2)) represented the main nitrogen form, followed by nitric oxide (NO) and ammonia (NH(3)). A combination of gradient method (NH(3) and NO(x)) and resistance modelling techniques (HNO(3), HONO, pNH(4) and pNO(3)) was used to calculate dry deposition of nitrogen compounds. Net flux of NH(3) amounted to -64 ng N m(-2) s(-1) over the measuring period. Net fluxes of NO(x) were upward (8.5 ng N m(-2) s(-1)) with highest emission in the morning. Fluxes of other gases or aerosols substantially contributed to dry deposition. Total nitrogen deposition was estimated at -48 kg N ha(-1) yr(-1) and consisted for almost 80% of NH(x). Comparison of throughfall nitrogen with total deposition suggested substantial uptake of reduced N (+/-15 kg N ha(-1) yr(-1)) within the canopy.     

Effect of nitrogen amendment on respiration and respiratory quotient (RQ) in three hydrocarbon contaminated soils of different type

Three soil types (sandy gravel, silty clay and sandy loam) from sites historically contaminated with total petroleum hydrocarbon (TPH) were amended with NH(4)NO(3) at concentrations ranging from 16 to 2133 mg/kg soil(dry weight). Microbial activity was measured as O(2) consumption and CO(2) production in order to assess nitrogen limitation. Although activity was stimulated in all three soils under NH(4)NO(3) amendment (after 72 h), the level of nitrogen required was soil specific. For the sandy gravel and silty clay soils, O(2) consumption and CO(2) production both showed enhanced microbial activity when amended with 16 mg/kg soil(dry weight) NH(4)NO(3), whereas, these two parameters gave differing results for the sandy loam soil. Specifically, CO(2) production and O(2) consumption were stimulated with 66 mg/kg and 133 mg/kg soil(dry weight) of NH(4)NO(3) respectively. In addition, respiratory quotient kinetic analysis suggested different decomposition processes occurring in this soil under different NH(4)NO(3) amendment concentrations.     

Simple model for estimating dry deposition velocity of ozone and its destruction in a polluted nocturnal boundary layer

Determining the destructions of both ozone and odd oxygen, O_x, in the nocturnal boundary layer (NBL) is important to evaluate the regional ozone budget and overnight ozone accumulation. This work develops a simple method to determine the dry deposition velocity of ozone and its destruction at a polluted nocturnal boundary layer. The destruction of O_x can also be determined simultaneously. The method is based on O₃ and NO₂ profiles and their surface measurements. Linkages between the dry deposition velocities of O₃ and NO₂ and between the dry deposition loss of O_x and its chemical loss are constructed and used. Field measurements are made at an agricultural site to demonstrate the application of the model. The model estimated nocturnal O₃ dry deposition velocities from 0.13 to 0.19 cm s^?1, very close to those previously obtained for similar land types. Additionally, dry deposition and chemical reactions account for 60 and 40% of the overall nocturnal ozone loss, respectively; ozone dry deposition accounts for 50% of the overall nocturnal loss of O_x, dry deposition of NO₂ accounts for another 20%, and chemical reactions account for the remaining 30%. The proposed method enables the use of measurements made in typical ozone field studies to evaluate various nocturnal destructions of O₃ and O_x in a polluted environment.     

Sensitivity analysis of an ozone deposition model

In this study, sophisticated sensitivity analyses of a detailed ozone dry deposition model were performed for five soil types (sand, sandy loam, loam, clay loam, clay) and four land use categories (agricultural land, grass, coniferous and deciduous forests). Deposition velocity and ozone flux depend on the weather situation, physiological state of the plants and numerous surface-, vegetation-, and soil-dependent parameters. The input data and the parameters of deposition-related calculations all have higher or lower spatial and temporal variability. We have investigated the effect of the variability of the meteorological data (cloudiness, relative humidity and air temperature), plant-dependent (leaf area index and maximum stomatal conductance) and soil-dependent (soil moisture) parameters on ozone deposition velocity. To evaluate this effect, two global methods, the Morris method and the Monte Carlo analysis with Latin hypercube sampling were applied. Additionally, local sensitivity analyses were performed to estimate the contribution of non-stomatal resistances to deposition velocity. Using the Monte Carlo simulations, the ensemble effect of several nonlinear processes can be recognised and described. Based on the results of the Morris method, the individual effects on deposition velocity are found to be significant in the case of soil moisture and maximum stomatal conductance. Temperature and leaf area index are also important factors; the former is primarily in the case of agricultural land, while the latter is for grass and coniferous forest. The results of local sensitivity analyses reveal the importance of non-stomatal resistances.     

