Role of atmospheric ammonia in the formation of inorganic secondary particulate matter: A study at Kanpur,India

Levels of fine Particulate Matter (PM_fine), SO₂ and NO_x are interlinked through atmospheric reactions to a large extent. NO_x, NH₃, SO₂, temperature and humidity are the important atmospheric constituents/conditions governing formation of fine particulate sulfates and nitrates. To understand the formation of inorganic secondary particles (nitrates and sulfates) in the atmosphere, a study was undertaken in Kanpur, India. Specifically, the study was designed to measure the atmospheric levels of covering winter and summer seasons and day and night samplings to capture the diurnal variations. Results showed are found to be significantly high in winter season compared to the summer season. In winter, the molar ratio of to was found to be greater than 2:1. This higher molar ratio suggests that in addition to (NH₄)₂SO₄, NH₄NO₃ will be formed because of excess quantity of present. In summer, the molar ratio was less than 2:1 indicating deficit of to produce NH₄NO₃. The nitrogen conversion ratio (NO₂ to NO₃) was found to be nearly 50% in the study area that suggested quick conversion of NO₂ into nitric acid. As an overall conclusion, this study finds that NH₃ plays a vital role in the formation of fine inorganic secondary particles particularly so in winter months and there is a need to identify and assess sources of ammonia emissions in India.     

Chemistry of Precipitation Events and Inter-Relationship with Ambient Aerosols over a Semi-Arid Region in Western India

The precipitation events (n = 91), collected for 3 years (2000–2002) during the period of SW-monsoon (Jun–Aug) from an urban site (Ahmedabad, 23.0°N, 72.6°E) of a semi-arid region in western India, are found to exhibit characteristic differences in terms of their solute contents. The low solute (<700 μeq L⁻¹) events are either marked by heavy precipitation amount or successive events collected during an extended rain spell; whereas light precipitation events occurring after antecedent dry period are characterized by high solutes (>700 μeq L⁻¹). The ionic composition of low solute events show large variability due to varying contribution of anthropogenic species (: 1%–74%; : 1%–25%; and : 8%–68%) to the respective ion balance. In high solute events, ionic abundances are dominated by mineral dust (Ca²⁺ and ) and sea-salts (Na⁺ and Cl⁻). These differences are also reflected in the pH of low solute events (range: 5.2–7.4, VWM: 6.4) and high solute events (range: 6.6–8.2, VWM: 7.3). The comparison of Ca²⁺/Na⁺ and nss- ratios (on equivalent basis) in rain and aerosols suggests that the ionic composition of high solute events is influenced by below-cloud scavenging; whereas evidence for in-cloud scavenging is significantly reflected in low solute events. The annual wet-deposition fluxes of and are 330 and 480 mg m⁻² y⁻¹, respectively, in contrast to their corresponding dry-deposition fluxes (14 and 160 mg m⁻² y⁻¹); whereas wet and dry removal of Ca²⁺, Mg²⁺ and are comparable.     

Chemical composition of wet deposition in a Mediterranean site Athens,Greece related to the origin of air masses

The goal of this study is to determine the chemical composition of rain, in the wider region of Athens, Greece for the time period 1st September 2001 to 31st August 2002. Two model automatic rain samplers were installed in the Meteorological Station of Laboratory of Climatology (latitude: 37° 58′ N, longitude: 23° 47′ E) inside the Athens University Campus and in a site at Heraklio Attica, a northern suburb of Athens (latitude: 38° 03′ N, longitude: 23° 45′ E). The concentrations (μeq l⁻¹) of the major cations (H⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and anions (Cl⁻, , και ), as well as pH and conductivity of rain in 39 total samples were determined. The figures of pH range from 6.4 to 8.4 and conductivity from 8 to 207 μS cm⁻¹. The analysis showed that Ca²⁺ ions are abundant within all examined samples, while and present the highest concentrations from the anions. In order to find out the origin of the air masses, the air mass back trajectories were calculated. Five sectors of the origin of air masses were revealed: the North, the South, the Local, the West and the East sector. Multivariate methods included Factor Analysis and Discriminant Analysis were applied to the examined ion concentrations and three main factors were extracted, which discriminated the ions according to their origin. The first group of ions is interpreted as the result of the anthropogenic activity, the second group represents the acidity–alkalinity independently of their source and the third one the marine influence.     

