Radiation-transfer modeling of snow-pack photochemical processes during ALERT 2000

The delta-Eddington radiation transfer model is used to calculate actinic fluxes and photolysis rates within the snow pack during the ALERT 2000 field campaign. Actinic fluxes are enhanced within the snow pack due to the high albedo of snow and conversion of direct light to diffuse light. The conversion of direct to diffuse light is highly dependent on the solar zenith angle, as demonstrated by model calculations. The optical properties of Alert snow are modeled as 100 μm radius ice spheres with impurity added to increase the absorption coefficient over that of pure water ice. Using these optical properties, the model achieves good agreement with observations of irradiance within the snow pack. The model is used to calculate the total actinic flux as a function of solar zenith angle and depth for either clear sky or cloudy conditions. The actinic flux is then used to calculate photochemical production of nitrogen oxides from nitrate photolysis assuming that nitrate in snow has the same absorption cross section and quantum yield in snow as in aqueous solution. Assuming all photo-produced nitrogen oxides are released to the gas phase, we derive a maximal flux of nitrogen oxides (NO_x+HONO and possibly other products) from the snow pack. The value of this maximal flux depends critically on the assumed quantum yield for production of NO₂, which is unknown in ice. Depending on the assumed quantum yield, the calculated maximal flux varies between values four times smaller than the observed NO_x+HONO flux to five times larger than the NO_x+HONO flux. Therefore, it appears that the calculated flux is in approximate agreement with the observations with a great need for improved understanding of nitrogen photochemistry in snow.     

Evaluation of nitrogen dioxide photolysis rates in an urban area using data from the 1997 Southern California Ozone Study

The photolysis of nitrogen dioxide and formaldehyde are two of the most influential reactions in the formation of photochemical air pollution, and their rates are computed using actinic flux determined from a radiative transfer model. In this study, we compare predicted and measured nitrogen dioxide photolysis rate coefficients (j_NO2). We used the Tropospheric Ultraviolet-Visible (TUV) radiation transfer model to predict j_NO2 values corresponding to measurements performed in Riverside, California as part of the 1997 Southern California Ozone Study (SCOS’97). Spectrally resolved irradiance measured at the same site allowed us to determine atmospheric optical properties, such as aerosol optical depth and total ozone column, that are needed as inputs for the radiative transfer model. Matching measurements of aerosol optical depth, ozone column, and j_NO2 were obtained for 14 days during SCOS’97. By using collocated measurements of the light extinction caused by aerosols and ozone over the full height of the atmosphere as model input, it was possible to predict sudden changes in j_NO2 resulting from atmospheric variability. While the diurnal profile of the rate coefficient was readily reproduced, j_NO2 model predicted values were found to be consistently higher than measured values. The bias between measured and predicted values was 17–36%, depending on the assumed single scattering albedo. By statistical analysis, we restricted the most likely values of the single scattering albedo to a range that produced bias on the order of 20–25%. It is likely that measurement error is responsible for a significant part of the bias. The aerosol single scattering albedo was found to be a major source of uncertainty in radiative transfer model predictions. Our best estimate indicates its average value at UV-wavelengths for the period of interest is between 0.77 and 0.85.     

Seasonal dependence of the oxidation capacity of the city of Santiago de Chile

The oxidation capacity of the highly polluted urban area of Santiago de Chile has been evaluated during a winter measurement campaign from May 25 to June 07, 2005, with the results compared and contrasted with those previously evaluated during a summer campaign from March 8 to 20, 2005. The OH radical budget was evaluated in both campaigns employing a simple quasi-photostationary state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O₃, NO, NO₂, j(O¹D), j(NO₂), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used for the analysis of the radical budgets and concentrations of OH, HO₂ and RO₂. Besides the above parameters, the MCM model has been constrained by the measured CO and other volatile organic compounds (VOCs) including alkanes and aromatics. Total production and destruction rates of OH and HO₂ in winter are about two times lower than that during summer. Simulated OH levels by both PSS and MCM models are similar during the daytime for both winter and summer indicating that the primary OH sources and sinks included in the simple PSS model are predominant. On a 24 h basis, HONO photolysis was shown to be the most important primary OH radical source comprising 81% and 52% of the OH initiation rate during winter and summer, respectively followed by alkene ozonolysis (12.5% and 29%), photolysis of HCHO (6.1% and 15%), and photolysis of O₃ (<1% and 4%), respectively. During both winter and summer, there was a balance between the OH secondary production (HO₂ + NO) and destruction (OH + VOCs) showing that initiation sources of RO₂ and HO₂ are no net OH initiation sources. This result was found to be fulfilled also for all other studies investigated. Seasonal impacts on the radical budgets are also discussed.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

