Hydrogen Peroxide, Organic Peroxides and Higher Carbonyl Compounds Determined during the BERLIOZ Campaign

Gas-phase H₂O₂, organic peroxides and carbonyl compoundswere determined at various sites from Mid-July to early August 1998 during the BERLIOZ campaign in Germany. The sites were located northwest of Berlin and were chosen to determine pollutants downwind of the city emissions during a summer smog episode. Hydrogen peroxide (H₂O₂),methyl hydroperoxide (MHP, CH₃OOH) and occasionally hydroxymethyl hydroperoxide (HMHP, HOCH₂OOH) were quantified in air samples by commercial fluorimetric methods and classical HPLC with post-column derivatisation by horseradish peroxidase/p-hydroxyphenyl acetic acid and fluorimetric detection. Carbonyl compounds were determined in ambient air by a novel method based onO-pentafluorobenzyl hydroxylamine as derivatisation agent.Mixing ratio profiles of the hydroperoxides and the carbonyl compounds are reported for the intensive phase of the campaign, 20–21 July, 1998. Peroxides showed pronounced diurnal variations with peak mixing ratios in the early afternoon. At times, a second maximum was observed in the late afternoon. The major part of the H₂O₂ was formed throughrecombination reactions of HO₂ radicals, but there is some evidencethat H₂O₂ is also formed from ozonolysis ofanthropogenic and/or biogenic alkenes. Diurnal variations of mixing ratios of various carbonyl compounds are reported: alkanals (C₂ to C₁₀,isobutanal), unsaturated carbonyl compounds (methacrolein, methylvinylketone, acrolein), hydroxycarbonyl (glycolaldehyde, hydroxyacetone) and dicarbonyl compounds (glyoxal, methylglyoxal, biacetyl), aromatic compounds (benzaldehyde, o- and m-tolylaldehyde) and pinonaldehyde.     

Products and Mechanism of the NO<Subscript>3</Subscript> Reaction with Thiophene

Products of the gas-phase reaction of the NO₃ radical with thiophene have been investigated using different experimental systems. On the one hand, experiments have been conducted in our laboratory using two different methods, a Teflon static reactor coupled to a gas chromatograph combined with mass-spectrometry (GC-MS) and a discharge flow tube with direct MS spectroscopic detection. A qualitative analysis in these cases indicates that possible products for the reaction of thiophene+NO₃ at room temperature include: sulphur dioxide, acetic and formic acids, a short-chain aldehyde, 2-nitrothiophene and 3-nitrothiophene. On the other hand, quantitative experiments have been performed in the European Photoreactor (EUPHORE) in Valencia, Spain. In this case, the major products were: HNO₃ (≈80%), nitrothiophenes (≈30%), SO₂ (≈20%), propanal (3%) and a fraction of particles (≈10%). The results obtained indicate that at least 70% of the reaction of NO₃ with thiophene proceeds by an H-abstraction process at room temperature. The mechanism of the reaction studied is proposed on the basis of experimental results.     

Influence of Atmospheric Carboxylic Acids on Catalytic Oxidation of Sulfur(IV)

The influence of some low weight mono- and di-carboxylic acids, which were selected on the basis of analysis of the water-soluble fraction of size segregated marine and urban aerosols collected in Slovenia, on the kinetics of S(IV) oxidation catalyzed by Mn(II) under conditions representative of tropospheric liquid water, was investigated. Mono-carboxylic acids inhibit the oxidation, with the strongest influence found for formic acid. Inhibition by glycolic and lactic acid was found to be very similar, while the lowest inhibition was caused by acetic acid. Our results are in agreement with the proposed mechanism, i.e. scavenging of sulfate radicals, since the inhibiting effect of the individual acid increases with higher dissociation constant. An exception is formic acid, where the additional inhibiting steps should be responsible for the induction period and thus for higher inhibition. Malic and malonic acids have practically no influence, while oxalic acid slows down the oxidation, although to a lesser extent than mono-carboxylic acids. An extended version of a previously derived generalized simple kinetic model was also derived and applied for predicting the reaction kinetics in the presence of all examined carboxylic acids at pH 3.5 and 4.5.     

