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Atmospheric ammonia (NH3) dominates global emissions of total reactive nitrogen (Nr), while emissions from agricultural production systems contribute about two-thirds of global NH3 emissions; the remaining third emanates from oceans, natural vegetation, humans, wild animals and biomass burning. On land, NH3 emitted from the various sources eventually returns to the biosphere by dry deposition to sink areas, predominantly semi-natural vegetation, and by wet and dry deposition as ammonium (NH4+ ) to all surfaces. However, the land/atmosphere exchange of gaseous NH3 is in fact bi-directional over unfertilized as well as fertilized ecosystems, with periods and areas of emission and deposition alternating in time (diurnal, seasonal) and space (patchwork landscapes). The exchange is controlled by a range of environmental factors, including meteorology, surface layer turbulence, thermodynamics, air and surface heterogeneous-phase chemistry, canopy geometry, plant development stage, leaf age, organic matter decomposition, soil microbial turnover, and, in agricultural systems, by fertilizer application rate, fertilizer type, soil type, crop type, and agricultural management practices. We review the range of processes controlling NH3 emission and uptake in the different parts of the soil-canopy-atmosphere continuum, with NH3 emission potentials defined at the substrate and leaf levels by different [NH4+ ]/ [H+] ratios (Γ). Surface/atmosphere exchange models for NH3 are necessary to compute the temporal and spatial patterns of emissions and deposition at the soil, plant, field, landscape, regional and global scales, in order to assess the multiple environmental impacts of airborne and deposited NH3 and NH4+ . Models of soil/vegetation/atmosphere NH3 exchange are reviewed from the substrate and leaf scales to the global scale. They range from simple steady-state, "big leaf" canopy resistance models, to dynamic, multi-layer, multi-process, multichemical species schemes. Their level of complexity depends on their purpose, the spatial scale at which they are applied, the current level of parameterization, and the availability of the input data they require. State-of-the-art solutions for determining the emission/sink 0 potentials through the soil/canopy system include coupled, interactive chemical transport models (CTM) and soil/ecosystem modelling at the regional scale. However, it remains a matter for debate to what extent realistic options for future regional and global models should be based on process-based mechanistic versus empirical and regression-type models. Further discussion is needed on the extent and timescale by which new approaches can be used, such as integration with ecosystem models and satellite observations. [ABSTRACT FROM AUTHOR]

Terrestrial ecosystems represent a major sink for ozone (O3) and also a critical control of tropospheric O3 budget. However, due to its deleterious effects, plant functioning is affected by the ozone absorbed. It is thus necessary to both predict total ozone deposition to ecosystems and partition the fluxes in stomatal and non-stomatal pathways. The Surfatm-O3 model was developed to predict ozone deposition to agroecosystems from sowing to harvest, taking into account each deposition pathways during bare soil, growth, maturity, and senescence periods. An additional sink was added during senescence: stomatal deposition for yellow leaves, not able to photosynthesise but transpiring. The model was confronted to measurements performed over three maize crops in different regions of France. Modelled and measured fluxes agreed well for one dataset for any phenological stage, with only 4% difference over the whole cropping season. A larger discrepancy was found for the two other sites, 15% and 18% over the entire study period, especially during bare soil, early growth and senescence. This was attributed to site-specific soil resistance to ozone and possible chemical reactions between ozone and volatile organic compounds emitted during late senescence. Considering both night-time and daytime conditions, non-stomatal deposition was the major ozone sink, from 100% during bare soil period to 70-80% on average during maturity. However, considering only daytime conditions, especially under optimal climatic conditions for plant functioning, stomatal flux could represent 75% of total ozone flux. This model could improve estimates of crop yield losses and projections of tropospheric ozone budget. [ABSTRACT FROM AUTHOR]

Ammonia concentration and fluxes were measured above a growing triticale field for two months during May and June 2010 at the NitroEurope crop site in Grignon (Fr-Gri) near Paris, France. The measurement campaign started 15 days following a 40 kg N ha-1 application of an ammonium nitrate solution. A new mini-WEDD (Wet Effluent Denuder) flow injection analyser with three channels (ROSAA, RObust and Sensitive Ammonia Analyser) was used to measure NH3 fluxes using the aerodynamic gradient method. The measured ammonia concentrations varied from 0.01 to 39 µg NH3 m-3 and were largely influenced by advection from the nearby farm. The ammonia fluxes ranged from -560 to 220 ng NH3 m-2 s-1 and averaged 29 ng NH3 m-2 s-1. During some periods the large deposition fluxes could only be explained by a very small surface resistance, which may be due to the high concentrations in certain acid gases (HNO3 and SO2) observed in this suburban area. Ammonia emissions were also measured occasionally. The canopy compensation point Cc was around 1.5 µg NH3 m-3 on average. The canopy emission potential Γc (Cc normalised for the temperature response of the Henry equilibrium) decreased over the course of the measurement campaign from Γc = 2200 to Γc = 450, the latter value being close to the median stomatal emission potential (Γs) for managed ecosystems reported in the literature. The temporal dynamics of the measured NH3 flux compared well with the Surfatm-NH3 model using fitted parameters. The subjectivity of the model fitting is discussed based on a sensitivity analysis. [ABSTRACT FROM AUTHOR]

