Wet-deposition fluxes of soluble chemical species and the elements in insoluble materials

From March to June 1996, eight rain events were collected by sequential sampling on time and volume basis in Kyoto University, Uji, Japan. Soluble chemical species Cl⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Ca²⁺ and Mg²⁺ were measured by Ion Chromatography (IC); and the elements Si, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br and Pb in insoluble materials were measured by proton-induced X-ray emission (PIXE) technique. The wet-deposition flux of a soluble chemical species (or an element in insoluble materials) was calculated by the product of the chemical species (or the element) concentration and the corresponding rain intensity. The characteristics of sequential cumulative wet-deposition flux of the soluble chemical species and the elements in insoluble materials were examined. The factor controlling wet-deposition flux was discussed.     

Ionic composition of precipitation at the Central Anatolia (Turkey)

Concentrations of major ions, SO₄²⁻, NO₃⁻, Cl⁻, H⁺, Ca²⁺, K⁺, Mg²⁺, Ca²⁺ and conductivity were measured in approximately 300 daily, wet-only rain samples collected at a permanent rural station between 1993 and 1998. Concentrations of anthropogenic ions NH₄⁺, SO₄²⁻ and NO₃⁻ were among the highest values reported in whole EMEP network, suggesting that the Anatolian plateau is under strong influence of distant emission sources. Although transport of pollutants have significant influence on the chemical composition of precipitation, average pH of the rainwater is 6.2 due to extensive neutralization of acidity. Approximately 95% of the acidity in collected samples is neutralized, particularly in summer season. The neutralizing agents are primarily CaCO₃ and NH₃. Concentrations of crustal ions are higher in summer season due to enhanced resuspension of soil particles from dry surface soil. Concentrations of anthropogenic ions SO₄²⁻ and NO₃⁻ do not change significantly between summer and winter due to higher intensity of rains in summer season. Although concentrations of ions measured in this study is among the highest reported in EMEP network, wet deposition fluxes are low compared to flux values reported for similar sites in Europe, due to low annual precipitation in the Anatolia. Wet deposition fluxes of all measured parameters are highly episodic. Source regions affecting chemical composition precipitation in the Central Anatolia is investigated using trajectory statistics.     

Deposition processes of ionic constituents to snow cover

Atmospheric deposition is an important removal process of aerosol particles and gases from the atmosphere. To elucidate the relative contributions of wet and dry processes and in-cloud and below-cloud scavenging based on deposition amounts in winter at Mt. Tateyama, central Japan, we obtained daily samples (December, 2006–March, 2007) of size-segregated aerosol particles and precipitation at Senjyugahara (SJ; 475 m a.s.l.) and vertical samples of spring snow cover at Murododaira (MR, 2450 m a.s.l., 13 km distance from SJ) on the western flank of Mt. Tateyama. The NH₄⁺ and nssSO₄^2? in aerosols were mostly found in the fine fraction (<2 μm), although Na⁺, NO₃^?, and nssCa²⁺ were mainly detected in the coarse fraction (>2 μm). Average ionic concentrations (μg g^?1) in precipitation at SJ were higher about 3.8 for Na⁺ and nssCa²⁺, 3.4 for NO₃^?, 3.7 for NH₄⁺, 2.5 for nssSO₄^2? than those at MR, whereas cumulative precipitation amounts at SJ and MR were, respectively, 84 and 175 cm of water equivalent. Wet and dry deposition amounts during the study period were estimated for sites using size-segregated aerosol data, winter averages of HNO₃, NH₃, and SO₂ concentrations, and dry deposition velocities. Particle-dry deposition comprised about 3% (Na⁺) to 11% (NH₄⁺) of the total deposition at MR. The maximum amounts of gas dry deposition were estimated, respectively, as 4, 13, and 3% of the total deposition at MR for NH₄⁺, NO₃^?, and nssSO₄^2?. The relative contributions of below-cloud scavenging (BCS) between MR and SJ were estimated as considering the wet only deposition amount at MR. Higher contributions of BCS were obtained for Na⁺ (56%) and nssCa²⁺ (45%), whereas BCSs for NH₄⁺, NO₃^?, and nssSO₄^2? were lower than 28%. Ionic constituents existing predominantly in the coarse fraction showed a large contribution of BCS.     

