Modeling of SO2, Pb and Cd atmospheric deposition over a one-year period

Atmospheric deposition of SO₂, and fine particles of Pb and Cd are calculated over a one-year period in a 66 km² airshed with a segment-puff model. Emission variations, hourly mixing heights and meteorological values are considered to compute monthly averages of concentrations and deposition. Dry deposition is calculated by means of deposition velocities which are season- and land use-dependent. Wet deposition is determined using a washout coefficient. To assess the simulation performance, calculated SO₂ results from the combination between the deposition velocity, the windspeed and direction and the location and type of sources. As annual averages, results for dry plus wet deposition are computed to be 0.84 mg m⁻²d⁻¹ for sulfur, 4.15 μgm⁻²d⁻¹ for lead and 0.0013 μgm⁻²d⁻¹ for cadmium. A variation factor is derived from a sensitivity analysis. This factor amounts to 2.3−2.8 for the concentrations and 2.6−3.1 for the deposition, depending on the pollutant.     

Soil crust formation by dust deposition at Shaartuz,Tadzhik, S.S.R.

The shrub-steppe area near Shaartuz, Tadzhik, S.S.R., is shown to be a net accumulator of dust despite being an occasional source of dust. For the accumulation of the dust to form the observed surface crust, a net deposition of about 290–490 g m⁻² yr⁻¹ of particles smaller than 20 μm is required, depending on the duration of the deposition period. The particles smaller than 20 μm are mixed with particles brought up from the sandy material below the surface crust by bioturbation and are incorporated into the surface crust. Measurements during the 16 and 20 September 1989 dust storms provided a total deposition of 41.1 g m⁻² of particles smaller than 20 μm. Because 10–30 dust storms are observed at Shaartuz, the measured average dust storm deposition would yield 206–617 g m⁻² yr⁻¹. This range of deposition is of the order of that needed to provide a mass balance for the observed crust formation. Cryptogams (including algae, lichen, and moss) and rainwater are the main agents of incorporation of the aeolian dust into a stable soil crust. The role that the vascular plants played at the Shaartuz site was to reduce the rate of soil movement to levels where the cryptogamic crusting was possible. the observed mechanisms of dust deposition followed by crust incorporation are possibly an important processes in loess formation in Central Asia.     

Design of an environmental chamber for high voltage testing in simulated dust and sand storms

This paper describes the design and the construction of an environmental chamber which enables the breakdown voltage of practically used electrodes to be determined during sand/dust storm conditions. The dust particles used were ⩽ 150 μm in dia. and ranged from a few mgm⁻³ to a few gm⁻³ in concentration. Studies were done using switching as well as lightning impulse voltages of up to 1 MV in addition to the high a.c. voltages of up to 200 kV. Using this facility, it was found that the presence of sand/dust particles can greatly affect the breakdown voltages of air gaps. This effect is dependent on the electrode shape, the gap length, and the type of applied voltage. Typical results are shown in this paper.     

The investigation of air quality and acid rain over the Gulf of Mexico

A research cruise was conducted in the summer of 1986 by a group of scientist from the U.S.A. and Mexico to investigate air chemistry over the Gulf of Mexico. Chemical, physical, meteorological and oceanographic measurements were carried out to survey temporal and spatial variations of diverse parameters throughout the Gulf. Emphases were placed on air-sea-land exchange of gases and aerosols, natural air quality, transport of anthropogenic air pollution, and acid rain deposition to the Gulf. Although the prevailing winds were easterly from the sea during the cruise, the air was highly polluted with continental aerosols, probably caused by local shifting winds and the oscillation between sea breeze and land breeze. Aerosol number concentrations were measured from 10⁵ cm⁻³ at ports to 10³ cm⁻³ in the open Gulf. The average aerosol mass concentration was ∼25μg M⁻³, consisting of 60% insoluble crustal particles that contained Si, Al, Fe; 30% seasalt particles that contained Na⁺ and Cl⁻; and 10% anthropogenic sulfate and nitrate particles. Samples of rain water collected near the coast were acidic (pH ∼4). The concentrations of dimethyl sulfide correlated with bio-particle concentrations in surface seawater and could be a significant precursor of atmospheric SO₄²⁻ particles. The life cycles of the aerosols in the Gulf, including sources, transport, transformation, and wet and dry deposition are discussed.     