The impact of megacity pollution on local climate and implications for the regional environment: Mexico City

We present calculations to estimate potential changes to the local climate and photochemistry caused by pollutants (gases and particles) produced in Mexico City, and the implications for the regional scale when pollutants are exported to surrounding regions. Measured aerosol optical properties are used in a 2-stream delta-Eddington radiative transfer model (Slingo and Schrecker, 1982. Quarterly Journal of the Royal Meteorological Society 108, 407–426) to estimate net radiative fluxes and heating rates, while photolysis rates for nitrogen dioxide and ozone are estimated from a much more detailed model (Madronich, 1987. Journal of Geophysical Research 92, 9740–9752). The presence of highly absorbing aerosols in Mexico City leads to a 17.6% reduction in solar radiative flux at the surface when an optical depth of 0.55 is considered. Photolysis rates for nitrogen dioxide and ozone are reduced between 18 and 21% at the surface, while an increase of between 15 and 17% is predicted above the boundary layer, for local noon calculations.The non-uniform vertical structure of aerosol concentrations observed (Pérez Vidal and Raga, 1998. Atmosfera 11, 95–108) plays a significant role in determining localized regions of heating, i.e. stabilization at the top of the boundary layer that results in a temperature increase of 0.4K h⁻¹ at that level. The presence of a 200 m-deep aerosol layer at the top of the boundary layer results in vertical profiles of the photolysis rates that are significantly different from the case where the aerosols are uniformly distributed in the mixed layer. At the bottom of the aerosol layer (about 1 km above the surface), the rates are about 28% lower than when there is a uniform aerosol distribution in the boundary layer. Finally, there is also an enhancement of photolysis rates at the top of the boundary layer that may lead to increased ozone production compared to the non-aerosol case.     

The Clean Air Act Amendments and Motor Vehicle Inspection/Maintenance

Seventeen days of detailed measurements of NO, NO₂, O₃, HNO₃ and the frequency of NO₂ photolysis—j(NO₂)—were carried out in Claremont, CA, in September 1980. Under conditions when the rate of change of NO concentration is small, there must be a balance between formation and loss processes. In the classical photostationary state this balance is between NO₂ photolysis: NO₂ + hv → NO + O and reaction with ozone: NO + O₃ → NO₂ + O₂. The results show that the latter reaction with ozone is inadequate to balance the formation step; a significant contribution is required from another NO oxidation process, possibly peroxy radical oxidation. If so, the inferred concentration of peroxy radicals shows a diurnal variation, peaking around solar noon.     

The influence of aerosols on photochemical smog in Mexico City

Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J_NO2) for the key reaction NO₂+hν→NO+O (λ<430 nm). The calculated values are in good agreement with previously published measurements of J_NO2at two sites in Mexico City: Palacio de Minerı́a (19°25′59″N, 99°07′58″W, 2233 masl), and IMP (19°28′48″N, 99°11′07″W, 2277 masl) and in Tres Marias, a town near Mexico City (19°03′N, 99°14′W, 2810 masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J_NO2 by 10–30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model.     

Hydroxyl (OH) radical production rates in snowpacks from photolysis of hydrogen peroxide (H2O2) and nitrate (NO3−)

Atmospheric chemistry directly above snowpacks is strongly influenced by ultraviolet (UV) radiation initiated emissions of chemicals from the snowpack. The emission of gases from the snowpack to the atmosphere is in part due to chemical reactions between hydroxyl radical, OH (produced from photolysis of hydrogen peroxide (H₂O₂) or nitrate (NO₃⁻)) and impurities in the snowpack. The work presented here is a radiative-transfer modelling study to calculate the depth-integrated production rates of hydroxyl radical from the photolysis of hydrogen peroxide and nitrate anion in snow for four different snowpacks and for solar zenith angles 30°–90°. This work also demonstrates the importance of hydrogen peroxide photolysis to produce hydroxyl radical relative to nitrate photolysis with (a) different snowpacks, (b) different ozone column depths, and (c) snowpack depths. The importance of hydrogen peroxide photolysis over nitrate photolysis for hydroxyl radical production increases with increasing depth in snowpack, column ozone depth, and solar zenith angle. With a solar zenith angle of 60° the production of hydroxyl radical from hydrogen peroxide photolysis accounts for 91–99% of all hydroxyl radical production from hydrogen peroxide and nitrate photolysis.     

