Tropospheric Gas-phase Chemistry Research Articles

Development of an atmospheric chemistry model coupled to the PALM model system 6.0: implementation and first applications

Abstract. In this article we describe the implementation of an online-coupled gas-phase chemistry model in the turbulence-resolving PALM model system 6.0 (formerly an abbreviation for Parallelized Large-eddy Simulation Model and now an independent name). The new chemistry model is implemented in the PALM model as part of the PALM-4U (PALM for urban applications) components, which are designed for application of the PALM model in the urban environment (Maronga et al., 2020). The latest version of the Kinetic PreProcessor (KPP, 2.2.3) has been utilized for the numerical integration of gas-phase chemical reactions. A number of tropospheric gas-phase chemistry mechanisms of different complexity have been implemented ranging from the photostationary state (PHSTAT) to mechanisms with a strongly simplified volatile organic compound (VOC) chemistry (e.g. the SMOG mechanism from KPP) and the Carbon Bond Mechanism 4 (CBM4; Gery et al., 1989), which includes a more comprehensive, but still simplified VOC chemistry. Further mechanisms can also be easily added by the user. In this work, we provide a detailed description of the chemistry model, its structure and input requirements along with its various features and limitations. A case study is presented to demonstrate the application of the new chemistry model in the urban environment. The computation domain of the case study comprises part of Berlin, Germany. Emissions are considered using street-type-dependent emission factors from traffic sources. Three chemical mechanisms of varying complexity and one no-reaction (passive) case have been applied, and results are compared with observations from two permanent air quality stations in Berlin that fall within the computation domain. Even though the feedback of the model's aerosol concentrations on meteorology is not yet considered in the current version of the model, the results show the importance of online photochemistry and dispersion of air pollutants in the urban boundary layer for high spatial and temporal resolutions. The simulated NOx and O3 species show reasonable agreement with observations. The agreement is better during midday and poorest during the evening transition hours and at night. The CBM4 and SMOG mechanisms show better agreement with observations than the steady-state PHSTAT mechanism.

The chemistry–climate model ECHAM6.3-HAM2.3-MOZ1.0

Abstract. The chemistry–climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

The Chemistry Climate Model ECHAM6.3-HAM2.3-MOZ1.0

The chemistry climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parametrisations of aerorols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A ten-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone (O<sub>3</sub>) and carbon monoxide (CO) from Infrared Atmospheric Sounding Interferometer (IASI) and Ozone Monitoring Instrument (OMI), Microwave Limb Sounder (MLS) observations of temperature, nitric acid (HNO<sub>3</sub>), chlorine monoxide (ClO), and O<sub>3</sub> for the evaluation of polar stratospheric processes, an ozone sonde climatology, surface ozone observations from the Tropospheric Ozone Assessment Report (TOAR) database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, hydroxide (OH), nitrogen oxides (NO<sub>x</sub>), aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NO<sub>x</sub> emissions are very low, and the impact of the heterogeneous reaction of HNO<sub>3</sub> on dust and seasalt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

Description and evaluation of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMB-MONARCH) version 1.0: gas-phase chemistry at global scale

