Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, α-thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether (, E_a/R=580 (±560) K), n-butyl acetate ( (±0.4)×10⁹ M⁻¹ s⁻¹, E_a/R=1000 (±200) K), acetone ( (±0.05)×10⁹ M⁻¹ s⁻¹, E_a/R=1400 (±500) K), methyl ethyl ketone (, E_a/R=1200 (±200) K), methyl iso-butyl ketone (, E_a/R=1200 (±300) K) and methylglyoxal (, E_a/R=1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.     

Trends of ambient carbonyl compounds in the urban environment of Hong Kong

The concentrations of C₁–C₈ carbonyl compounds were measured at two urban sites in Hong Kong from October 1997 to September 2000. The daily total carbonyl concentrations were found to range from 2.4 to 37 μg m⁻³. Formaldehyde was the most abundant species, which comprised from 36 to 43% of the total detected carbonyls, followed by acetaldehyde (18–21%) and acetone (8–20%). The highest 24-hour average concentrations measured were 10 and 7.7 μg m⁻³ for formaldehyde and acetaldehyde, respectively. Seasonal and temporal variations in the concentrations of formaldehyde and acetaldehyde were not obvious, but lowest concentrations often occurred from June to August. The mean formaldehyde/acetaldehyde molar ratios at the two sites in summer (2.8±1.1 and 2.5±1.2) were significantly higher (p⩽0.01) than those in winter periods (1.9±0.6 and 2.0±0.6). The phenomena were explained by influences of both photochemical reactions and local meteorological conditions. Better correlations between formaldehyde and acetaldehyde, and between NO_x and each of the two major carbonyls were obtained in winter periods indicating direct vehicular emissions were the principal sources. The ambient formaldehyde and acetaldehyde concentrations in the urban atmosphere of Hong Kong were within the normal ranges reported in the literature for other urban sites world-wide.     

Do aerosols act as catalysts in the OH radical initiated atmospheric oxidation of volatile organic compounds?

Smog chamber/FTIR techniques were used to study the relative reactivity of OH radicals with methanol, ethanol, phenol, C₂H₄, C₂H₂, and p-xylene in 750 Torr of air diluent at 296±2 K. Experiments were performed with, and without, 500–8000 μg m⁻³ (4000–50 000 μm² cm⁻³ surface area per volume) of NaCl, (NH₄)₂SO₄ or NH₄NO₃ aerosol. In contrast to the recent findings of Oh and Andino (Atmospheric Environment 34 (2000) 2901, 36 (2002) 149; International Journal of Chemical Kinetics 33 (2001) 422) there was no discernable effect of aerosol on the rate of loss of the organic compounds via reaction with OH radicals. Gas kinetic theory arguments cast doubt upon the findings of Oh and Andino. The available data suggest that the answer to the title question is “No”. As part of this work the rate constants for reactions of OH radicals with methanol, ethanol, and phenol in 750 Torr of air at 296 K were determined to be: k_OH+CH3OH=(8.12±0.54)×10⁻¹³, k_OH+C2H5OH=(3.47±0.32)×10⁻¹² and k_OH+phenol=(3.27±0.31)×10⁻¹¹ cm³ molecule⁻¹ s⁻¹.     

A study of the atmospheric reaction of CH3S with O3 as a function of temperature

The atmospheric reaction of the methylthiyl radical (CH₃S) with O₃ was investigated as a function of temperature (259–381 K), in the pressure range of 25–300 Torr, using the technique of laser photolysis/laser-induced fluorescence. The resulting Arrhenius expression, with an uncertainty of ±2σ, was k₁(T=259–381 K)=(1.02±0.30)×10⁻¹² exp[(432±77) K/T] cm³ molecule⁻¹ s⁻¹. The obtained rate constant k₁ was independent of pressure over the limited range employed. Our results are compared with the previous studies carried out, at single temperature and as a function of temperature, by different techniques.     