NO<Subscript>3</Subscript> Vertical Profile Measurements from Remote Sensing Balloon-Borne Spectrometers and Comparison with Model Calculations

Eleven vertical profiles of stratospheric NO₃ have been obtained since 1992 using the AMON and SALOMON balloon-borne UV-visible spectrometers. The measurements are compared to the SLIMCAT 3D model and calculations based on the steady-state hypothesis for NO₃. The calculations cannot reproduce some parts of the profiles which exhibit strong concentration fluctuations over few kilometres, as a consequence of the dependence of NO₃ on local temperature variations. A statistical use of the data allows us to estimate the influence of the temperature dependence of the absorption cross-section on the data analysis, and the validity of the recommended reaction rates available in the literature. Discrepancies exist between the model based on recommended kinetics and observations at warmer temperatures. Nevertheless, the analysis is biased by local temperature inhomogeneities, and only a low-resolution vertical shape of the NO₃ profiles can be retrieved.     

Chemical characterization and multivariate analysis of atmospheric PM<Subscript>2.5</Subscript> particles

The new European Council Directive (PE-CONS 3696/07) frames the inhalable (PM₁₀) and fine particles (PM_2.5) on priority to chemically characterize these fractions in order to understand their possible relation with health effects. Considering this, PM_2.5 was collected during four different seasons to evaluate the relative abundance of bulk elements (Cl, S, Si, Al, Br, Cu, Fe, Ti, Ca, K, Pb, Zn, Ni, Mn, Cr and V) and water soluble ions (F⁻, Cl⁻, NO₂ ⁻, NO₃ ⁻, SO₄ ²⁻, Na⁺, NH₄ ⁺, Ca²⁺ and Mg²⁺) over Menen, a Belgian city near the French border. The air quality over Menen is influenced by industrialized regions on both sides of the border. The most abundant ionic species were NO₃ ⁻, SO₄ ²⁻ and NH₄ ⁺, and they showed distinct seasonal variation. The elevated levels of NO₃ ⁻ during spring and summer were found to be related to the larger availability of the NO_x precursor. The various elemental species analyzed were distinguished into crustal and anthropogenic source categories. The dominating elements were S and Cl in the PM_2.5 particles. The anthropogenic fraction (e.g. Zn, Pb, and Cu) shows a more scattered abundance. Furthermore, the ions and elemental data were also processed using principal component analysis and cluster analysis to identify their sources and chemistry. These approach identifies anthropogenic (traffic and industrial) emissions as a major source for fine particles. The variations in the natural/anthropogenic fractions of PM_2.5 were also found to be a function of meteorological conditions as well as of long-range transport of air masses from the industrialized regions of the continent. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Solubilities of pyruvic acid and the lower (C1-C6) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions

Henry's law constantsK _H (mol kg^–1 atm^–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×10³); acetic acid (5.50±0.29×10³); propionic acid (5.71±0.34×10³);n-butyric acid (4.73±0.18×10³); isobutyric acid (1.13±0.12×10³); isovaleric acid (1.20±0.11×10³) and neovaleric acid (0.353±0.04×10³). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K _H)=–14.3371+6582.96/T);n-caproic acid (ln(K _H)=–13.9424+6303.73/T) and pyruvic acid (ln(K _H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m^–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.     

Estimates of anthropogenic CO<Subscript>2</Subscript> uptake in a global ocean model

A global ocean general circulation model (L30T63) is employed to study the uptake and distribution of anthropogenic CO₂ in the ocean. A subgrid-scale mixing scheme called GM90 is used in the model. There are two main GM90 parameters including isopycnal diffusivity and skew (thickness) diffusivity. Sensitivities of the ocean circulation and the redistribution of dissolved anthropogenic CO₂ to these two parameters are examined. Two runs estimate the global oceanic anthropogenic CO₂ uptake to be 1.64 and 1.73 Pg C yr^-1 for the 1990s, and that the global ocean contained 86.8 and 92.7 Pg C of anthropogenic CO₂ at the end of 1994, respectively. Both the total inventory and uptake from our model are smaller than the data-based estimates. In this presentation, the vertical distributions of anthropogenic CO₂ at three meridional sections are discussed and compared with the available data-based estimates. The inventory in the individual basins is also calculated. Use of large isopycnal diffusivity can generally improve the simulated results, including the exchange flux, the vertical distribution patterns, inventory, storage, etc. In terms of comparison of the vertical distributions and column inventory, we find that the total inventory in the Pacific Ocean obtained from our model is in good agreement with the data-based estimate, but a large difference exists in the Atlantic Ocean, particularly in the South Atlantic. The main reasons are weak vertical mixing and that our model generates small exchange fluxes of anthropogenic CO₂ in the Southern Ocean. Improvement in the simulation of the vertical transport and sea ice in the Southern Ocean is important in future work.     