Chemical composition of rainwater and anthropogenic influences in the Piracicaba River Basin,Southeast Brazil

The influences of different kinds of anthropogenic activities on rainwater chemistry in a tropical area were studied during one uninterrupted year at Piracicaba River Basin (Southeast Brazil). A total of 272 rainwater samples collected continuously from August 1997 to July 1998 at four different sites were analyzed for F⁻, CH₃COO⁻, HCOO⁻, MSA, Cl⁻, NO₂⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻, PO₄³⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, DOC (dissolved organic carbon), DIC (dissolved inorganic carbon), pH and conductivity. The most abundant ion was H⁺ and rain acidity was significant at all sampling sites (average pH of 4.4–4.5). The sources of this free acidity differ among sites and appear to be correlated to the different land-uses. The composition of rainwater appeared to be controlled mostly by three sources: soil dust, sugar cane burning and industrial emissions.     

Dry deposition of particles and canopy exchange: Comparison of wet,bulk and throughfall deposition at five forest sites in Italy

The contribution of dry deposition to the total atmospheric input of acidifying compounds and base cations is of overwhelming importance. Throughfall measurements provide an estimate of the total deposition to forest soils, including dry deposition, but some uncertainties, related to the canopy interaction processes, affect this approach. We compared the concentrations and the fluxes of the main ions determined in wet-only, bulk and throughfall samples collected at five forest sites in Italy. The contribution of coarse particles deposited onto the bulk samplers was of prime importance for base cations, representing on average from 16% to 46% of the bulk deposition. The extent of this dry deposition depended on some geographical features of the sites, such as the distance from the sea and the annual rainfall. The possibility of applying specific bulk/wet ratios to estimate the wet deposition proved to be limited by the temporal variability of these ratios, which must be considered together with the spatial variability. A direct comparison of the dry contribution deriving from the bulk–wet and the throughfall–wet demonstrated that an extensive natural surface (forest canopy) performs better than a small synthetic surface (funnel of the bulk sampler) in collecting dry deposition of SO₄²⁻, NO₃⁻ and Na⁺. The canopy exchange model was applied to both bulk and wet data to estimate the contribution of dry deposition to the total input of base cations, and the uncertainty associated to the model discussed. The exclusive use of bulk data led to a considerable underestimation of base cation dry deposition, which varies among the study sites.     

Sampling and chemical analysis of ice crystals as a function of size

Size-classified ice crystal samples were collected during the Spring of 1998, at the Jungfraujoch High-Alpine Research Station (3454 m), located in Switzerland. A procedure modified from the Guttalgor method, originally developed for size-selective sampling of raindrops by Bächmann et al. (Atmos. Environ. 26A (1992) 1795) was used to sample ice crystals during precipitation events. The size-classified ice crystal samples were analyzed using ion chromatography to determine the concentrations of Na⁺, NH₄⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃⁻, and SO₄²⁻ in each size class. For ions associated with coarse mode aerosol, Na⁺, K⁺, Ca²⁺, Mg²⁺, and Cl⁻, concentration increased with decreasing ice crystal size, suggesting scavenging by nucleation. For the remaining ions, mixed behavior was observed suggesting a combination of gas phase scavenging and scavenging via riming.     

Some results of snow chemical surveys in the Kunnes River valley,East Tienshan mountains,China

Chemical surveys of snow were carried out in the upper reaches of the Kunnes River, a tributary of the Yili River in East Tienshan Mountains, China. Some surprisingly high values of sodium and potassium (K⁺+Na⁺) ranging from 4.44 to 8.99 mg/l compared with other data from neighboring areas are detected. Moreover, some relative high values of SO₄²⁻ with mean concentration 15.8 mg/l for new snow and 14.40 mg/l for deposited snow, ranging from 10.43 to 23.71 mg/l are also found. Therefore, it is inferred that the sodium and potassium (K⁺+Na⁺) are in the forms of sulfate and that the sources of the sulfate are deserts and some dried lakes in Central Asia. It is also found that there is obviously spatial variation of ions such as K⁺+Na⁺, Ca²⁺, SO₄²⁻ and HCO₃⁻. The concentrations of K⁺+Na⁺ and SO₄²⁻, and that of Ca²⁺ and HCO₃⁻ have similar spatial pattern. The temporal pattern of ion concentration of new snow is considered to be mainly controlled by the depth and area of snow cover in the study area and in the areas to the west.     

