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Dry deposition is an important removal mechanism for tropospheric ozone (O3). Currently, O3 deposition to oceans in atmospheric chemistry and transport models (ACTMs) is generally represented using constant surface uptake resistances. This occurs despite the role of solubility, waterside turbulence and O3 reacting with ocean water reactants such as iodide resulting in substantial spatiotemporal variability in O3 deposition and concentrations in marine boundary layers. We hypothesize that O3 deposition to the Arctic Ocean, having a relatively low reactivity, is overestimated in current models with consequences for the tropospheric concentrations, lifetime and long-range transport of O3. We investigate the impact of the representation of oceanic O3 deposition to the simulated magnitude and spatiotemporal variability in Arctic surface O3. We have integrated the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG) into the mesoscale meteorology and atmospheric chemistry model Polar-WRF-Chem (WRF) which introduces a dependence of O3 deposition on physical and biogeochemical drivers of oceanic O3 deposition. Also, we reduced the O3 deposition to sea ice and snow. Here, we evaluate WRF and CAMS reanalysis data against hourly averaged surface O3 observations at 25 sites (latitudes > 60∘ N). This is the first time such a coupled modeling system has been evaluated against hourly observations at pan-Arctic sites to study the sensitivity of the magnitude and temporal variability in Arctic surface O3 on the deposition scheme. We find that it is important to nudge WRF to the ECMWF ERA5 reanalysis data to ensure adequate meteorological conditions to evaluate surface O3. We show that the mechanistic representation of O3 deposition over oceans and reduced snow/ice deposition improves simulated Arctic O3 mixing ratios both in magnitude and temporal variability compared to the constant resistance approach. Using COAREG, O3 deposition velocities are in the order of 0.01 cm s−1 compared to ∼ 0.05 cm s−1 in the constant resistance approach. The simulated monthly mean spatial variability in the mechanistic approach (0.01 to 0.018 cm s−1) expresses the sensitivity to chemical enhancement with dissolved iodide, whereas the temporal variability (up to ±20 % around the mean) expresses mainly differences in waterside turbulent transport. The mean bias for six sites above 70∘ N reduced from −3.8 to 0.3 ppb with the revision to ocean and snow/ice deposition. Our study confirms that O3 deposition to high-latitude oceans and snow/ice is generally overestimated in ACTMs. We recommend that a mechanistic representation of oceanic O3 deposition is preferred in ACTMs to improve the modeled Arctic surface O3 concentrations in terms of magnitude and temporal variability.

Dry deposition is an important removal mechanism for tropospheric ozone (O3). Its deposition to oceans is generally represented in atmospheric chemistry transport models using constant surface uptake resistances. However, observations show quite large spatiotemporal variability expressing differences in solubility, waterside turbulence and O3 reacting with iodide and dissolved organic matter. We hypothesize that for the Arctic O3 deposition is overestimated with consequences for background concentrations and lifetime of O3 also due to changes in long-range transport of O3 and its precursors. These are focal points of a project on observing and modelling of Arctic climate-active trace gas exchange as a contribution to the MOSAiC observational campaign with the icebreaker Polarstern being trapped in the Arctic sea-ice for ~1 year.We have coupled the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG) to the mesoscale meteorology and atmospheric chemistry model Polar-WRF-Chem (PWRF-C). This includes a further development including a two-layer scheme for O3 deposition to oceans and coupling to recently updated ocean water composition databases. We have also reduced the deposition of O3 to sea ice based on a previous study of snow-ice O3 deposition.In this study, we evaluate the performance of PWRF-C with hourly-averaged surface O3 measurements above 60 ºN and with O3 sondes. We show that the more mechanistic representation of O3 deposition over oceans and strongly reduced deposition over snow and ice results in improved simulated Arctic O3 mixing ratios. We found that it is important to nudge PWRF-C to the ECMWF ERA-Interim wind fields which secures a fair comparison of the model with measurements regarding their footprint. Our study indicates that representation of ocean and sea-ice O3 deposition in atmospheric chemistry models must be revised to improve the representation of Arctic O3 concentrations and chemistry.

In Colombia, industrialization and a shift towards intensified agriculture have led to increased emissions of air pollutants. However, the baseline state of air quality in Colombia is relatively unknown. In this study we aim to assess the baseline state of air quality in Colombia with a focus on the spatial and temporal variability in emissions and atmospheric burden of nitrogen oxides ( NOx = NO + NO2 ) and evaluate surface NOx , ozone ( O3 ) and carbon monoxide (CO) mixing ratios. We quantify the magnitude and spatial distribution of the four major NOx sources (lightning, anthropogenic activities, soil biogenic emissions and biomass burning) by integrating global NOx emission inventories into the mesoscale meteorology and atmospheric chemistry model, namely Weather Research and Forecasting (WRF) coupled with Chemistry (collectively WRF-Chem), at a similar resolution ( ∼25 km) to the Emission Database for Global Atmospheric Research (EDGAR) anthropogenic emission inventory and the Ozone Monitoring Instrument (OMI) remote sensing observations. The model indicates the largest contribution by lightning emissions (1258 Gg N yr −1 ), even after already significantly reducing the emissions, followed by anthropogenic (933 Gg N yr −1 ), soil biogenic (187 Gg N yr −1 ) and biomass burning emissions (104 Gg N yr −1 ). The comparison with OMI remote sensing observations indicated a mean bias of tropospheric NO2 columns over the whole domain (WRF-Chem minus OMI) of 0.02 (90 % CI: [ −0.43 , 0.70]) ×1015 molecules cm −2 , which is % of the mean column. However, the simulated NO2 columns are overestimated and underestimated in regions where lightning and biomass burning emissions dominate, respectively. WRF-Chem was unable to capture NOx and CO urban pollutant mixing ratios, neither in timing nor in magnitude. Yet, WRF-Chem was able to simulate the urban diurnal cycle of O3 satisfactorily but with a systematic overestimation of 10 parts per billion (ppb) due to the equally large underestimation of NO mixing ratios and, consequently, titration. This indicates that these city environments are in the NOx -saturated regime with frequent O3 titration. We conducted sensitivity experiments with an online meteorology–chemistry single-column model (SCM) to evaluate how WRF-Chem subgrid-scale-enhanced emissions could explain an improved representation of the observed O3 , CO and NOx diurnal cycles. Interestingly, the SCM simulation, showing especially a shallower nocturnal inversion layer, results in a better representation of the observed diurnal cycle of urban pollutant mixing ratios without an enhancement in emissions. This stresses that, besides application of higher-resolution emission inventories and model experiments, the diurnal cycle in boundary layer dynamics (and advection) should be critically evaluated in models such as WRF-Chem to assess urban air quality. Overall, we present a concise method to quantify air quality in regions with limited surface measurements by integrating in situ and remote sensing observations. This study identifies four distinctly different source regions and shows their interannual and seasonal variability during the last 1.5 decades. It serves as a base to assess scenarios of future air quality in Colombia or similar regions with contrasting emission regimes, complex terrain and a limited air quality monitoring network.

International audience; With the Arctic rapidly changing, the needs to observe, understand, and model the changes are essential. To support these needs, an annual cycle of observations of atmospheric properties, processes, and interactions were made while drifting with the sea ice across the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition from October 2019 to September 2020. An international team designed and implemented the comprehensive program to document and characterize all aspects of the Arctic atmospheric system in unprecedented detail, using a variety of approaches, and across multiple scales. These measurements were coordinated with other observational teams to explore cross-cutting and coupled interactions with the Arctic Ocean, sea ice, and ecosystem through a variety of physical and biogeochemical processes. This overview outlines the breadth and complexity of the atmospheric research program, which was organized into 4 subgroups: atmospheric state, clouds and precipitation, gases and aerosols, and energy budgets. Atmospheric variability over the annual cycle revealed important influences from a persistent large-scale winter circulation pattern, leading to some storms with pressure and winds that were outside the interquartile range of past conditions suggested by long-term reanalysis. Similarly, the MOSAiC location was warmer and wetter in summer than the reanalysis climatology, in part due to its close proximity to the sea ice edge. The comprehensiveness of the observational program for characterizing and analyzing atmospheric phenomena is demonstrated via a winter case study examining air mass transitions and a summer case study examining vertical atmospheric evolution. Overall, the MOSAiC atmospheric program successfully met its objectives and was the most comprehensive atmospheric measurement program to date conducted over the Arctic sea ice. The obtained data will support a broad range of coupled-system scientific research and provide an important foundation for advancing multiscale modeling capabilities in the Arctic.