A dual site study of the rainwater chemistry within the Western Pacific region

The two-year (1999–2000) rainwater chemistry at two monitoring sites in nearby coastal areas [Taiwan (TW) and Hong Kong (HK)] within the Western Pacific region has been studied. The volume weighted average pH values for the entire sampling period in TW and HK were 4.6 and 4.2, respectively. Sea salt Na⁺ and Cl⁻ were the most abundant species in the TW samples but and H⁺ were the most abundant in the HK samples. The sea salt and concentrations at TW were higher than those at HK both in the cold and warm seasons. Chloride depletion was minimal in the rainwater samples at both sites. Non seasalt- was associated with . Under the influence of the East Asian Winter Monsoon, the back-trajectory studies revealed that elevated anthropogenic species concentrations were associated with trajectories (1) very near to the continental boundary layer of Mainland China; or (2) along the coastline of Eastern China where large cities/industrial areas are located or (3) passing through the region of stagnant air over Northern/Eastern China. The lowest anthropogenic and crustal species concentrations measured in HK are associated with the summer monsoon and are attributed not only to the clean marine air masses but also to the relatively low SO₂, NO _x and NH₃ emissions from the South/ South East Asian countries, as well as infrequent biomass burning activities and wet scavenging at sources during the summer months. Approaching tropical cyclones led to the lowest pH values (4.2 in TW and 3.8 in HK) amongst the other weather categories. The findings here have been compared with other studies within East Asia and elsewhere.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

The aqueous phase acid-catalyzed reaction of methanol (CH₃OH) with nitric acid (HNO₃) to yield methyl nitrate (CH₃ONO₂) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH₃OH] = 0.00005–0.005 M and [HNO₃] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH₃OH and HNO₃ concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k _obs [CH₃OH][HNO₃], where k _obs  = 2.337 × 10⁻¹³(exp(0.3198*wt.% H₂SO₄)) when the solubility of CH₃ONO₂ in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H₂SO₄, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at     

Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature

The reactions of three structurally similar unsaturated alcohols, 2-buten-1-ol (crotyl alcohol), 2-methyl-2-propen-1-ol (MPO221) and 3-methyl-2-buten-1-ol (MBO321) with Cl atoms, have been investigated for the first time, using a 400 l Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID). The experiments were performed at atmospheric pressure and at temperatures between 255 and 298 K, in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions , , (in units of cm³ molecule⁻¹ s⁻¹). Finally, atmospheric lifetimes of those unsaturated alcohols with respect to OH, NO₃, O₃ and Cl have been calculated.     

Mass closure of total suspended particles over the coal burning power production area of western Macedonia, Greece

Ambient suspended particles (TSP) were collected from January to June 2001 at seven sampling sites in western Macedonia, Greece, where four thermal power stations are located. TSP samples were chemically characterized for minerals (Fe, Al, Mg, Ca, K, Ti and Si), trace elements (P, Cd, Cr, Cu, Mn, Pb, V, Zn, Te, Co, Ni, Se, Sr, As, and Sb), water-soluble ions , carbonaceous compounds (OC/EC) and polycyclic aromatic hydrocarbons (PAHs). These classes of compounds were consequently compared with PM mass concentrations of TSP in order to perform mass closure. PM chemical compositions exhibited differences at the seven sites. Minerals were found to be more abundant at four sites, electrolytes dominated the composition at two of the sites while carbonaceous material was most abundant only at one site. The fraction unaccounted for ranged between 22 and 34%. Spatial variations of atmospheric concentrations showed significantly higher levels of minerals, some trace metals and TC at the site that was closest to the power plants. At the same site ions exhibited high correlations with minerals and the majority of trace elements.     

Simulation Chamber Studies of the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol: Reaction with Hydroxyl Radicals and Ozone Under a Variety of Conditions