Chemical characterization of acid precipitation in Albany,New York

Chemical composition of precipitation in Albany, NY from July 1986 to December 1988 has been studied. Mean volume-weighted concentrations (μeq^ℓ−1) were: acidity, 104.0; alkalinity, −63.7; SO₄²⁻, 52.8; NO₃⁻, 29.8; Cl⁻, 5.6; F⁻, 0.50; NH₄⁺, 19.3; Ca²⁺, 6.5; Mg²⁺, 2.8; Na⁺, 3.5; and K⁺, 1.4. Mean pH was 4.2 . Seasonal patterns were pronounced for most species. Concentrations of H⁺, SO₄²⁻, NO₃⁻, NH₄⁺ and Ca²⁺ peaked in the summer and spring. Deposition was related to rainfall amount by a power law relationship in which the exponent of the equation was ∮.6. Wet SO₄²⁻ deposition was 2.35 keq ha⁻¹ over a 30-month period. The SO₄²⁻ and NO₃⁻ deposition rates observed at Albany indicate that transport from midwestern sources have a major influence at this site. On the average, free H⁺ ion concentrations determined from pH measurements accounted for 51% of the measured total acidity. There were unknown species, most likely organic acids, that could contribute to the acidity. Correlation and regression analyses indicated that major anions, SO₄²⁻ and NO₃⁻, were closely associated with H⁺ and NH₄⁺ ions. Factor analysis revealed four common factors which are related to fossil-fuel combustion, sea spray, cement factory and biomass burning.     

Chemistry of atmospheric precipitation at the Western Arabian Gulf Coast

Rainwater and atmospheric bulk deposition samples were collected at a station on the rooftop of the Research Institute of King Fahd University of Petroleum and Minerals in Dhahran. Continuous sampling was carried out manually throughout the rainy season between December 1987 and February 1988, and for one rainfall event in March 1987. A total number of 13 samples were collected and investigated for pH and dissolved ionic composition using inductivity coupled plasma emission spectrometry (ICP) and ion chromatography (IC). The range and volume-weighted average pH were 5.1–7.2 and 5.48, respectively. Significant negative linear correlations were observed between the precipitation pH and rain depth, and between pH and the summation of dissolved {(Ca²⁺ + Mg²⁺)−(SO₄²⁻ + NO₃⁻ + NO₂⁻)} (in μeqℓ⁻¹). The ionic summation also correlated negatively with rain depth. The ionic abundance in rainwater (in μeqℓ⁻¹) expressed in concentration order showed the general trend SO₄²⁻ > HCO₃⁻¹ = Cl⁻ = NO₃⁻ > NO₂⁻ for anions and Ca²⁺ > Na⁺ > Mg²⁺ > NH₄⁺ > K⁺ > H⁺ > Sr²⁺ for cations. Good mass balance between cations and anions was observed. Total NO₃⁻ contribute equally to precipitation acidity as SO₄²⁻ and Ca²⁺ plus Mg²⁺ in alkaline suspended particulates from natural sources are the major ions which buffer the acidity of precipitation. The NH₄⁺ ion which is also present plays an insignificant role in the acid/base equilibrium of rainwater.     

Estimates of ion sources in deciduous and coniferous throughfall

Estimates of external and internal sources of ions in net througfall deposition were derived for a deciduous and coniferous canopy by use of multiple regression. The external source component appears to be dominated by dry deposition of Ca²⁺, SO₂ and NO₃⁻ during dormant and growing seasons for the two canopy types. Increases in the leaching rates of K⁺ and Mg²⁺ during the growing season reflect the presence of leaves in the deciduous canopy and increased physiological activity in both canopies. Internal leaching rates for SO₄²⁻ doubled during the growing season presumably caused by increased physiological activity and uptake of SO₂ through stomates. Net deposition of SO₄²⁻ in throughfall during the growing season appears highly dependent on stomatal uptake of SO₂. Estimates of SO₂ deposition velocities were 0.06 cm s⁻¹ and 0.13 cm s⁻¹ for the deciduous and coniferous canopies, respectively, during the dormant seasons, and 0.30 cm s⁻¹ and 0.43 cm s⁻¹ for the deciduous and coniferous canopies, respectively, during the growing season. For the ions of major interest with respect to ecosystem effects, namely H⁺, NO₃⁻ and SO₄²⁻, precipitation inputs generally outweighed estimates of dry deposition input. However, net throughfall deposition of NO₃⁻ and SO₄²⁻ accounted for 20–47 and 34–50 per cent, respectively, of total deposition of those ions. Error estimates of ion sources were at least 50–100 per cent and the method is subject to several assumptions and limitations.     