Ozone ( O3 ) is a secondary air pollutant that negatively affects human and ecosystem health. Ozone simulations with regional air quality models suffer from unexplained biases over Europe, and uncertainties in the emissions of ozone precursor group nitrogen oxides ( NO x = NO + NO 2 ) contribute to these biases. The goal of this study is to use NO2 column observations from the Ozone Monitoring Instrument (OMI) satellite sensor to infer top-down NOx emissions in the regional Weather Research and Forecasting model with coupled chemistry (WRF-Chem) and to evaluate the impact on simulated surface O3 with in situ observations. We first perform a simulation for July 2015 over Europe and evaluate its performance against in situ observations from the AirBase network. The spatial distribution of mean ozone concentrations is reproduced satisfactorily. However, the simulated maximum daily 8 h ozone concentration (MDA8 O3 ) is underestimated (mean bias error of − 14.2 µ g m −3 ), and its spread is too low. We subsequently derive satellite-constrained surface NOx emissions using a mass balance approach based on the relative difference between OMI and WRF-Chem NO2 columns. The method accounts for feedbacks through OH, NO2 's dominant daytime oxidant. Our optimized European NOx emissions amount to 0.50 Tg N (for July 2015), which is 0.18 Tg N higher than the bottom-up emissions (which lacked agricultural soil NOx emissions). Much of the increases occur across Europe, in regions where agricultural soil NOx emissions dominate. Our best estimate of soil NOx emissions in July 2015 is 0.1 Tg N, much higher than the bottom-up 0.02 Tg N natural soil NOx emissions from the Model of Emissions of Gases and Aerosols from Nature (MEGAN). A simulation with satellite-updated NOx emissions reduces the systematic bias between WRF-Chem and OMI NO2 (slope =0.98 , r2=0.84 ) and reduces the low bias against independent surface NO2 measurements by 1.1 µ g m −3 ( −56 %). Following these NOx emission changes, daytime ozone is strongly affected, since NOx emission changes particularly affect daytime ozone formation. Monthly averaged simulated daytime ozone increases by 6.0 µ g m −3 , and increases of >10 µ g m −3 are seen in regions with large emission increases. With respect to the initial simulation, MDA8 O3 has an improved spatial distribution, expressed by an increase in r2 from 0.40 to 0.53, and a decrease of the mean bias by 7.4 µ g m −3 (48 %). Overall, our results highlight the dependence of surface ozone on its precursor NOx and demonstrate that simulations of surface ozone benefit from constraining surface NOx emissions by satellite NO2 column observations.

Dry deposition is an important removal mechanism for tropospheric ozone (O3). Currently, O3 deposition to oceans in atmospheric chemistry and transport models (ACTMs) is generally represented using constant surface uptake resistances. This is despite the fact that considering the role of solubility, waterside turbulence and O3 reacting with ocean water reactants such as iodide and dissolved organic matter results in substantial spatiotemporal variability in O3 deposition and concentrations in marine boundary layers. We hypothesize that O3 deposition to the cold Arctic ocean, with relatively low reactivity, is also overestimated in current models with consequences for background concentrations, lifetime of O3 and long-range transport of O3. In this study, we investigate the role of the representation of oceanic O3 deposition to the simulated magnitude and spatiotemporal variability in Arctic surface O3. This study also serves as a preparatory study to understand the year-round Arctic O3 concentration and deposition flux measurements as part of the MOSAiC field campaign. Furthermore, it is also important to enhance our understanding and quantification of Arctic ocean-atmosphere exchange of O3 and other climate-active trace gases given the anticipated opening of the Arctic ocean. We have coupled the Coupled Ocean-Atmosphere Response Experiment Gas transfer algorithm (COAREG) to the mesoscale meteorology and atmospheric chemistry model Polar-WRF-Chem (WRF) and introduced a dependence of O3 deposition on ocean waterside turbulent mixing conditions and biogeochemical composition. We have also reduced the O3 deposition to sea ice and snow. Here, we evaluate the performance of WRF and the CAMS reanalysis data against hourly-averaged surface O3 observations at 25 sites (latitudes > 60º N) including the ASCOS campaign observations. This is the first time such a coupled modelling system has been evaluated against hourly observations at Pan-Arctic sites to study the sensitivity of the deposition scheme to the magnitude and short-term temporal variability in Arctic surface O3. We also analyze the impact of nudging WRF to the synoptic conditions from the ECMWF ERA5 reanalysis data on simulated Arctic meteorology and comparison of observed and simulated O3 concentrations. We show that the more mechanistic representation of O3 deposition over oceans and reduced snow/ice deposition improves simulated Arctic O3 mixing ratios both in terms of magnitude but also regarding observed temporal variability. Using the newly implemented approach, O3 deposition velocities have been simulated in the order of 0.01 cm s−1 compared to ~0.05 cm s−1 in the constant surface uptake resistance approach. The simulated spatial variability in the mechanistic approach (0.01 to 0.018 cm s−1) expresses the sensitivity to chemical enhancement with dissolved iodide whereas the temporal variability (up to ±20 % around the mean) expresses differences in waterside turbulent transport. The bias for all observational sites above 70º N reduced from −7.7 ppb to 0.3 ppb with nudging and the revision to ocean and snow/ice deposition. Our study confirms that O3 deposition to oceans and snow/ice is overestimated in current models. We recommend that a mechanistic representation of oceanic O3 deposition is used in ACTMs to improve the representation of Arctic surface O3 concentrations in terms of magnitude and short-term temporal variability. The revised ocean-atmosphere exchange representation can be further refined using the MOSAiC flux measurements as well as complementary observations such as sea ice and ocean water iodide concentrations.

During the Program for Research on Oxidants: PHotochemistry, Emissions, and Transport (PROPHET) campaign from July 21 to August 3, 2016, field experiments of leaf-level trace gas exchange of nitric oxide (NO), nitrogen dioxide (NO2), and ozone (O3) were conducted for the first time on the native American tree species Pinus strobus (eastern white pine), Acer rubrum (red maple), Populus grandidentata (bigtooth aspen), and Quercus rubra (red oak) in a temperate hardwood forest in Michigan, USA. We measured the leaf-level trace gas exchange rates and investigated the existence of an NO2 compensation point of 1 ppb, hypothesized based on a comparison of a previously observed average diurnal cycle of NOx (NO2 + NO) concentrations with that simulated using a multi-layer canopy exchange model. Known amounts of trace gases were introduced into a tree branch enclosure and a paired blank reference enclosure. The trace gas concentrations before and after the enclosures were measured, as well as the enclosed leaf area (single-sided) and gas flow rate to obtain the trace gas fluxes with respect to leaf surface. There was no detectable NO uptake for all tree types. The foliar NO2 and O3 uptake largely followed a diurnal cycle, correlating with that of the leaf stomatal conductance. NO2 and O3 fluxes were driven by their concentration gradient from ambient to leaf internal space. The NO2 loss rate at leaf surface, equivalently, the foliar NO2 deposition velocity toward the leaf surface, ranged from 0–3.6 mm s−1 for bigtooth aspen, and 0–0.76 mm s−1 for red oak, both of which are ~ 90 % of the expected values based on the stomatal conductance of water. The deposition velocity for red maple and white pine ranged from 0.3–1.6 mm s−1 and from 0.01–1.1 mm s−1, respectively, and were lower than predicted from the stomatal conductance, implying a mesophyll resistance to the uptake. Additionally, for white pine, the extrapolated velocity at zero stomatal conductance was 0.4 ± 0.08 mm s−1, indicating a non-stomatal uptake pathway. The NO2 compensation point was ≤ 60 ppt for all four tree species and indistinguishable from zero at the 95 % confidence level. This agrees with recent reports for several European and California tree species but contradicts some earlier experimental results where the compensation points were found to be on the order of 1 ppb or higher. Given that the sampled tree types represent 80–90 % of the total leaf area at this site, these results negate the previously hypothesized important role of a leaf-scale NO2 compensation point. Consequently, to reconcile these findings, further detailed comparisons between the observed and the simulated in- and above-canopy NOx concentrations, and the leaf- and canopy-scale NOx fluxes, using the multi-layer canopy exchange model with consideration of the leaf-scale NOx deposition velocities as well as stomatal conductances reported here, are recommended.