Aqueous Phase Reaction of HNO4: The Impact on Tropospheric Chemistry

We use a global atmospheric chemistry transport model to study the possible influence of aqueous phase reactions of peroxynitric acid (HNO₄) on the concentrations and budgets of NO_x, SO_x, O₃ and H₂O₂. Laboratory studies have shown that the aqueous reaction of HNO_4aq withHSO^– _3aq, and the uni-molecular decomposition of the NO₄ ^– anion to form NO₂ ^– (nitrite) occur on a time scale of about a second. Despite a substantial contribution of the reaction of HSO^– _3aq with HNO_4aq to the overall in-cloud conversion of SO₂ to SO₄ ^2–, a simultaneous decrease of other oxidants (most notably H₂O₂) more than compensated the increase in SO₄ ^2– production. The strongest influence of heterogeneous HNO₄ chemistry was found in the boundary layer, where calculated monthly average ozone concentrations were reduced between 2% to 10% andchanges of H₂O₂ between –20% to +10%compared to a simulation which ignores this reaction. Furthermore, SO₂ was increased by 10% to 20% and SO₄ ^2–depleted by up to 10%. Since the resolution of our global model does not enable a detailed comparison with measurements in polluted regions, it is not possible to verify whether considering heterogeneous HNO₄ reactions results in a substantial improvement of atmospheric chemistry transport models. However, the conversion of HNO₄ in the aqueous phase seems to be efficient enough to warrant further laboratory investigations and more detailed model studies on this topic.     

Urban Atmospheric Chemistry During the PUMA Campaign 2: Radical Budgets for OH,HO<Subscript>2</Subscript> and RO<Subscript>2</Subscript>

A detailed photochemical box model was used to investigate the key reaction pathways between OH, HO₂ and RO₂ radicals during the summer and winter PUMA field campaigns in the urban city-centre of Birmingham in the UK. The model employed the most recent version of the Master Chemical Mechanism and was constrained to 15-minute average measurements of long-lived species determined in situ at the site. The results showed that in the summer, OH initiation was dominated by the reactions of ozone with alkenes, nitrous acid (HONO) photolysis and the reaction of excited oxygen atoms atoms with water. In the winter, ozone+alkene reactions were the primary initiation route, with a minor contribution from HONO photolysis. Photolysis of aldehydes was the main initiation route for HO₂, in both summer and winter. RO₂ initiation was dominated by the photolysis of aldehydes in the summer with a smaller contribution from ozone+alkenes, a situation that was reversed in the winter. At night, ozone+alkene reactions were the main radical source. Termination, under all conditions, primarily involved reactions with NO (OH) and NO₂ (OH and RCO₃). These results demonstrate the importance of ozone+alkene reactions in urban atmospheres, particularly when photolysis reactions were less important during winter and at nighttime. The implications for urban atmospheric chemistry are discussed.     

Satellite Measurements of Tropospheric Column O<Subscript>3</Subscript> and NO<Subscript>2</Subscript> in Eastern and Southeastern Asia: Comparison with a Global Model (MOZART-2)

Satellite measurements of tropospheric column O₃ and NO₂ in eastern and southeastern Asia are analyzed to study the spatial and seasonal characteristics of pollution in these regions. Tropospheric column O₃ is derived from differential measurements of total column ozone from Total Ozone Mapping Spectrometer (TOMS), and stratospheric column ozone from the Microwave Limb Sounder (MLS) instrument on the Upper Atmosphere Research Satellite (UARS). The tropospheric column NO₂ is measured by Global Ozone Monitoring Experiment (GOME). A global chemical and transport model (Model of Ozone and Related Chemical Tracers, version 2; MOZART-2) is applied to analyze and interpret the satellite measurements. The study, which is based on spring, summer, and fall months of 1997 shows generally good agreement between the model and satellite data with respect to seasonal and spatial characteristics of O₃ and NO₂ fields. The analysis of the model results show that the industrial emission of NO_x (NO + NO₂) contributes about 50%–80% to tropospheric column NO₂ in eastern Asia and about 20%–50% in southeastern Asia. The contribution of industrial emission of NO_x to tropospheric column O₃ ranges from 10% to 30% in eastern Asia. Biomass burning and lightning NO_x emissions have a small effect on tropospheric O₃ in central and eastern Asia, but they have a significant impact in southeastern Asia. The varying effects of NO_x on tropospheric column ozone are attributed to differences in relative abundance of volatile organic compounds (VOCs) with respect to total nitrogen in the two regions.     

