Wet deposition of phosphorus in Florida

Wet deposition of phosphorus was measured at 10 sites across Florida originally established as part of the Florida Atmospheric Mercury Study conducted between 1992 and 1996. Monthly integrated samples were collected and analyzed using a total analytical protocol that incorporated “clean lab” conditions for sample equipment preparation and Aerochem Metrics collectors modified for suitability to use for ultra-trace elements. Samples also were collected aboard 15 m towers to minimize any influence on measured deposition by insects, etc., and locally originating particles that do not contribute to true net deposition. Extensive replication of samples in the field was conducted (ca. 83%). The average absolute difference between replicates was 16.2%, with a median absolute difference of 9.5%. Replicate precision was poorest for concentrations above 0.080 mg P l⁻¹, suggesting that concentrations above this level are contaminated.The wet deposition concentrations and fluxes of phosphorus measured in this study are appreciably lower than those reported by previous investigators for wet deposition in Florida, and lie at the lower end of measurements reported in the recent literature. For example, the volume weighted mean concentration and flux for wet deposition across all our study sites averaged 0.005 mg P l⁻¹ and 7.5 mg P m⁻² yr⁻¹, respectively, which is approximately 50% and 32% lower than that reported by Hendry et al. (1981 in Atmospheric Pollutants in Natural Waters. Ann Arbor Science, Ann Arbor. MI, pp. 199–215). Our lower measurements likely reflect three factors: (1) the ultra-trace element sampling and analytical protocols; (2) improved collector design to eliminate sampling artifacts (e.g., splash-off contamination and transfer of contaminants from the dry bucket); and (3) placement of collectors off the ground surface. Lower VWM concentrations were observed near the Florida coast; otherwise, strong spatial patterns across the state were absent. Seasonal variations in VWM also were not pronounced, although deposition fluxes were highest during the summer wet season in response to the strong seasonal distribution of rainfall.     

Influence of usage and chemical–physical properties on the atmospheric transport and deposition of pesticides to agricultural regions of Manitoba,Canada

This study quantified the masses of 14 pesticides deposited as wet (precipitation) versus dry (gaseous and particle) atmospheric deposition at a research farm in southwestern Manitoba, Canada. The concentration in air of these pesticides was also measured. Total bulk deposition amounts (wet + dry) ranged from 0.009 to 2.3 μg m^?2 for the 12 pesticides detected, and for the six pesticides with both wet and dry deposition detections, dry deposition contributed 12–51% of the total deposition over the crop growing season. Although not applied at the site, eight herbicides registered for use in Canada, as well as lindane (γ-HCH), were all frequently detected (92–100%) in the 12 air samples analyzed during the crop growing season, with by-product isomer α-HCH (75%), clopyralid (50%) and atrazine (8%) detected to a lesser extent. The chemical’s physicochemical properties and the relative mean mass of each agricultural pesticide applied in the province of Manitoba and in a 13 km radius were significant parameters in explaining the trends in the concentrations of pesticides detected in our samples. The important contribution of dry deposition to total pesticide deposition warrants greater attention in arid and semi-arid areas such as the Prairie Region of Canada, also because under a changing climate this region is estimated to experience more severe droughts while the more favorable conditions predicted for pest infestations could lead to increased pesticide applications in agricultural and urban areas.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in Guangzhou,China

Atmospheric deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was investigated at four locations, namely at Yuancun, Wushan, Haizhu and Changban in Guangzhou City, Guangdong Province. The annual deposition fluxes of tetra- to octa-CDD/Fs (total PCDD/Fs) were found to range from 170 to 3000 (mean 1500) pg m⁻² day⁻¹, and the fluxes of total 2, 3, 7, 8-substituted PCDD/F congeners ranged from 2.1 to 41 (mean 20) pg WHO-TEQ m⁻² day⁻¹ at Wushan. The average deposition fluxes of total 2, 3, 7, 8-substituted PCDD/F congeners in rainy season were found to be 37, 27 and 28 pg WHO-TEQ m⁻² day⁻¹ at Yuancun, Haizhu and Changban, respectively, and the PCDD/F deposition fluxes behaved obviously higher in rainy season than in dry season. Results from regression analysis showed that number of rainy days, the amount of wet precipitation, PCDD/F concentrations in particles and organic carbon content played important roles in the variation of PCDD/F deposition fluxes. Monthly average temperatures change little over the year. Therefore, it only played a minor role in monthly variation of PCDD/F deposition fluxes. Particle deposition fluxes were generally not considered as the factor that could cause the differences in PCDD/F deposition fluxes between rainy and dry season, but were found to be related with PCDD/F deposition fluxes in rainy season or dry season. It was found that the profiles of PCDD/F homologs or congeners in the samples were the same either spatially or temporally, indicating that the PCDD/F emission sources were similar to one another. The similarities in PCDD/F homolog patterns and the differences in deposition fluxes between samples collected from heavy-traffic roadside and nearby residence house roof indicated that vehicle exhaust might be an important source for PCDD/F in Guangzhou. PCDD/F concentrations and profiles of PCDD/F homologs in atmospheric deposition were compared with those in both total suspended particles in air and soils, and conclusions indicated that atmospheric deposition possibly tended to remove lower-chlorinated DD/Fs from air and was one of sources for PCDD/Fs in soils.     