Dry deposition and internal circulation of nitrogen,sulphur and base cations to a coniferous forest

The dry deposition of sulphur, nitrogen and base cations to a spruce stand was estimated during a five year period using a surrogate surface resembling needles, throughfall and bulk deposition measurements. The deposition was calculated from the ratio between the deposition of an ion and sodium on the surrogate surface and the net throughfall of sodium to the forest. The dry deposition represented a large fraction of the total atmospheric input of base cations. For Na⁺, Mg²⁺, Ca²⁺, and K⁺ they were 66, 67, 53 and 42%, respectively. The internal circulation was 95% of non-marine net throughfall fro K⁺ and 76% for Ca²⁺. The dry deposition of SO₂ to the canopies regulates the internal circulation of Ca²⁺. The dry deposition of SO₂ to the canopies regulates the internal circulation of Ca²⁺. The dry depositions of ammonium and nitrate are close to the net throughfall of Kjeldahl-N and nitrate, respectively. The obtained deposition velocities are comparable to other studies. The calculated dry deposition of ammonium was compared to the net throughfall of ammonium at three nearby forest stands receiving different ammonium amounts on the soils. No correlation to nitrogen level was found, but most ammonium was lost and converted to organic nitrogen in the canopies of the wettest forest stand.     

Precision of atmospheric dry deposition data from the Clean Air Status and Trends Network

A collocated, dry deposition sampling program was begun in January 1987 by the US Environmental Protection Agency to provide ongoing estimates of the overall precision of dry deposition and supporting data entering the Clean Air Status and Trends Network (CASTNet) archive. Duplicate sets of dry deposition sampling instruments were installed adjacent to existing instruments and have been operated for various periods at 11 collocated field sites. All sampling and operations were performed using standard CASTNet procedures. The current study documents the bias-corrected precision of CASTNet data based on collocated measurements made at paired sampling sites representative of sites across the network. These precision estimates include the variability for all operations from sampling to data storage in the archive. Precision estimates are provided for hourly, instrumental ozone (O₃) concentration and meteorological measurements, hourly model estimates of deposition velocity (V_d) from collocated measurements of model inputs, hourly O₃ deposition estimates, weekly filter pack determinations of selected atmospheric chemical species, and weekly estimates of V_d and deposition for each monitored filter pack chemical species and O₃.Estimates of variability of weekly pollutant concentrations, expressed as coefficients of variation, depend on chemical species: NO₃⁻∼8.1%; HNO₃∼6.4%; SO₂∼4.3%; NH₄⁺∼3.7%; SO₄²⁻∼2.3%; and O₃∼1.3%. Precision of estimates of weekly V_d from collocated measurements of model inputs also depends on the chemical species: aerosols ∼2.8%; HNO₃∼2.6%; SO₂∼3.0%; and O₃∼2.0%. Corresponding precision of weekly deposition estimates are: NO₃⁻∼8.6%; HNO₃⁻∼5.2%; SO₂∼5.6%; NH₄⁺∼3.9%; SO₄²⁻∼3.5%; and O₃∼3.3%. Precision of weekly concentration, V_d estimates, and deposition estimates are comparable in magnitude and slightly smaller than the corresponding hourly values. Annual precision estimates, although uncertain due to their small sample size in the current study, are consistent with the corresponding weekly values.     

PM2.5–10, PM2.5 and associated water-soluble inorganic species at a coastal urban site in the metropolitan region of Rio de Janeiro

The concentrations of PM_2.5−10, PM_2.5 and associated water-soluble inorganic species (WSIS) were determined in a coastal site of the metropolitan region of Rio de Janeiro, Southeastern Brazil, from October 1998 to September 1999 (n=50). Samples were dissolved in water and analyzed for major inorganic ions. The mean (± standard deviation; median) concentrations of PM_2.5−10 and PM_2.5 were, respectively, 26 (± 16; 21) μg m⁻³ and 17 (± 13; 14) μg m⁻³. Their mean concentrations were 1.7–1.8 times higher in dry season (May–October) than in rainy season (November–April). The WSIS comprised, respectively, 34% and 28% of the PM_2.5−10 and PM_2.5 masses. Chloride, Na⁺ and Mg²⁺ were the predominant ions in PM_2.5−10, indicating a significant influence of sea-salt aerosols. In PM_2.5, SO₄²⁻ (∼97% nss-SO₄²⁻) and NH₄⁺ were the most abundant ions and their equivalent concentration ratio (SO₄²⁻/NH₄⁺ ∼1.0) suggests that they were present as (NH₄)₂SO₄ particles. The mean concentration of (NH₄)₂SO₄ was 3.4 μg m⁻³. The mean equivalent PM_2.5 NO₃⁻ concentration was eight times smaller than those of SO₄²⁻ and NH₄⁺. The PM_2.5 NO₃⁻ concentration in dry season was three times higher than in rainy season, probably due to reaction of NaCl (sea salt) with HNO₃ as a result of higher levels of NO_y during the dry season and/or reduced volatilization of NH₄NO₃ due to lower wintertime temperature. Chloride depletion was observed in both size ranges, although more pronouncely in PM_2.5.     