A multi-layer ozone (O3) dry deposition model has been implemented into SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to improve the representation of O3 within and above the forest canopy in the planetary boundary layer where O3 is a key oxidant agent of biogenic volatile organic compounds (BVOCs) and thus affecting organic aerosol processes. We aim to predict the O3 uptake by a boreal forest canopy under varying environmental conditions and analyse the influence of different factors on total O3 uptake by the canopy as well as the vertical distribution of deposition sinks inside the canopy. We evaluated the newly implemented canopy deposition model by an extensive comparison of simulated and observed O3 fluxes and concentration profiles within and above the boreal forest canopy at SMEAR II (the Station to Measure Ecosystem-Atmosphere Relation II) in Hyytiälä, Finland, in August, 2010. The first half of August showed extremely warm and dry conditions which were probably representative for summer conditions prevailing at this site in future. The simulated O3 turbulent fluxes at the canopy top and the O3 concentration profiles inside the canopy agreed well with the measurement, which indicated that the turbulent transport and the O3 dry deposition onto the canopy and soil surface appeared to be properly represented in the model. In this model, the fraction of wet surface on vegetation leaves was parameterised according to the ambient relative humidity (RH). Model results showed that when RH was larger than 70 % the O3 uptake onto wet skin contributed 48.6 % to the total deposition during nighttime and 22.0 % during daytime. In addition, most of the O3 deposition occurred below 0.8 hc (canopy height) at this site. The contribution of sub-canopy deposition below 4.2 m was modelled to be about 40 % of the total O3 deposition during daytime which was similar to previous studies. Whereas for nighttime, the simulated sub-canopy deposition contributed 40–65 % to the total O3 deposition which was about two times as that in previous studies (25–30 %). The overall contribution of soil uptake was estimated as 36.5 %. These results indicated the importance of non-stomatal O3 uptake processes, especially the uptake on wet skin and soil surface. Furthermore, a qualitative evaluation of the chemical removal time scales indicated that the chemical removal rate within canopy was about 5 % of the total deposition flux at daytime and 16 % at nighttime under current knowledge of air chemistry. The evaluation of the O3 deposition processes provides improved understanding about the mechanisms involved in the removal of O3 for this boreal forest site which are also relevant to the removal of other reactive compounds such as the BVOCs and their oxidation products, which will be focus of a follow-up study.

Plants that are subject to insect herbivory emit a blend of so‐called herbivore‐induced plant volatiles (HIPVs), of which only a few serve as cues for the carnivorous enemies to locate their host. We lack understanding which HIPVs are reliable indicators of insect herbivory. Here, we take a modelling approach to elucidate which physicochemical and physiological properties contribute to the information value of a HIPV. A leaf‐level HIPV synthesis and emission model is developed and parameterized to poplar. Next, HIPV concentrations within the canopy are inferred as a function of dispersion, transport and chemical degradation of the compounds. We show that the ability of HIPVs to reveal herbivory varies from almost perfect to no better than chance and interacts with canopy conditions. Model predictions matched well with leaf‐emission measurements and field and laboratory assays. The chemical class a compound belongs to predicted the signalling ability of a compound only to a minor extent, whereas compound characteristics such as its reaction rate with atmospheric oxidants, biosynthesis rate upon herbivory and volatility were much more important predictors. This study shows the power of merging fields of plant–insect interactions and atmospheric chemistry research to increase our understanding of the ecological significance of HIPVs., Plants communicate with other organisms through volatile organic compounds. Deciphering this language is important for our knowledge on plant communication. We show that the ability of a compound to serve as cue for insect herbivory is affected by its physicochemical and physiological properties.

The interaction between vegetation and the atmosphere is highly complex in fog affected ecosystems like Tropical Montane Cloud Forests (TMCFs). Despite acknowledging fog effects on the canopy’s water balance, quantifying their influence remains challenging. While the reduction in potential evaporation that is caused by fog presence, is largely independent of land cover, fog interception itself strongly depends on the land-cover’s vegetation characteristics. A better understanding of how these two fog related processes affect the water balance is highly relevant under current land-use and climate-change pressures. In this study we evaluate the different fog effects on TMCFs’ canopy interception combining model simulations and high temporal resolution (10 min) observations that were collected in different TMCF regeneration stages: early succession, secondary and old-growth TMCFs. We also analyse the difficulties in closing catchment water balances caused by limitations on the interpretation of throughfall data to properly represent these fog effects. Results show that different fog frequencies along elevation affect potential evaporation. The higher elevation old-growth TMCFs have a lower simulated evaporation and a lower dry canopy frequency than the low elevation secondary and early succession forests. Furthermore, we show that fog water inputs during fog-only events, even though higher at the higher elevation, are irrelevant as water inputs (from 0.8% to 1.6% of measured rainfall), but fog’s contribution to through-fall during foggy rainfall events can be more relevant (from 5.8%–12.8% of measured rainfall). Additional to the fog trends along the elevation, we also uncover variable fog-vegetation interactions controlled by differences in canopy water storages as a function of forest cover. Each evaluated process has associated uncertainties, which together cumulatively explain why closing a water budget in TMCF catchments is limited by data collection methods that probably do not capture all relevant fog effects. In addition, this study also indicates that the temporal resolution of measured rainfall and through-fall and compensating effects of canopy parameters that are estimated by the commonly used Rutter canopy-rainfall interception model, pose an additional challenge to understand and quantify fog effects in the water budgets of TMCFs.

Observed depth profiles of nitric oxide (NO), nitrogen dioxide (NO2), and ozone (O3) in snowpack interstitial air at Summit, Greenland were best replicated by a 1-D process-scale model, which included (1) geometrical representation of snow grains as spheres, (2) aqueous-phase chemistry confined to a quasi-liquid layer (QLL) on the surface of snow grains, and (3) initialization of the species concentrations in the QLL through equilibrium partitioning with mixing ratios in snowpack interstitial air. A comprehensive suite of measurements in and above snowpack during a high O3 event facilitated analysis of the relationship between the chemistry of snowpack and the overlying atmosphere. The model successfully reproduced 2 maxima (i.e., a peak near the surface of the snowpack at solar noon and a larger peak occurring in the evening that extended down from 0.5 to 2 m) in the diurnal profile of NO2 within snowpack interstitial air. The maximum production rate of NO2 by photolysis of nitrate (NO3−) was approximately 108 molec cm−3 s−1, which explained daily observations of maxima in NO2 mixing ratios near solar noon. Mixing ratios of NO2 in snowpack interstitial air were greatest in the deepest layers of the snowpack at night and were attributed to thermal decomposition of peroxynitric acid, which produced up to 106 molec NO2 cm−3 s−1. Highest levels of NO in snowpack interstitial air were confined to upper layers of the snowpack and observed profiles were consistent with photolysis of NO2. Production of nitrogen oxides (NOx) from NO3− photolysis was estimated to be two orders of magnitude larger than NO production and supports the hypothesis that NO3− photolysis is the primary source of NOx within sunlit snowpack in the Arctic. Aqueous-phase oxidation of formic acid by O3 resulted in a maximum consumption rate of ∼106–107 molec cm−3 s−1 and was the primary removal mechanism for O3.