This article presents a complete study of the diurnal chemical reactivity of the biogenic volatile organic compound (BVOC), 2-methyl-3-buten-2-ol (MBO) in the troposphere. Reactions of MBO with OH and with ozone were studied to analyse the respective parts of both processes in the global budget of MBO atmospheric reactivity. They were investigated under controlled conditions for pressure (atmospheric pressure) and temperature (298 ± 2 K) using three complementary European simulation chambers. Reaction with OH radicals was studied in the presence of and in the absence of NO _x . The kinetic study was carried out by relative rate study using isoprene as a reference. The rate constant found for this reaction was molecule⁻¹ cm³ s⁻¹. FTIR spectroscopy, DNPH- and PFBHA-derivatisation analyses were performed for reactions with both OH radicals and ozone. In both reactions, the hydroxycarbonyl compound, 2-hydroxy-2-methylpropanal (HMPr) was positively identified and quantified, with a yield of in the reaction with OH, and a yield of and 0.84 ± 0.08 in the reaction with ozone under dry (HR < 1%) and humid conditions (HR = 20%–30%). A primary production of two other carbonyl compounds, acetone , and formaldehyde was found in the case of the dry ozonolysis experiments. Under humid conditions, only formaldehyde was co-produced with HMPr as a primary carbonyl compound, with a yield of . For the reaction with OH, three other carbonyl compounds were detected, acetone , formaldehyde and glycolaldehyde . In addition some realistic photo-oxidation experiments were performed to understand in an overall way the transformations of MBO in the atmosphere. The realistic photo-oxidation experiments were conducted in the EUPHORE outdoor simulation chamber. It was found that this compound is a weak secondary aerosol producer (less than 1% of the carbon balance). But it was confirmed that it is a potentially significant source of acetone, Δ[Acetone]/Δ[MBO] = 0.45. With our experimental conditions ([MBO]₀ = 200 ppb, [NO]o = 50 ppb), an ozone yield of Δ[O₃]/Δ[MBO] = 1.05 was found.     

Characterization of nutrients in the atmospheric wet and dry deposition observed at the two monitoring sites over Yellow Sea and East China Sea

To investigate the atmospheric deposition of nutrients into the coastal and shelf regions of the northwest Pacific Ocean, observation sites were established upon Qianliyan Island (within the Yellow Sea) and the Shengsi Archipelago (within the East China Sea), respectively. Nutrient concentrations, including , were determined in both aerosols and rainwater samples. The analytical results contain clear seasonal signatures, with high values during the dry season and low values during the rainy season. Similar trends are observed for deposition fluxes. The amount of wet deposition is greater than that of dry deposition for the studied nutrient species. The influence of meteorological factors such as rainfall means that samples from Qianliyan Island record higher nutrient values than those from Shengsi. Along with riverine inputs, atmospheric deposition plays an important role in determining the biogeochemistry of nutrient species in coastal and shelf oceans. An erratum to this article can be found at     

An Investigation on Temperature Variance Scaling in the Atmospheric Surface Layer

We present surface-layer measurements of temperature fluctuation variance from a site characterized by small-scale inhomogeneities. Periods of marked radiative forcing are selected. The data characterized by diabatic conditions and vertical heat flux larger than some threshold (here, chosen to be 0.01 K ms⁻¹) agree quite well with the convective scaling in unstable cases, and with the z-less parameterisation (with a large scatter) in stable cases. For near-neutral cases, the similarity function diverges because of the loss of significance of the temperature scale. Departures from similarity are highlighted in cases with smaller thermal fluxes, because horizontal heterogeneity and unsteadiness become important as production terms.     

Kinetics of ammonia and ammonium ion inhibition of the atmospheric oxidation of aqueous sulfur dioxide by oxygen

This is the first study, which shows both NH₃ and NH₄⁺ to inhibit the autoxidation of aqueous SO₂ in the pH range 7.0–8.5. The rate of the autoxidation, R _aut , in both buffered and unbuffered media at a fixed pH is in conformity with the rate law:

Oxidized Nitrogen in the Remote Pacific: The Role of Electrical Discharges over the Oceans

Simulations of oxidized nitrogen performed withglobal transport tracer models systematicallyunderestimate the concentrations of total nitrate atremote marine locations in the Mid-Pacific. Higheremission rates in the models of nitrogen oxides( ) from continental sources or alarger influx from the stratosphere do not seem tobe able to account for the shortfall. We are led toconclude that there has to be a substantial sourcelocated in oceanic areas. We speculate that -emission from electrical discharges overthe oceans could be the source we are looking for.Airborne observations of atmospheric concentrationsof oxidized nitrogen and ozone in the remoteatmosphere and observations of nitrate wetdeposition in remote sites are used as additionalconstraints to check the plausibility of thishypothesis. We find that a larger emission of due to lightning activity over the oceansindeed results in a much improved simulation oftotal nitrate in the remote Pacific, particularly inthe Equatorial and Tropical South Pacific and thatsuch a scenario is generally consistent withavailable observations of nitrate wet deposition andatmospheric concentrations of oxidized nitrogen andozone. An alternative hypothesis is that there is ahitherto unknown in situ source of over thePacific Ocean.     