Reconstructed light extinction coefficients using chemical compositions of PM<Subscript>2.5</Subscript> in winter in Urban Guangzhou,China

The objective of this study was to reconstruct light extinction coefficients (b ext ) according to chemical composition components of particulate matter up to 2.5 μm in size (PM 2.5 ). PM 2.5 samples were collected at the monitoring station of the South China of Institute of Environmental Science (SCIES, Guangzhou, China) during January 2010, and the online absorbing and scattering coefficients were obtained using an aethalometer and a nephelometer. The measured values of light absorption coefficient by particle (b ap ) and light scattering coefficient by particle (b sp ) significantly correlated (R 2 > 0.95) with values of b ap and b sp that were reconstructed using the Interagency Monitoring of Protected Visual Environments (IMPROVE) formula when RH was <70%. The measured b ext had a good correlation (R 2 > 0.83) with the calculated b ext under ambient RH conditions. The result of source apportionment of b ext showed that ammonium sulfate [(NH 4 ) 2 SO 4 ] was the largest contributor (35.0%) to b ext , followed by ammonium nitrate (NH 4 NO 3 , 22.9%), organic matter (16.1%), elemental carbon (11.8%), sea salt (4.7%), and nitrogen dioxide (NO 2 , 9.6%). To improve visibility in Guangzhou, the effective control of secondary particles like sulfates, nitrates, and ammonia should be given more attention in urban environmental management.     

Behaviour of H2O2, NH3, and black carbon in mixed-phase clouds during CIME

We investigated the partitioning of trace substances during the phase transition from supercooled to mixed-phase cloud induced by artificial seeding. Simultaneous determination of the concentrations of H₂O₂, NH₃ and black carbon (BC) in both condensed and interstitial phases with high time resolution showed that the three species undergo different behaviour in the presence of a mixture of ice crystals and supercooled droplets. Both H₂O₂ and NH₃ are efficiently scavenged by growing ice crystals, whereas BC stayed predominantly in the interstitial phase. In addition, the scavenging of H₂O₂ is driven by co-condensation with water vapour onto ice crystals while NH₃ uptake into the ice phase is more efficient than co-condensation alone. The high solubility of NH₄⁺ in the ice could explain this result. Finally, it appears that the H₂O₂–SO₂ reaction is very slow in the ice phase with respect to the liquid phase. Our results are directly applicable for clouds undergoing limited riming.     

The Heterogeneous Reaction of NO<Subscript>2</Subscript> with NH<Subscript>4</Subscript>Cl: A Molecular Diffusion Tube Study

The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τ_surf) of NO₂ on NH₄Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τ_surf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO₂ on NH₄Cl followed a rate law first order in [NO₂] and the uptake coefficient γ is equal to 7 × 10⁻⁵ at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10⁻⁴) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO₂ with NH₄Cl is a reverse disproportionation reaction where two moles of NO₂ result in ammonium nitrite, NH₄NO₂, as an intermediate, and nitryl chloride, NO₂Cl. NH₄NO₂ decomposes in two pathways, one to nitrous acid, HONO and NH₃, the other to nitrogen and water. The branching ratio for the production of HONO + NH₃ to that of N₂ + H₂O is approximately 20 at 298 K and increases with increasing temperature.     