Abstract. This paper presents a comprehensive description and benchmark evaluation of the tropospheric gas-phase chemistry component of the Multiscale Online Nonhydrostatic AtmospheRe CHemistry model (NMMB-MONARCH), formerly known as NMMB/BSC-CTM, that can be run on both regional and global domains. Here, we provide an extensive evaluation of a global annual cycle simulation using a variety of background surface stations (EMEP, WDCGG and CASTNET), ozonesondes (WOUDC, CMD and SHADOZ), aircraft data (MOZAIC and several campaigns), and satellite observations (SCIAMACHY and MOPITT). We also include an extensive discussion of our results in comparison to other state-of-the-art models. We note that in this study, we omitted aerosol processes and some natural emissions (lightning and volcano emissions). The model shows a realistic oxidative capacity across the globe. The seasonal cycle for CO is fairly well represented at different locations (correlations around 0.3–0.7 in surface concentrations), although concentrations are underestimated in spring and winter in the Northern Hemisphere, and are overestimated throughout the year at 800 and 500 hPa in the Southern Hemisphere. Nitrogen species are well represented in almost all locations, particularly NO2 in Europe (root mean square error – RMSE – below 5 ppb). The modeled vertical distributions of NOx and HNO3 are in excellent agreement with the observed values and the spatial and seasonal trends of tropospheric NO2 columns correspond well to observations from SCIAMACHY, capturing the highly polluted areas and the biomass burning cycle throughout the year. Over Asia, the model underestimates NOx from March to August, probably due to an underestimation of NOx emissions in the region. Overall, the comparison of the modeled CO and NO2 with MOPITT and SCIAMACHY observations emphasizes the need for more accurate emission rates from anthropogenic and biomass burning sources (i.e., specification of temporal variability). The resulting ozone (O3) burden (348 Tg) lies within the range of other state-of-the-art global atmospheric chemistry models. The model generally captures the spatial and seasonal trends of background surface O3 and its vertical distribution. However, the model tends to overestimate O3 throughout the troposphere in several stations. This may be attributed to an overestimation of CO concentration over the Southern Hemisphere leading to an excessive production of O3 or to the lack of specific chemistry (e.g., halogen chemistry, aerosol chemistry). Overall, O3 correlations range between 0.6 and 0.8 for daily mean values. The overall performance of the NMMB-MONARCH is comparable to that of other state-of-the-art global chemistry models.

The 1-way on-line coupled model system MECO(n) – Part 4: Chemical evaluation (based on MESSy v2.52)

Abstract. For the first time, a simulation incorporating tropospheric and stratospheric chemistry using the newly developed MECO(n) model system is performed. MECO(n) is short for MESSy-fied ECHAM and COSMO models nested n times. It features an online coupling of the COSMO-CLM model, equipped with the Modular Earth Submodel System (MESSy) interface (called COSMO/MESSy), with the global atmospheric chemistry model ECHAM5/MESSy for Atmospheric Chemistry (EMAC). This online coupling allows a consistent model chain with respect to chemical and meteorological boundary conditions from the global scale down to the regional kilometre scale. A MECO(2) simulation incorporating one regional instance over Europe with 50 km resolution and one instance over Germany with 12 km resolution is conducted for the evaluation of MECO(n) with respect to tropospheric gas-phase chemistry. The main goal of this evaluation is to ensure that the chemistry-related MESSy submodels and the online coupling with respect to the chemistry are correctly implemented. This evaluation is a prerequisite for the further usage of MECO(n) in atmospheric chemistry-related studies. Results of EMAC and the two COSMO/MESSy instances are compared with satellite, ground-based and aircraft in situ observations, focusing on ozone, carbon monoxide and nitrogen dioxide. Further, the methane lifetimes in EMAC and the two COSMO/MESSy instances are analysed in view of the tropospheric oxidation capacity. From this evaluation, we conclude that the chemistry-related submodels and the online coupling with respect to the chemistry are correctly implemented. In comparison with observations, both EMAC and COSMO/MESSy show strengths and weaknesses. Especially in comparison to aircraft in situ observations, COSMO/MESSy shows very promising results. However, the amplitude of the diurnal cycle of ground-level ozone measurements is underestimated. Most of the differences between COSMO/MESSy and EMAC can be attributed to differences in the dynamics of both models, which are subject to further model developments.

Influence of the choice of gas-phase mechanism on predictions of key gaseous pollutants during the AQMEII phase-2 intercomparison