Chemistry of HOx radicals in the upper troposphere

Aircraft observations from three recent missions (STRAT, SUCCESS, SONEX) are synthesized into a theoretical analysis of the factors controlling the concentrations of HO_x radicals (HO_x=OH+peroxy) and the larger reservoir family HO_y (HO_y=HO_x+2H₂O₂+2CH₃OOH+HNO₂+HNO₄) in the upper troposphere. Photochemical model calculations capture 66% of the variance of observed HO_x concentrations. Two master variables are found to determine the variance of the 24 h average HO_x concentrations: the primary HO_x production rate, P(HO_x), and the concentration of nitrogen oxide radicals (NO_x=NO+NO₂). We use these two variables as a coordinate system to diagnose the photochemistry of the upper troposphere and map the different chemical regimes. Primary HO_x production is dominated by the O(¹D)+H₂O reaction when [H₂O]>100 ppmv, and by photolysis of acetone (and possibly other convected HO_x precursors) under drier conditions. For the principally northern midlatitude conditions sampled by the aircraft missions, the HO_x yield from acetone photolysis ranges from 2 to 3. Methane oxidation amplifies the primary HO_x source by a factor of 1.1–1.9. Chemical cycling within the HO_x family has a chain length of 2.5–7, while cycling between the HO_x family and its HO_y reservoirs has a chain length of 1.6–2.2. The number of ozone molecules produced per HO_y molecule consumed ranges from 4 to 12, such that ozone production rates vary between 0.3 and 5 ppbv d⁻¹ in the upper troposphere. Three chemical regimes (NO_x-limited, transition, NO_x-saturated) are identified to describe the dependence of HO_x concentrations and ozone production rates on the two master variables P(HO_x) and [NO_x]. Simplified analytical expressions are derived to express these dependences as power laws for each regime. By applying an eigenlifetime analysis to the HO_x–NO_x–O₃ chemical system, we find that the decay of a perturbation to HO_y in the upper troposphere (as from deep convection) is represented by four dominant modes with the longest time scale being factors of 2–3 times longer than the steady-state lifetime of HO_y.     

Simplified model for the prediction of ozone generation in polluted urban areas with continuous precursor species emissions

In this paper we study the transient ozone generation process in polluted urban areas, using a simplified set of chemical reactions for the NO_x and hydrocarbon photolysis. We obtained a reduced kinetic mechanism and it is solved using the boundary layer theory due to the appearance of two time scales in the problem associated with the photo-chemical reactions of the NO₂ and unburned fuel, respectively. Assuming a temporal addition of ozone precursor species, we obtained in closed form, the temporal evolution of the ozone concentration as a function of the physico-chemical parameters.     

Measurements of JNO3− in snow by nitrate-based actinometry

Chemical actinometry was used to measure nitrate photolysis rate coefficients, J_NO3⁻, on and in snowpack at Summit, Greenland. Sealed glass tubes containing nitrate and a hydroxyl radical trapping system were buried in snow and exposed for between 2 and 24 h. Average J_NO3⁻ values for 2-h midday exposures in early June on surface snow were 10–14×10⁻⁷ s⁻¹. Averages over 24 h were 3.5–4.5×10⁻⁷ s⁻¹. These values reflect the integrated photon flux and also any variation of the nitrate photolysis rate with temperature. Attenuation of J_NO3⁻ within the firn was 0.03–0.04 cm⁻¹ for 24-h exposures and 0.08 cm⁻¹ for a 2-h exposure. Different attenuation coefficients may relate to differential light penetration due to changes in sun angle over the course of 24 h.     

Effect of high concentrations of inorganic seed aerosols on secondary organic aerosol formation in the m-xylene/NOx photooxidation system

High concentrations (>15 μm³ cm^?3) of CaSO₄, Ca(NO₃)₂ and (NH₄)₂SO₄ were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NO_x photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO₄ and aqueous Ca(NO₃)₂), even at elevated concentrations. The presence of high concentrations of (NH₄)₂SO₄ aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH₄)₂SO₄ on SOA yield is found to be positively correlated with the (NH₄)₂SO₄ surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH₄)₂SO₄ seed aerosols.     