Carboxylic Acids: Seasonal Variation and Relation to Chemical and Meteorological Parameters

Formic and acetic acid measured as daily averages in 1993–1994show equal and highly correlated concentrations up to 3 ppb in the summer(May–August). In the winter (October–March) the formicacid/acetic acid ratio was 0.6 and the formic acid concentrations wereusually below 1 ppb. In winter the carboxylic acids correlate withO_x, NO_y, SO₂ and particulatesulphur. The main sources are suggested to be ozonolysis of anthropogenicalkenes and reactions between peroxyacetyl radicals and RO₂radicals. In spring–summer the carboxylic acids correlate withO₃, O_x, HNO₃, PAN,NO_y, SO₂, particulate sulphur and temperature.In addition to the sources of the winter a contribution from ozonolysis ofbiogenic alkenes is likely. Quite similar formic acid/acetic acid ratios forall wind directions suggest that the source(s) are atmospheric oxidationprocesses distributed over large areas. The highest concentrations occurringfor winds from east to south and the correlation with e.g., particulatesulphur indicate chemical production in polluted air masses during longrange transport.     

Growth of monodisperse,submicron aerosol particles exposed to SO2, H2O2, and NH3

The growth of monodisperse particles (0.07 to 0.5 µm) exposed to SO₂ (0–860 ppb), H₂O₂ (0–150 ppb) and sometimes NH₃ (0–550 ppb) in purified air at 22 °C at relative humidities ranging from 25 to 75% were measured using the Tandem Differential Mobility Analyzer technique. The experiments were performed in a flow reactor with aqueous (NH₄)₂SO₄ and Na₂SO₄ droplets. For (NH₄)₂SO₄ droplets the fractional diameter growth was independent of size above 0.3 µm but decreased with decreasing size below that. When NH₃ was added the fractional growth increased with decreasing size. Measurements were compared with predictions of a model that accounts for solubility of the reactive gases, the liquid phase oxidation of SO₂ by H₂O₂, and ionic equilibria. Agreement between measured and predicted droplet growth is reasonable when the ionic strength effects are included. Theory and experiments suggest that NH₃ evaporation is responsible for the decrease in relative growth rates for small aqueous ammonium sulfate particles. The observed droplet growth rates are too slow to explain observed growth rates of secondary atmospheric sulfate particles.     

Practical applicability of high frequency correction theories to CO<Subscript>2</Subscript> flux measured by a closed-path system

The theoretical correction of CO₂ fluxes for high frequency attenuation in closed-path systems was re-summarized and its applicability examined using both measurements obtained at an Asiaflux forest site and empirical transfer functions used in previous studies. For our measurement system, the theoretical transfer function was applicable to high frequency correction, even when condensation occurred in the sampling line. Further, in respect to some measurement systems described in previous studies, it was found that the theoretical function was potentially applicable along with the empirical functions used. Meanwhile, in some systems significant errors could not be resolved by re-estimation of the theories. In these systems, because of undefined buffering effects, the actual response lag time decided by the maximum covariance method or by measurement of the system response time using tracer gas was significantly different from the lag time calculated from the tube dimensions and the measured flow rate. If the average flow rate calculated by the actual lag time was used to determine the theoretical function, the theoretical function became closer to, and sometimes agreed with, the empirical function. Any remaining deviation from each function might be associated with pressure fluctuations, but this problem was unable to be examined here. The results suggested that an empirical formulation for each site is considered applicable rather than a theoretical approach, although the theories are being developed to practical application.     

Products and mechanisms of the gas phase reactions of NO3 with CH3SCH3, CD3SCD3, CH3SH and CH3SSCH3

Products and mechanisms of the reaction between the nitrate radical (NO₃) and three of the most abundant reduced organic sulphur compounds in the atmosphere (CH₃SCH₃, CH₃SH and CH₃SSCH₃), have been studied in a 480 L reaction chamber using in situ FT-IR and ion chromatography as analytical techniques. In the three reactions, methanesulphonic acid was found to be the most abundant sulphur containing product. In addition the stable products SO₂, H₂SO₄, CH₂O, and CH₃ONO₂ were identified and quantified and thionitric acid-S-methyl ester (CH₃SNO₂) was observed in the i.r. spectrum from all of the three reactions. Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction Deuterated dimethylsulphide (CD₃SCD₃) showed an isotope effect on the reaction rate constant (k_H/k_D) of 3.8±0.6, indicating that hydrogen abstraction is the first step in the NO₃+CH₃SCH₃ reaction, probably after the formation of an inital adduct.Based on the products and intermediates identified, reaction mechanisms are proposed for the three reactions.     