The formulations of tropospheric gas-phase chemistry (“mechanisms”) used in the regional-scale chemistry-transport models participating in the Air Quality Modelling Evaluation International Initiative (AQMEII) Phase 2 are intercompared by the means of box model studies. Simulations were conducted under idealized meteorological conditions, and the results are representative of mean boundary layer concentrations. Three sets of meteorological conditions – winter, spring/autumn and summer – were used to capture the annual variability, similar to the 3-D model simulations in AQMEII Phase 2. We also employed the same emissions input data used in the 3-D model intercomparison, and sample from these datasets employing different strategies to evaluate mechanism performance under a realistic range of pollution conditions.Box model simulations using the different mechanisms are conducted with tight constraints on all relevant processes and boundary conditions (photolysis, temperature, entrainment, etc.) to ensure that differences in predicted concentrations of pollutants can be attributed to differences in the formulation of gas-phase chemistry. The results are then compared with each other (but not to measurements), leading to an understanding of mechanism-specific biases compared to the multi-model mean. Our results allow us to quantify the uncertainty in predictions of a given compound in the 3-D simulations introduced by the choice of gas-phase mechanisms, to determine mechanism-specific biases under certain pollution conditions, and to identify (or rule out) the gas-phase mechanism as the cause of an observed discrepancy in 3-D model predictions.We find that the predictions of the median diurnal cycle of O3 over a set of emission conditions representing a network of station observations is within 4 ppbv (5%) across the different mechanisms. This variability is found to be very similar on both continents. There are considerably larger differences in predicted concentrations of NOx (up to ± 25%), key radicals like OH (40%), HO2 (25%) and especially NO3 (>100%). Secondary substances like H2O2 (25%) or HNO3 (10%), as well as key volatile organic compounds like isoprene (>100%) or CH2O (20%) differ substantially as well. Calculation of an indicator of the chemical regime leads to up to 20% of simulations being classified differently by different mechanism, which would lead to different predictions of the most efficient emission reduction strategies.All these differences are despite identical meteorological boundary conditions, photolysis rates, as well as identical biogenic and inorganic anthropogenic emissions. Anthropogenic VOC emissions only vary in the way they are translated in mechanism-specific compounds, but are identical in the total emitted carbon mass and its spatial distribution.Our findings highlight that the choice of gas-phase mechanism is crucial in simulations for regulatory purposes, emission scenarios, as well as process studies that investigate other components like secondary formed aerosol components. We find that biogenic VOCs create considerable variability in mechanism predictions and suggest that these, together with nighttime chemistry should be areas of further mechanism improvement.

Gas-phase tropospheric chemistry of 2,3,7,8-tetrafuorinated dibenzo-p-dioxin

Growing attention has been devoted to understanding the formation and destruction of polyfluorinated dibenzo-p-dioxins (PFDDs). High-accuracy molecular orbital calculations have been performed to investigate the tropospheric oxidation reaction of 2,3,7,8-tetrafuorinated dibenzo-p-dioxin (TFDD) initiated by OH radical, NO3 radical and O3. The rate constant of TFDD reaction triggered by the OH radical, NO3 radical and O3 is about 2.30×10−11cm3molecule−ls−l, 3.18×10−13cm3molecule−ls−l, and 3.30×10−19cm3molecule−ls−l, respectively. OH radical is the major gas phase tropospheric sink for TFDD. Once TFDD-OH intermediates are produced in the initial reactions, they can react with tropospheric O2 subsequently to generate peroxy radical isomers. The TFDD-OH-O2 can further react with tropospheric NO via isomerization or combination, resulting that the dioxin ring will be ruptured completely. This study can serve as a template for tropospheric degradation of the gaseous PFDDs, which is beneficial for assessing their tropospheric behaviors.

A compilation of tropospheric measurements of gas-phase and aerosol chemistry in polar regions

Abstract. Measurements of atmospheric chemistry in polar regions have been made for more than half a century. Probably the first Antarctic ozone data were recorded in 1958 during the International Geophysical Year. Since then, many measurement campaigns followed, and the results are now spread over many publications in several journals. Here, we have compiled measurements of tropospheric gas-phase and aerosol chemistry made in the Arctic and the Antarctic. It is hoped that this data collection is worth more than the sum of its components and serves as a basis for future analyses of spatial and temporal trends in polar atmospheric chemistry.