A multi-year investigation of ozone (O 3 ) and nitrogen oxides (NO x ) in snowpack interstitial air down to a depth of 2.8 m was conducted at Summit, Greenland, to elucidate mechanisms controlling the production and destruction of these important trace gases within the snow. Snowpack O 3 values ranged from 30 to 40 ppbv during winter months, and dropped below 10 ppbv in summer. Wintertime NO x levels were low at all depths in the snowpack (below 10 pptv for NO and below 25 pptv for NO 2 ). In the summer, NO values up to 120 pptv, and NO 2 mixing ratios up to ∼700 pptv were observed. O 3 loss within the snowpack was observed throughout all seasons. The magnitude of the O 3 loss rate tracked the seasonal and diurnal cycle of incoming short wave solar radiation. Production of NO within a shallow layer of the snowpack was recorded during the spring and summer months. NO 2 production also occurred, and heightened levels were measured down to 2.5 m in the snowpack. The average daily maximum in NO was observed at solar noon, and the minimum was seen during night. The daily peak in NO 2 was on average 7 h shifted from the incoming solar radiation and NO maxima. NO x levels in interstitial air during spring were enhanced relative to summer and fall. The influence of meteorological effects such as wind pumping on snowpack interstitial air levels of O 3 and NO x was investigated using case study periods. Increased snowpack ventilation during high wind events was found to yield enhancement in snowpack NO x , with this effect being enhanced during times when O 3 was elevated in ambient air. This behavior suggests that O 3 is involved in NO x production in the snowpack. This extensive set of observations is used to re-evaluate physical and chemical processes that describe the dynamic O 3 and NO x chemistry occurring within snowpack interstitial air at Summit.

Speciated monoterpene measurements in the Amazon rainforest air are scarce, but important in order to understand their contribution to the overall reactivity of volatile organic compound (VOCs) emissions towards the main atmospheric oxidants, such as hydroxyl radical (OH), ozone (O3) and nitrate radical (NO3). In this study, we present the chemical speciation of gas phase monoterpenes measured in the tropical rainforest at the Amazon Tall Tower Observatory (ATTO, Amazonas, Brazil). Samples of VOCs were collected by two automatic sampling systems positioned on a tower at 12 and 24 m height and analysed using Gas Chromatography Flame Ionization Detection (GC-FID). The samples were collected in October 2015, representing the dry season, and compared with previous wet and dry season studies at the site. In addition, vertical profile measurements (at 12 and 24 m) of total monoterpene mixing ratios were made using Proton-Transfer Reaction Mass Spectrometry (PTR-MS). The results showed a distinctly different chemical speciation between day and night. For instance, α-pinene was more abundant during the day, whereas limonene was more abundant at night. Reactivity calculations showed that the most abundant compounds may not be the most atmospheric chemically relevant compounds. Furthermore, inter- and intra-annual results demonstrate similar chemodiversity during the dry seasons analysed. Simulations with a canopy exchange modelling system compare relatively well with the observed temporal variability in speciated monoterpene mixing ratios, but also indicate the necessity of more experiments to enhance our understanding of in-canopy sinks of these monoterpenes.

A multi-layer gas dry deposition model has been developed and implemented into a 1-dimensional chemical transport model SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g., monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes and oxidation products of mono- and sesquiterpenes) in July, 2010 at the boreal forest site SMEAR II (Station to Measure Ecosystem-Atmosphere Relations II). According to the significance of modeled monthly averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: (1) most of emitted gases are transported out of the canopy (monoterpenes, isoprene+MBO), (2) chemical reactions remove a significant portion of emitted gases (sesquiterpenes), (3) bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde), (4) gases removed by deposition inside the canopy are compensated by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH), and finally (5) the chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 4 m for oxidation products and above about 8 m for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understory vegetation) contributed 11–61 % to the overall in-canopy deposition. The emission sources peaked at about 14–16 m which was higher than 10 m where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modeling system this study analysed both the temporal and spatial variations of individual in-caonpy sources and sinks, as well as their combined effects on driving BVOCs exchange. Twelve featured BVOCs or BVOC groups were analyzed in this study, more compounds could also be investigated similarly by being classified into the five categories.

Mountain areas are characterized by a large heterogeneity in hydrological and meteorological conditions. This heterogeneity is currently poorly represented by gauging networks and by the coarse scale of global and regional climate and hydrological models. Tropical Montane Cloud Forests (TMCFs) are found in a narrow elevation range and are characterized by persistent fog. Their water balance depends on local and upwind temperatures and moisture, therefore, changes in these parameters will alter TMCF hydrology. Until recently the hydrological functioning of TMCFs was mainly studied in coastal regions, while continental TMCFs were largely ignored. This study contributes to fill this gap by focusing on a TMCF which is located on the northern eastern Andes at an elevation of 1550–2300 m asl, in the Orinoco river basin highlands. In this study, we describe the spatial and seasonal meteorological variability, analyse the corresponding catchment hydrological response to different land cover, and perform a sensitivity analysis on uncertainties related to rainfall interpolation, catchment area estimation and streamflow measurements. Hydro-meteorological measurements, including hourly solar radiation, temperature, relative humidity, wind speed, precipitation, soil moisture and streamflow, were collected from June 2013 to May 2014 at three gauged neighbouring catchments with contrasting TMCF/grassland cover and less than 250 m elevation difference. We found wetter and less seasonally contrasting conditions at higher elevations, indicating a positive relation between elevation and fog or rainfall persistence. This pattern is similar to that of other eastern Andean TMCFs, however, the study site had higher wet season rainfall and lower dry season rainfall suggesting that upwind contrasts in land cover and moisture can influence the meteorological conditions at eastern Andean TMCFs. Contrasting streamflow dynamics between the studied catchments reflect the overall system response as a function of the catchments’ elevation and land cover. The forested catchment, located at the higher elevations, had the highest seasonal streamflows. During the wet season, different land covers at the lower elevations were important in defining the streamflow responses between the deforested catchment and the catchment with intermediate forest cover. Streamflows were higher and the rainfall-runoff responses were faster in the deforested catchment than in the intermediate forest cover catchment. During the dry season, the catchments’ elevation defined streamflows due to higher water inputs and lower evaporative demand at the higher elevations.

The Tropical Montane Cloud Forest (TMCF) is a hydrologically unique and highly vulnerable ecosystem to changes in land-use and climate. Assessing the impacts of these changes needs to consider soil-water dynamics. In particular, the organic layer and its functioning requires attention because its difference in water retention characteristics and root density compared to the underlying mineral soils. A higher root density and a higher water storage capacity of the organic layer compared to the mineral soils suggests that most nutrient and water uptake occurs in this layer. However, hydraulic properties of mineral soils and their impact on hydrology of TMCFs have been poorly studied. Here we provide organic layer water retention curves for TMCF soils that were measured in the laboratory. With these data we assessed the potential land-use and climate change impacts on TMCF soil moisture dynamics. From the land-use change perspective, we estimated the water storage capacity loss by slash-and-burn deforestation practices. These estimates show that the storage loss ranges from 35 to 59 mm when TMCFs are converted to pastures. This is several times higher than the estimated TMCF canopy storage capacity (2 to 5 mm). Therefore, the higher peak flow observations in deforested catchments might not only be explained by a decreasing canopy water storage but also likely due to a decreasing soil water storage. From the climate change perspective, we evaluated the effect of contrasting dry season conditions on soil moisture and transpiration using a 1-D water-flow model, and assessed the sensitivity of these hydrological variables to uncertainties in saturated hydraulic conductivity. Although transpiration was not limited by soil moisture during the mild dry season, it was affected during the severe dry season and continued to decline under expected climate change with the prolongation of dry spells. Our results show that the organic layer is a key element in TMCF's hydrological functioning and call for an increased focus on the role of organic soils when evaluating effects of land-use change.