Diffusion of HTO, Cl and I in Opalinus Clay samples from Mont Terri: Effect of confining pressure

Diffusion coefficients (T=23±2 °C) and accessible porosities for HTO, ³⁶Cl⁻ and ¹²⁵I⁻ were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na⁺ and Cl⁻ as the main components (I=0.42 M).The measured values of the effective diffusion coefficients (D_e) and rock capacity factors (α) are: D_e=1.2–1.5×10⁻¹¹ m² s⁻¹ and α=0.09–0.11 for HTO, D_e=4.0–5.5×10⁻¹² m² s⁻¹ and α=0.05 for ³⁶Cl⁻ and D_e=3.2–4.6×10⁻¹² m² s⁻¹ and α=0.07–0.10 for ¹²⁵I⁻. For non-sorbing tracers (HTO, ³⁶Cl) the rock capacity factor α is equal to the diffusion-accessible porosity . The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of 17% for HTO, 28% for ³⁶Cl⁻ and 30% for ¹²⁵I⁻. Moreover, the diffusion coefficients for ³⁶Cl⁻ and ¹²⁵I⁻ are smaller than for HTO, which is consistent with an effect arising from anion exclusion.The diffusion coefficients of HTO and ¹²⁵I⁻ measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.     

Long-term variation of PM2.5 levels and composition at rural, urban, and roadside sites in Hong Kong: Increasing impact of regional air pollution

Long-term study of air pollution plays a decisive role in formulating and refining pollution control strategies. In this study, two 12-month measurements of PM_2.5 mass and speciation were conducted in 00/01 and 04/05 to determine long-term trend and spatial variations of PM_2.5 mass and chemical composition in Hong Kong. This study covered three sites with different land-use characteristics, namely roadside, urban, and rural environments. The highest annual average PM_2.5 concentration was observed at the roadside site (58.0±2.0 μg m⁻³ (average±2σ) in 00/01 and 53.0±2.7 μg m⁻³ in 04/05), followed by the urban site (33.9±2.5 μg m⁻³ in 00/01 and 39.0±2.0 μg m⁻³ in 04/05), and the rural site (23.7±1.9 μg m⁻³ in 00/01 and 28.4±2.4 μg m⁻³ in 04/05). The lowest PM_2.5 level measured at the rural site was still higher than the United States’ annual average National Ambient Air Quality Standard of 15 μg m⁻³. As expected, seasonal variations of PM_2.5 mass concentration at the three sites were similar: higher in autumn/winter and lower in summer. Comparing PM_2.5 data in 04/05 with those collected in 00/01, a reduction in PM_2.5 mass concentration at the roadside (8.7%) but an increase at the urban (15%) and rural (20%) sites were observed. The reduction of PM_2.5 at the roadside was attributed to the decrease of carbonaceous aerosols (organic carbon and elemental carbon) (>30%), indicating the effective control of motor vehicle emissions over the period. On the other hand, the sulfate concentration at the three sites was consistent regardless of different land-use characteristics in both studies. The lack of spatial variation of sulfate concentrations in PM_2.5 implied its origin of regional contribution. Moreover, over 36% growth in sulfate concentration was found from 00/01 to 04/05, suggesting a significant increase in regional sulfate pollution over the years. More quantitative techniques such as receptor models and chemical transport models are required to assess the temporal variations of source contributions to ambient PM_2.5 mass and chemical speciation in Hong Kong.     

An aerosol flow tube study of the interaction of N2O5 with calcite, Arizona dust and quartz

The interaction of N₂O₅ with dispersed samples of Arizona Test Dust (ATD), Calcite (CaCO₃) and quartz (SiO₂) was investigated at varying relative humidity using an aerosol flow reactor. Reactive uptake coefficients, γ, obtained at close to zero relative humidity were (4.8 ± 0.7) × 10⁻³ for CaCO₃, (8.6 ± 0.6) × 10⁻³ for Quartz and (9.8 ± 1.0) × 10⁻³ for ATD. In the case of calcite, evidence was obtained for an enhanced rate of uptake at relative humidities above ≈ 50%. The results are compared to literature values obtained using bulk substrates and to previous aerosol uptake data on Saharan dust.     

Simulation of aerosol radiative properties with the ORISAM-RAD model during a pollution event (ESCOMPTE 2001)