Atmospheric deposition of organochlorine contaminants to Galveston Bay,Texas

Atmospheric monitoring of PCBs and chlorinated pesticides (e.g., HCHs, chlordanes, and DDTs) in Galveston Bay was conducted at Seabrook, Texas. Air and wet deposition samples were collected from 2 February 1995 and continued through 6 August 1996. Vapor total PCB (tPCB) concentrations in air ranged from 0.21 to 4.78 ng m⁻³ with a dominance of tri-chlorinated PCBs. Dissolved tPCBs in rain ranged from 0.08 to 3.34 ng l⁻¹, with tetra-chlorinated PCBs predominating. The predominant isomers found in air and rain were α- and γ-HCH, α- and γ-chlordanes, 4,4′-DDT, and dieldrin. The concentrations of PCBs and pesticides in the air and rain revealed no clear seasonal trend. Elevated levels of PCBs in the air occurred when temperatures were high and wind came from urban and industrialized areas (S, SW, NW, and W of the site). Concentrations of HCHs were elevated in April, May, and October, perhaps due to local and/or regional applications of γ-HCH (lindane). Other pesticides showed no notable temporal variation. When winds originated from the Gulf of Mexico (southeasterly), lower concentrations of organochlorines were detected in the air. The direct deposition rate (wet+dry) of PCBs to Galveston Bay (6.40 μg m⁻² yr⁻¹) was significantly higher than that of pesticides by a factor of 5–10. The net flux from gas exchange estimated for PCBs was from Galveston Bay water to the atmosphere (78 μg m⁻² yr⁻¹). Gas exchange of PCBs from bay water to the atmosphere was the dominant flux.     

Effects of missing seasonal data on estimates of period means of dry and wet deposition

The current study uses resampling to investigate the impacts of cyclic seasonal behavior on 1- and 5-year period means composed from seasonal mean values in the presence of missing data. This is an empirical study using complete years of seasonal monitoring data collected in the eastern US and extracted from the clean air status and trends network (CASTNET) dry and the National Atmospheric Deposition Program/National Trends Network (NADP/NTN) wet deposition data archives. Estimators of period means with missing seasonal data are determined using means of the non-missing values as estimates of the missing data. Estimates are evaluated in terms of 95% inclusion intervals (e.g., estimates are within ±X% of the true value ⩾95% of the time). For dry deposition, missing transition seasons (i.e., spring or fall) usually yield estimates of annual means that are within ±20% of the true annual mean ⩾95% of the time. Missing summers or winters usually have larger impacts on estimates of annual means of dry deposited species than missing transition seasons. A missing summer has the largest impact on estimates of annual means of dry deposition for all constituents, except SO₂, where winter is especially important. For wet deposition, a missing season yields estimates of annual means that are within ±30% of the true annual mean ⩾95% of the time. A missing summer has the largest impact on estimates of annual means of wet deposition for all constituents, except NH₄⁺, where spring and fall are important. A strategy requiring at least 3 years of seasonal representation for three seasons with the fourth season having at least two seasonal values, yields estimates of wet deposition that are within ±17% of the true 5-year means ⩾95% of the time for all species. Corresponding confidence statements for dry deposition results are considerably stronger, with estimates that are within ±10% of the true 5-year mean ⩾95% of the time.     

