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).     

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.     

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.     

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.     

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.     

Atmospheric dry deposition to leaf surfaces at a rural site of India

Dry deposition flux of major ions (Na+, K+, Ca2+, Mg2+, NH4+, F-, Cl-, NO3- and SO4(2-) to natural surfaces [guava (Psidium guyava) and peepal (Ficus religiosa) leaves] are determined at Rampur, a rural site of semi-arid region of India. Dry deposition flux is the highest for Ca2+ on guava leaves and for NH4+ on peepal leaves. Overall dry deposition flux is higher on guava leaves than of peepal leaves. The variation in deposition flux may be due to surface characteristics (surface roughness) and arrangement of leaves. Peepal leaves are arranged along the axis of the stem, whereas guava leaves are at right angles to the stem. The deposition flux of cations contributes 66% and 76% of dry deposition of all major ions on guava and peepal leaves, respectively as soil is major contributor towards dry deposition flux in tropical regions. ANOVA revealed no significant seasonal difference in deposition, although there is a trend for higher in winter. Deposition velocities of NH4+, NO3- and SO4(2-) are greater on guava leaves than peepal leaves, which can be attributed to the rougher surface of the guava leaf.     

Measurement of the dry deposition flux of NH3 on to coniferous forest

The dry deposition flux of NH3 to coniferous forest was determined by the micrometeorological gradient method using a 36 m high tower. Aerodynamic characteristics of the site were studied, using a second tower erected in the forest 100 m from the first. Fluxes and gradients of heat and momentum measured on both towers indicated a fairly homogeneous turbulent flow field over the studied area of the forest. Site specific flux profile functions for heat were derived from continuous measurements of turbulent fluxes and gradients. These functions were used to derive fluxes from the observed gradients of NH3. In total, eighty 90-min NH3 flux runs were performed. The results indicate a strong nonstomatal uptake of NH3 by the forest. A representative dry deposition velocity for NH3 of 3.6 cm(-1) s was derived. The annual average flux was roughly estimated to be equivalent to 50 kg N ha(-1) yr, significantly higher than the critical load for coniferous forest.     

Characterization of atmospheric dry deposition particulates in Kobe, Japan

The sources and character of individual metal and metalloid particles from atmospheric dry depositions in Kobe, Japan were investigated. Japan faces long-range pollutant transportation from northeastern Asia during winter and spring. Information regarding their properties and sources is useful for evaluating their affects on the environment and human health. Individual metal and metalloid particles that were collected for every 24 h on the plate, which was designed to reduce a local turbulence, were characterized for their composition, diameter, and deposition fluxes using a field emission scanning electron microscope with an energy dispersive X-ray spectrometer. Approximately 3,000 metal and metalloid particles were classified into 14 types based on their composition and further classified into four groups based on their distribution patterns. They are (A) Fe-O, Fe-Ba-Sb-Cu-S-Ti-O, Fe-Zn-O, Zn-O, Ni-O, and Mn-Fe-O; (B) Cu-Zn-O and Cu-Sn-O; (C) Pb-O, Sn-Sb-O, and Ag-O; (D) Pb-Zn-Cl-Si-S-O and Bi-Cl-O. From these data, this study suggests their sources as the Asian continent (Group A), local source (Group B), multiple sources (Group C), and incineration process (Group D). This study shows (1) the sources and character of individual metal and metalloid particles from short-term atmospheric depositions in Kobe, Japan and (2) application of individual particle analysis for atmospheric depositions.     

A multi-layer model for pollutant dispersion with dry deposition to the ground

This paper presents a semi-analytical solution for the steady advection–diffusion equation that allows simulating the vertical turbulent dispersion of air pollution with deposition to the ground. The performances of the solution, with a proper parameterization of the vertical profiles of wind and eddy diffusivity, were evaluated against Hanford diffusion experiment dataset using two tracers (Doran and Horst, 1985): a non-depositing gas (SF₆) and depositing particles (ZnS). Results show that the dispersion model with the K-parameterization included produces a good fitting of the measured ground-level concentration data and there are no big differences between the parameterizations taken from literature. A comparison with other models was shown and discussed.     

Reconciling models and measurements to assess trends in atmospheric mercury deposition

Changes in atmospheric mercury deposition are used to evaluate the effectiveness of regulations controlling emissions. This analysis can be complicated by seemingly incongruent data from different model runs, model types, and field measurements. Here we present a case study example that describes how to identify trends in regional scale mercury deposition using best-available information from multiple data sources. To do this, we use data from three atmospheric chemistry models (CMAQ, GEOS-Chem, HYSPLIT) and multiple sediment archives (ombrotrophic bog, headwater lake, coastal salt marsh) from the Bay of Fundy region in Canada. Combined sediment and modeling data indicate that deposition attributable to US and Canadian emissions has declined in recent years, thereby increasing the relative significance of global sources. We estimate that anthropogenic emissions in the US and Canada account for 28-33% of contemporary atmospheric deposition in this region, with the rest from natural (14-32%) and global sources (41-53%).     

A laboratory investigation of the routes of HNO3 dry deposition to coniferous seedlings

White pine, Norway spruce and red spruce seedlings were exposed to nitric acid vapor concentrations of 10 to 120 ppb in constant stirred tank reactors. Nitric acid dry deposition rates were determined from both the change in nitric acid concentration in the reactor flow stream and from the amount of nitrogen recovered from the seedlings. Nitric acid labeled with 15N was used to distinguish dry-deposited nitrogen in the plant from the nitrogen that was already present. It was found that dry deposition occurs via three routes: surface deposition, trans-cuticular deposition, and stomatal deposition. Resistance to surface deposition is very low (< 4.8 m2-s mol(-1)) for a freshly washed surface, but increases as the surface adsorption sites are occupied. Resistance to trans-cuticular uptake averaged 206 m2-s mol(-1). Stomatal resistance can be calculated from the rate of water diffusion out of the plant. Eighty per cent of the nitric acid deposited via the trans-cuticular and stomatal routes was assimilated by the plant. However, none of the nitric acid deposited on the surface was assimilated. In rural areas with coniferous forests, the combination of low ambient nitric acid concentrations and low initial surface resistance means that most nitric acid will be dry deposited on the tree surface, and thus will not be directly assimilated.     