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.     

On the Relationship between Acid Rain and Cloud Type

Abstract

Spanish European Monitoring and Evaluation Programme (EMEP) stations were selected to relate acid rain episodes with the meteorological structure that caused the rainfall during a 5-year period. A principal component analysis (PCA) was used to determine the origin of major ions (SO₄ ^2?, NO₃ ^?, Cl^?, Ca²⁺, K⁺, Mg²⁺, and Na⁺) in the rainwater. In addition, the meteorological origin of the rain was identified.

Previous works suggested a relationship between acid rain and storm convective clouds. However, statistical analyses of pH values show that only the short-lived con-vective phenomena may cause acid rain in Spain. In fact, rain generated by fronts and that related to long-lived convective systems is neutral or even slightly basic. Results suggest that the acid rain might be related to the meteorological time scale instead of to the cloud type.     

Spatial distribution of wet deposition of nitrogen in South Korea

A method is developed to estimate wet deposition of nitrogen in a 11×14 km (0.125°Lon.×0.125°Lat.) grid scale using the precipitation chemistry monitored data at 10 sites scattered over South Korea supplemented by the routinely available precipitation rate data at 65 sites and the estimated emissions of NO₂ and NH₃ at each precipitation monitoring site. This approach takes into account the contributions of local NO₂ and NH₃ emissions and precipitation rates on wet deposition of nitrogen. Wet deposition of nitrogen estimated by optimum regression equations for NO₃⁻ and NH₄⁺ derived from annual total monitored wet deposition and that of emissions of NO₂ and NH₃ is incorporated to normalize wet deposition of nitrogen at each precipitation rate class, which is divided into 6 classes. The optimum regression equations for the estimation of wet deposition of nitrogen at precipitation monitoring sites are developed using the normalized wet deposition of nitrogen and the precipitation rate at 10 precipitation chemistry monitoring sites. The estimated average annual total wet depositions of NO₃⁻ and NH₄⁺ are found to be 260 and 500 eq ha⁻¹ yr⁻¹ with the maximum values of 400 and 930 eq ha⁻¹ yr⁻¹, respectively. The annual mean total wet deposition of nitrogen is found to be about 760 eq ha⁻¹ yr⁻¹, of which more than 65% is contributed by wet deposition of ammonium while, the emission of NH₃ is about half of that of NO₂, suggesting the importance of NH₃ emission for wet deposition of nitrogen in South Korea.     

Water soluble ions of atmospheric aerosols in three New Zealand cities: seasonal changes and sources

The results of one year's measurements (typically a two week sampling campaign in each season) of the concentrations of eight major water soluble ions, namely Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, NO₃⁻ and SO₄²⁻, in atmospheric aerosols collected in three New Zealand cities (Auckland, Christchurch and Hamilton) are presented. The data has provided important information on particulate soluble ion profiles in New Zealand urban areas and revealed some useful trends.A significant correlation has been found between the average meteorological conditions in a sampling campaign and the average particulate concentrations of some of these soluble ions in the campaign. For example, average particulate NO₃⁻ concentration in a campaign was found to correlate well with the average calm or weak wind duration percentage in the campaign, and the average concentrations of Na⁺, Mg²⁺ and Cl⁻ related closely to the average wind pattern and rainfall in the campaign.Significant site and seasonal variations have been observed with Hamilton having the lowest overall concentrations of all the soluble ions in the particles sampled. On average all sites had the highest particulate concentrations of Na⁺, Mg²⁺ and Cl⁻ in the summer but the highest particulate concentrations of NH₄⁺ and non-sea-salt Ca²⁺ (nss-Ca²⁺) in the winter. The possible sources of PM₁₀ mass have been deduced and in particular the relative contribution of sea salts to PM₁₀ mass in the cities are reported.     

Chemical characteristics of atmospheric aerosols over southwest coast of India

Ambient aerosol samples, collected from Mangalore region in the southwest coast of India during the period of late winter (February and March) to early summer (April and May), have been analysed for water-soluble ionic species. Their abundance pattern is dominated by HCO₃⁻, SO₄²⁻, Na⁺, Cl⁻, with minor contribution from NO₃⁻, Ca²⁺, NH₄⁺, K⁺ and Mg²⁺ indicating the contribution from not only sea salt, but also from anthropogenic and dust sources; with pronounced seasonal variability. The suspended particulate matter concentration varied from 35 to 160 μg m⁻³, with consistently higher values during the late winter. Back trajectory analysis suggests the origin of the air masses shifting from Indo-Gangetic Plains (during late winter) to those from the Arabian Sea and the area around Persian Gulf during April–May. Air masses passing over Northern India (Indo-Gangetic Plains) impart characteristic contribution of ionic species from fossil fuel combustion, biomass burning and eolian dust as asserted by the factor analysis. A detailed study on characterisation of aerosols from south Asian region is rather sparse but essential for modelling the effect of tropospheric aerosols on climate.     

