An experimental study of the dry deposition of gaseous nitric acid to snow

A chamber placed in a constant temperature freezing room was used to study the surface resistance during deposition of HNO₃ to a snow surface. The resistance decreased with increasing temperature from larger than 5 s mm⁻¹ at − 18°C to about l s mm⁻¹ at −3°C. Measurements of gaseous and particulate nitrate concentrations during winter at a rural site in south central Sweden gave concentrations in the range of 0.4–5 μg HNO₃ m⁻¹ and 0.3–3 μg NO⁻₃ m⁻³ with a mean value of 1.3 μg HNO₃ m⁻³ and 0.7 μg NO⁻₃ m⁻³, respectively. The results indicate that for periods with temperatures below − 2°C estimated dry deposition of HNO₃ to snow is at most 4 % of measured wet deposition of nitrate in the area.     

A theoretical assessment of pollutant deposition to individual land types during a regional-scale acid deposition episode

A mesoscale model of pollutant transport, transformation and deposition was used to perform a detailed analysis of acidic deposition to the states of New York and Ohio during a 3-day springtime deposition episode. This model can be used to assess the roles of wet and dry deposition to individual land types in the removal of pollutants from the atmosphere. Over two-thirds (67 %, Ohio; 78 %, New York) of the acidic deposition during this rainy period fell as wet deposition, primarily in the form of H₂SO₄. Dry deposition of SO₂ accounted for 70–75 % of the total dry acidic deposition in both areas, and most of the remaining dry deposition occurred as HNO₃. Over both deposition areas, particulate sulfate deposition accounted for <1 % of the total acid deposition. Due to the highly surface-specific nature of the dry deposition process, individual land types displayed unique patterns of pollutant uptake. Water surfaces absorbed primarily SO₂, while rougher forested areas absorbed a larger proportion of HNO₃ vapor. Urban areas, with their associated material surfaces, were found to absorb significantly less acid in the dry form, and during dry periods most of this deposition may occur as HNO₃ vapor, although considerable uncertainty exists regarding the treatment of rainfall-wetted surfaces. These model results suggest that dry pollutant fluxes to individual surface types will show significant variability from any ‘averaged’ flux estimates over larger areas encompassing numerous land types.     

The interfacial mass transfer resistances of the ozone dry deposition over the field soil of Taichung County in Taiwan

This study aims to design a dry deposition chamber and to measure ozone depletion over the Taichung field soil. This study seeks to verify the phenomena by an experimental and mathematical model. It is demonstrated that interfacial mass transfer resistances of ozone dry deposition involve reactive resistance (R(sr)) and kinetic resistance (R(sk)). It reveals the chemical reaction (O3 + NO --> NO2) to produce the reactive resistance, and verifies that the interfacial mass transfer resistances depend on nitrogen oxide emission and soil temperature. It shows that the interfacial mass transfer resistances are reduced with increasing soil temperature (T(S)). The model profiles are smaller than the observed data within a relative error of 15%. The reactive resistance decreases exponentially with increasing soil temperature; R(sr)(-1) (cm x sec(-1)) = 0.0001 exp (0.1455T(S)). The kinetic resistance decreases linearly with increasing soil temperature; R(sk)(-1)(cm x sec(-1)) = 0.0108T(S) + 1.4012. This model is more accurate with higher soil temperature and larger ozone concentration. Results are consistent with thermodynamics and reaction kinetics. Ozone dry deposition over agricultural soil causes conversion of nitrogen oxide (NO) to nitrogen dioxide (NO2).     

Comparison of surrogate surface techniques for estimation of sulfate dry deposition

The dry deposition rates of sulfate particles to artificial surfaces within and above a mature hardwood forest were measured over an annual range of synoptic weather conditions. Artificial, or ‘surrogate’, surfaces representing both rough and smooth textural types included deposition buckets, petri dishes, filter paper, Teflon configurations and polycarbonate membranes. Ambient concentrations of sulfate and sulfur dioxide were also monitored.The artificial surfaces were evaluated on the basis of the magnitude of the sulfate dry deposition rates and measurement precision. Correlations between techniques and the magnitude of the deposition velocities identified technique similarities. Ambient concentrations of the sulfur oxides and the deposition rates were not well correlated. For diverse reasons, many of the techniques were found to have limited reliability. The petri dish, bucket inside and filter plate surfaces were found to represent the most precise devices for the estimation of dry deposition to smooth, complex and rough artificial surfaces, respectively. Seasonal averages for samplers exposed at all heights were 11.2, 27.7 and 71.2μg SO₄²⁻m⁻²h⁻¹, yielding mean deposition velocities to surfaces exposed within the forest canopy of 0.03,0.11 and 0.14 cm s⁻¹ and an annual estimate of the potential dry deposition to a foliated hardwood forest of 4.0, 11.5 and 21.0 kg SO₄²⁻ha⁻¹ for the petri dish, bucket inside and filter plate surfaces, respectively. The indirect ratio between deposition rates and velocities results from varying concentrations of ambient sulfate between sampling periods. The accuracy of the filter plate data is suspect due to a significant correlation with sulfur dioxide concentrations. Sulfur concentration and deposition rate gradients indicate the forest is providing a net sink for sulfur pollutants during periods with foliage.The wide range of dry deposition rates estimated from the variety of deposition surfaces emphasizes the uncertainty of the artificial surface measurement techniques. In spite of these limitations, surrogate surfaces provide an estimate of sulfate flux rates not currently obtainable from natural surfaces.     