Measurements of ammonia flux to a spruce stand in Denmark

This work demonstrates the existence of a linear relation between the deposition velocity of ammonia and the friction velocity measured above a spruce stand in the western part of Denmark. In order to estimate the ammonia deposition velocity and flux to a Norway spruce forest, concentration gradients of ammonia and several meteorological parameters were measured in a meteorology tower during two periods, 1 week in spring and 1 week in late summer 1991. The estimated deposition velocities lie in the range −0.125 to 0.201 m s⁻¹, with a mean of 0.026 m s⁻¹. The deposition velocity and the flux were generally largest in the afternoon. On the basis of 24-h measurements of ammonia and routine meteorological measurements the relation between deposition velocity and friction velocity is extrapolated to an estimate of the average flux for the growing season May to September 1991. The estimate gave an average flux of 87 μg NH₃N m⁻² h⁻¹ (=0.02 μg NH₃N m⁻² s⁻¹). The average deposition velocity for the period was 0.045 m s⁻¹.     

The chemical composition of intercepted cloudwater in the Sierra Nevada

The chemical composition of cloudwater in the Sierra Nevada is dominated by NO₃⁻, SO₄²⁻, and NH₄⁺. Cloudwater pH is determined largely by the balance between the concentrations of these three species, although inputs of formic and acetic acid also are believed to be important, particularly when anthropogenic inputs are small. Cloudwater samples collected in Sequoia National Park (SNP) exhibited pH values ranging from 3.9 to 6.5; Yosemite National Park (YNP) cloudwater samples had pH values ranging from 3.8 to 5.2. Samples collected at YNP were more acidic than those collected at SNP. The difference in pH between the two regions appears to be due to relatively small differences in inputs of NO₃⁻, SO₄²⁻, and NH₄⁺. In the absence of inputs of NH₃, cloudwater pH values in the Sierra may fall below 3.Over 250 h of cloud interception were observed during a 12 month period at a cloud monitoring site at 1856 m elevaton in SNP. Estimates of cloudwater deposition of NO₃⁻, SO₄²⁻, and NH₄⁺ indicate that cloud interception contributes significantly to regional acid deposition for closed forest canopies. Cloud interception may be the dominant deposition mechanism for isolated conifers and ridgetop canopies, where wind speeds are higher and cloudy air parcels can impact directly on foliar surfaces.     

Rainwater composition in Athens,Greece

Wet precipitation-only samplers were used to collect wet deposition at two sites in the Athens basin, Greece for the period March 1986–February 1987.Concentrations of major cations (H⁺, NH⁺₄, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and major anions (Cl⁻, NO⁻₃ and SO²⁻₄) were determined for the first time in rainwater samples in Greece. Bicarbonate concentrations were calculated. The relative importance of natural and anthropogenic sources were estimated by a chemical balance. The majority of rain collected has a neutral or alkaline character. Acidity was due to the presence of H₂SO₄ and HNO₃. The statistical analysis of the correlation between the concentration of chemical species confirm the influence of natural and anthropogenic sources. In all samples, SO²⁻₄ concentrations exceed NO⁻₃ concentrations despite the dominance of low S oil burning in the region. The wet flux of S was calculatd to be 0.34 gm⁻²a⁻¹.     