Implementation and evaluation of online gas-phase chemistry within a regional climate model (RegCM-CHEM4)

Abstract. The RegCM-CHEM4 is a new online climate-chemistry model based on the International Centre for Theoretical Physics (ICTP) regional climate model (RegCM4). Tropospheric gas-phase chemistry is integrated into the climate model using the condensed version of the Carbon Bond Mechanism (CBM-Z; Zaveri and Peters, 1999) with a fast solver based on radical balances. We evaluate the model over continental Europe for two different time scales: (1) an event-based analysis of the ozone episode associated with the heat wave of August 2003 and (2) a climatological analysis of a six-year simulation (2000–2005). For the episode analysis, model simulations show good agreement with European Monitoring and Evaluation Programme (EMEP) observations of hourly ozone over different regions in Europe and capture ozone concentrations during and after the summer 2003 heat wave event. For long-term climate simulations, the model captures the seasonal cycle of ozone concentrations with some over prediction of ozone concentrations in non-heat wave summers. Overall, the ozone and ozone precursor evaluation shows the feasibility of using RegCM-CHEM4 for decadal-length simulations of chemistry-climate interactions.

Development and evaluation of an Earth-System model – HadGEM2

Abstract. We describe here the development and evaluation of an Earth system model suitable for centennial-scale climate prediction. The principal new components added to the physical climate model are the terrestrial and ocean ecosystems and gas-phase tropospheric chemistry, along with their coupled interactions. The individual Earth system components are described briefly and the relevant interactions between the components are explained. Because the multiple interactions could lead to unstable feedbacks, we go through a careful process of model spin up to ensure that all components are stable and the interactions balanced. This spun-up configuration is evaluated against observed data for the Earth system components and is generally found to perform very satisfactorily. The reason for the evaluation phase is that the model is to be used for the core climate simulations carried out by the Met Office Hadley Centre for the Coupled Model Intercomparison Project (CMIP5), so it is essential that addition of the extra complexity does not detract substantially from its climate performance. Localised changes in some specific meteorological variables can be identified, but the impacts on the overall simulation of present day climate are slight. This model is proving valuable both for climate predictions, and for investigating the strengths of biogeochemical feedbacks.

Simulation of the diurnal variations of the oxygen isotope anomaly (Δ<sup>17</sup>O) of reactive atmospheric species

Abstract. The isotope anomaly (Δ17O) of secondary atmospheric species such as nitrate (NO3−) or hydrogen peroxide (H2O2) has potential to provide useful constrains on their formation pathways. Indeed, the Δ17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero Δ17O in the atmosphere. Interpreting variations of Δ17O in secondary species requires an in-depth understanding of the Δ17O of their precursors taking into account non-linear chemical regimes operating under various environmental settings. This article reviews and illustrates a series of basic concepts relevant to the propagation of the Δ17O of ozone to other reactive or secondary atmospheric species within a photochemical box model. We present results from numerical simulations carried out using the atmospheric chemistry box model CAABA/MECCA to explicitly compute the diurnal variations of the isotope anomaly of short-lived species such as NOx and HOx. Using a simplified but realistic tropospheric gas-phase chemistry mechanism, Δ17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the mass-balance equations, through the implementation of various sets of hypotheses pertaining to the transfer of Δ17O during chemical reactions. The model results confirm that diurnal variations in Δ17O of NOx predicted by the photochemical steady-state relationship during the day match those from the explicit treatment, but not at night. Indeed, the Δ17O of NOx is "frozen" at night as soon as the photolytical lifetime of NOx drops below ca. 10 min. We introduce and quantify the diurnally-integrated isotopic signature (DIIS) of sources of atmospheric nitrate and H2O2, which is of particular relevance to larger-scale simulations of Δ17O where high computational costs cannot be afforded.

Adsorption and Reaction of Trace Gas-Phase Organic Compounds on Atmospheric Water Film Surfaces: A Critical Review

The air-water interface in atmospheric water films of aerosols and hydrometeors (fog, mist, ice, rain, and snow) presents an important surface for the adsorption and reaction of many organic trace gases and gaseous reactive oxidants (hydroxyl radical (OH(.)), ozone (O(3)), singlet oxygen (O(2)((1)Delta(g))), nitrate radicals (NO(3)(.)), and peroxy radicals (RO(2)(.)). Knowledge of the air-water interface partition constant of hydrophobic organic species is necessary for elucidating the significance of the interface in atmospheric fate and transport. Various methods of assessing both experimental and theoretical values of the thermodynamic partition constant and adsorption isotherm are described in this review. Further, the reactivity of trace gases with gas-phase oxidants (ozone and singlet oxygen) at the interface is summarized. Oxidation products are likely to be more water-soluble and precursors for secondary organic aerosols in hydrometeors. Estimation of characteristic times shows that heterogeneous photooxidation in water films can compete effectively with homogeneous gas-phase reactions for molecules in the atmosphere. This provides further support to the existing thesis that reactions of organic compounds at the air-water interface should be considered in gas-phase tropospheric chemistry.