Bacterial deposition in unsaturated porous media as related to surface properties

Transport of Escherichia coli, Pseudomonas fluorescens and Bacillus subtilis in silica sand under water-unsaturated conditions was investigated using column experiments. It was hypothesised that bacterial deposition was due to their interactions within the pore environment, which was a function of their surface physicochemical properties as well as pore water chemistry. Surface thermodynamic properties of these bacterial strains were measured independently by means of contact angle measurements under different water saturation conditions using variable lawn moisture contents. Bacterial interactions with the liquid-gas interface and the porous media were calculated based on their surface properties and were related to their transport observations.     

Outlier detection in phosphorus dry deposition rates measured in South Florida

Dry atmospheric deposition contributes a significant amount of phosphorus to the Everglades of South Florida. Measurement of this deposition is problematic, because samples often are contaminated to varying degrees by bird droppings and other foreign materials. This study attempted to detect and remove the outliers in phosphorus (P) flux rates measured from dry deposition samples. Visual inspection of the samples, recorded in field notes, found that 30.1% of the samples contained animal droppings and frogs. Some of the samples with droppings and frogs (2.3%) had P values greater than 884 μg P m⁻² d⁻¹ (a value twice the standard deviation of the raw data mean), and were removed from further analysis. Outlier detection statistics based on a linear regression were then used for additional data screening. Eight stations in the network of 19 were removed because high contamination precluded the use of the regression model. Of the remaining samples, 15.7% were identified through the regression procedure as contaminated and were removed. The 11 station mean for P dry deposition was 85.8±79.0 μg P m⁻² d⁻¹, prior to the regression analysis, and 74.8±75.1 μg P m⁻² d⁻¹ after removal.     

Atmospheric nitrogen deposition on the east coast of Spain: relevance of dry deposition in semi-arid Mediterranean regions

Bulk deposition composition and pine branch washing were measured from April 1999 to March 2000 on the east coast of Spain. The main objective was to characterise N deposition patterns with special emphasis on dry deposition. Bulk deposition in the region is dominated by neutralisation processes by Ca2+ and HCO3-, ClNa of marine origin and a high correlation between NO3- and SO4(2-). SO4(2-) concentrations show a decrease with respect to previous studies in the region in agreement with generalized sulfur emission decreases while the remaining ions, including NO3-, are higher due to their general increase as well as to the inclusion of dry deposition in bulk collectors in the present study. An enrichment in NO3- has been observed in dry deposition composition branch washing) with respect to bulk deposition, while an impoverishment has been observed in the case of NH4+. Annual bulk deposition varies between 7.22-3.1 and 3.5-1.8 Kg ha(-1) year(-1) for S- SO4(2-) and N- NO3-, respectively. N total deposition goes from 9.78 to 6.8 Kg ha(-1) year(-1) at most stations, with the lowest deposition at the control station and Alcoi. The relative dry deposition with respect to the total was over 40% at most stations, going up to 75% at the southern station. N-deposition is expected to be higher considering that N-NH4+ deposition has been underestimated in this study.     

Apply appropriate models in the study of dry deposition fluxes of particulate matter and polycyclic aromatic hydrocarbons (PAHs) in Tsukuba, Japan

In this study, plates for downward flux and upward flux were used to measure atmospheric dry deposition fluxes for particulate mass and polycyclic aromatic hydrocarbons (PAHs) in TERC (Tsukuba), Japan. Ambient particles concentrations were also collected using a high-volume air sampler, and ambient particle size distributions between 0.01 μm and 13.1 μm were measured using a low-pressure cascade impactor to characterise the PAHs levels and dry deposition. The results indicated that the average cumulative fraction of dry deposition flux for particles and PAHs which attached with them was caused by the particle size of greater than 1.2-6.3 μm (97%).     

Atmospheric dry deposition fluxes of trace elements measured in Bursa, Turkey

Trace element dry deposition fluxes were measured using a smooth, greased, knife-edge surrogate surface (KSS) holding greased Mylar strips in Bursa, Turkey. Sampling program was conducted between October 2002 and June 2003 and 46 dry deposition samples were collected. The average fluxes of crustal metals (Mg, Ca, and Fe) were one to four orders of magnitude higher than the fluxes of anthropogenic metals. Trace element fluxes ranged from 3 (Cd) to 24,230 (Ca) microg m(-2) d(-1). The average trace element dry deposition fluxes measured in this study were similar to those measured in other urban areas. In addition, ambient air samples were also collected simultaneously with flux samples and concentrations of trace elements, collected with a TSP sampler, were between 0.7 and 4900 ng m(-3) for Cd and Ca, respectively. The overall trace element dry deposition velocities, calculated by dividing the fluxes to the particle phase concentrations ranged from 2.3+/-1.7 cm s(-1) (Pb) to 11.1+/-6.4 cm s(-1) (Ni). These values are in good agreement with the values calculated using similar techniques. The anthropogenic and crustal contributions were estimated by employing enrichment factors (EFs) calculated relative to the average crustal composition. Low EFs for dry deposition samples were calculated. This is probably due to contamination of local dust and its important contribution to the collected samples.