Cereal waste burning pollution observed in the town of Vitoria (northern Spain)

Agricultural waste burning is a widespread practice throughout the world but there is little information about its pollutant impact. This paper deals with a preliminary study of the pollution observed in Vitoria (Northern Spain) caused by cereal waste burning. The mean hourly flux of pollutants produced by cereal waste burning fires can reach values of 1.4 kt of CO₂, 13 t of TPM and 3 t of NO_x in the area around Vitoria. Measurements obtained in the area of emission and inside fire plumes show high ratios (NO₂/NO_x) indicating that nitrogen oxides emitted by the source undergo a rapid transformation in the same area of emission. Results relating to aerosol composition collected in Vitoria during burning periods show an increase in the concentration of K⁺, NO₃⁻ and Cl⁻ ions, that are inter-correlated. The modification of the ionic composition of aerosols also affects the chemistry of the rain collected in Vitoria. During the burning period, it is particularly noticeable that anthropogenic pollution (usually identifiable by the correlation between SO₄²⁻ and NO₃⁻ concentrations) disappears, indicating the existence of an independent source of NO₃⁻ not linked to the SO₄²⁻ source. Similar results were deduced studying BAPMON data collected in Spain during cereal waste burning. Finally, we note that ozone concentration measured at Vitoria is not affected by the pollution generated by the burning fires.     

The impacts of reactive terpene emissions from plants on air quality in Las Vegas,Nevada

A three-part study was conducted to quantify the impact of landscaped vegetation on air quality in a rapidly expanding urban area in the arid southeastern United States. The study combines in situ, plant-level measurements, a spatial emissions inventory, and a photochemical box model. Maximum plant-level basal emission rates were moderate: 18.1 μgC gdw^?1 h^?1 (Washingtonia spp., palms) for isoprene and 9.56 μgC gdw^?1 h^?1 (Fraxinus velutina, Arizona ash) for monoterpenes. Sesquiterpene emission rates were low for plant species selected in this study, with no measurement exceeding 0.1 μgC gdw^?1 h^?1. The high ambient temperatures combined with moderate plant-level emission factors resulted in landscape emission factors that were low (250–640 μgC m^?2 h^?1) compared to more mesic environments (e.g., the southeastern United States). The Regional Atmospheric Chemistry Mechanism (RACM) was modified to include a new reaction pathway for ocimene. Using measured concentrations of anthropogenic hydrocarbons and other reactive air pollutants (NO_x, ozone), the box model employing the RACM mechanism revealed that these modest emissions could have a significant impact on air quality. For a suburban location that was downwind of the urban core (high NO_x; low anthropogenic hydrocarbons), biogenic terpenes increased time-dependent ozone production rates by a factor of 50. Our study demonstrates that low-biomass density landscapes emit sufficient biogenic terpenes to have a significant impact on regional air quality.     

Field observations of regional and urban impacts on NO2, ozone,UVB, and nitrate radical production rates in the Phoenix air basin

In the May and June of 1998, field measurements were taken at a site near the Usery Pass Recreation Area, ∼27 miles from the downtown Phoenix area, overlooking Phoenix and Mesa, Arizona. This site was selected to examine the impacts of the Phoenix urban plume on the Usery Pass Recreation Area and surrounding regions. Data were obtained for ultraviolet-B (UVB) radiation, nitrogen dioxide (NO₂), peroxyacetyl nitrate (PAN), ozone (O₃), and carbon monoxide (CO). Nocturnal plumes of NO₂ (in tens of ppb), observed near midnight, were correlated with CO and anti-correlated with O₃. This behavior was consistent with the titration of locally generated NO by boundary layer O₃ to form the nighttime NO₂ plumes that were subsequently transported into the Usery Pass Recreation area. Nitrate radical (NO₃) production rates were calculated to be very high on the edges of these nocturnal plumes. Examination of O₃ and PAN data also indicates that Phoenix is being affected by long-range transport of pollutants from the Los Angeles to San Diego areas. A regional smoke episode was observed in May, accompanied by a decrease in UVB of factor of two and a decrease in O₃ and an increase in methyl chloride. Low level back trajectories and chemical evidence confirm that the smoke event originated in northern Mexico and that the reduced O₃ levels observed at Usery Pass could be partially due to reduced photolysis rates caused by carbonaceous soot aerosols transported in the smoke plume. The results are discussed with regard to potential effects of local pollution transport from the Phoenix air basin as well as an assessment of the contributions from long-range transport of pollutants to the background levels in the Phoenix-Usery Pass area.     