Deposition to forests in Europe: most important factors influencing dry deposition and models used for generalisation

Dry deposition of gases and particles to forests is influenced by factors influencing the turbulent transport, such as wind speed, tree height, canopy closure, LAI, etc. as well as by factors influencing surface condition, such as precipitation, relative humidity, global radiation, etc. In this paper, an overview of these factors is given and it is shown which are the most important determining temporal and spatial variation of dry deposition of sodium and sulphur. Furthermore, it is evaluated how well current deposition models are able to describe the temporal and spatial variation in dry deposition. It is concluded that the temporal variation is not modelled well enough, because of limited surface-wetness exchange parameterisations. The influence of forest characteristics are modelled reasonably well, provided enough data describing the forests and the spatial variation in concentration is available. For Europe these data are not available. The means to decrease the atmospheric deposition through forest management is discussed.     

Parameterization of wet deposition of sulfate by precipitation rate

A method for the estimation of wet deposition of sulfate is developed using routinely available meteorological data and the observed airborne sulfate concentration. This approach takes into account different mechanisms of precipitation formation that determine sulfate concentration in precipitation water. Four different precipitating cloud types, including cold cloud, warm cloud, stratified layered cloud and convective cloud, according to their precipitation formations are incorporated differently to estimate sulfate concentration in precipitation water. This method is implemented to estimate wet deposition of sulfate in Seoul for the days when the airborne sulfate concentration is available. The estimated wet deposition of sulfate shows that the model slightly overestimates the wet deposition of sulfate especially for the warm cloud case while it does underestimate sulfate deposition for the Bergeron process in developing precipitation particularly when the input airborne sulfate concentration is small. The precipitation amount weighted mean wet deposition of sulfate obtained from the model, overestimates that observed by a factor of 1.6 for this case study. This discrepancy might be associated with non-steady revolutional features of precipitating clouds and the resolvable scaling difference between the model and observation.     

PAH deposition to snow surface

The urban snowpack effectively acts as a collection device for atmospheric-deposited PAHs. When these PAHs are flushed out in a short time interval along with springtime snowmelt, these cause shockloading to receiving waters. In order to assess the PAH deposition and accumulation in urban snowpacks, a deposition survey of PAH for the winter months of 1991-92 from the city of Sault Ste. Marie, Ontario, Canada was undertaken. The results of the survey are interpreted in view of prevailing meteorology and various emission sources in the study area. The relative PAH deposition levels (to BaP) are compared with relative source emission fingerprints to examine consistency in sampling and analysis. While analyzing the PAH samples using the ASTM (1987) method, the problem of concentration levels being below the detection level was encountered. The ASTM method for PAH analysis was modified to enhance the detection limit of the PAHs by concentrating the PAH extract to very low volumes, on the order of 200-300 microL.     

Assessing the relative importance of surface ozone influential variables in regional-scale analysis

The multilayer perceptron (MLP) model is frequently used to assess the relative importance (RI) of surface ozone influential variables when they are used to investigate ozone variation mechanisms. Previous studies, however, suffer from two limitations: 1) indentifying or searching the optimal MLP topology to avoid a biased RI assessment inevitably incurs a heavy computational burden, and 2) the model is suitable only for local-scale analysis of ozone variation mechanisms. To tackle both problems, we selected three typical air-quality monitoring sites in Hong Kong as our study targets, as the ozone variations at these sites are inhomogeneously affected by regional and local factors. An MLP model trained by automatic relevance determination (referred to as MLP-ARD), a Bayesian MLP approach, was employed to assess the RI for both regional and local ozone influential variables. The results indicated the following remarks: 1) The MLP-ARD model, due to its high degree of resistance to both the over-fitting and the under-fitting problems, is exempt from identifying or searching the optimal MLP topology when used to obtain an unbiased RI assessment and thus avoid the heavy computational burden. Furthermore, the RI assessment results obtained with the MLP-ARD method are comparable to those of the best assessment method in the literature. Based on these findings, decision-makers can scientifically promulgate a site-specific air pollution control strategy site; 2) Regional-scale analysis of ozone variation is indispensable, as taking the key regional ozone influential variables into account significantly improves the prediction accuracy of the MLP-ARD model, especially on peak ozone days.     