Impacts of aerosol-cloud interactions on past and future changes in tropospheric composition

Abstract. The development of effective emissions control policies that are beneficial to both climate and air quality requires a detailed understanding of all the feedbacks in the atmospheric composition and climate system. We perform sensitivity studies with a global atmospheric composition-climate model to assess the impact of aerosols on tropospheric chemistry through their modification on clouds, aerosol-cloud interactions (ACI). The model includes coupling between both tropospheric gas-phase and aerosol chemistry and aerosols and liquid-phase clouds. We investigate past impacts from preindustrial (PI) to present day (PD) and future impacts from PD to 2050 (for the moderate IPCC A1B scenario) that embrace a wide spectrum of precursor emission changes and consequential ACI. The aerosol indirect effect (AIE) is estimated to be −2.0 Wm−2 for PD-PI and −0.6 Wm−2 for 2050-PD, at the high end of current estimates. Inclusion of ACI substantially impacts changes in global mean methane lifetime across both time periods, enhancing the past and future increases by 10% and 30%, respectively. In regions where pollution emissions increase, inclusion of ACI leads to 20% enhancements in in-cloud sulfate production and ~10% enhancements in sulfate wet deposition that is displaced away from the immediate source regions. The enhanced in-cloud sulfate formation leads to larger increases in surface sulfate across polluted regions (~10–30%). Nitric acid wet deposition is dampened by 15–20% across the industrialized regions due to ACI allowing additional re-release of reactive nitrogen that contributes to 1–2 ppbv increases in surface ozone in outflow regions. Our model findings indicate that ACI must be considered in studies of methane trends and projections of future changes to particulate matter air quality.

Comparison of tropospheric gas-phase chemistry schemes for use within global models

Abstract. Methane and ozone are two important climate gases with significant tropospheric chemistry. Within chemistry-climate and transport models this chemistry is simplified for computational expediency. We compare the state of the art Master Chemical Mechanism (MCM) with six tropospheric chemistry schemes (CRI-reduced, GEOS-CHEM and a GEOS-CHEM adduct, MOZART-2, TOMCAT and CBM-IV) that could be used within composition transport models. We test the schemes within a box model framework under conditions derived from a composition transport model and from field observations from a regional scale pollution event. We find that CRI-reduced provides much skill in simulating the full chemistry, yet with greatly reduced complexity. We find significant variations between the other chemical schemes, and reach the following conclusions. 1) The inclusion of a gas phase N2O5+H2O reaction in one scheme and not others is a large source of uncertainty in the inorganic chemistry. 2) There are significant variations in the calculated concentration of PAN between the schemes, which will affect the long range transport of reactive nitrogen in global models. 3) The representation of isoprene chemistry differs hugely between the schemes, leading to significant uncertainties on the impact of isoprene on composition. 4) Differences are found in NO3 concentrations in the nighttime chemistry. Resolving these four issues through further investigative laboratory studies will reduce the uncertainties within the chemical schemes of global tropospheric models.