Influence of soil conditions on dissolved organic matter leached from forest and wetland soils: a controlled growth chamber study

This study investigated the effects of various soil conditions, including drying-rewetting, nitrogen deposition, and temperature rise, on the quantities and the composition of dissolved organic matter leached from forest and wetland soils. A set of forest and wetland soils with and without the nitrogen deposition were incubated in the growth chambers under three different temperatures. The moisture contents were kept constant, except for two-week drying intervals. Comparisons between the original and the treated samples revealed that drying-rewetting was a crucial environmental factor driving changes in the amount of dissolved organic carbon (DOC). The DOC was also notably increased by the nitrogen deposition to the dry forest soil and was affected by the temperature of the dry wetland soil. A parallel factor (PARAFAC) analysis identified three sub-fractions of the fluorescent dissolved organic matter (FDOM) from the fluorescence excitation–emission matrices (EEMs), and their compositions depended on drying-rewetting. The data as a whole, including the DOC and PARAFAC components and other optical indices, were possibly explained by the two main variables, which were closely related with the PARAFAC components and DOC based on principal component analysis (PCA). Our results suggested that the DOC and PARAFAC component information could provide a comprehensive interpretation of the changes in the soil-leached DOM in response to the different environmental conditions.     

Nitrate reductase activity as an indicator of ponderosa pine response to atmospheric nitrogen deposition in the San Bernardino Mountains

Determinations of nitrate reductase (NR) activity in ponderosa pine (Pinus ponderosa Dougl. ex. Laws.) needles were performed during summer 1994 in two areas (consisting of six different sites) with different nitrogen (N) deposition levels in the San Bernardino Mountains, southern California. Nitrate reductase activity was used as an integrative indicator of atmospheric nitrogen deposition to pine trees (direct uptake of N species from the atmosphere and N transported from the soil). Deposition of nitrate (NO3-) to pine branches was measured in order to determine dry atmospheric inputs of the oxidized N species to tree foliage. High NR activity was detected in all of the experimental sites. Activity of the enzyme was significantly higher at the locations characterized by higher NO3- deposition to branches--slight positive correlation between branch deposited NO3- and NR activity was found. However, high variability of NR in time and between the experimental sites discredit the NR assay as a reliable indicator of N deposition for ponderosa pine in the field conditions. This could be caused by substantial interference from other abiotic and biotic factors with tropospheric ozone as probably the most important one.     

The relationship between foliar injury, nitrogen metabolism, and growth parameters in ozonated soybeans

A single 12 h ozone exposure peaking at 0.20 ppm proved phytotoxic to greenhouse-grown 'Cutler 71' soybeans at each growth stage tested from V5 to R6. Visible injury occurred within 40 h on the unifoliodate leaves and middle-aged and older trifoliolates while the younger leaves were free from toxicity symptoms. In some instances visible injury was accompanied by a decrease in chlorophyll and an increase in leaf diffusive resistance. Although nitrogen fixation was not significantly altered except at early pod formation (R3), and nitrate reductase activity was significantly reduced only if the ozone exposure occurred at the time of maximal enzyme activity (V5), nitrogen content of the leaves was reduced by ozone treatment. Shoot dry weight was not affected 40 h after ozone treatment, but root dry weight was significantly reduced. Plants grown with supplemental NO(3)(-) were more sensitive to ozone than those dependent on fixed nitrogen. At plant maturity, there was no evidence of an ozone effect on shoot, root, or seed dry weight, NO(3)(-) -grown plants showed a significant increase in growth and yield over N(2)(-) plants; but no ozone effect was observed, despite the increased foliar sensitivity. Multiple ozone exposures at growth stages V3, R1 and R3 exacerbated the effects noted with a single episode and also reduced nitrogenase activity (reflected in specific and total nodule activity) and shoot and root dry weight. At plant maturity, there was again no evidence of a significant effect of multiple ozone treatment on shoot dry weight or seed yield although root weight remained low. The results would tend to support the hypothesis that older leaves of soybean do not make a significant contribution to seed yield. Although they may be injured by ozone during the reproductive phases of growth, seed yield may not be affected if the younger O(3)-tolerant leaves remain functional.     

