Orographic enhancement of wet deposition in the United Kingdom: case studies and modelling

Two field experiments to observe the detailed response of wet deposition to orography in a polluted environment are reported. Rain events were classed as frontal, convective or mixed on the basis of meteorological data. Analysis of the deposition enhancement and cap cloud composition confirmed that for the frontal events the seeder-feeder effect (scavenging of cap cloud by rain drops) dominates. The greater concentration of ions in the water scavenged from the cap cloud than in the rain means that deposition is enhanced for all ions. For marine ions the scavenged water was found to be between five and six times as concentrated as the rain and for anthropogenically produced ions it was about twice as concentrated.A computational model of rainfall incorporating the seeder-feeder effect has been broadly successful in predicting enhancement although some details of the observed pattern remain to be explained.     

The application of210Pb inventories in soil to measure long-term average wet deposition of pollutants in complex terrain

The radionuclide²¹⁰Pb derived from gaseous²²²Rn is present in particle form in the atmosphere attached to the same aerosols which contain the bulk of the pollutant sulphur and nitrogen. When scavenged from the atmosphere by precipitation, the²¹⁰Pb is readily attached to organic matter in the surface horizons of soil. The inventory of²¹⁰Pb in soil can be used to measure the spatial variation in wet (or cloud) deposition within a region due to orography or land use, averaged over several decades (half life of²¹⁰Pb is 22.3 years). Measurements of soil²¹⁰Pb inventories along a transect through complex terrain in north Britain were made to quantify the orographic enhancement of wet deposition, at Great Dun Fell in Cumbria. At the hill summit (～800m asl) precipitation of approximately 2000 mm year^?1 exceeds that on the low ground upwind by a factor of 2.0. The inventory of²¹⁰Pb increases along the same transect by a factor of 3.3, due to seeder-feeder scavenging of orographic cloud. The measurements show that the average ratio of concentrations in scavenged orographic cloud to rain upwind of the hills is 2.2. These data are entirely consistent with the studies of the variation in major ion concentration with altitude at Great Dun Fell and elsewhere. The modelling procedures developed to provide estimates of wet deposition throughout the UK uplands are shown to be consistent with these new field data.     

Wet and dry deposition of nutrients in Central Alberta

Dry and wet deposition rates of various forms of phosphate and N and of Fe, sulphate, Na, K, and silica ions are reported for a 1 yr period in central Alberta. The results are extrapolated from event samples of rain and snow, and from dry deposition samples in distilled water collectors and snowpack. Following corrections for contamination and evaporation the most reliable dry deposition rates are found for orthophosphate, organic and nitrate N, and Fe, sulphate, and K ions. Ion concentrations in snow are significantly lower than those in rain for ammonia, organic, and total N and for sulphate and silica ions. More than 50% of the concentrations of total phosphate and total N in wet deposition samples is dissolved or in fine particles (less than 0.45 μ) but only about one third of dry deposition sample concentrations is in such form. Dry-to-wet deposition ratios for the year exceed one for filtered total N, filtered total phosphate, Fe, and sulphate. The largest dry-to-wet deposition ratios are about 5 for sulphate and unfiltered total N.     

ACID DEPOSITION DURING TWO CONTRASTING FRONTAL RAINFALL EVENTS

Analysis of the chemical composition of rain at high temporal resolution provides additional information on wet deposition processes. High resolution data was obtained using a microprocessor-based acid rain monitor at two sites in SW Scotland and SE England. Meteorological details of the transport and wet deposition processes during two frontal rain events were examined and related to rainfall composition. Rapid depletions of ion concentrations during heavy rainfall in the first event were interpreted using a rainfall scavenging model. The sub-event data for the second event showed the influence of frontal discontinuities. Increasing ionic concentrations during this second event were attributed both to the change in air mass, and to diminished upwind precipitation scavenging.     

Contributions of cloud processes to precipitation chemistry in mixed phase clouds

The role clouds play as processors of atmospheric aerosols and trace gases was studied along the slope of Mt. Rigi in central Switzerland. Upon cloud formation many aerosols and trace gases are efficiently scavenged by cloud drops. The cloud drops can enhance removal of pollutants from the atmosphere by transferring them to snow or rain which falls rapidly to the ground. This often occurs through a process known as riming, where falling ice crystals capture cloud drops. When ice crystals are grown primarily via water vapor deposition, without significant capture of cloud drops, however, the cloud drops isolate atmospheric pollutants from the precipitation process, thereby inhibiting their deposition. Increased riming results in increased precipitation ion concentrations. The extent of ice crystal riming at times exhibits spatial inhomogeneities with greater riming apparent near the mountain summit. Variations in cloud chemistry with drop size indicate that bulk cloudwater composition is not an accurate predictor for the composition of cloud drops captured by the ice crystals.     