The response of surface ozone to climate change over the Eastern United States

Abstract. We investigate the response of surface ozone (O3) to future climate change in the eastern United States by performing simulations corresponding to present (1990s) and future (2050s) climates using an integrated model of global climate, tropospheric gas-phase chemistry, and aerosols. A future climate has been imposed using ocean boundary conditions corresponding to the IPCC SRES A2 scenario for the 2050s decade. Present-day anthropogenic emissions and CO2/CH4 mixing ratios have been used in both simulations while climate-sensitive emissions were allowed to vary with the simulated climate. The severity and frequency of O3 episodes in the eastern U.S. increased due to future climate change, primarily as a result of increased O3 chemical production. The 95th percentile O3 mixing ratio increased by 5 ppbv and the largest frequency increase occured in the 80–90 ppbv range; the US EPA's current 8-h ozone primary standard is 80 ppbv. The increased O3 chemical production is due to increases in: 1) natural isoprene emissions; 2) hydroperoxy radical concentrations resulting from increased water vapor concentrations; and, 3) NOx concentrations resulting from reduced PAN. The most substantial and statistically significant (p<0.05) increases in episode frequency occurred over the southeast and midatlantic U.S., largely as a result of 20% higher annual-average natural isoprene emissions. These results suggest a lengthening of the O3 season over the eastern U.S. in a future climate to include late spring and early fall months. Increased chemical production and shorter average lifetime are two consistent features of the seasonal response of surface O3, with increased dry deposition loss rates contributing most to the reduced lifetime in all seasons except summer. Significant interannual variability is observed in the frequency of O3 episodes and we find that it is necessary to utilize 5 years or more of simulation data in order to separate the effects of interannual variability and climate change on O3 episodes in the eastern United States.

Sensitivity of global tropospheric ozone and fine particulate matter concentrations to climate change

An integrated global model of climate, tropospheric gas phase chemistry, and aerosols has been used to investigate the sensitivity of global ozone and fine particulate matter concentrations to climate change. Two simulations corresponding to present (1990s) and future (2050s) climates have been performed and compared. A future climate has been imposed using ocean boundary conditions corresponding to the Intergovernmental Panel on Climate Change SRES A2 scenario for the 2050s decade, resulting in an increase in the global annual average values of the surface air temperature by 1.7°C, the lower tropospheric specific humidity by 0.9 g H2O/kg air, and the precipitation by 0.15 mm d−1. Present‐day anthropogenic emissions have been used in both simulations while climate‐sensitive natural emissions were allowed to vary with the simulated climate. The tropospheric ozone burden in the future climate run decreased by 5%, and its lifetime decreased from 27.8 to 25.3 days. The tropospheric ozone change is driven primarily by increased ozone loss rates through ozone photolysis in the presence of water vapor, which on a global scale, more than compensate for the increased ozone chemical production associated with increased temperatures. At the model surface layer, over remote regions, ozone mixing ratios decreased by 1–3 ppbv, while polluted regions showed a relatively smaller decrease of 0–1 ppbv and increased by 1–5 ppbv in some cases. The global burdens and lifetimes of fine particulate matter species in the future climate run decreased by 2 to 18% because of increased wet deposition loss rates associated with increased precipitation. At the model surface layer, there are regions of decreases and increases in the concentrations of fine particulate matter species. The increased surface layer concentrations of some fine particulate matter species is primarily driven by lower regional‐scale precipitation and increased secondary production, where applicable. The robustness of the predicted regional‐scale changes for fine particulate matter species is strongly dependent upon the predicted regional‐scale precipitation changes.

A Review of Instrumentation and Measurement Techniques for Ground-Based and Airborne Field Studies of Gas-Phase Tropospheric Chemistry

ABSTRACT The development, applications and intercomparisons of instrumentation and measurement techniques for ground-based and airborne field studies of gas-phase tropospheric chemistry are reviewed. Filter radiometry, chemical actinometry and scanning spectroradiometry for j-NO2 and j-(O1D) are described. Detection of OH using L-POAS/DOAS, MOAS, LIF/FAGE and CIMS is discussed. Observations of NO3 using DOAS, MIESR and CRDS, and of HO2 and RO2 with CA, CIMS/IMR-MS, MIESR, and LIF/FAGE are also reviewed. GC-FID, GC-ECD and GC-MS analyses of NMHCs and alkyl, peroxyacyl and bi-functional organic nitrates are described, together with applications of CIMS/PTR-MS, DOAS and LIF. CO measurements utilising GFC, GC-HgO/UV, VUV-RF and TDLAS are presented. Measurements of O3 using UV photometry, chemiluminescence, electrochemistry, LIDAR/DIAL and DOAS are discussed. Chemiluminescence and LIF detection methods for NO with photochemical and thermal convertors for NO2 and NOy are also discussed, as are TDLAS, MIESR, DOAS, CRDS and other approaches for NO2. HONO measurements using DOAS, CIMS, CRDS, TDLAS, denuder systems, chemiluminescence and on-line analyses of NO2 − are described. For HONO2, filter packs, denuder systems, chemiluminescence methods, mist chambers, TDLAS, CIMS and LIF are presented. Direct and indirect fluorimetric, chromatographic and spectroscopic detection techniques are discussed for CH2O and higher carbonyls. Observations of H2O2 and ROOH utilising colorimetry, chemiluminescence, fluorescence, HPLC and TDLAS are also described.