Laser induced fluorescence instrument for NO2 measurements: Observations at a central Italy background site

A laser induced fluorescence (LIF) instrument has been developed to measure tropospheric NO₂ with low detection limit. The instrument design, development and first measurements are reported. There are also details of the temporal gate system built for the fluorescence acquisition. The instrument is able to make fast measurements (up to 4 Hz) and shows a limit of detection of 10 pptv/60 s. Continuous observations (2 weeks in summer 2007) in a small town in central Italy were used to test the performance of the instrument and to study the photochemistry of ozone in a background site. LIF and a commercial chemiluminescence (CL) instrument simultaneous observations of NO₂ show a good linearity (LIF = 1.02 CL + 0.6 (ppb), R² = 0.98) but there is a bias of the commercial instrument of about 0.60 ppbv on average. The overestimation of the CL system is probably due to conversion of NO_y species into NO by the molybdenum converter used in the CL instrument to detect NO₂. Analysis of 1 s data is used to test the instrument response and the coupling between nitrogen oxides and ozone.     

Impacts of a strong cold front on concentrations of HONO,HCHO, O3, and NO2 in the heavy traffic urban area of Beijing

Much rain and strong winds caused by a cold front occurred in Beijing during the period of Sep. 27 to Oct. 4, 2004 and led to sharp drops in maximum and mean concentrations of HONO, HCHO, O₃, and NO₂, i.e., the maximum concentrations were reduced by 5.9, 21.3, 45.6, and 44.4 ppb, respectively, and the mean concentrations were decreased by 4.0, 5.5, 30.3, and 32.3 ppb, respectively. For daily HO_x production rates HONO photolysis was the largest contributor and over 90% contributions were from photolysis of HONO and HCHO. Large number and area percentages of soot aggregate from PM10, and high correlations between concentrations of PM10 and chemical formation of HONO suggested that heterogeneous reactions of NO₂ on surfaces of soot aggregate could be a key source of HONO in the heavy traffic areas of Beijing during the night and should be considered in air quality simulations for such areas.     

Establishing ozone flux–response relationships for winter wheat: Analysis of uncertainties based on data for UK and Polish genotypes

The work outlined in this paper had three objectives. The first was to explore the effects of ozone pollution on grain yield and quality of commercially-grown winter wheat cultivars. The second was to derive a stomatal ozone flux model for winter wheat and compare with those already developed for spring wheat. The third was to evaluate exposure- versus flux–response approaches from a risk assessment perspective, and explore the implications of genetic variation in modelled ozone flux.Fifteen winter wheat cultivars were grown in open-top chambers where they were exposed to four levels of ozone. During fumigation, stomatal conductance measurements were made over the lifespan of the flag leaf across a range of environmental conditions. Although significant intra-specific variation in ‘ozone sensitivity’ (in terms of impacts on yield) was identified, yield was inversely related (R² = 0.63, P < 0.001) to the accumulated hourly averaged ozone exposure above 40 ppb during daylight hours (AOT40) across the dataset. The adverse effect of ozone on yield was principally due to a decline in seed weight. Algorithms defining the influence of environmental variables on stomatal uptake were subtly different from those currently in use, based on data for spring wheat, to map ozone impacts on pan-European cereal yield. Considerable intra-specific variation in phenological effects was identified. This meant that an ‘average behaviour’ had to be derived which reduced the predictive capability of the derived stomatal flux model (R² = 0.49, P < 0.001, 15 cultivars included). Indeed, given the intra-specific variability encountered, the flux model that was derived from the full dataset was no better in predicting O₃ impacts on wheat yield than was the AOT40 index. The study highlights the need to use ozone risk assessment tools appropriate to specific vegetation types when modelling and mapping ozone impacts at the regional level.     

Ozone flux over a Norway spruce forest and correlation with net ecosystem production

Daily ozone deposition flux to a Norway spruce forest in Czech Republic was measured using the gradient method in July and August 2008. Results were in good agreement with a deposition flux model. The mean daily stomatal uptake of ozone was around 47% of total deposition. Average deposition velocity was 0.39 cm s⁻¹ and 0.36 cm s⁻¹ by the gradient method and the deposition model, respectively. Measured and modelled non-stomatal uptake was around 0.2 cm s⁻¹. In addition, net ecosystem production (NEP) was measured by using Eddy Covariance and correlations with O₃ concentrations at 15 m a.g.l., total deposition and stomatal uptake were tested. Total deposition and stomatal uptake of ozone significantly decreased NEP, especially by high intensities of solar radiation.