Measurement of dry deposition to surfaces in deciduous and pine canopies

The importance of dry deposition was assessed at perimeter and interior locations in two vegetative canopies. Dry deposition was measured directly by washing particles from leaves. Ambient particles and gases were also collected at both locations within the canopies. Ambient concentrations on the canopy interior were decreased relative to perimeter concentrations due to dry deposition scavenging by the canopy. The least scavenging was found for SO(4)(2-) and NH(4)(+) and the highest scavenging was found for HNO(3). Dry deposition of all species was higher to perimeter vegetative and surrogate surfaces than to interior surfaces, due both to the lower concentrations and the lower wind speeds in the sheltered interior. Deposition velocities compared well with other experimental and theoretical values.     

A canopy stomatal resistance model for gaseous deposition to vegetated surfaces

A gaseous deposition model, based on a realistic canopy stomatal resistance submodel, is described, analyzed and tested. This model is designed as one of a hierarchy of simulations, leading up to a “big-leaf” model of the processes contributing to the exchange of trace gases between the atmosphere and vegetated surfaces. Computations show that differences in plant species and environmental and physiological conditions can affect the canopy stomatal resistance by a factor of four. Canopy stomatal resistances to water vapor transfer computed with the present model are compared against values measured with a porometer and computed with the Penman-Monteith equation. Computed stomatal resistances from a soybean canopy in both well-watered and water-stressed conditions yield good agreement with test data. The stomatal resistance submodel responds well to changing environmental and physiological conditions. Model predictions of deposition velocities are evaluated for the case of ozone, transferred to maize. Calculated deposition velocities of O₃ overestimate measured values on the average by about 30%, probably largely as a consequence of uncertainties in leaf area index, soil and cuticle resistances, and other modeling parameters, but also partially due to imperfect measurement of O₃ deposition velocities.     

Numerical modeling of dry deposition coupled to 22 photochemical reactions

Three Eulerian models for the dry deposition of photochemically reactive species were formulated and evaluated: a K-theory model with independent transport and deposition of each species, a K-theory model coupled with 22 gas-phase reactions, and a second-order flux-budget model coupled with 22 reactions. Operator splitting was used to separately solve the reaction and dispersion terms in the models including photochemistry. In an evaluation of numerical method performance, the Adams–Moulton method with a pseudo-steady-state approximation for the free radicals was found to be consistent with, but more computationally efficient than Gear’s method for the solution of the reaction terms. The sensitivity of profiles of vertical concentration and flux to the Eulerian model formulation varied according to the species’ Damköhler number. Although a K-theory model is adequate for weakly depositing species with Damköhler numbers <10^-3, a second-order flux-budget model is required for species with Damköhler numbers that exceed unity, such as nitrogen oxides, free radicals, and those sensitive to net flux production by chemical reactions. Selection of an appropriate model formulation for the entire system depended on the most reactive species. Simple K-theory models may not accurately predict dry deposition fluxes in the urban surface layer.     

Sources and deposition of reactive gaseous mercury in the marine atmosphere

Observations of reactive gaseous mercury (RGM) in marine air show a consistent diurnal cycle with minimum at night, rapid increase at sunrise, maximum at midday, and rapid decline in afternoon. We use a box model for the marine boundary layer (MBL) to interpret these observations in terms of RGM sources and sinks. The morning rise and midday maximum are consistent with oxidation of elemental mercury (Hg⁰) by Br atoms, requiring <2 ppt BrO in most conditions. Oxidation of Hg⁰ by Br accounts for 35–60% of the RGM source in our model MBL, with most of the remainder contributed by oxidation of Hg⁰ by ozone (5–20%) and entrainment of RGM-rich air from the free troposphere (25–40%). Oxidation of Hg⁰ by Cl is minor (3–7%), and oxidation by OH cannot reproduce the observed RGM diurnal cycle, suggesting that it is unimportant. Fitting the RGM observations could be achieved in the model without oxidation of Hg⁰ by ozone (leaving Br as the only significant oxidant) by increasing the entrainment flux from the free troposphere. The large relative diurnal amplitude of RGM concentrations implies rapid loss with a lifetime of only a few hours. We show that this can be quantitatively explained by rapid, mass-transfer-limited uptake of RGM into sea-salt aerosols as HgCl₃^? and HgCl₄^2?. Our results suggest that 80–95% of Hg^II in the MBL should be present in sea-salt aerosol rather than gas-phase, and that deposition of sea-salt aerosols is the major pathway delivering Hg^II to the ocean.     