Gas-phase tropospheric chemistry of biogenic volatile organic compounds: a review

Large quantities of non-methane organic compounds are emitted into the atmosphere from biogenic sources, mainly from vegetation. These organic compounds include isoprene, C 10 H 16 monoterpenes, C 15 H 24 sesquiterpenes, and a number of oxygenated compounds including methanol, hexene derivatives, 2-methyl-3-buten-2-ol, and 6-methyl-5-hepten-2-one. In the troposphere these organic compounds react with hydroxyl (OH) radicals, nitrate (NO 3 ) radicals and ozone (O 3 ), and play an important role in the chemistry of the lower troposphere. In this article the kinetics, products and mechanisms of the tropospheric reactions of biogenic organic compounds are presented and briefly discussed.

Application of a multi-laser tunable diode laser absorption spectrometer for atmospheric trace gas measurements at sub-ppbv levels

We describe the application of a three-laser tunable diode laser absorption spectrometer (TDLAS), called ‘tracer in-situ TDLAS for atmospheric research’ (TRISTAR), to measure nitrogen dioxide (NO 2), formaldehyde (HCHO) and hydrogen peroxide (H 2O 2), during an intensive measurement campaign on Mt. Cimone (44°11′N, 10°42′E, 2165 m asl), Northern Appenines, Italy in June 2000 as part of the EU-project ‘mineral dust and tropospheric chemistry’ (MINATROC). The TRISTAR instrument was a major component of an instrument package, provided by the Max-Planck-Insitut für Chemie, to investigate free tropospheric gas-phase chemistry over the Appenines. Here we discuss the optical, electronic, gas flow, and calibration setup of the TDLAS used during the campaign. We characterized extensively the instrument's performance during a preparatory phase in the laboratory and compared the laboratory results to the in-field results. Consistency checks with additional trace gas measurements obtained during the campaign create high confidence in the measured concentrations. Correlations between different trace gas species, along with other evaluation tools, allow a full chemical characterization of air masses to meet the goals of the campaign.

Evaluation of a Lagrangian box model using field measurements from EASE (Eastern Atlantic Summer Experiment) 1996

The Cambridge Tropospheric Trajectory model of Chemistry and Transport (CiTTyCAT), a Lagrangian chemistry model, has been evaluated using atmospheric chemical measurements collected during the East Atlantic Summer Experiment 1996 (EASE '96). This field campaign was part of the UK Natural Environment Research Council's (NERC) Atmospheric Chemistry Studies in the Oceanic Environment (ACSOE) programme, conducted at Mace Head, Republic of Ireland, during July and August 1996. The model includes a description of gas-phase tropospheric chemistry, and simple parameterisations for surface deposition, mixing from the free troposphere and emissions. The model generally compares well with the measurements and is used to study the production and loss of O 3 under a variety of conditions. The mean difference between the hourly O 3 concentrations calculated by the model and those measured is 0.6 ppbv with a standard deviation of 8.7 ppbv. Three specific air-flow regimes were identified during the campaign – westerly, anticyclonic (easterly) and south westerly. The westerly flow is typical of background conditions for Mace Head. However, on some occasions there was evidence of long-range transport of pollutants from North America. In periods of anticyclonic flow, air parcels had collected emissions of NO x and VOCs immediately before arriving at Mace Head, leading to O 3 production. The level of calculated O 3 depends critically on the precise details of the trajectory, and hence on the emissions into the air parcel. In several periods of south westerly flow, low concentrations of O 3 were measured which were consistent with deposition and photochemical destruction inside the tropical marine boundary layer.