Cloudwater chemistry in the subcooled droplet regime at Mount Sonnblick (3106 M A.S.L., Salzburg,Austria)

Cloudwater and wet precipitation (snow) samples were collected at Mount Sonnblick during two field campaigns in May and November 1991. A newly designed active cloud water samples was used. Concentrations of major anions, cations and carboxylic acids were determined. Cloudwater and wet precipitation samples were generally more acidic in the warm season than in the cold season. Average cloudwater pH was 4.2 in May and 4.5 in November, average pH in snow was 4.4 in May and 5.1 in November. Average levels for sulfate (May: 96 μeq L^?1, November: 64 μeq L^?1) and nitrate (May: 27 μeq L^?1, November: 32 μeq L^?1) in cloudwater at SBO (3 km altitude) were considerably lower than at high mountain sites (0.9–2 km altitude) in the Eastern U.S.A. Cold season levels of sulfate in cloud water at SBO were as low as cloud water levels observed in Alaska. Equivalent concentrations of sulfate, nitrate and ammonium in snow precipitation were basically lower or equal compared to cloudwater but showed higher concentrations and stronger acidity in both phases in May than in November. Cloud to snow ratios for major ions were higher in November showing a wider spread than in May. Average cloud to snow ratios for sulfate were 2.4 in May and 3.5 in November. For nitrate the ratio was 1.7 in May and 2.1 in November. The lower cloud to snow ratios for nitrate are explained by the ability of the ice phase to scavenge nitric acid. Cloud to snow ratios were similar to measurements from the Swiss Alps and generally equal or lower than high elevation cloud to rain ratios from the U.S.A. Cloud to snow ratios for sulfate were used to reconstruct the mixing ratio of sublimation grown ice phase and cloud water droplets during the riming process of the ice particles in the seeder-feeder mechanism. The mixing ratio of ice phase and cloud droplets was estimated to be 1.4 in May and 2.5 in November. Sulfate to nitrate ratios were higher in cloud water than in snow and within the range of values found in North America. Generally, sulfate was more concentrated than nitrate at an equivalent basis for both cloudwater and rainwater. Total equivalent concentrations of acetate were generally higher than those of formate which is in contrast to measurements at remote high elevation sites in the U.S.A.     

Precipitation chemistry within Kvarner Bay area,Northern Adriatic (Croatia), 1984–1991

The results of rainwater analyses collected at five sampling sites within Kvarner Bay area are presented for the period 1984–1991. The samples were collected on a daily basis in open buckets thus representing bulk samples. Although measurements are referred to as wet deposition samples, they are actually an upper limit for the wet deposition. The rainwater was initially analysed for pH, sulphate and nitrate content, while during the period March 1990 — May 1991 the analyses were extended to major ion concentrations: hydrogen, sulphate, nitrate, chloride, ammonium, sodium, potassium, calcium and magnesium. The pH frequency distribution, pH medians and precipitation weighted average (PWA) concentrations of hydrogen, sulphate and nitrate are presented, as well as wet deposition rates of sulphur (as sulphate) and nitrogen (as nitrate). The dependence of hydrogen, sulphate and nitrate mean concentrations on wind directions and seasons for Site 1 is also given. The highest precipitation acidity is obtained at urban and industrial Site 1 (city of Rijeka) because of the local washout of the atmosphere and influence of dry deposition, and at remote Site 4 (Lake Vrana) due to long-range transport. The neutralizing potential of sea salt and soil dust is responsible for partial neutralization of rainwater at other sites. The influence of sea salt on chemical composition of rainwater is observed at all sites. The estimated wet deposition rates of sulphate and nitrate are close to the values reported for Southeast Europe. The wet deposition rate for ammonium ion at Site 1 is almost double comparative regional values.     

Some approximations for the wet and dry removal of particles and gases from the atmosphere

Semi-empirical formulae are presented which can be used to estimate precipitation scavenging and dry deposition of particles and gases. The precipitation scavenging formulae are appropriate both for in- and below-cloud scavenging and comparisons with data indicate the importance of accounting for aerosol particle growth by water vapor condensation and attachment of the pollutant to plume or cloud particles. It is suggested that both wet and dry removal of gases is usually dictated by other than atmospheric processes. Dry deposition of particles to a canopy is shown to depend on canopy height, biomass, vegetative type and mean wind. Two large-scale practical problems are addressed dealing with the relative importance of wet and dry deposition and with the sources which contribute to deposition in a specific location.     

Pollutant wet deposition mechanisms in precipitation and fog water

Wet deposition of acid-related substances takes place by two processes: precipitation scavenging and fog water impaction/sedimentation on natural surfaces. The relative importance of each deposition pathway depends on the frequency of occurrence of precipitation or fog, the magnitude of the event and the efficiency of pollutant removal by each mechanism. The latter, in turn, is governed by the type of cloud or fog, complex precipitation formation mechanisms and cloud-surface interactions. These factors are examined in the light of our current knowledge. Particular emphasis is placed on how cloud micro-physical as well as air and precipitation measurements, made aloft by aircraft and at the ground, have been used to further our knowledge of wet deposition mechanisms. Future research is needed to quantify the importance of the fog-water deposition pathway in eastern North America to better understand the interaction of gaseous pollutants with cloud and fog-water and to improve our knowledge of pollutant scavenging processes in mesoscale and synoptic weather systems.     