Analysis of chemical characteristics of PM<Subscript>2.5</Subscript> in Beijing over a 1-year period

Beijing is one of the largest and most densely populated cities in China. PM_2.5 (fine particulates with aerodynamic diameters less than 2.5 μm) pollution has been a serious problem in Beijing in recent years. To study the temporal and spatial variations in the chemical components of PM_2.5 and to discuss the formation mechanisms of secondary particles, SO₂, NO₂, PM_2.5, and chemical components of PM_2.5 were measured at four sites in Beijing, Dingling (DL), Chegongzhuang (CG), Fangshan (FS), and Yufa (YF), over four seasons from 2012 to 2013. Fifteen chemical components, including organic carbon (OC), elemental carbon (EC), K⁺, NH₄ ⁺, NO₃ ^?, SO₄ ^2?, Cl^?, Al, Ca, Fe, Mg, Na, Pb, Si, and Zn, were selected for analysis. Overall, OC, SO₄ ^2?, NO₃ ^?, and NH₄ ⁺ were dominant among 15 components, the annual average concentrations of which were 22.62 ± 21.86, 19.39 ± 21.06, 18.89 ± 19.82, and 13.20 ± 12.80 μg·m^?3, respectively. Compared with previous studies, the concentrations of NH₄ ⁺ were significantly higher in this study. In winter, the average concentrations of OC and EC were, respectively, 3 and 2.5 times higher than in summer, a result of coal combustion during winter. The average OC/EC ratios over the four sites were 4.9, 7.0, 8.1, and 8.4 in spring, summer, autumn, and winter, respectively. The annual average [NO₃ ^?]/[SO₄ ^2?] ratios in DL, CG, FS, and YF were 1.01, 1.25, 1.08, and 1.12, respectively, which were significantly higher than previous studies in Beijing, indicating that the contribution ratio of mobile source increased in recent years in Beijing. Analysis of correlations between temperature and relative humidity and between SOR ([SO₄ ^2?]/([SO₄ ^2?] + [SO₂])) and NOR ([NO₃ ^?]/([NO₃ ^?] + [NO₂])) indicated that gas-phase oxidation reactions were the major formation mechanism of SO₄ ^2? in spring and summer in urban Beijing, whereas slow gas-phase oxidation reactions and heterogeneous reactions both occurred in autumn and winter. NO₃ ^? was mainly formed through year-round heterogeneous reactions in urban Beijing.     

Henry's law and the behavior of weak acids and bases in fog and cloud

Experimental data from two field experiments on ground based clouds were used to study the distribution of formic acid, acetic acid, ammonia and S(IV) species between liquid and gas phase. The ratio of the concentrations of these compounds between the phases during concurrent measurements was compared to ratios expected according to Henry's law (considering the pH influence). Large discrepancies of several orders of magnitude were seen. Three hypotheses have been investigated to explain the observed discrepancies: The existence of a microscale equilibrium which does not persist in a bulk sample, a thermodynamic shift of the equilibrium due to competing reactions, and nonequilibrium conditions due to mass transfer limitations. Approximate quantitative calculations show that none of these hypotheses is sufficient to explain all of the discrepancies, so a combination of different effects seems to be responsible for this observation. The same theoretical considerations also suggest that mass transfer limitation may be an important factor for highly soluble compounds. The data presented here indicates that it is not possible to simply extrapolate interstitial gas phase composition from measured bulk liquid phase concentrations of a fog or cloud.Notation [r _max] liquid phase molar uptake rate (mol l^–1 s^–1) - [A _g ] concentration ofA in gas phase (atm) - [A _l ] concentration ofA in liquid phase (mol l^–1) - [A _g , 0] concentration ofA in gas phase (atm) at time 0 - LWC liquid water content (g m^–3) - R universal gas constant (0.082 l atm mol^–1 K^–1 - D _g diffusivity (for all gases 0.1 cm² s^–1 was used) - K _H ^* effective Henry's law coefficient (mol l^–1 atm^–1) - t _f lifetime of fog droplet (s) - a droplet radius (cm) - accommodation coefficient - R factor of discrepancy - T temperature (K) - v mean molecular speed (cm s^–1) formic acid: 35 000 acetic acid: 31 000 ammonia: 58 000