A Parameterization of Third-order Moments for the Dry Convective Boundary Layer

We describe one-dimensional (1D) simulations of the countergradient zone of mean potential temperature observed in the convective boundary layer (CBL). The method takes into account the third-order moments (TOMs) in a turbulent scheme of relatively low order, using the turbulent kinetic energy equation but without prognostic equations for other second-order moments. The countergradient term is formally linked to the third-order moments and , and a simple parameterization of these TOMs is proposed. It is validated for several cases of a dry CBL, using large-eddy simulations that have been realized from the MESO-NH model. The analysis of the simulations shows that TOMs are responsible for the inversion of the sign of in the higher part of the CBL, and budget analysis shows that the main terms responsible for turbulent fluxes and variances are now well reproduced.     

Oligomerization of levoglucosan by Fenton chemistry in proxies of biomass burning aerosols

Reactions of levoglucosan with produced from Fenton chemistry were studied in solution serving as a proxy for biomass burning aerosols. Two modes of oligomerization (≤2000 u) were observed for reaction times between 1 and 7 days using matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS). Single-mass unit continuum mass distributions with dominant −2 u patterns were measured and superimposed by a +176/+162 u oligomer series. This latter oligomer pattern was attributed to a Criegee rearrangement (+14 u) of levoglucosan, initiated by , forming a lactone (176 u). The acid-catalyzed reaction of any ROH from levoglucosan (+162 u) forms an ester through transesterification of the lactone functionality, whereupon propagation forms polyesters. Proposed products and chemical mechanisms are suggested as sources and precursors of humic-like substances (HULIS), which are known to possess a large saccharic component and are possibly formed from biomass burning aerosols (Andreae, Global Biomass Burning, MIT Press, Cambridge, Massachusetts, 3–21, 1991).     

Observed winds,turbulence, and dispersion in built-up downtown areas of Oklahoma City and Manhattan

Wind and tracer data from the Oklahoma City Joint Urban 2003 (JU2003) and the Manhattan Madison Square Garden 2005 (MSG05) urban field experiments are being analyzed to aid in understanding air flow and dispersion near street-level in built-up downtown areas. The mean winds are separately calculated for groups of anemometers having similar exposures such as “near street level” and “on building top”. Several general results are found, such as the scalar wind speed at street level is about 1/3 of that at building top. Turbulent standard deviations of wind speed components and temperature, and vertical fluxes of momentum and sensible heat, are calculated from sonic anemometers near street level at 20 locations in JU2003 and five locations in MSG05, and from two rooftop locations in MSG05. The turbulence observations are consistent with observations in the literature at other cities, although the JU2003 and MSG05 data are unique in that many data are available near street level. For example, it is found that the local (i.e., at the measuring height) averages about 1.5 and the local averages about 0.25 in the two cities, where is the standard deviation of vertical velocity fluctuations, is the friction velocity, and u is the wind speed. The ratio of temperature fluctuations to temperature scale, , averages about −3 in both cities, consistent with similarity theory for slightly unstable conditions, where is the standard deviation of temperature fluctuations, and is the temperature scale. The calculated Obukhov length, L, is also consistent with slightly unstable conditions near street level, even at night during JU2003. The SF₆ tracer concentration observations from JU2003 are analyzed. Values of for the continuous releases are calculated for each release and arc distance, where is the 30-min average arc maximum concentration, Q is the continuous source emission rate, and u is the spatial-averaged wind speed in the downtown area. The basic characteristics of the JU2003 plot of averaged agree reasonably well with similar plots for other urban experiments in Salt Lake City and London (i.e., at . A is found to be about 3 during the day and about 10 during the night.     

Energy- and flux-budget (EFB) turbulence closure model for stably stratified flows. Part I: steady-state,homogeneous regimes

We propose a new turbulence closure model based on the budget equations for the key second moments: turbulent kinetic and potential energies: TKE and TPE (comprising the turbulent total energy: TTE = TKE + TPE) and vertical turbulent fluxes of momentum and buoyancy (proportional to potential temperature). Besides the concept of TTE, we take into account the non-gradient correction to the traditional buoyancy flux formulation. The proposed model permits the existence of turbulence at any gradient Richardson number, Ri. Instead of the critical value of Richardson number separating—as is usually assumed—the turbulent and the laminar regimes, the suggested model reveals a transitional interval, , which separates two regimes of essentially different nature but both turbulent: strong turbulence at ; and weak turbulence, capable of transporting momentum but much less efficient in transporting heat, at . Predictions from this model are consistent with available data from atmospheric and laboratory experiments, direct numerical simulation and large-eddy simulation.     