Photochemical oxidant pollution and vegetation: effects of mixtures of gases, fog and particles

Photochemical 'smog' contains mixtures of gases (e.g. ozone, nitrogen dioxide), and dry particles (e.g. nitrates). Intermittent fog in the same geographical area can be acidic with high concentrations of nitric acid. Results from recent field studies in the Los Angeles Basin have emphasized the relative toxicity of these components of photochemical air pollution. Studies have focused on gaseous+fog or gaseous+dry particulate effects on conifers, gaseous+fog effects on crops, and the effects of trace pollutants produced during generation of ozone on crops. Data from these studies indicate that direct alterations in growth and physiological responses were observed only with gaseous pollutants (primarily ozone), or repeated applications of highly acidic fogs (pH < 2.7). Direct particle dry deposition effects are unclear. Few interactions have been found between gaseous pollutants and acidic fog. Charcoal-filtered open-top chambers are highly effective in removing pollutants in the following order: fog (100%) > peroxyacetyl nitrate > ozone > nitrogen dioxide > sulfur dioxide > nitrate ion > ammonium ion > sulfate ion. However, nitric oxide concentrations are higher in charcoal-filtered chambers than in ambient air. The studies point out the importance of considering other components of photochemical pollution in addition to ozone, especially when investigating subtle, long-term effects on vegetation.     

Phenolic compounds content in Pinus halepensis Mill. needles: a bioindicator of air pollution

Foliar phenol concentrations (total and simple phenols) were determined in Aleppo pine (Pinus halepensis Mill.) needles collected in June 2000, from 6 sites affected by various forms of atmospheric pollutants (NO, NO(2), NO(x), O(3) and SO(2)) monitored during two months. Results show an increase in total phenol content with exposure to sulphur dioxide and a reduction with exposure to nitrogen oxide pollution. p-Coumaric acid, syringic acid and 4-hydroxybenzoic acid concentrations increase with exposure to nitrogen oxide pollution, whereas gallic acid and vanillin decrease in the presence respectively of sulphur dioxide and ozone. This in situ work confirms the major interest of using total and simple phenolic compounds of P. halepensis as biological indicators of air quality.     

The contribution of ammonia emissions from agriculture to the deposition of acidifying and eutrophying compounds onto forests

In the vicinity of a large ammonia emission area, dry and wet deposition of acidifying and eutrophying compounds onto Douglas Fir forests was studied by sampling throughfall, stemflow and bulk precipitation. Deposition amounts of NH(4)(+) and SO(4)(2-) were recognised to be among the highest of Central Europe, resulting in extremely high inputs of (potential) acid to the forest soils (13.1 kEq ha(-1) year(-1)). The contribution of NH(3) emissions from agriculture to the total acid deposition to the forests was 52%. The total nitrogen deposition amounted to 115.0 kg ha(-1) year(-1), 83% originating from NH(3) emissions and 17% from NO(x) emissions. Calculated mean dry deposition velocities of NH(3) and SO(2) were much larger than reported in the literature. A synergistic effect between NH(3) and SO(2) in the process of dry deposition is suggested and evidence for this effect is discussed. When deposition models do not take this interaction into account, they will underestimate NH(3) and SO(2) deposition amounts in areas with intensive animal husbandry.     

Calculation of σz and H for an Observed Vertical Profile of Concentration

ABSTRACT

In the present work, nitrous oxide emissions were estimated [mg/L] by the use of lysimeters under the closed chamber technique for a six month period. The lysimeters were classified by the type of irrigation used: one for drinking water, and the other for treated wastewater. Each lysimeter had two different types of soil (sand and clay), based on the types of soil in Chihuahua City, Mexico. An additional classification based on the depth was done (reticular and vadose zone). Each zone collected gas by the use of a closed chamber technique, allowing the samples to be taken for subsequent quantification and analysis by gas chromatography. A statistical analysis of variance (ANOVA) and principal components analysis (PCA) were conducted to identify the most influential variables or parameters in the formation of nitrous oxide. The variables that were considered for analysis were total Kjeldahl nitrogen (TKN), ammoniacal nitrogen (NH3-N), nitrate nitrogen (NO3-N), and nitrite nitrogen (NO2-N), along with meteorological parameters. In total, 58944 mg/L of N2O were emitted during the measurement period. The results showed that concentration emissions of N2O where the type of soil is sandy were smaller than those of clay soil, while the mean concentration in the vadose zone was higher than those in the reticular zone, regardless the type of soil. The parameters that showed greater influence in the N2O emissions were NO2-N and NO3-N concentrations. Temperature also played an important role in the emissions (the highest emissions were emitted during the cold months). Furthermore, denitrification appeared to be the dominant process in the production of nitrous oxide in soils.