The aim of this study is to present the organic and inorganic spectral aerosol module-radiative (ORISAM-RAD) module, allowing the 3D distribution of aerosol radiative properties (aerosol optical depth, single scattering albedo and asymmetry parameter) from the ORISAM module. In this work, we test ORISAM-RAD for one selected day (24th June) during the ESCOMPTE (expérience sur site pour contraindre les modèles de pollution atmosphérique et de transport d’emissions) experiment for an urban/industrial aerosol type. The particle radiative properties obtained from in situ and AERONET observations are used to validate our simulations. In a first time, simulations obtained from ORISAM-RAD indicate high aerosol optical depth (AOD)0.50–0.70±0.02 (at 440 nm) in the aerosol pollution plume, slightly lower (10–20%) than AERONET retrievals. In a second time, simulations of the single scattering albedo (ω_o) have been found to well reproduce the high spatial heterogeneities observed over this domain. Concerning the asymmetry parameter (g), ORISAM-RAD simulations reveal quite uniform values over the whole ESCOMPTE domain, comprised between 0.61±0.01 and 0.65±0.01 (at 440 nm), in excellent agreement with ground based in situ measurements and AERONET retrievals. Finally, the outputs of ORISAM-RAD have been used in a radiative transfer model in order to simulate the diurnal direct radiative forcing at different locations (urban, industrial and rural). We show that anthropogenic aerosols strongly decrease surface solar radiation, with diurnal mean surface forcings comprised between −29.0±2.9 and −38.6±3.9 W m⁻², depending on the sites. This decrease is due to the reflection of solar radiations back to space (−7.3±0.8<ΔF_TOA<−12.3±1.2 W m⁻²) and to its absorption into the aerosol layer (21.1±2.1<ΔF_ATM<26.3±2.6 W m⁻²). These values are found to be consistent with those measured at local scale.     

Effective diffusivity of the uranyl ion in a granite from Inada, Ibaraki, Japan

The effective diffusivity of uranium(VI) in Inada granite has been determined by through-diffusion. Experiments were performed at room temperature (20–25°C) in a 0.1 mol 1⁻¹ KCl solution where uranium is present predominantly as the poorly sorbing UO₂²⁺. An effective diffusivity (D_e) of (3.6 ± 1.6) × 10⁻¹⁴ m² s⁻¹ was obtained, close to that for uranine (nonsorbing organic tracer), but one order of magnitude lower than those obtained for Sr²⁺ and NpO₂⁺, and two orders of magnitude lower than that obtained for I⁻. According to well established theory, a proportional relationship exists between D_e and the diffusivity in the bulk of the solution (D_v). The effective diffusivity obtained in granite was not proportional to D_v. This agrees with results obtained for effective diffusivity in a Swedish granite. The ratio D_e/D_v was found to be not constant but increased with D_e or D_v. This result suggests a limit to the application of the theory.     

Characteristics of carbonyl compounds in public vehicles of Beijing city: Concentrations,sources, and personal exposures

The characteristics of carbonyl compounds (carbonyls) including concentrations, major sources, and personal exposure were investigated for 29 vehicles including taxi, bus and subway in Beijing. It was found that the taxis (Xiali, TA) and buses (Huanghe, BA) fueled by gasoline with longer service years had the higher indoor carbonyl levels (178±42.7 and 188±31.6 μg m⁻³) while subways energized by electricity without exhaust and the jingwa buses (BB) driven in the suburb had the lower levels with total concentrations of 98.5±26.3 and 92.1±20.3 μg m⁻³, respectively. Outdoor carbonyls of taxi cars and buses were nearly at the same level with their total concentrations varying from 80 to 110 μg m⁻³. The level of outdoor subways carbonyls was equal with the ambient air levels. Exhaust leakage, indoor material emissions, photochemical formation, and infiltration of outdoor air were considered to be the major sources to in-vehicle carbonyls. Personal exposures and cancer risk to formaldehyde and acetaldehyde were calculated for professional bus and taxi drivers, respectively. Taxi drivers had the highest cancer risk with personal exposure to formaldehyde and acetaldehyde of 212 and 243 μg day⁻¹, respectively. The public concern should pay considerable attention to professional drivers’ health.     

Variability of tropospheric hydroperoxides at a coastal surface site in Antarctica

The annual cycles of hydrogen peroxide (H₂O₂) and methylhydroperoxide (MHP) have been investigated at a remote site in Antarctica in order to study seasonal variations as well as chemical processes in the troposphere. The measurements have been performed from March 1997 to January 1998 and in February 1999 at the German Antarctic research station Neumayer which is located at 70°39′S, 8°15′W. The obtained time series for hydrogen peroxide and methylhydroperoxide in near-surface air represents the first all-year measurements in Antarctica and indicates clearly the occurrence of seasonal variations. During polar night mean values of 0.054±0.046 ppbv (range<0.03–0.11 ppbv) for hydrogen peroxide and 0.089±0.052 ppbv (range<0.05–0.14 ppbv) for methylhydroperoxide were detected. At the sunlit period higher Mixing ratios were found, 0.20±0.13 ppbv (range<0.03–0.91 ppbv) for hydrogen peroxide and 0.19±0.10 ppbv (range<0.05–0.89 ppbv) for methylhydroperoxide. Occasional long-range transport of air masses from mid-latitudes caused enhanced peroxide concentrations at polar night. During the period of stratospheric ozone depletion we observed peroxide mixing ratios comparable to typical winter levels.     