Optimal estimation of atmospheric 14C production over the Holocene: paleoclimate implications

A tree-ring ¹⁴C record and a simple box model of the global ¹⁴C cycle are combined using a method of optimal estimation theory (Rauch-Tung-Striebel smoother). The combination is used to infer information about the time evolution of ¹⁴C production in the atmosphere for the period 9400 year BC to AD 1900 year. Unlike previous attempts to infer changes from the tree-ring record, the errors in both the ¹⁴C data and the model, which are assumed to be purely random (not systematic), are formally considered. The optimal time evolution of is compared to independent evidence of changes in cosmogenic nuclide production over the Holocene from a variety of records on their original chronology, e.g., a record of the virtual axial dipole moment (VADM) based on a compilation of archeomagnetic data, the record of ¹⁰Be concentration from the GISP2 ice core (Central Greenland), and the record of ¹⁰Be concentration from the PS1 ice core (South Pole). The rank correlations between and are highly significant (p < 0.01), indicating that geomagnetic field intensity and ¹⁰Be concentration in GISP2 and PS1 changed monotonically with ¹⁴C production. The linear correlation coefficients between are also highly significant (p<0.01) but relatively small (–0.76, 0.48, and 0.60, respectively). Thus, an important fraction (42–77%) of the variance in the geomagnetic and ¹⁰Be data is not accounted for by linear regression on the ¹⁴C productions implied by the tree-ring record. The variance near the 1500 yr period, which previous authors interpreted as solar variability, represents a small fraction of the total variance in the time series (<15% for the band 1200–1800 yr) and does not correspond to a spectral peak. Hence, the hypothesis of a direct solar forcing mechanism for the postulated millennial climate variability during the Holocene is not supported.     

Aqueous Oxidation of Sulfur(IV) Catalyzed by Manganese(II): A Generalized Simple Kinetic Model

The reaction kinetics of S(IV) autoxidation catalyzed by Mn(II) in the pH range 3–5 typical for atmospheric liquid water, was investigated. For reactions with pH maintained constant during the reaction course, the predictions obtained by a simple integral approach cover kinetic results only for concentrations of HSO ₃ ⁻ up to 0.2 mM at pH 4.5. Thus, a generalized simple kinetic model, which can be used for predicting the reaction kinetics in wider concentration, pH and temperature ranges, was derived. This model is based on the assumption that the reaction rate is proportional to the concentration of a transient manganese-sulfito complex formed in the initial step of a radical chain mechanism. In the proposed power law rate equation

Interpolation between Businger–Dyer Formulae and Free Convection Forms: A Revised Approach

In this study, profile functions for flux calculations during unstable conditions are proposed and examined. These functions are based on a direct interpolation for the dimensionless wind speed and temperature gradients between the standard Businger–Dyer formulae, , , and free convection forms, , being the Monin–Obukhov stability parameter. A previously presented interpolation between the corresponding profile relationships, in attempting to provide a general relationship for the whole unstable regime, leads to serious restrictions for the values of in the free convection forms. These restrictions rendered available experimental data almost inapplicable, since the behaviour of the formulae in the near-neutral range controls the values of those parameters. The proposed interpolation provides functions that, firstly, fit the standard Businger–Dyer forms for near-neutral conditions and, secondly, satisfy the asymptotic behaviour as , permitting wider ranges of possible values. This step is very important, taking into account the large spread of the experimental data. Thus, as further and more accurate observations at strong instability become available, this approach could prove very efficient in fitting these data while retaining correct near-neutral behaviour.     