A multilayer gas dry deposition model has been developed and implemented into a one-dimensional chemical transport model SOSAA (model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition, and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g. monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes, and oxidation products of mono- and sesquiterpenes) in July 2010 at the boreal forest site SMEAR II (Station for Measuring Ecosystem–Atmosphere Relations). According to the significance of modelled monthly-averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: 1. Most of emitted gases are transported out of the canopy (monoterpenes, isoprene + MBO). 2. Chemical reactions remove a significant portion of emitted gases (sesquiterpenes). 3. Bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde). 4. Gases removed by deposition inside the canopy are compensated for by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH). 5. The chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 0.2 hc (canopy height) for oxidation products and above about 0.4 hc for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understorey vegetation) contributed 11–61 % to the overall in-canopy deposition. The emission sources peaked at about 0.8–0.9 hc, which was higher than 0.6 hc where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modelling system, this study analysed both the temporal and spatial variations in individual in-canopy sources and sinks, as well as their combined effects on driving BVOC exchange. In this study 12 featured BVOCs or BVOC groups were analysed. Other compounds could also be investigated similarly by being classified into these five categories.

We study the organic aerosol (OA) budget in a tropical forest by analyzing a case that is representative for the OP3 campaign at Borneo. A model is designed that combines the essential dynamical and chemical processes that drive the diurnal evolution of reactants in the atmospheric boundary layer (BL). In this way, the model simultaneously represents the effects and interactions of various dynamical and chemical factors on the OA budget. The model is able to reproduce the observed diurnal dynamics of the BL, including the evolution of most chemical species involved in secondary organic aerosol (SOA) formation. A budget analysis of the contributions of the dynamic and chemical processes reveals the significance of the entrainment process in the diurnal evolution of SOA. Further, we perform a series of sensitivity analyses to determine the effect of meteorological forcings and isoprene chemical pathways on the OA budget. Subsidence and advection of cool air have opposing effects on the OA concentration, although both suppress BL growth. Recycling of the OH radical in the oxidation of isoprene may affect the amount of SOA that is formed, but must be understood better before its impact can be definitely determined. SOA formation from isoprene is calculated for both the low- and high-NOx pathway, with the latter dominating the isoprene peroxy radical chemistry. Finally, we study the significance of SOA formation through the reactive uptake of isoprene epoxydiols on acidic sulfate aerosol. Despite the incorporation of these new pathways, the OA concentration is systematically underestimated by about a factor of 2.

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3month periods for the years 2001-2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27Gmol in April-June and 4.9, 14, and 0.19Gmol in September-November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%-9.1% for iron, 6.1%-15% for aluminum, and 54%-73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

The dynamic behavior of nitrogen oxides (NOx = NO + NO2) and ozone (O3) above and within the canopy at the University of Michigan Biological Station AmeriFlux (UMBS Flux) site was investigated by continuous multi-height vertical gradient measurements during the summer and the fall of 2008. A daily maximum in nitric oxide (NO) mixing ratios was consistently observed during the morning hours between 06:00 and 09:00 EST above the canopy. Daily NO maxima ranged between 0.1 and 2 ppbv (with a median of 0.3 ppbv), which were 2 to 20 times above the atmospheric background. The sources and causes of the morning NO maximum were evaluated using NOx and O3 measurements and synoptic and micrometeorological data. Numerical simulations with a multi-layer canopy-exchange model were done to further support this analysis. The observations indicated that the morning NO maximum was caused by the photolysis of NO2 from non-local air masses, which were transported into the canopy from aloft during the morning breakup of the nocturnal boundary layer. The analysis of simulated process tendencies indicated that the downward turbulent transport of NOx into the canopy compensates for the removal of NOx through chemistry and dry deposition. The sensitivity of NOx and O3 concentrations to soil and foliage NOx emissions was also assessed with the model. Uncertainties associated with the emissions of NOx from the soil or from leaf-surface nitrate photolysis did not explain the observed diurnal behavior in NOx (and O3) and, in particular, the morning peak in NOx mixing ratios. However, a ~30% increase in early morning NOx and NO peak mixing ratios was simulated when a foliage exchange NO2 compensation point was considered. This increase suggests the potential importance of leaf-level, bidirectional exchange of NO2 in understanding the observed temporal variability in NOx at UMBS.

We study the combined effects of land surface conditions, atmospheric boundary layer dynamics and chemistry on the diurnal evolution of biogenic secondary organic aerosol in the atmospheric boundary layer, using a model that contains the essentials of all these components. First, we evaluate the model for a case study in Hyytiälä, Finland, and find that it is able to satisfactorily reproduce the observed dynamics and gas-phase chemistry. We show that the exchange of organic aerosol between the free troposphere and the boundary layer (entrainment) must be taken into account in order to explain the observed diurnal cycle in organic aerosol (OA) concentration. An examination of the budgets of organic aerosol and terpene concentrations show that the former is dominated by entrainment, while the latter is mainly driven by emission and chemical transformation. We systematically investigate the role of the land surface, which governs both the surface energy balance partitioning and terpene emissions, and the large-scale atmospheric process of vertical subsidence. Entrainment is especially important for the dilution of organic aerosol concentrations under conditions of dry soils and low terpene emissions. Subsidence suppresses boundary layer growth while enhancing entrainment. Therefore, it influences the relationship between organic aerosol and terpene concentrations. Our findings indicate that the diurnal evolution of secondary organic aerosols (SOA) in the boundary layer is the result of coupled effects of the land surface, dynamics of the atmospheric boundary layer, chemistry, and free troposphere conditions. This has potentially some consequences for the design of both field campaigns and large-scale modeling studies.

Global climate models simulate the Earth's climate impressively at scales of continents and greater. At these scales, large-scale dynamics and physics largely define the climate. At spatial scales relevant to policy makers, and to impacts and adaptation, many other processes may affect regional and local climate and perhaps trigger teleconnections that provide significant feedbacks on the global climate. These processes include fire, irrigation, land cover change (including crops and urban landscapes), and the emissions of biogenic volatile organic compounds by vegetation. Many of these interact within the atmosphere via dynamical, physical, and chemical mechanisms that lead to boundary-layer feedbacks. It is unlikely that any of these processes have a significant global-scale impact on the Earth's climate in the sense that the amount of warming due to a doubling of well mixed greenhouse gases would change if these processes were explicitly represented in climate models. These phenomena are usually local in space (e.g. urban) or in time (e.g. fire) and probably do not provide the on-going and sustained forcing to affect the global climate. However, for most impacts and adaptation research it is the regional and local climate that defines climate risk. At these scales, processes missing in climate models can have a substantially larger local-scale impact than the additional radiative forcing due to increasing greenhouse gases. Thus, while climate models are well designed for global and continental scales they exclude a suite of important processes that are locally and/or regionally important. We review these missing processes and highlight the research required to resolve the representation of these regional-scale processes in climate models. We also discuss the experimental methodology required to rigorously determine whether these processes are restricted to a local or regional-scale role or whether they do trigger robust teleconnections that would demonstrate global-scale significance. Copyright (c) 2011 Royal Meteorological Society (Less)

Whole air drawn from four heights within the high elevation (3,340 m asl), deep, winter snowpack at Niwot Ridge, Colorado, were sampled into stainless steel canisters, and subsequently analyzed by gas chromatography for 51 volatile inorganic and organic gases. Two adjacent plots with similar snow cover were sampled, one over bare soil and a second one from within a snow-filled chamber where Tedlar/Teflon-film covered the ground and isolated it from the soil. This comparison allowed for studying effects from processes in the snowpack itself versus soil influences on the gas concentrations and fluxes within and through the snowpack. Samples were also collected from ambient air above the snow surface for comparison with the snowpack air. Analyzed gas species were found to exhibit three different kinds of behavior: (1) One group of gases, i.e., carbon dioxide (CO2), chloroform (CHCl3), dimethylsulfide (CH3)2S, carbondisulfide (CS2), and dichlorobromomethane (CHBrCl2), displayed higher concentrations inside the snow, indicating a formation of these species and release into the atmosphere. (2) A second group of compounds, including carbon monoxide (CO), carbonyl sulfide (COS), the hydrocarbons methane, ethane, ethyne, benzene, and the halogenated compounds methylchloride (CH3Cl), methylbromide (CH3Br), dibromomethane (CH2Br2), bromoform (CHBr3), tetrachloromethane (CCl4), CFC-11, CFC-12, HCFC-22, CFC-113, 1,2-dichloroethane, methylchloroform, HCFC-141b, and HCFC-142b, were found at lower concentrations in the snow, indicating that the snow and/or soil constitute a sink for these gases. (3) For 21 other gases absolute concentrations, respectively concentration gradients, were too low to unequivocally identify their uptake or release behavior. For gases listed in the first two groups, concentration gradients were incorporated into a snowpack gas diffusion model to derive preliminary estimates of fluxes at the snow-atmosphere interface. The snowpack gradient flux technique was found to offer a highly sensitive method for the study of these surface gas exchanges. Microbial activities below this deep, winter snowpack appear to be the driving mechanism behind these gas sources and sinks. Flux results were applied to a simple box model to assess the potential contribution of the snowpack uptake rates to atmospheric lifetimes of these species.