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.     

Atmospheric deposition of macronutrients by pollen at a semi-remote site in northern Wisconsin

Pine pollen concentrations in air at a semi-remote site in northern Wisconsin attained levels of 18 and 25 μ m⁻³ in late May and early June of 1979 and 1981, respectively. The upper and lower limits for the deposition velocity of pine pollen at this site are approximately 30 and 1.3 cm s⁻¹, respectively. Consequently, the average annual pine pollen flux at this location for 1979 and 1981 was between 8.0 and 0.35 g m⁻². Deposition of total phosphorus and organic C by pollen dispersal are about 5–100% and 11–240%, respectively, of the measured bulk atmospheric loading rate in the region. Pine pollen fluxes of water-extractable K are about 10–230% of the average annual wet deposition, while the fluxes of waterextractable NO₃⁻ and SO₄⁻² by pollen appear to be negligible in comparison to the total atmospheric deposition (wet plus dry deposition) by other particles. The annual pine pollen flux to Crystal Lake, an oligotrophic seepage lake in the region, was estimated to be 6.5 g m⁻² during 1981. The deposition of total P by pollen to this lake was 5.8 kg a⁻¹, which is 45 % of the external input of total phosphorus. About 60% of the total P in samples of Pinus strobus and P. resinosa was dissolved reactive P, which is readily available for plant uptake. Because P is the limiting nutrient for many lacustrine systems and pine pollen dispersal coincides with the period of phytoplankton blooms in temperate-region lakes, this episodic input of P may represent an important source for seepage lakes whose external inputs are dominated by atmospheric deposition.     

Vertical distribution of gases and aerosols: The behaviour of ammonia and related components in the lower atmosphere

Vertical concentration profiles for NH₃, HNO₃ and HCl-gas and for NH₄⁺, NO₃⁻, SO²⁻₄, Cl⁻ and Na⁺ aerosol were obtained from a meteorological tower in the central part of the Netherlands. An upward NH₃ flux of 0.12 μgm⁻² s⁻¹ was calculated from the NH₃ profiles and meteorological data. From the HNO₃ profiles a maximum HNO₃ dry deposition velocity of 4 cm s⁻¹ was calculated. Good agreement was found between the measured concentration products [NH₃]_(g) × [HNO₃]_(g) and the theoretical values at temperatures above 0°C and relative humidities below 80%. In other cases, higher NH₃ and/or HNO concentrations in the gas phase were measured than theoretically predicted.     

Chemical composition of the fine and coarse fraction of aerosols in the northeastern Mediterranean

Two-stage aerosol samples (PM_10–2.5 and PM_2.5) were collected at a coastal rural site located in the northeastern Mediterranean, between April 2001 and 2002. A total of 562 aerosol samples were analyzed for trace elements (Fe, Ti, Mn, Ca, V, Ni, Zn, Cr) and water-soluble ions (Na⁺, NH₄⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, Br⁻, NO₃⁻, SO₄²⁻, C₂O₄²⁻ and MS⁻:methane sulfonate). PM₁₀, crustal elements, sea salt aerosols and NO₃⁻ were mainly associated with the coarse mode whereas non-sea salt (nss)SO₄²⁻, C₂O₄²⁻; MS⁻, NH₄⁺, Cr and Ni were found predominantly in the fine fraction. Concentrations of aerosol species exhibited orders of magnitude change from day to day and the aerosol chemical composition is heavily affected by dust events under the influence of airflow from North Africa. During the sampling period, 11 specific mineral dust events of duration varying from 1 day to a week have been identified and their influence on the chemical composition of aerosols has been studied in detail. Ionic balance analysis performed in the coarse and fine aerosol fractions indicated anion and cation deficiency due to CO₃²⁻ and H⁺, respectively. A relationship between nssSO₄²⁻ and NH₄⁺ denoted that sulfate particles were partially neutralized (70%) by ammonium. Excess-K/BC presented two distinct ratios for winter and summer, indicating two different sources: fossil fuel burning in winter and biomass burning in summer.     

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.