Atmospheric deposition of nitrogen emitted in the Metropolitan Area of Buenos Aires to coastal waters of de la Plata River

The Metropolitan Area of Buenos Aires (MABA) is the third mega-city in Latin America. Atmospheric N emitted in the area deposits to coastal waters of de la Plata River. This study describes the parameterizations included in DAUMOD-RD (v.3) model to evaluate concentrations of nitrogen compounds (nitrogen dioxide, gaseous nitric acid and nitrate aerosol) and their total (dry and wet) deposition to a water surface. This model is applied to area sources and CALPUFF model to point sources of NO_x in the MABA. The models are run for 3 years of hourly meteorological data, with a spatial resolution of 1 km². Mean annual deposition is 69, 728 kg-N year^?1 over 2 339 km² of river. Dry deposition contributions of N-NO₂, N-HNO₃ and N-NO₃^? to this value are 44%, 22% and 20%, respectively. Wet deposition of N-HNO₃ and N-NO₃^? represents 3% and 11% of total annual value, respectively. This very low contribution results from the rare occurrence of rainy hours with wind blowing from the city to the river. Monthly dry deposition flux estimated for coastal waters of MABA varies between 7 and 13 kg-N km^?2 month^?1. These results are comparable to values reported for other coastal zones in the world.     

Monthly and annual bias in weekly (NADP/NTN) versus daily (AIRMoN) precipitation chemistry data in the Eastern USA

Previous comparisons of the data from the National Atmospheric Deposition Program, National Trends Network (NTN) against collocated event sampled data and daily sampled data suggest a substantial bias in the concentration of ammonium [NH₄⁺] and concentrations of several base cations, while the comparability of other ion concentrations ranges among the studies. Eight years of collocated data from five NTN and Atmospheric Integrated Research and Monitoring Network (AIRMoN) sites are compared here. Unlike previous analyses, the data from these two data sets were analyzed in the same laboratory using the same analytical methods; therefore, factors that influence concentration differences can be isolated to sampling frequency and sample preservation techniques. For comparison, the relative biases for these data have been calculated using both median value and volume-weighted mean concentrations, following two different approaches in the literature. The results suggest a relative bias of about 10% in [NH₄⁺] (NTN less than AIRMoN), which is smaller than previous estimates that included the influence of inter-laboratory comparisons. The annual relative bias of [H⁺] increases over the analysis period, which results in a larger total relative bias for [H⁺] than found in a previous analysis of AIRMoN and NTN data. When comparing NTN and AIRMoN data on monthly time scales, strong seasonal variations are evident in the relative bias for [H⁺], [NH₄⁺], and [SO₄²⁻]. Large biases in [SO₄²⁻] (NTN greater than AIRMoN) on monthly times scales have not been detected in previous analyses where data for all seasons were considered together.     

The effect of humidity and state of water surfaces on deposition of aerosol particles onto a water surface

Deposition processes of particles with dry diameter larger than about 10 μm are dominated by gravitational settling, while molecular diffusion and Brownian motion predominate the deposition processes of particles smaller than 0.1 μm in dry diameter. Many air pollution derived elements exhibit characteristics common to sub-micron particles. The objective of the present study is to examine the effects of meteorological conditions within the turbulent transfer layer on the deposition velocity of particles with dry diameter between 0.1 and 1 μm. It is for these sub-micron particles that particle growth by condensation in the deposition layer, the broken water surface effect and the enhanced transfer process due to atmospheric turbulence in the turbulent transfer layer play important roles in controlling the particle deposition velocity. Results of the present study show that the `dry air’ assumption of Williams’ model is unrealistic. Effects of ambient air relative humidity and water surface temperature cannot be ignored in determining the deposition velocity over a water surface. Neglecting effects of ambient air relative humidity and water surface temperature will result in defining atmospheric stability incorrectly. It is found that the largest effect of air relative humidity on deposition velocity occurs at an air–water temperature difference corresponding to the point of `displaced neutral stability'. For a given wind speed of U=5 m s⁻¹ the additive effects of water surface temperature, T_w, changes from 5 to 25°C and ambient air relative humidity variations from 85 to 60%, respectively, lead to a maximum difference in v_d of about 20%. For a higher wind speed of 10 m s⁻¹, however, the corresponding change in v_d reduces to less than 5%. This is further confirmation that wind speed is one of the strongest variables that governs the magnitude of v_d. The present study also found that the broken surface transfer coefficient, k_bs, given as a multiple of the smooth surface transfer coefficient, k_ss, is physically more meaningful than assigning it a constant value independent of particle size. The method used in this study requires only a single level of atmospheric data coupled with the surface temperature measurement. The present method is applicable for determining deposition velocity not only at the conventional measurement height of 10 m but also at any other heights that are different from the measurement height.     