Terrestrial vegetation, especially tropical rain forest, releases vast quantities of volatile organic compounds (VOCs) to the atmosphere1, 2, 3, which are removed by oxidation reactions and deposition of reaction products4, 5, 6. The oxidation is mainly initiated by hydroxyl radicals (OH), primarily formed through the photodissociation of ozone4. Previously it was thought that, in unpolluted air, biogenic VOCs deplete OH and reduce the atmospheric oxidation capacity5, 6, 7, 8, 9, 10. Conversely, in polluted air VOC oxidation leads to noxious oxidant build-up by the catalytic action of nitrogen oxides5, 6, 7, 8, 9, 10 (NOx = NO + NO2). Here we report aircraft measurements of atmospheric trace gases performed over the pristine Amazon forest. Our data reveal unexpectedly high OH concentrations. We propose that natural VOC oxidation, notably of isoprene, recycles OH efficiently in low-NOx air through reactions of organic peroxy radicals. Computations with an atmospheric chemistry model and the results of laboratory experiments suggest that an OH recycling efficiency of 40¿80 per cent in isoprene oxidation may be able to explain the high OH levels we observed in the field. Although further laboratory studies are necessary to explore the chemical mechanism responsible for OH recycling in more detail, our results demonstrate that the biosphere maintains a remarkable balance with the atmospheric environment

Recent research on snowpack processes and atmosphere-snow gas exchange has demonstrated that chemical and physical interactions between the snowpack and the overlaying atmosphere have a substantial impact on the composition of the lower troposphere. These observations also imply that ozone deposition to the snowpack possibly depends on parameters including the quantity and composition of deposited trace gases, solar irradiance, snow temperature and the substrate below the snowpack. Current literature spans a remarkably wide range of ozone deposition velocities (vdO3); several studies even reported positive ozone fluxes out of the snow. Overall, published values range from ~–3

A parameterization for the deposition velocity of an ocean-reactive atmospheric gas (such as ozone) is developed. The parameterization is based on integration of the turbulent-molecular transport equation (with a chemical source term) in the ocean. It extends previous work that only considered reactions within the oceanic molecular sublayer. The sensitivity of the ocean-side transport to reaction rate and wind forcing is examined. A more complicated case with a much more reactive thin surfactant layer is also considered. The full atmosphere-ocean deposition velocity is obtained by matching boundary conditions at the interface. For an assumed ocean reaction rate of 103 s−1, the enhancement for ozone deposition by oceanic turbulence is found to be up to a factor of three for meteorological data obtained in a recent cruise off the East Coast of the U.S.

The integrated land ecosystem-atmosphere processes study (iLEAPS) is an international research project focussing on the fundamental processes that link land-atmosphere exchange, climate, the water cycle, and tropospheric chemistry. The project, iLEAPS, was established 2004 within the International Geosphere-Biosphere Programme (IGBP). During its first decade, iLEAPS has proven to be a vital project, well equipped to build a community to address the challenges involved in understanding the complex Earth system: multidisciplinary, integrative approaches for both observations and modeling. The iLEAPS community has made major advances in process understanding, land-surface modeling, and observation techniques and networks. The modes of iLEAPS operation include elucidating specific iLEAPS scientific questions through networks of process studies, field campaigns, modeling, long-term integrated field studies, international interdisciplinary mega-campaigns, synthesis studies, databases, as well as conferences on specific scientific questions and synthesis meetings. Another essential component of iLEAPS is knowledge transfer and it also encourages community- and policy-related outreach activities associated with the regional integrative projects. As a result of its first decade of work, iLEAPS is now setting the agenda for its next phase (2014–2024) under the new international initiative, future Earth. Human influence has always been an important part of land-atmosphere science but in order to respond to the new challenges of global sustainability, closer ties with social science and economics groups will be necessary to produce realistic estimates of land use and anthropogenic emissions by analysing future population increase, migration patterns, food production allocation, land management practices, energy production, industrial development, and urbanization., Anthropocene, 12, ISSN:2213-3054

This discussion was based on the background document “Review on modelling atmosphere-biosphere exchange of Ozone and Nitrogen oxides”, which reviews the processes contributing to biosphere-atmosphere exchange of O3 and NOx, including stomatal and non-stomatal exchange of O3 and NO, NO2. Non-stomatal exchange, including soil and chemical reactions in the canopy airspace is discussed, with a focus on how these processes are influenced by turbulent transport in the canopy. Existing models are reviewed, from big-leaf and two layer resistance to multi-layer models. Based on this background document, the discussion in the working group was organized to discuss the current gaps in modelling O3-NO-NO2 exchange and the ideal model that should be developed.

Ozone concentrations in the Po Valley of northern Italy often exceed international regulations. As both a source of radicals and an intermediate in the oxidation of most volatile organic compounds (VOCs), formaldehyde (HCHO) is a useful tracer for the oxidative processing of hydrocarbons that leads to ozone production. We investigate the sources of HCHO in the Po Valley using vertical profile measurements acquired from the airship Zeppelin NT over an agricultural region during the PEGASOS 2012 campaign. Using a 1-D model, the total VOC oxidation rate is examined and discussed in the context of formaldehyde and ozone production in the early morning. While model and measurement discrepancies in OH reactivity are small (on average 3.4 ± 13%), HCHO concentrations are underestimated by as much as 1.5 ppb (45%) in the convective mixed layer. A similar underestimate in HCHO was seen in the 2002–2003 FORMAT Po Valley measurements, though the additional source of HCHO was not identified. Oxidation of unmeasured VOC precursors cannot explain the missing HCHO source, as measured OH reactivity is explained by measured VOCs and their calculated oxidation products. We conclude that local direct emissions from agricultural land are the most likely source of missing HCHO. Model calculations demonstrate that radicals from degradation of this non-photochemical HCHO source increase model ozone production rates by as much as 0.6 ppb h−1 (12%) before noon.

International audience; Vegetation canopies are efficient in removing ozone (O3) from the atmosphere making surface dry deposition an important process in air quality but also in climate change. O3 is the 3rd most important greenhouse gas (IPCC) responsible for ~25 % of the total net radiative forcing attributed to human activities.

International audience; The turbulence within and immediately above a vegetation canopy is the driver of the exchange processes of heat, trace gases and particles between the soil, the plants and the atmosphere above.

We present the submodels DRYDEP and SEDI for the Modular Earth Submodel System (MESSy). Gas phase and aerosol dry deposition are calculated within DRYDEP, whereas SEDI deals with aerosol particle sedimentation. Dry deposition velocities depend on the near-surface turbulence and the physical and chemical properties of the surface cover (e.g. the roughness length, soil pH or leaf stomatal exchange). The dry deposition algorithm used in DRYDEP is based on the big leaf approach and is described in detail within this Technical Note. The sedimentation submodel SEDI contains two sedimentation schemes: a simple upwind zeroth order scheme and a first order approach.