Wintertime wet and dry deposition in northern Michigan

Wet and dry deposition were monitored at the University of Michigan Biological Station in rural northern Michigan for three winters. Dry deposition was measured by both the conventional bucket method and by measuring increases in concentration in exposed, elevated snow samples. Average results of the two methods were in reasonable agreement. The cumulative wet and dry deposition quantities are in good agreement with snowpack accumulations until the first thaw period. Dry deposition to snow accounts for less than 15% of the total H⁺, SO²⁻₄, NO⁻₃ and NH⁺₄ and approximately 25% of the Ca ²⁺, Mg ²⁺, Na⁺, K⁺ and Cl⁻ during an average precipitation year. Snowpack measurements were also made under deciduous and red pine canopies. Decreases in H⁺ and NO⁻₃ were observed under the red pine canopy.     

Wet and dry deposition monitoring in Southeastern Michigan

Wet and dry deposition as collected by a bucket were measured at two sites in southeastern Michigan for two years. The precipitation had an average pH of 4.27 and a SO²⁻₄ to NO⁻₃ ratio of 2.0. Particulate dry deposition velocities of 0.6 cm s⁻¹ for SO²⁻₄ and NO⁻₃ and > 2 cm s⁻¹ for Cl⁻, Ca²⁺, Mg²⁺,Na⁺ and K⁺ were calculated. The ambient particle composition, dry bucket collection and wet deposition were compared at two sites, one urban and the other rural. Higher ambient particle concentrations and dry deposition rates were measured at the urban site than the rural site, indicating the influence of local emissions. However, local emissions had no effect on the wet deposition concentrations. The influence of more distant source regions was examined by separating the precipitation events by wind direction. The events from the south and east had the highest SO²⁻₄ to NO⁻₃ ratios, which corresponded to the areas with the highest sulfur emissions. NO⁻₃ showed no directional dependence.Wet deposition was examined for the effect of storm type and seasonal trends. Contrary to a recent study on Long Island, we found higher concentrations of H⁺, SO²⁻₄ and NH⁺₄ in winter rain compared to snow. The wet deposition concentrations of H⁺, SO²⁻₄, and NH⁺₄ were highest in the summer, while only Na⁺ and Cl⁻ concentrations were highest in the winter, presumably due to winter road salting. The total deposition of acidic ions was highest in the summer and lowest in the winter, due both to lower concentrations and lower precipitation volumes in the winter. The dry deposition as collected by a bucket accounted for 1 % of total H⁺ deposition, 21 % of SO²⁻₄ deposition, 27% of NO⁻₃ deposition, 50% of Cl⁻ deposition and 61 % of Ca²⁺ deposition.     

Error estimations of dry deposition velocities of air pollutants using bulk sea surface temperature under common assumptions

It is well known that skin sea surface temperature (SSST) is different from bulk sea surface temperature (BSST) by a few tenths of a degree Celsius. However, the extent of the error associated with dry deposition (or uptake) estimation by using BSST is not well known. This study tries to conduct such an evaluation using the on-board observation data over the South China Sea in the summers of 2004 and 2006. It was found that when a warm layer occurred, the deposition velocities using BSST were underestimated within the range of 0.8–4.3%, and the absorbed sea surface heat flux was overestimated by 21 W m^?2. In contrast, under cool skin only conditions, the deposition velocities using BSST were overestimated within the range of 0.5–2.0%, varying with pollutants and the absorbed sea surface heat flux was underestimated also by 21 W m^?2. Scale analysis shows that for a slightly soluble gas (e.g., NO₂, NO and CO), the error in the solubility estimation using BSST is the major source of the error in dry deposition estimation. For a highly soluble gas (e.g., SO₂), the error in the estimation of turbulent heat fluxes and, consequently, aerodynamic resistance and gas-phase film resistance using BSST is the major source of the total error. In contrast, for a medium soluble gas (e.g., O₃ and CO₂) both the errors from the estimations of the solubility and aerodynamic resistance are important. In addition, deposition estimations using various assumptions are discussed. The largest uncertainty is from the parameterizations for chemical enhancement factors. Other important areas of uncertainty include: (1) various parameterizations for gas-transfer velocity; (2) neutral-atmosphere assumption; (3) using BSST as SST, and (4) constant pH value assumption.