Deposition velocity of PM2.5 sulfate in the summer above a deciduous forest in central Japan

In order to increase knowledge of aerosol dry deposition for the regional assessment of acid deposition and transboundary air pollution in East Asia, an experimental study on PM2.5 sulfate deposition was implemented in the early summer of 2009. The experimental field was located in a deciduous forest at the foot of Mt. Asama, central Japan. Aerosol fluxes were obtained using the aerodynamic gradient method. Three aerosol samplers were placed on an experimental tower at 21, 24 and 27 m above the ground surface, and collected PM2.5 on filters for chemical analysis. Vertical concentration differences between 21 m and 27 m of PM2.5 sulfate were detected significantly when the concentration exceeded 1 μg m^?3. Mean deposition velocity was estimated to be 0.9 ± 1.0 cm s^?1 in the daytime and 0.3 ± 0.3 cm s^?1 in the nighttime. In the case that a height-dependent correction in the roughness sub-layer was taken into account, the deposition velocities increased more, especially in daytime. Higher deposition velocities in the daytime were associated with larger friction velocities and unstable conditions. The deposition velocities observed in this study were in agreement with other experimental results found in the literature. On the other hand, they were higher than those calculated by theoretical models. Two empirical parameterizations (Wesely, M.L., Cook, D.R., Hart, R.L., 1985. Measurement and parameterization of particulate sulfur dry deposition over grass. Journal of Geophysical Research 90, 2131–2143; Ruijgrok, W., Tieben, H., Eisinga, P., 1997. The dry deposition of particles to a forest canopy: a comparison of model and experimental results. Atmospheric Environment 31, 399–415) were validated by the observations. The general trend of higher daytime and lower nighttime deposition velocities was similar among the observation and the two parameterizations. The large variability found in the measurement was not reproduced by the parameterizations, because it is attributable to random error from the differences between the samplers. The observations were in accordance with the parameterization of Ruijgrok et al. (1997) for a forest, although much larger than that of Wesely et al. (1985) for grasslands. This indicates the large difference in aerosol deposition velocities between forests and grasslands.     

Influence of the surface microlayer on atmospheric deposition of aerosols and polycyclic aromatic hydrocarbons

Atmospheric dry deposition is an important process for the introduction of aerosols and pollutants to aquatic environments. The objective of this paper is to assess, for the first time, the influence that the aquatic surface microlayer plays as a modifying factor of the magnitude of dry aerosol deposition fluxes. The occurrence of a low surface tension (ST) or a hydrophobic surface microlayer has been generated by spiking milli-Q water or pre-filtered seawater with a surfactant or octanol, respectively. The results show that fine mode (<2.7 μm) aerosol phase PAHs deposit with fluxes 2–3 fold higher when there is a low ST aquatic surface due to enhanced sequestration of colliding particles at the surface. Conversely, for PAHs bound to coarse mode aerosols (>2.7 μm), even though there is an enhanced deposition due to the surface microlayer for some sampling periods, the effect is not observed consistently. This is due to the importance of gravitational settling for large aerosols, rendering a lower influence of the aquatic surface on dry deposition fluxes. ST (mN m⁻¹) is identified as one of the key factor driving the magnitude of PAH dry deposition fluxes (ng m⁻² d⁻¹) by its influence on PAH concentrations in deposited aerosols and deposition velocities (v_d, cm s⁻¹). Indeed, v_d values are a function of ST as obtained by least square fitting and given by Ln(v_d)=−1.77 Ln(ST)+5.74 (r²=0.95) under low wind speed (average 4 m s⁻¹) conditions.     