A one-dimensional multi-layer scheme describing the coupled exchange of energy and CO2, the emission of isoprene and the dry deposition of ozone is applied to a rain forest canopy in southwest Amazonia. The model was constrained using mean diel cycles of micrometeorological quantities observed during two periods in the wet and dry season 1999. Predicted net fluxes and concentration profiles for both seasonal periods are compared to observations made at two nearby towers. The predicted day- and nighttime thermal stratification of the canopy layer is consistent with observations in dense canopies. The observed and calculated net fluxes above and H2O and CO2 concentration profiles within the canopy show a good agreement. The predicted net carbon sink decreases from 2.5 t C ha-1yr-1 for wet season conditions to 1 t C ha-1yr-1 for dry season conditions, whereas observed and predicted midday Bowen ratio increases from 0.5 to 0.8. The evaluation results confirmed a seasonal variability of leaf physiological parameters, as already suggested in the companion study. The predicted midday canopy net flux of isoprene increased from 7.1 mg C m-2h-1 during the wet season to 11.4 mg C m-2h-1 during the late dry season. Applying a constant emission capacity in all canopy layers, resulted in a disagreement between observed and simulated profiles of isoprene concentrations, suggesting a smaller emission capacity of shade adapted leaves and deposition to the soil or leaf surfaces. Assuming a strong light acclimation of emission capacity, equivalent to a 66% reduction of the standard emission factor for leaves in the lower canopy, resulted in a better agreement of observed and calculated concentration profiles and a 30% reduction of the canopy net flux. The mean calculated ozone flux for dry season condition at noontime was ≈12 nmol m-2s-1, agreeing well with observed values. The corresponding deposition velocity increased from 0.8 cm s-1 to >1.6 cm s-1 in the wet season, which can not be explained by increased stomatal uptake. Considering reasonable physiological changes in stomatal regulation, the predicted value was not larger than 1.05 cm s-1. Instead, the observed fluxes could be explained with the model by decreasing the cuticular resistance to ozone deposition from 5000 to 1000 s m-1. For doubled atmospheric CO2 concentrations the model predicts a strong increase of surface temperatures (0.1–1°C) and net assimilation (22%), a considerable shift in the energy budget (≈25% decreasing transpiration and increasing sensible heat), a slight increase of isoprene emissions (10%) and a strong decrease of ozone deposition (35%).

The present study focuses on the description of the vertical dispersion of trace gases within the Amazon rain forest. A Lagrangian approach is parameterised using in-canopy turbulence measurements made at a site in Rondonia (Reserva Jaru). In contrast to common scaling schemes that solely depend on friction parameters measured above the canopy, a combined scaling that also includes night-time free convective mixing in the lower part of dense vegetation canopies is proposed here. 222Rn concentration profiles and soil flux measurements made at a second site near Manaus (Reserva Cuieiras) are used to evaluate the derived parameterisation and the uncertainties of the forward (prediction of concentration profiles) and inverse (prediction of vertical source/sink distributions) solution of the transfer equations. Averaged day- and night-time predictions of the forward solution agree with the observations within their uncertainty range. During night-time, a weak, but effective free convective mixing process in the lower canopy ensures a relatively high flushing rate with residence times of

Detailed one-dimensional multilayer biosphere-atmosphere models, also referred to as CANVEG models, are used for more than a decade to describe coupled water-carbon exchange between the terrestrial vegetation and the lower atmosphere. Within the present study, a modified CANVEG scheme is described. A generic parameterization and characterization of biophysical properties of Amazon rain forest canopies is inferred using available field measurements of canopy structure, in-canopy profiles of horizontal wind speed and radiation, canopy albedo, soil heat flux and soil respiration, photosynthetic capacity and leaf nitrogen as well as leaf level enclosure measurements made on sunlit and shaded branches of several Amazonian tree species during the wet and dry season. The sensitivity of calculated canopy energy and CO2 fluxes to the uncertainty of individual parameter values is assessed. In the companion paper, the predicted seasonal exchange of energy, CO2, ozone and isoprene is compared to observations. A bi-modal distribution of leaf area density with a total leaf area index of 6 is inferred from several observations in Amazonia. Predicted light attenuation within the canopy agrees reasonably well with observations made at different field sites. A comparison of predicted and observed canopy albedo shows a high model sensitivity to the leaf optical parameters for near-infrared short-wave radiation (NIR). The predictions agree much better with observations when the leaf reflectance and transmission coefficients for NIR are reduced by 25?40%. Available vertical distributions of photosynthetic capacity and leaf nitrogen concentration suggest a low but significant light acclimation of the rain forest canopy that scales nearly linearly with accumulated leaf area. Evaluation of the biochemical leaf model, using the enclosure measurements, showed that recommended parameter values describing the photosynthetic light response, have to be optimized. Otherwise, predicted net assimilation is overestimated by 30?50%. Two stomatal models have been tested, which apply a well established semi-empirical relationship between stomatal conductance and net assimilation. Both models differ in the way they describe the influence of humidity on stomatal response. However, they show a very similar performance within the range of observed environmental conditions. The agreement between predicted and observed stomatal conductance rates is reasonable. In general, the leaf level data suggests seasonal physiological changes, which can be reproduced reasonably well by assuming increased stomatal conductance rates during the wet season, and decreased assimilation rates during the dry season. The sensitivity of the predicted canopy fluxes of energy and CO2 to the parameterization of canopy structure, the leaf optical parameters, and the scaling of photosynthetic parameters is relatively low (1?12%), with respect to parameter uncertainty. In contrast, modifying leaf model parameters within their uncertainty range results in much larger changes of the predicted canopy net fluxes (5?35%).

Ozone concentrations in the Po Valley of Northern Italy often exceed international regulations. As both a source of radicals and an intermediate in the oxidation of most volatile organic compounds (VOCs), formaldehyde (HCHO) is a useful tracer for the oxidative processing of hydrocarbons that leads to ozone production. We investigate the sources of HCHO in the Po Valley using vertical profile measurements acquired from the airship Zeppelin NT over an agricultural region during the PEGASOS 2012 campaign. Using a 1-D model, the total VOC oxidation rate is examined and discussed in the context of formaldehyde and ozone production in the early morning. While model and measurement discrepancies in OH reactivity are small (on average 3.4±11%), HCHO concentrations are underestimated by as much as 1.5 ppb (45%) in the convective mixed layer. A similar underestimate in HCHO was seen in the 2002–2003 FORMAT Po-Valley measurements, though the additional source of HCHO was not identified. Oxidation of unmeasured VOC precursors cannot explain the missing HCHO source, as measured OH reactivity is explained by measured VOCs and their calculated oxidation products. We conclude that local direct emissions from agricultural land are the most likely source of missing HCHO. Model calculations demonstrate that radicals from degradation of this non-photochemical HCHO source increase model ozone production rates by as much as 0.7 ppb h−1 (10%) before noon.

A sulfur cycle model is coupled to a global chemistry-climate model. The simulated surface sulfate concentrations are generally within a factor of 2 of observed concentrations, and display a realistic seasonality for most background locations. However, the model tends to underestimate sulfate and overestimate surface SO 2 at relatively polluted locations. A possible explanation for this is that additional oxidation reactions not considered in the model, may be important. Calculated tropospheric sulfate column abundances exceed those of previous studies, which is predominantly associated with a less efficient nucleation scavenging in wet convective updrafts. Through the simultaneous calculation of the sulfur cycle and tropospheric photochemistry, simulated H 2 O 2 and SO 2 concentrations are strongly linked, especially in polluted areas. The coupled model simulates a stronger oxidant limitation and, consequently, a smaller contribution to sulfate formation by H 2 O 2 oxidation of SO 2 when compared to sulfur cycle models that use monthly averaged oxidant distributions as input. In the polluted NH, the differences in calculated sulfate columns are largest in winter and relatively small in summer. Therefore, the coupling between the sulfur cycle and the oxidant chemistry is expected to have a minor impact on the calculation of the indirect and direct radiative forcing by sulfate. An empirical relation between sulfate concentration and cloud drop number concentration, derived from cloud measurements at Grean Dun Fell (UK), is applied to the simulated cloud and sulfate fields to derive distributions of effective could drop radii. Additionally, a relation between wind speed and cloud drop number concentration is applied over marine regions to account for the effect of seasalt aerosol on cloud formation when sulfate concentrations are relatively low. Calculated droplet radii are systematically underestimated by about 10–20% in the NH compared to satellite derived values, but they agree relatively well in the SH. DOI: 10.1034/j.1600-0889.1998.t01-2-00002.x