Processes affecting the movement of organochlorine pesticides (OCPs) between soil and air in an industrial site in Turkey

Soil and atmospheric concentrations, dry deposition and soil-air gas exchange of organochlorine pesticides (OCPs) were investigated at an industrial site in Aliaga, Izmir, Turkey. Current-use pesticides, endosulfan and chlorpyrifos, had the highest atmospheric levels in summer and winter. Summertime total (gas + particle) OCP concentrations in air were higher, probably due to increased volatilization at higher temperatures and seasonal local/regional applications of current-use pesticides. Particle deposition fluxes were generally higher in summer than in winter. Overall average dry particle deposition velocity for all the OCPs was 4.9 ± 4.1 cm s⁻¹ (average ± SD). ΣDDXs (sum of p,p′-DDT, p,p′-DDD, and p,p′-DDE) were the most abundant OCPs in Aliaga soils (n = 48), probably due to their heavy historical use and persistence. Calculated fugacity ratios and average net gas fluxes across the soil-air interface indicated volatilization for α-CHL, γ-CHL, heptachlorepoxide, cis-nonachlor, trans-nonachlor, and p,p′-DDT in summer, and for α-CHL, γ-CHL, trans-nonachlor, endosulfan sulfate, and p,p′-DDT in winter. For the remaining OCPs, soil acted as a sink during both seasons. Comparison of the determined fluxes showed that dry particle, gas-phase, and wet deposition are significant OCP input mechanisms to the soil in the study area.     

Cation exchange in a glacial till drumlin at a road salt storage facility

At a former wood preservation plant severely contaminated with coal tar oil, in situ bulk attenuation and biodegradation rate constants for several monoaromatic (BTEX) and polyaromatic hydrocarbons (PAH) were determined using (1) classical first order decay models, (2) Michaelis–Menten degradation kinetics (MM), and (3) stable carbon isotopes, for o-xylene and naphthalene. The first order bulk attenuation rate constant for o-xylene was calculated to be 0.0025 d^− 1 and a novel stable isotope-based first order model, which also accounted for the respective redox conditions, resulted in a slightly smaller biodegradation rate constant of 0.0019 d^− 1. Based on MM-kinetics, the o-xylene concentration decreased with a maximum rate of k_max = 0.1 µg/L/d. The bulk attenuation rate constant of naphthalene retrieved from the classical first order decay model was 0.0038 d^− 1. The stable isotope-based biodegradation rate constant of 0.0027 d^− 1 was smaller in the reduced zone, while residual naphthalene in the oxic part of the plume further downgradient was degraded at a higher rate of 0.0038 d^− 1. With MM-kinetics a maximum degradation rate of k_max = 12 µg/L/d was determined. Although best fits were obtained by MM-kinetics, we consider the carbon stable isotope-based approach more appropriate as it is specific for biodegradation (not overall attenuation) and at the same time accounts for the dominant electron-accepting process. For o-xylene a field based isotope enrichment factor ε_field of − 1.4 could be determined using the Rayleigh model, which closely matched values from laboratory studies of o-xylene degradation under sulfate-reducing conditions.     

Comparison of carbonyl compounds emissions from diesel engine fueled with biodiesel and diesel

The characteristics of carbonyl compounds emissions were investigated on a direct injection, turbocharged diesel engine fueled with pure biodiesel derived from soybean oil. The gas-phase carbonyls were collected by 2,4-dinitrophenylhydrazine (DNPH)-coated silica cartridges from diluted exhaust and analyzed by HPLC with UV detector. A commercial standard mixture including 14 carbonyl compounds was used for quantitative analysis. The experimental results indicate that biodiesel-fueled engine almost has triple carbonyls emissions of diesel-fueled engine. The weighted carbonyls emission of 8-mode test cycle of biodiesel is 90.8 mg (kW h)^?1 and that of diesel is 30.7 mg (kW h)^?1. The formaldehyde is the most abundant compound of carbonyls for both biodiesel and diesel, taking part for 46.2% and 62.7% respectively. The next most significant compounds are acetaldehyde, acrolein and acetone for both fuels. The engine fueled with biodiesel emits a comparatively high content of propionaldehyde and methacrolein. Biodiesel, as an alternative fuel, has lower specific reactivity (SR) caused by carbonyls compared with diesel. When fueled with biodiesel, carbonyl compounds make more contribution to total hydrocarbon emission.     