Dry deposition fluxes and deposition velocities of PAHs at an urban site in Turkey

Even though dry deposition and air–water exchange of semivolatile organic compounds (SOCs) are important for surfaces in and around the urban areas, there is still no generally accepted direct measurement technique for dry deposition. In this study, a modified water surface sampler (WSS) configuration, including a filter holder and an XAD-2 resin column, was employed to investigate the polycyclic aromatic hydrocarbon (PAH) dry deposition in an urban area. The measured total (particle+dissolved) PAH fluxes to the WSS averaged to be 34 960±16 540 ng m⁻² d⁻¹. Average particulate PAH flux, determined by analyzing the filter in the WSS, was about 8% of the total PAH flux. Temporal flux variations indicated that colder months (October–April) had the highest PAH fluxes. This increase could be attributed to the residential heating as well as meteorological effects including lower mixing height. A high volume air sampler was concurrently employed to collect ambient air concentrations. The average total (gas+particle) atmospheric PAH concentration (456±524 ng m⁻³) was within the range of previously measured values at different urban locations. PAH concentrations in urban areas are more than two orders of magnitude higher than those measured in pristine areas and this result may indicate that urban areas have major source sectors and greater deposition rates are expected near to these areas. The average contribution of particle phase was about 10% in total concentration. Simultaneous particulate phase dry deposition and ambient air samples were collected in this study. Then, particulate phase apparent dry deposition velocities were calculated using the fluxes and concentrations for each PAH compound and they ranged from 0.1 to 1.2 cm s⁻¹. These values are in good agreement with previously reported values.     

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by ²¹⁰Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m^?2 yr^?1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m^?2 yr^?1. The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m^?2 yr^?1 for preindustrial and 11.7 μg m^?2 yr^?1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m^?2 yr^?1, which are lower than the modern sediment-based estimate of 11.7 μg m^?2 yr^?1, perhaps owing to inputs of dry-deposited Hg to the lakes.     

Atmospheric distribution of polycyclic aromatic hydrocarbons and deposition to Galveston Bay,Texas, USA

Estimates of the atmospheric deposition to Galveston Bay of polycyclic aromatic hydrocarbons (PAHs) are made using precipitation and meteorological data that were collected continuously from 2 February 1995 to 6 August 1996 at Seabrook, TX, USA. Particulate and vapor phase PAHs in ambient air and particulate and dissolved phases in rain samples were collected and analyzed. More than 95% of atmospheric PAHs were in the vapor phase and about 73% of PAHs in the rain were in the dissolved phase. Phenanthrene and napthalene were the dominant compounds in air vapor and rain dissolved phases, respectively, while 5 and 6 ring PAH were predominant in the particulate phase of both air and rain samples. Total PAH concentrations ranged from 4 to 161 ng m⁻³ in air samples and from 50 to 312 ng l⁻¹ in rain samples. Temporal variability in total PAH air concentrations were observed, with lower concentrations in the spring and fall (4–34 ng m ⁻³) compared to the summer and winter (37–161 ng m⁻³). PAHs in the air near Galveston Bay are derived from both combustion and petroleum vaporization. Gas exchange from the atmosphere to the surface water is estimated to be the major deposition process for PAHs (1211 μg m^{− 2} yr^{− 1}), relative to wet deposition (130 μg m⁻² yr^{− 1}) and dry deposition (99 μg m⁻² yr^{− 1}). Annual deposition of PAHs directly to Galveston Bay from the atmosphere is estimated as 2  t yr⁻¹.     

Direct wet and dry deposition of ammonia,nitric acid,ammonium and nitrate to the Tampa Bay Estuary,FL, USA

The average total (wet plus dry) nitrogen deposition to the Tampa Bay Estuary was 7.3 (±1.3) kg-N ha⁻¹ yr⁻¹ or 760 (±140) metric tons-N yr⁻¹ for August 1996–July 1999, estimated as a direct deposition rate to the 104,000-ha water surface. This nitrogen flux estimate accounted for ammonia exchange at the air–sea interface. The uncertainty estimate was based on measurement error. Wet deposition was 56% of the total nitrogen deposition over this period, with an average 0.78 ratio of dry-to-wet deposition. Wet nitrogen deposition rates varied considerably, from near zero to 1.3 kg-N ha⁻¹ month⁻¹. About 40% of the total nitrogen flux occurred during the summer months of June, July and August when rainfall was the highest, except for 1997–1998 when the El Niño phenomenon brought unseasonal rainfall. Ammonia/ammonium contributed to 58%, and nitric acid/nitrate 42%, of the total nitrogen deposition over the 3-yr period. In one summer as waters of Tampa Bay warmed above 28°C and ammonium concentrations reached 0.03 mg l⁻¹, the estimated net flux of ammonia was from the Bay waters to the atmosphere.     