Implications: Nitrous oxide (N₂O) emissions produced in lysimeters with two types of soil (sand and clay) at two different depths (vadose and reticular zones) using treated waste water showed that the higher emissions of N₂O are derived from clay soils in vadose zone; it could be due to the formation of clogging that favors the formation of anoxic conditions for the denitrification process. The parameters that showed more influence in the N₂O emissions were nitrite (NO₂-N) and nitrate (NO₃-N) concentrations along with the temperature.     

Photocatalytic oxidation of NOx using composite sheets containing TiO2 and a metal compound

The photocatalytic oxidation of nitrogen oxides (NO(x)) over titanium dioxide (TiO(2)) sheets containing metal compounds (MCs) had been studied. Calcium oxide (CaO), magnesium oxide (MgO), calcium carbonate (CaCO(3)), aluminium oxide (Al(2)O(3)) and ferric oxide (Fe(2)O(3)) were used as MCs. Al(2)O(3) and Fe(2)O(3) added to the TiO(2) sheet did not affect the photooxidation of nitrogen oxides (NO(x)). The CaO sheet treated with TiO(2) sol had the greatest efficiency as a NO(x) remover under UV irradiation. It is believed that CaO has a high adsorptivity for nitrogen dioxide (NO(2)) and nitric acid (HNO(3)). The amount of NO(x) removed by a TiO(2) sheet including MC showed a tendency to increase with increasing pH of the MC suspension, i.e. there is a good correlation between the alkalinity of the MC and the retention of NO(2) and HNO(3).     

Nitrogen deposition in California forests: a review

Atmospheric concentrations and deposition of the major nitrogenous (N) compounds and their biological effects in California forests are reviewed. Climatic characteristics of California are summarized in light of their effects on pollutant accumulation and transport. Over large areas of the state dry deposition is of greater magnitude than wet deposition due to the arid climate. However, fog deposition can also be significant in areas where seasonal fogs and N pollution sources coincide. The dominance of dry deposition is magnified in airsheds with frequent temperature inversions such as occur in the Los Angeles Air Basin. Most of the deposition in such areas occurs in summer as a result of surface deposition of nitric acid vapor (HNO3) as well as particulate nitrate (NO3-) and ammonium (NH4+). Internal uptake of gaseous N pollutants such as nitrogen dioxide (NO2), nitric oxide (NO), HNO3, peroxyacetyl nitrate (PAN), ammonia (NH3), and others provides additional N to forests. However, summer drought and subsequent lower stomatal conductance of plants tend to limit plant utilization of gaseous N. Nitrogen deposition is much greater than S deposition in California. In locations close to photochemical smog source areas, concentrations of oxidized forms of N (NO2, HNO3, PAN) dominate, while in areas near agricultural activities the importance of reduced N forms (NH3, NH4+) significantly increases. Little data from California forests are available for most of the gaseous N pollutants. Total inorganic N deposition in the most highly-exposed forests in the Los Angeles Air Basin may be as high as 25-45 kg ha(-1) year(-1). Nitrogen deposition in these highly-exposed areas has led to N saturation of chaparral and mixed conifer stands. In N saturated forests high concentrations of NO3- are found in streamwater, soil solution, and in foliage. Nitric oxide emissions from soil and foliar N:P ratios are also high in N saturated sites. Further research is needed to determine the ecological effects of chronic N deposition, and to develop appropriate management options for protecting water quality and managing plant nutrient resources in ecosystems which no longer retain excess N.     

Trends in atmospheric reactive nitrogen for the Eastern United States

Reactive nitrogen can travel far from emission sources and impact sensitive ecosystems. From 2002 to 2006, policy actions have led to decreases in NO(x) emissions from power plants and motor vehicles. In this study, atmospheric chemical transport modeling demonstrates that these emissions reductions have led to a downward trend in ambient measurements of transported reactive nitrogen, especially atmospheric concentrations and wet deposition of nitrate. The trend in reduced nitrogen, namely ammonium, is ambiguous. As reduced nitrogen becomes a larger fraction of the reactive nitrogen budget, wide-spread NH(3) measurements and improved NH(3) emissions assessments are a critical need.     