Absolute OH quantum yields in the laser photolysis of nitrate,nitrite and dissolved H2O2 at 308 and 351 nm in the temperature range 278–353 K

Absolute quantum yields for the formation of OH radicals in the laser photolysis of aqueous solutions of NO₃ ^-, NO₂ ^- and H₂O₂ at 308 and 351 nm and as a function of pH and temperature have been measured. A scavenging technique involving the reaction between OH and SCN^- ions and the time resolved detection by visible absorption of the (SCN)₂ ^- radical ion was used to determine the absolute OH yields. The following results were obtained:

1. NO ₃ ^- -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFWaam% cqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFZaWmcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKjYOcaqGGaGaam% iCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMdaaeaacqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqqHMoGr% daWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaWGubGaaiykai% abg2da9iabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiik% aiaaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqWFGaaica% qGLbGaaeiEaiaabchacaqGGaWaamWaaeaacaqGOaGaaeymaiaabIda% caqGWaGaaeimaiaabccacqGHXcqScaaI0aGaaGioaiaaicdacaqGPa% GaaeikamaalaaabaGaaeymaaqaaiaabkdacaqG5aGaaeioaaaacaqG% GaGaeyOeI0IaaeiiamaalaaabaGaaeymaaqaaiaadsfaaaGaaeykaa% Gaay5waiaaw2faaiaac6caaaaa!9673!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = 0.017 \pm 0.003 {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm 480{\text{)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\] Selected experiments at 351 nm indicate that these results are essentially unchanged.
2. NO ₂ ^- -photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWFWaamcqWFXaqmcqWF3aWncqWFGaaicqGHXc% qScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWFWaamcqWFXaqmcqWF% PaqkcqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacq% GHKjYOcaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaaeiiaiaabMda% caqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8% hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab-D5aibqaba% GccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaaWcbaGae83N% d8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIdacqWFGaaicq% WFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaaeiiamaadmaa% baGaaeikaiaabgdacaqG1aGaaeOnaiaabcdacaqGGaGaeyySaeRaae% iiaiaabodacaqG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaa% baGaaeOmaiaabMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaae% aacaqGXaaabaGaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiilaaqa% aiaaiodacaaI1aGaaGymaiaabccacaqGUbGaaeyBaiaabQdacqWFGa% aicqqHMoGrdaWgaaWcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaI% YaGaaGyoaiaaiIdacqWFGaaicqWFAoWscaGGPaGaeyypa0Jae8hiaa% Iae8hkaGIae8hmaaJae8Nla4Iae8hmaaJae8hnaqJae8NnayJae8hi% aaIaeyySaeRae8hiaaIae8hmaaJae8Nla4Iae8hmaaJae8hmaaJae8% xoaKJae8xkaKIae8hiaaIaaeOzaiaab+gacaqGYbGaaeiiaiaabsda% caqGGaGaeyizImQaaeiiaiaadchacaqGibGaaeiiaiaab2dacaqGGa% GaaeioaiaabYcaaeaacqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWF% GaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicqWFGaaicq% WFGaaicqWFGaaicqWFGaaicqqHMoGrdaWgaaWcbaGae83Nd8Kae83L% dGeabeaakiaacIcacaWGubGaaiykaiabg2da9iabfA6agnaaBaaale% aacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5aGaaGioaiab% -bcaGiab-P5aljaacMcacqWFGaaicaqGLbGaaeiEaiaabchacaqGGa% WaamWaaeaacaqGOaGaaeymaiaabIdacaqGWaGaaeimaiaabccacqGH% XcqScaqGGaGaaeinaiaabcdacaqGWaGaaeykaiaabIcadaWcaaqaai% aabgdaaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabcca% daWcaaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaaca% GGUaaaaaa!FC61!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.017 \pm 0.001) {\text{for 4 }} \leqslant {\text{ }}p{\text{H }} \leqslant {\text{ 9,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1560 }} \pm {\text{ 360)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.046 \pm 0.009) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 8,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(1800 }} \pm {\text{ 400)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\]