A chemical characterization of atmospheric aerosol in Sapporo

Monthly mean chemical composition of aerosol with diameter less than 8 μm was identified in Sapporo in 1982. The mass of aerosol was made up of nine components: elemental C, organics, SO₄²⁻, NO₃⁻, NH₄⁺, Cl⁻, Na⁺, soil particles and water. The concentrations of carbonaceous particles (elemental C and organics) was relatively high (12.7–16.0μ m⁻³) in autumn and winter (October–February) due to emission from domestic heating and comprised 36–41% of total aerosol mass. Higher concentration of soil particles was observed in spring (March–May) (9.7–13.1 μg m⁻³) and comprised 22–29% of total aerosol mass due to suspension by strong wind. On the other hand, the concentration of excess SO₄²⁻ (non-sea salt SO₄²⁻), which ranged from 2.6–5.2 μg m⁻³, did not change remarkably with season, and the fraction of excess sulfate increased to 21% in summer (July–August) probably due to photochemical transformation from SO₂. Nitrate concentration was far less than that of SO₄²⁻ throughout the year in Sapporo.     

Stability of the pH and the contents of ammonium and nitrate in precipitation samples

The changes in the pH and the contents of NH₄⁺, NO₃⁻ and 10 other components including trace elements were studied in precipitation samples for a period of up to 300 days. The concentration of free H⁺ ions is affected after deposition by several processes, the most important being bioconsumption of NH₄⁺ leading to an increase in the H⁺ ion level depending on the length of the sampling interval, the time of year and the way of storing the samples prior to their analysis. It is proposed that, for the purpose of comparing the acidities of precipitation waters and their effects on acidification of the environment, the corrected H⁺ ion concentration (H_c⁺) be calculated from the pH value and the concentrations of NH₄⁺ and NO₃⁻ (H_c⁺ = H⁺+NH₄⁺−NO₃⁻). The H_c⁺ value depends little on the bioconsumption of NH₄⁺ and NO₃⁻ after deposition and thus is not very sensitive to the way of storing the samples, the sampling interval and the time elapsed between deposition and the sample analysis. Dissolution of Fe, Al, Si and some trace elements from the particles scavenged during precipitation was slow in the studied samples; it is advantageous to digest the sample in a microwave oven prior to determination of these elements.     

Changing sources of impurities to the Greenland ice sheet over the last 250 years

Because the composition of precipitation reflects the composition of the atmosphere, polar ice cores provide a useful way of investigating past and present atmospheres. We have measured concentrations of major ions in nine sections of a central Greenland ice core and we found that concentrations of both SO₄²⁻ and NO₃⁻ have increased dramatically over the last 250 years, up to three to four times the 18th century levels. Large changes have also occurred in the average concentrations of several other chemical species, such as NH₄⁺, excess Cl, and Ca²⁺. We used a principal-component analysis to characterize variations of the season of maximum deposition rate of HNO₃ and H₂SO₄ to the snow. We found that source fluctuations of H₂SO₄ are faithfully recorded in the Greenland snow and appear to switch their preferential time of deposition in the snow from summer to winter early in the 20th century. On the other hand, HNO₃ is deposited preferentially during summer throughout the core, emphasizing the role of photochemistry in understanding nitrogen cycling in the Arctic. Anthropogenic inputs have clearly modified the behavior of several chemical compounds in the atmosphere.     

A case study of Asian dust storm particles: Chemical composition, reactivity to SO2 and hygroscopic properties

Mineral dust comprises a great fraction of the global aerosol loading, but remains the largest uncertainty in predictions of the future climate due to its complexity in composition and physico-chemical properties. In this work, a case study characterizing Asian dust storm particles was conducted by multiple analysis methods, including SEM-EDS, XPS, FT-IR, BET, TPD/mass and Knudsen cell/mass. The morphology, elemental fraction, source distribution, true uptake coefficient for SO₂, and hygroscopic behavior were studied. The major components of Asian dust storm particles are aluminosilicate, SiO₂ and CaCO₃, with organic compounds and inorganic nitrate coated on the surface. It has a low reactivity towards SO₂ with a true uptake coefficient, 5.767×10^-6, which limits the conversion of SO₂ to sulfate during dust storm periods. The low reactivity also means that the heterogeneous reactions of SO₂ in both dry and humid air conditions have little effect on the hygroscopic behavior of the dust particles.     