Lichen-based critical loads for atmospheric nitrogen deposition in Western Oregon and Washington Forests, USA

Critical loads (CLs) define maximum atmospheric deposition levels apparently preventative of ecosystem harm. We present first nitrogen CLs for northwestern North America’s maritime forests. Using multiple linear regression, we related epiphytic-macrolichen community composition to: 1) wet deposition from the National Atmospheric Deposition Program, 2) wet, dry, and total N deposition from the Communities Multi-Scale Air Quality model, and 3) ambient particulate N from Interagency Monitoring of Protected Visual Environments (IMPROVE). Sensitive species declines of 20-40% were associated with CLs of 1-4 and 3-9 kg N ha⁻¹ y⁻¹ in wet and total deposition. CLs increased with precipitation across the landscape, presumably from dilution or leaching of depositional N. Tight linear correlation between lichen and IMPROVE data suggests a simple screening tool for CL exceedance in US Class I areas. The total N model replicated several US and European lichen CLs and may therefore be helpful in estimating other temperate-forest lichen CLs.     

Ambient concentrations and dry deposition fluxes of trace elements in Izmir,Turkey

Dry deposition samples were collected using a smooth surrogate surface at the Kaynaklar Campus of the Dokuz Eylul University in Izmir, Turkey. Concurrently ambient aerosol samples were collected. All samples were analyzed for anthropogenic and crustal trace elements. The average trace element concentrations and fluxes measured in this study were generally higher than those reported previously for urban and rural areas. The contribution of local terrestrial and anthropogenic sources were also investigated using enrichment factors (EFs) calculated relative to the local soil. Relatively lower EFs for ambient samples and high ambient concentrations indicated that the local soil was polluted and contributed significantly to ambient trace element concentrations. Deposition samples had higher EFs than the air samples. The EF sequences of trace elements were also different for deposition and ambient samples, probably due to the fact they have different mass median diameters and deposition velocities. The overall dry deposition velocities for trace elements calculated by dividing the particulate fluxes measured with the surrogate surfaces by ambient concentrations ranged from 0.6 (Al) to 6.2 cm s⁻¹ (Fe). The agreement between the experimental dry deposition velocities determined in this study and the previously reported ones using similar techniques for trace elements was good.     

Ammonia fluxes and derived canopy compensation points over non-fertilized agricultural grassland in The Netherlands using the new gradient ammonia—high accuracy—monitor (GRAHAM)

During a measurement period from June till November 2004, ammonia fluxes above non-fertilized managed grassland in The Netherlands were measured with a Gradient Ammonia—High Accuracy—Monitor (GRAHAM). Compared with earlier ammonia measurement systems, the GRAHAM has higher accuracy and a quality control system.Flux measurements are presented for two different periods, i.e. a warm, dry summer period (from 18 July till 15 August) and a wet, cool autumn period (23 September till 23 October). From these measurements canopy compensation points were derived. The canopy compensation point is defined as the effective surface concentration of ammonia. In the summer period (negative) deposition fluxes are observed in the evening, night and early morning due to leaf surface wetness, while in the afternoon emission fluxes are observed due to high canopy compensation points. The mean NH₃-flux in this period was 4 ng m⁻² s⁻¹, which corresponds to a net emission of 0.10 kg N ha⁻¹ over the 28 day sampling period. The NH₃-flux in the autumn period mainly shows (negative) deposition fluxes due to small canopy compensation points caused by low temperatures and a generally wet surface. The mean NH₃-flux in this period is −24 ng m⁻² s⁻¹, which corresponds to a net deposition of 0.65 kg N ha⁻¹ over the 31 day sampling period.Frequency distributions of the NH₃-concentration and flux show that despite higher average ambient NH₃-concentrations (13.3 μg m⁻³ in the summer period vs. 6.4 μg m⁻³ in the autumn period) there are more emission events in the summer period than in the autumn period (about 50% of the time in summer vs. 20% in autumn). This is caused by the high canopy compensation points in summer due to high temperatures and a dry surface. In autumn, deposition dominates due to a generally wet surface that induces low canopy compensation points.For our non-fertilized agricultural grassland site, the derived canopy compensation points (at temperatures between 7 and 29 °C) varied from 0.5 to 29.7 μg m⁻³ and were on an average 7.0 μg m⁻³, which is quite high for non-fertilized conditions and probably caused by high nitrogen inputs in the past or high dry deposition amounts from local sources. The average value for the ratio between NH₄⁺ and H⁺ concentration in the canopy, Γ_c, that was derived from our data was 2200.     