3. H₂O₂-photolysis:% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGceaqabeaacaaIWa% GaaGioaGGaaiab-bcaGiaab6gacaqGTbGaaeOoaiab-bcaGiabfA6a% gnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikaiaaikdacaaI5a% GaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWFGaaicqWFOaak% cqWFWaamcqWFUaGlcqWF5aqocqWF4aaocqWFGaaicqGHXcqScqWFGa% aicqWFWaamcqWFUaGlcqWFWaamcqWFZaWmcqWFPaqkcqWFGaaicaqG% MbGaae4BaiaabkhacaqGGaGaamiCaiaabIeacaqGGaGaeyizImQaae% iiaiaabEdacaqGSaaabaGae8hiaaIae8hiaaIae8hiaaIae8hiaaIa% e8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaaIae8hiaa% Iae8hiaaIae8hiaaIae8hiaaIaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaamivaiaacMcacqGH9aqpcqqHMoGrdaWgaa% WcbaGae83Nd8Kae83LdGeabeaakiaacIcacaaIYaGaaGyoaiaaiIda% cqWFGaaicqWFAoWscaGGPaGae8hiaaIaaeyzaiaabIhacaqGWbGaae% iiamaadmaabaGaaeikaiaabAdacaqG2aGaaeimaiaabccacqGHXcqS% caqGGaGaaeymaiaabMdacaqGWaGaaeykaiaabIcadaWcaaqaaiaabg% daaeaacaqGYaGaaeyoaiaabIdaaaGaaeiiaiabgkHiTiaabccadaWc% aaqaaiaabgdaaeaacaWGubaaaiaabMcaaiaawUfacaGLDbaacaGGSa% aabaGaaG4maiaaiwdacaaIXaGaaeiiaiaab6gacaqGTbGaaeOoaiab% -bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaaiikai% aaikdacaaI5aGaaGioaiab-bcaGiab-P5aljaacMcacqGH9aqpcqWF% GaaicqWFOaakcqWFWaamcqWFUaGlcqWF5aqocqWF2aGncqWFGaaicq% GHXcqScqWFGaaicqWFWaamcqWFUaGlcqWFWaamcqWF0aancqWFPaqk% cqWFGaaicaqGMbGaae4BaiaabkhacaqGGaGaaeinaiaabccacqGHKj% YOcaqGGaGaamiCaiaabIeacaqGGaGaaeypaiaabccacaqG3aGaaeil% aaqaaiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGi% ab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bcaGiab-bca% Giab-bcaGiabfA6agnaaBaaaleaacqWFFoWtcqWFxoasaeqaaOGaai% ikaiaadsfacaGGPaGaeyypa0JaeuOPdy0aaSbaaSqaaiab-95apjab% -D5aibqabaGccaGGOaGaaGOmaiaaiMdacaaI4aGae8hiaaIae8NMdS% Kaaiykaiab-bcaGiaabwgacaqG4bGaaeiCaiaabccadaWadaqaaiaa% bIcacaqG1aGaaeioaiaabcdacaqGGaGaeyySaeRaaeiiaiaabgdaca% qG2aGaaeimaiaabMcacaqGOaWaaSaaaeaacaqGXaaabaGaaeOmaiaa% bMdacaqG4aaaaiaabccacqGHsislcaqGGaWaaSaaaeaacaqGXaaaba% GaamivaaaacaqGPaaacaGLBbGaayzxaaGaaiOlaaaaaa!F3D0!\[\begin{gathered}08 {\text{nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.98 \pm 0.03) {\text{for }}p{\text{H }} \leqslant {\text{ 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(660 }} \pm {\text{ 190)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right], \hfill \\351{\text{ nm:}} \Phi _{{\rm O}{\rm H}} (298 {\rm K}) = (0.96 \pm 0.04) {\text{for 4 }} \leqslant {\text{ }}p{\text{H = 7,}} \hfill \\\Phi _{{\rm O}{\rm H}} (T) = \Phi _{{\rm O}{\rm H}} (298 {\rm K}) {\text{exp }}\left[ {{\text{(580 }} \pm {\text{ 160)(}}\frac{{\text{1}}}{{{\text{298}}}}{\text{ }} - {\text{ }}\frac{{\text{1}}}{T}{\text{)}}} \right]. \hfill \\\end{gathered}\] Together with the absorption coefficients and an assumed actinic flux within atmospheric droplets of twice the clear air value, the partial photolytic lifetimes (τ_OH) of these molecules at 298 K are estimated as 10.5 d, 5.4 h and 30.3 h for NO₃ ^-, NO₂ ^- and H₂O₂, respectively. These lifetimes will increase by a factor of two (NO₃ ^-, NO₂ ^-) and by 15% (H₂O₂) at T=278 K. Using average ambient concentrations in tropospheric aqueous droplets, the photolytic OH source strengths from these species are calculated to be 2.8×10^-11, 1.3×10^-11 and 1.4×10^-11 mol 1^-1 s^-1 for NO₃ ^-, NO₂ ^- and H₂O₂ respectively.