Characteristics of airborne particles inside southern California museums

The concentrations and chemical composition of suspended particulate matter were measured in both the fine and total size modes inside and outside five southern California museums over summer and winter periods. The seasonally averaged indoor/outdoor ratios for particulate matter mass concentrations ranged from 0.16 to 0.96 for fine particles and from 0.06 to 0.53 for coarse particles, with the lower values observed for buildings with sophisticated ventilation systems which include filters for particulate matter removal. Museums with deliberate particle filtration systems showed indoor fine particle concentrations generally averaging less than 10 μg m⁻³. One museum with no environmental control system showed indoor fine particle concentrations averaging nearly 60 μg m⁻³ in winter and coarse particle concentrations in the 30–40 μg m⁻³ range. Analyses of indoor vs outdoor concentrations of major chemical species indicated that indoor sources of organic matter may exist at all sites, but that none of the other measured species appear to have major indoor sources at the museums studied. Significant fractions of the dark-colored fine elemental (black) carbon and soil dust particles present in outdoor air are able to penetrate to the indoor atmosphere of the museums studied, and may constitute a soiling hazard to works of art displayed in museums.     

Atmospheric trace elements over source regions for Chinese dust: concentrations,sources and atmospheric deposition on the Loess plateau

The mass-particle size distributions of up to 17 trace elements in aerosol particle samples from dust storm and non-dust storm periods were determined for three sites in or near the source regions of Chinese dust. The mass of particulate material in the atmosphere at the sites is dominated by mineral aerosol particles. An absolute principal component analysis of the non-dust storm elemental data for the loess region allows the estimation of the mass contributions from two coarse-particle classes (soil dust and dust associated with pollutants), and two fine-particle classes (soil dust and anomalously enriched). For most elements (Al, Si, Ca, Fe, Ti, K, S and As), the mass-particle size distributions (MSDs) were approximately log-normal. The mass-median diameters (MMDs) of the soil-derived elements tended to decrease with distance from the desert region and when the dust storms subsided. Total dry deposition velocities were calculated by fitting a log-normal distribution to the aerosol data and calculating deposition rates for 100 particle-size intervals using a two-layer deposition model. The mean dry-deposition rates and fluxes were highest during dust storms over desert regions. In thloess region, the calculated dry deposition velocities of soil derived elements (Al, Si, Ca, Fe and Ti) during non-dust storm periods were from 3.1 to 3.7 cm s⁻¹. From the estimated mass-particles size distributions, the coarser and finer mineral particles were found to benriched with Ca, Fe, Ti and K relative to Al or Si. On a yearly basis, the dry atmospheric input to the Loess Plateau was mainly attributable to normal transport processes, i.e. non-dust storm conditions. Wet deposition fluxes estimated from scavenging ratios indicate that dry deposition dominated the total atmospheric deposition of mineral aerosol. The deposition of aerosol particles associated with coal burning or other anthropogenic sources also was considerable on the Loess Plateau.     

雨季玉龙雪山白水1号冰川表层雪中无机离子特征及环境意义

分析了玉龙雪山白水1号冰川雨季(5-10月)表层雪中无机离子的组成和特征,并与其他高海拔地区湿沉降进行对比。结果表明:白水1号冰川表层雪一定程度上受到了人类活动的影响;由于雨季强烈的淋溶作用,表层雪SO₄^2-含量较低,酸度的主要贡献离子是NO₃^-;pH值较高的原因是碱性金属离子的中和作用;海盐示踪结果显示雨季表层雪中离子来源主要以海源为主。在6-9月之间由于降水的淋洗作用,表层雪中离子浓度较低。表层雪中NO₃^-、SO₄^2-、Ca²⁺高于大多数其他高海拔区域降水,是表层雪中无机离子浓度的主要贡献者,Ca²⁺浓度较高说明该地区高空水汽也受到了局地岩石岩性的强烈影响。     

Cloud chemistry measurements and estimates of acidic deposition on an above cloudbase coniferous forest