A new biophysical model SURFATM-NH3, simulating the ammonia (NH3) exchange between terrestrial ecosystems and the atmosphere is presented. SURFATM-NH3 consists of two coupled models: (i) an energy budget model and (ii) a pollutant exchange model, which distinguish the soil and plant exchange processes. The model describes the exchanges in terms of adsorption to leaf cuticles and bi-directional transport through leaf stomata and soil. The results of the model are compared with the flux measurements over grassland during the GRAMINAE Integrated Experiment at Braunschweig, Germany. The dataset of GRAMINAE allows the model to be tested in various climatic and agronomic conditions: prior to cutting, after cutting and then after the application of mineral fertilizer. The whole comparison shows close agreement between model and measurements for energy budget and ammonia fluxes. The major controls on the soil and plant emission potential are the physicochemical parameters for liquid-gas exchanges which are integrated in the compensation points for live leaves, litter and the soil surface. Modelled fluxes are highly sensitive to soil and plant surface temperatures, highlighting the importance of accurate estimates of these terms. The model suggests that the net flux depends not only on the foliar (stomatal) compensation point but also that of leaf litter. SURFATM-NH3 represents a comprehensive approach to studying pollutant exchanges and its link with plant and soil functioning. It also provides a simplified generalised approach (SVAT model) applicable for atmospheric transport models. [ABSTRACT FROM AUTHOR]

Volatilization from plant foliage is known to have a great contribution to pesticide emission to the atmosphere. However, its estimation is still difficult because of our poor understanding of processes occurring at the leaf surface. A compartmental approach for dissipation processes of pesticides applied on the leaf surface was developed on the base of experimental study performed under controlled conditions using laboratory volatilization chamber. This approach was combined with physicochemical properties of pesticides and was implemented in SURFATM-Pesticides model in order to predict pesticide volatilization from plants in a more mechanistic way. The new version of SURFATM-Pesticide model takes into account the effect of formulation on volatilization and leaf penetration. The model was evaluated in terms of 3 pesticides applied on plants at the field scale (chlorothalonil, fenpropidin and parathion) which display a wide range of volatilization rates. The comparison of modeled volatilization fluxes with measured ones shows an overall good agreement for the three tested compounds. Furthermore the model confirms the considerable effect of the formulation on the rate of the decline in volatilization fluxes especially for systemic products. However, due to the lack of published information on the substances in the formulations, factors accounting for the effect of formulation are described empirically. A sensitivity analysis shows that in addition to vapor pressure, the octanol-water partition coefficient represents important physicochemical properties of pesticides affecting pesticide volatilization from plants. Finally the new version of SURFATM-Pesticides is a prospecting tool for key processes involved in the description of pesticide volatilization from plants., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Estimation of pesticide volatilization from plants is difficult because of our poor understanding of foliar penetration by pesticides, which governs the amount of pesticide available for volatilization from the leaf surface. The description of foliar penetration is still incomplete because experimental measurements of this complex process are difficult. In this study, the dynamics of leaf penetration of C-chlorothalonil and C-epoxiconazole applied to wheat leaves were measured in a volatilization chamber, which allowed us to simultaneously measure pesticide volatilization. Fungicide penetration into leaves was characterized using a well-defined sequential extraction procedure distinguishing pesticide fractions residing at different foliar compartments; this enabled us to accurately measure the penetration rate constant into the leaves. The effect of pesticide formulation was also examined by comparing formulated and pure epoxiconazole. We observed a strong effect of formulation on leaf penetration in the case of a systemic product. Furthermore, the penetration rate constant of formulated epoxiconazole was almost three times that of pure epoxiconazole (0.47 ± 0.20 and 0.17 ± 0.07, respectively). Our experimental results showed high recovery rates of the radioactivity applied within the range of 90.5 to 105.2%. Moreover, our results confirm that pesticide physicochemical properties are key factors in understanding leaf penetration of pesticide and its volatilization. This study provides important and useful parameters for mechanistic models describing volatilization of fungicides applied to plants, which are scarce in the literature., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Existing descriptions of bi-directional ammonia (NH3) land-atmosphere exchange incorporate temperature and moisture controls, and are beginning to be used in regional chemical transport models. However, such models have typically applied simpler emission factors to upscale the main NH3 emission terms. While this approach has successfully simulated the main spatial patterns on local to global scales, it fails to address the environment- and climate-dependence of emissions. To handle these issues, we outline the basis for a new modelling paradigm where both NH3 emissions and deposition are calculated online according to diurnal, seasonal and spatial differences in meteorology. We show how measurements reveal a strong, but complex pattern of climatic dependence, which is increasingly being characterized using ground-based NH3 monitoring and satellite observations, while advances in process-based modelling are illustrated for agricultural and natural sources, including a global application for seabird colonies. A future architecture for NH3 emission-deposition modelling is proposed that integrates the spatio-temporal interactions, and provides the necessary foundation to assess the consequences of climate change. Based on available measurements, a first empirical estimate suggests that 5°C warming would increase emissions by 42 per cent (28-67%). Together with increased anthropogenic activity, global NH3 emissions may increase from 65 (45-85) Tg N in 2008 to reach 132 (89-179) Tg by 2100.