Modeling toxic compounds from nitric oxide emission measurements

Determining the amount and rate of degradation of toxic pollutants in soil and groundwater is difficult and often requires invasive techniques, such as deploying extensive monitoring well networks. Even with these networks, degradation rates across entire systems cannot readily be extrapolated from the samples. When organic compounds are degraded by microbes, especially nitrifying bacteria, oxides or nitrogen (NO_x) are released to the atmosphere. Thus, the flux of nitric oxide (NO) from the soil to the lower troposphere can be used to predict the rate at which organic compounds are degraded. By characterizing and applying biogenic and anthropogenic processes in soils the rates of degradation of organic compounds. Toluene was selected as a representative of toxic aromatic compounds, since it is inherently toxic, it is a substituted benzene compound and is listed as a hazardous air pollutant under Section 12 of the Clean Air Act Amendments of 1990. Measured toluene concentrations in soil, microbial population growth and NO fluxes in chamber studies were used to develop and parameterize a numerical model based on carbon and nitrogen cycling. These measurements, in turn, were used as indicators of bioremediation of air toxic (i.e. toluene) concentrations. The model found that chemical concentration, soil microbial abundance, and NO production can be directly related to the experimental results (significant at P < 0.01) for all toluene concentrations tested. This indicates that the model may prove useful in monitoring and predicting the fate of toxic aromatic contaminants in a complex soil system. It may also be useful in predicting the release of ozone precursors, such as changes in reservoirs of hydrocarbons and oxides of nitrogen. As such, the model may be a tool for decision makers in ozone non-attainment areas.     

Dry deposition and internal circulation of nitrogen,sulphur and base cations to a coniferous forest

The dry deposition of sulphur, nitrogen and base cations to a spruce stand was estimated during a five year period using a surrogate surface resembling needles, throughfall and bulk deposition measurements. The deposition was calculated from the ratio between the deposition of an ion and sodium on the surrogate surface and the net throughfall of sodium to the forest. The dry deposition represented a large fraction of the total atmospheric input of base cations. For Na⁺, Mg²⁺, Ca²⁺, and K⁺ they were 66, 67, 53 and 42%, respectively. The internal circulation was 95% of non-marine net throughfall fro K⁺ and 76% for Ca²⁺. The dry deposition of SO₂ to the canopies regulates the internal circulation of Ca²⁺. The dry deposition of SO₂ to the canopies regulates the internal circulation of Ca²⁺. The dry depositions of ammonium and nitrate are close to the net throughfall of Kjeldahl-N and nitrate, respectively. The obtained deposition velocities are comparable to other studies. The calculated dry deposition of ammonium was compared to the net throughfall of ammonium at three nearby forest stands receiving different ammonium amounts on the soils. No correlation to nitrogen level was found, but most ammonium was lost and converted to organic nitrogen in the canopies of the wettest forest stand.     

Stack Sampling of Organic Compounds: Application to the Measurement of Catalytic Incinerator Efficiency

Abstract

Ozone dry deposition fluxes and velocities were measured in 1994 in a semi–arid steppe of central Spain and in a forest in southern France during the period of photochemical activity using the gradient method. Downward fluxes were systematically obtained in both sites, with lower values at nighttime and maximum values during the central period of the day, which showed the important role of stomata in ozone uptake. The range of deposition velocities was –0.005 to 1.160 in the forested site and 0.001 to 1.430 cm s–1 in the semi–arid steppe. The nocturnal deposition velocities observed in the semi–arid steppe were considerably higher than in the forest, with values up to 0.35 cm s–1.

A single layer canopy model was applied and validated at both sites. The model fitted the daily patterns well but underestimated the observed values by 34% in the forest and by 10% in the semi–arid steppe. To improve the accuracy of the model, both soil and internal stomatal resistances, Rsoil and Ri, were estimated using a least square technique. The interdependence of both parameters and the relative humidity, rH, was evaluated through a statistical analysis of the residual between the observed deposition velocity and the aerodynamic, sub–layer, and stomatal resistances. The comparison between the parameter estimates under wet and dry conditions in both sites showed (1) the influence of rH on stomatal parameter and soil resistance, (2) the large contribution of stomatal conductance to ozone uptake during the daytime, and (3) the importance of soil as an additional pathway for ozone exchange, especially in the steppe. Taking into account the parameter estimates, the underestimate of the modeled results was 3% in the forest and 5% in the semi–arid steppe.