The wet, dry and cloud water deposition of acidic substances on the forest canopy are considered as major mechanisms for pollutant induced forest decline at high elevations. Direct cloud capture plays a predominant role of intercepting acidic substances in above cloud-base forests. We conducted a field study at Mt. Mitchell, North Carolina (35°44′05″N, 82°17′15″W; 2038 m MSL)—the highest peak in the eastern U.S.—during May–September 1986 and 1987 in order to analyze the chemistry of clouds in which the red spruce and Fraser fir stands stay immersed. It was found that Mt. Mitchell was exposed to cloud episodes 71% of summer days, the cloud immersion time being 28% for 1986 (a record drought summer in southeastern U.S.) and 41% for 1987. Sulfate, NO₃⁻, NH₄⁺ and H⁺ ions were found to be the major constituents of the cloud water, which was collected atop a 16.5 m tall meteorological tower situated among 6–7 m tall Fraser fir trees. The initiation of precipitation in clouds invariably diluted the cloud water acidity. The cloud water pH during short episodes (8 h duration or less), which resulted from the orographic lifting mechanisms, was substantially lower than that during long episodes, which were associated with meso-scale and synoptic-scale disturbances. Sulfate accounted for 65% acidity in cloud water, on the average, and contributed 2–3 times more than the NO₃⁻. Inferential micrometeorological models were used to determine deposition of SO₄²⁻ and NO₃⁻ on the forest canopy and the hydrological input due to direct cloud capture mechanism. The cloud water deposition ranged between 32 and 55 cm a⁻¹ in contrast to the bulk precipitation which was about 130 cm a⁻¹ as measured by an on-site NADP (National Atmospheric Deposition Program) collector. For S compounds, wet, dry and cloud water deposition accounted for 19%, 11% and 70%, respectively for 1986, and 16%, 8% and 76%, respectively for 1987. For N compounds, dry deposition contributed 35% and 23% for 1986 and 1987, respectively, whereas, cloud water deposition contributed 50% and 65% for 1986 and 1987, respectively. Our estimates are compared with the reported literature values for the other sites.     

Wet deposition of volcanic gases and ash in the vicinity of Mount Sakurajima

Wet deposition of soluble materials was monitored for a 7-month period in the vicinity of Mount Sakurajima, which has been very active since 1955. Data obtained for the ionic composition of samples were used as a basis for considering the scavenging of volcanic emissions by precipitation. Precipitation samples with pH < 4 were often collected in the vicinity of Mount Sakurajima during the course of the study. HCl, H₂SO₄ and HF were the primary contributors to the acidity of precipitation. The exCl⁻/exSO₄²⁻ mole ratio of precipitation was several times that of volcanic ash in the vicinity of the volcano and declined with distance from the volcano. Although most of the S in volcanic emissions is in the form of SO₂, relatively little of this is washed out by precipitation in the immediate vicinity of the volcano. The deposition of S in the vicinity of the volcano can be adequately accounted for by assuming the scavenging of SO₄²⁻ particles despite the relatively small share of total atmospheric S loading of particulate SO₄²⁻ in the vicinity of Mount Sakurajima.     

Dry deposition of PM10 over the Yellow Sea during Asian dust events from 2001 to 2007

Dry deposition velocities and fluxes of PM10during Asian dust events over the Yellow Sea from 2001 to 2007 were investigated using observation data in Qingdao, China and Jeju, Korea. The dry deposition velocities of PM10 during dust events over the Yellow Sea ranged from 0.19 to 8.17 cm/sec, with an average of 3.38 cm/sec. Dry deposition fluxes of PM10during dust events over the Yellow Sea were in the range of 68.5–2647.1 mg/(m2·day), with an average of 545.4 mg/(m2·day), which is 2–10 times higher than those reported by other studies for both dust and non-dust periods. It was estimated that 2.6 × 1011–48.7 × 1011g dust particles deposit to the Yellow Sea during dust events through dry deposition every year. Compared with the results in previous studies, it was found that the dry deposition of PM10over the Yellow Sea during dust events in the years with high frequency of dust could account for a large or overwhelming fraction of the annual total dry deposition. Backward air mass trajectory analysis showed that dust events influenced Jeju mainly originated from the desert regions located in Mongolia and Inner Mongolia, China. There were 119 backward trajectories influenced both Qingdao and Jeju during 15 dust events from 2001 to 2007, accounting for 61.3% of the total trajectories of 194, indicating that Qingdao and Jeju were usually on the same pathway of dust transport downwind from source areas.