A dry deposition scheme, originally developed to calculate the deposition velocities for the trace gases O3, NO2, NO, and HNO3 in the chemistry and general circulation European Centre Hamburg Model (ECHAM), is extended to sulfur dioxide (SO2) and sulfate (SO42−). In order to reduce some of the shortcomings of the previous model version a local surface roughness and a more realistic leaf area index (LAI), derived from a high-resolution ecosystem database are introduced. The current model calculates the deposition velocities from the aerodynamic resistance, a quasi-laminary boundary layer resistance and a surface resistance of the surface cover, e.g., snow/ice, bare soil, vegetation, wetted surfaces, and ocean. The SO2 deposition velocity over vegetated surfaces is calculated as a function of the vegetation activity, the canopy wetness, turbulent transport through the canopy to the soil, and uptake by the soil. The soil resistance is explicitly calculated from the relative humidity and the soil pH, derived from a high-resolution global soil pH database. The snow/ice resistance of SO2 is a function of temperature. The SO2 deposition velocity over the oceans is controlled by turbulence. The sulfate deposition velocity is calculated considering diffusion, impaction, and sedimentation. Over sea surfaces the effect of bubble bursting, causing the breakdown of the quasi-laminary boundary layer, scavenging of the sulfate aerosol by sea spray, and aerosol growth due to high local relative humidities are considered. An integrated sulfate deposition velocity is calculated, applying a unimodal mass size distribution over land and a bimodal mass size distribution over sea. The calculated sulfate deposition velocity is about an order of magnitude larger than that based on a monodisperse aerosol, which is often applied in chemistry-transport models. Incorporation of the new dry deposition scheme in the ECHAM model yields significant relative differences (up to ∼50%) in mass flux densities and surface layer concentrations compared to those calculated with a simple, constant dry deposition scheme.

The general circulation model ECHAM has been coupled to a chemistry and sulphur cycle model to study the impact of terrestrial, i.e. mostly anthropogenic sulphur dioxide (SO2), sources on global distributions of sulphur species in the atmosphere. We briefly address currently available source inventories. It appears that global estimates of natural emissions are associated with uncertainties up to a factor of 2, while anthropogenic emissions have uncertainty ranges of about +/− 30 per cent. Further, some recent improvements in the model descriptions of multiphase chemistry and deposition processes are presented. Dry deposition is modelled consistently with meteorological processes and surface properties. The results indicate that surface removal of SO2is less efficient than previously assumed, and that the SO2lifetime is thus longer. Coupling of the photochemistry and sulphur chemistry schemes in the model improves the treatment of multiphase processes such as oxidant (hydrogen peroxide) supply in aqueous phase SO2oxidation. The results suggest that SO2oxidation by ozone (O3) in the aqueous phase is more important than indicated in earlier work. However, it appears that we still overestimate atmospheric SO2concentrations near the surface in the relatively polluted Northern Hemisphere. On the other hand, we somewhat underestimate sulphate levels in these regions, which suggests that additional heterogeneous reaction mechanisms, e.g. on aerosols, enhance SO2oxidation.

The chemical segregation of isoprene has been investigated over heterogeneous surface conditions, and first results are presented and analysed.

We measured the mixing ratios of NO, NO2, O-3, and volatile organic carbon as well as the aerosol light-scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large-Scale Biosphere-Atmosphere Experiment in Amazonia-Cooperative LBA Airborne Regional Experiment-2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground-based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single-Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region similar to 150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, sigma(s), was below 11 Mm(-1), NOx mixing ratios remained below 0.6 ppb, daytime O-3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Phi, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east-northeast to south-southeast in the afternoon often caused a substantial increase of ss and trace gas mixing ratios (about threefold for sigma(s), fivefold for NOx, and twofold for O-3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio F reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating "steady-state" conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (sigma(s)

A ship-based eddy covariance ozone flux system was deployed to investigate the magnitude and variability of ozone surface fluxes over the open ocean. The flux experiments were conducted on five cruises on board the NOAA research vessel Ronald Brown during 2006-2008. The cruises covered the Gulf of Mexico, the southern as well as northern Atlantic, the Southern Ocean, and the persistent stratus cloud region off Chile in the eastern Pacific Ocean. These experiments resulted in the first ship-borne open-ocean ozone flux measurement records. The median of 10 min oceanic ozone deposition velocity (v(d)) results from a combined similar to 1700 h of observations ranged from 0.009 to 0.034 cm s(-1). For the Gulf of Mexico cruise (Texas Air Quality Study (TexAQS)) the median v(d) (interquartile range) was 0.034 (0.009-0.065) cm s(-1) (total number of 10 min measurement intervals, N-f = 1953). For the STRATUS cruise off the Chilean coast, the median v(d) was 0.009 (0.004-0.037) cm s(-1) (N-f = 1336). For the cruise from the Gulf of Mexico and up the eastern U. S. coast (Gulf of Mexico and East Coast Carbon cruise (GOMECC)) a combined value of 0.018 (0.006-0.045) cm s(-1) (N-f = 1784) was obtained (from 0.019 (-0.014-0.043) cm s(-1), N-f = 663 in the Gulf of Mexico, and 0.018 (-0.004-0.045) cm s(-1), N-f = 1121 in the North Atlantic region). The Southern Ocean Gas Exchange Experiment (GasEx) and African Monsoon Multidisciplinary Analysis (AMMA), the Southern Ocean and northeastern Atlantic cruises, respectively, resulted in median ozone v(d) of 0.009 (-0.005-0.026) cm s(-1) (N-f = 2745) and 0.020 (-0.003-0.044) cms(-1) (N-f = 1147). These directly measured ozone deposition values are at the lower end of previously reported data in the literature (0.01-0.12 cm s(-1)) for ocean water. Data illustrate a positive correlation (increase) of the oceanic ozone uptake rate with wind speed, albeit the behavior of the relationship appears to differ during these cruises. The encountered wide range of meteorological and ocean biogeochemical conditions is used to investigate fundamental drivers of oceanic O-3 deposition and for the evaluation of a recently developed global oceanic O-3 deposition modeling system.

We present an evaluation of a nested high-resolution Goddard Earth Observing System (GEOS)-Chem chemistry transport model simulation of tropospheric chemistry over tropical South America. The model has been constrained with two isoprene emission inventories: (1) the canopy-scale Model of Emissions of Gases and Aerosols from Nature (MEGAN) and (2) a leaf-scale algorithm coupled to the Lund-Potsdam-Jena General Ecosystem Simulator (LPJ-GUESS) dynamic vegetation model, and the model has been run using two different chemical mechanisms that contain alternative treatments of isoprene photo-oxidation. Large differences of up to 100 Tg C yr-1 exist between the isoprene emissions predicted by each inventory, with MEGAN emissions generally higher. Based on our simulations we estimate that tropical South America (30-85°W, 14°N-25°S) contributes about 15-35% of total global isoprene emissions. We have quantified the model sensitivity to changes in isoprene emissions, chemistry, boundary layer mixing, and soil NOx emissions using ground-based and airborne observations. We find GEOS-Chem has difficulty reproducing several observed chemical species; typically hydroxyl concentrations are underestimated, whilst mixing ratios of isoprene and its oxidation products are overestimated. The magnitude of model formaldehyde (HCHO) columns are most sensitive to the choice of chemical mechanism and isoprene emission inventory. We find GEOS-Chem exhibits a significant positive bias (10-100%) when compared with HCHO columns from the Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY) and Ozone Monitoring Instrument (OMI) for the study year 2006. Simulations that use the more detailed chemical mechanism and/or lowest isoprene emissions provide the best agreement to the satellite data, since they result in lower-HCHO columns. Copyright © 2011 by the American Geophysical Union.