Application of simple soil-water flow models to the transfer of surface-applied solutes to streams

In the context of leaching of surface-applied nitrate fertilizer to runoff, this paper evaluates the performance of five simple predictive models, based upon: (1) field capacity; (2) uniform displacement; (3) wetting front; (4) by-passing (preferential) flow; and (5) soil-water domains. Predicted behaviour and observed on an 85-cm depth soil are compared for leaching depth and outflow response. Predictive success of outflow by the models for 40 monitored rainfall events were: (1) 60%; (2) 52%; and (3) 76%. For the by-passing flow model (4), simple prediction of pedal excess flow (4a) gave a success of 80%; where calculations of the operational volume in preferential flow were involved (4b), variations from 20 to 100% success occurred for a range of operational volumes, the lowest volumes giving the greatest success (4c). The soil-water domain model (5) is a simple, predictive scheme involving the classification of outflow events according to antecedent soil moisture (θ_a); the method uses the mobile: retained water content (θ_r) at 2 bars and field capacity (θ_fc). Using soil-water domains alone was of limited success but when the domains were combined with rainfall intensity, the scheme specified outflow exactly. Thus, for θ_a < θ_r, no soil-water outflow occurred, even at high rainfall intensity; for θ_a >θ_fc outflow always occurred, even at low rainfall intensity and for θ_a >θ_r < θ_fc the simple by-passing model (4a) achieved 100% predictive success. The implications for fertilizer application are discussed.     

Comportement photochimique du nitro-4 phenol en solution aqueuse

The quantum yield of the phototransformation of 4-nitrophenol has been evaluated as 4.5×10⁻⁵±0.6×10⁻⁵ at pH=2; at 3.0×10⁻⁵±0.6×10⁻⁵ at pH=5.5; 1.8×10⁻⁵±0.5×10⁻⁵ at pH=8.3. However the half-life is relatively low and no accumulation of aromatic or quinonic products was observed. Hydroquinone (QH₂) is the main organic primary product formed when an air-saturated or degassed solution was irradiated in 365 nm monochromatic light (about 80% of the 4-nitrophenol initially converted at pH=5.5 in the absence of oxygen). In air-saturated neutral or acidic solution, the formation of NO⁻₃ ions accounted for about 80% of the 4-nitrophenol converted, but in degassed medium a mixture NO : NO⁻₂ : NO⁻₃ is formed. An heterolytical mechanism of photohydrolysis with primary formation of QH₂ and HNO₂ is suggested. Several by-products as benzoquinone, 4-nitrosophenol, 4-nitrocatechol and nitrohydroquinone are formed according to the conditions. Many secondary reactions are involved as the disproportionation or the oxidation of HNO₂, the oxidation of QH₂ by HNO₂ and oxidations induced by excitation of NO⁻₂ and NO⁻₃.     

Modeling secondary organic aerosol formation from oxidation of α-pinene, β-pinene, and d-limonene

The biogenic species α-pinene, β-pinene, and d-limonene are among the most abundant monoterpenes emitted globally. They are also important precursors to secondary organic aerosol (SOA) formation in the atmosphere. This study involves the development of proposed oxidation mechanisms for these three species. Semi- and non-volatile oxidation products with the potential to lead to SOA formation are predicted explicitly. Simulation code that describes the gas-phase oxidation mechanisms including reactions that lead to ozone (O₃) formation is coupled to an equilibrium absorptive partitioning code. The coupled model is used to simulate both gas-phase chemistry and SOA formation associated with oxidation of these three species in chamber experiments involving single as well as multiple oxidants. For the partitioning model, required molecular properties of the oxidation products are taken from the literature or estimated based on structural characteristics. The predicted O₃ and SOA concentrations are typically within ±50% of measured values for most of the experiments except for the experiments with low initial hydrocarbon concentrations and the nitrate radical experiments with α-pinene. The developed model will be used to update a gas-phase chemical mechanism and a SOA formation module used in a three-dimensional air quality model.