Dry deposition and foliar leaching of mercury and selected trace elements in deciduous forest throughfall

The estimated annual throughfall deposition flux of Hg in a northern mixed-hardwood forest in the Lake Huron Watershed was 10.5±1.0 μg m⁻² compared to an annual precipitation Hg flux of 8.7±0.5 μg m⁻² (June 1996–June 1997). The source of this additional Hg in throughfall is often attributed to wash-off of dry deposition, but foliar leaching of Hg may also be important. To determine the influence of both dry deposition and foliar leaching of Hg and other elements in throughfall, we measured a suite of trace elements (Hg, Al, Mg, V, Mn, Cu, Zn, As, Rb, Sr, Cd, Ba, La, Ce, and Pb) in throughfall, precipitation, and ambient air samples from a northern mixed-hardwood forest. Based on a multiple linear regression model, dry deposition had the most important influence on Hg, Al, La, Ce, V, As, Cu, Zn, Cd, and Pb fluxes while foliar leaching strongly influenced Mg, Mn, Rb, Sr, and Ba fluxes in net throughfall. The Hg dry deposition flux was estimated using gaseous and aerosol Hg measurements and modeled deposition velocities. The calculated dry deposition flux (∼12–14 μg m⁻²) of Hg to the canopy indicated that atmospheric deposition of Hg could easily account for all of the Hg deposited in net throughfall (1.9±0.1 μg m⁻²). Although there is a large uncertainty associated with these techniques, the modeling estimates indicate that atmospheric Hg may account for all of the Hg deposited in litterfall (11.4±2.8 μg m⁻²).     

Dry deposition of particles to wave surfaces: I. Mathematical modeling

Previous estimates of dry deposition to water surfaces were generally based on deposition to flat, solid surfaces. This paper examines the effects of waves on dry deposition rates by numerically simulating particle trajectories over wave surfaces. Airflows over two-dimensional sine waves with height-to-length ratios 2a/λ=0.1, 0.07, and 0.03 were calculated with a commercial computational fluid dynamics model. Results from the airflow simulations (velocity, kinetic energy, energy dissipation rate, and shear stress) provided inputs for a stochastic particle trajectory model. Particles were released from a height of 300 non-dimensional wall units at different locations along the wave. For those between 1 and 20 μm, deposition was found to be greatest for particles released to the upslope portion of the wave, followed by the trough, crest and downslope. Overall deposition rates were enhanced due to the presence of waves. Increases ranged from 5% (d_p=80 μm) to 100% (d_p=1 μm) for waves with 2a/λ=0.07 and 0.1 and were approximately 50% greater (d_p=1−80 μm) for 2a/λ=0.03. Deposition rates were enhanced due to increases in impaction and turbulent transport, both of which increase with increasing wave slope. However, an increased slope also produced regions of low or reversed flow in the trough and downslope, which decreased deposition rates. Due to these competing effects with respect to wave slope, deposition rates did not increase monotonically with wave slope.     

Modelling the behaviour of PAHs during atmospheric transport from the UK to the Arctic

Persistent organic pollutants (POPs) such as PAHs are subject to long-range atmospheric transport, which can result in the contamination of remote areas such as the Arctic. A simple model was developed to describe the removal processes of four PAHs; fluorene (FLU), phenanthrene (PHEN), fluoranthene (FLA) and benzo[a]pyrene (B[a]P) transported over a 5 day period from a source area over the UK to the Russian Arctic. The purpose of this model was to study processes affecting the PAHs within the atmosphere, rather than their interaction with the earth's surface. The components to the model included gas/particle partitioning, reaction with OH radicals and dry and wet deposition (both rain and snow). Atmospheric/meteorological parameters for the geographical region of interest were generated from three-dimensional atmospheric models. Air concentrations were prescribed in the source area with no additional PAH inputs along the transect, both winter and summer scenarios were modelled. Reaction with OH was a major removal mechanism for gas-phase FLU, PHEN and FLA, most notably in the temperate atmosphere. Wet deposition in the form of snow accounted for the majority of PAH loss in the winter, although the gas and particle scavenging ratios used in this model ranged over several orders of magnitude. Using a 5 day transport scenario in a `1-hop’ event, the model predicted that a primary emission of FLA and B[a]P to the atmosphere of the southern UK, would not reach the Russian Arctic at a distance of ∼3500 km, assuming a constant windspeed of 10 m s⁻¹. However, both FLU and PHEN with calculated half-lives of >60 h during the winter could be transported to this area under this scenario.