Deposition around a coal-fired power station during a wintertime precipitation event

The contribution to local wet deposition of emissions from a coal-fired power station at Inkoo on the south coast of Finland has been investigated during a wintertime precipitation event. Making use of intensive radiosonde and weather radar observations of meteorological factors, concentrations of sulphur in deposition due to plume washout were predicted by a short-range deposition model. The model used the scavenging coefficient to parametrize the wet removal of pollutants, and it took into account the wind drift of falling precipitation particles within the plume. The model predictions were then compared with the chemical analysis results from snowfall samples collected within 10 km of the power station during the experiment.The experiment was performed ahead of a deeply-occluded front during a period with strong advection of long-range transported pollutants. No reliable sign of the influence of the power station on the sulphate deposition could be identified. On the other hand, the deviations of acidity from the mean pH-value of 4.1 were concentrated in one sector near the expected area of deposited plume pollutants. If local emissions were responsible for these deviations, the explanation may lie in a slightly incorrectly estimated plume direction or the effects of alkaline fly ash. Nevertheless, definite conclusions cannot be drawn, because only a few collectors happened to be sited in the modelled sector of plume washout and none in its maximum area.     

Nine years of measurements of atmospheric nitrogen and sulphur deposition to Danish forest

Since 1985 measurements of gasses, aerosols, precipitation and throughfall have been carried out at three forest sites in Denmark with equal aged Norway Spruce plantations. The times series show a downward trend in the concentration of sulphur dioxide. Particulate sulphate, ammonia and particulate ammonium and the total nitrate seem to have a more constant concentration level. The wet deposition measurements show a decreasing trend in the content of acid (protons), sulphate, ammonium and nitrate, though for the nitrogen compounds it is only a slight fall. A decrease in concentrations of protons and sulphate is also seen in the throughfall measurements, in throughfall the nitrogen compounds hardly seem to decrease.     

The acidifying potential of atmospheric deposition in Canada

It is proposed that the value of ([SO₄ ^??] - [Ca⁺⁺ + Mg⁺⁺]) in precipitation is a suitable way to describe the acidifying potential (AP) of the wet desposition. In eastern North America, the AP of precipitation varies from 20 to 85% of the total sulphate, the remainder of the sulphate being neutralized H₂SO₄, sulphate from salts in dust or from sea salt. The AP ranges from 20 to 80% of the H⁺ in the wet deposition. The rest of the H⁺ is contributed by the net effect of N compounds. Ammonium and nitrate ions from ammonia and NO_Xemissions do not represent a net acidic loading to the terrestrial ecosystem if they are taken up by vegetation. However, when N leaches from watersheds in the form nitrate, it constitutes an acidifying demand on the ecosystem. Therefore, the overall net acidifying potential (NAP) applied to the terrestrial ecosystem is defined by the value of ([SO₄ ^??] - [Ca⁺⁺ + Mg⁺⁺]) in precipitation plus [NO₃ ^??] in runoff from the watershed.     

Preliminary analysis of atmospheric scavenging processes in the industrial region of Cubatao,Southeastern Brazil

During a German-Brazilian research project on vegetation damage, atmospheric scavenging processes were investigated, considering transport and local emissions. For this goal, radar precipitation data was evaluated together with analyses of fractionated rain samples of one stratiform and one convective rain event. The temporal variation of pollutant concentration in rain water and the meteorological conditions were compared for both rain events at two stations: one at the top of the Serra do Mar mountain ridge ( 900 m) with minor influence of local emissions and one at sea level, close to the high indutrialized area of Cubatao. At the station close to the industrial plants, major influence of the local sources on wet deposition was determined. During the stratiform rain event, an additional influence of transport could be observed. On the top of the Serra do Mar, major influence of the local sources could only be observed during the convective rain event, while transport is mainly responsible for wet deposition during the stratiform event.     

Bulk and wet atmospheric deposition chemistry at pallanza (N. Italy)

The chemistry of wet only and bulk depositions collected weekly at Pallanza from May, 1984 to December, 1986 is compared and discussed in relation to the composition of dust fall. The comparison shows a very good agreement between pH values (volume weighted mean values of 4.35 and 4.36, respectively, for wet only and bulk samples) and differences between 6 and 12% for ammonium, sulphate, nitrate, and Na. For Ca, Mg, and K the difference range is 30 to 50%. The amount of precipitation over Pallanza (mean value 1951–1985,1709 mm), together with the solute concentrations in atmospheric deposition, mean that there is high bulk deposition of acidifing substances. The values found during the study period were 76, 93, 143, and 81 meq m² yr^?1 for H⁺, ammonium, sulphate, and nitrate, respectively.     

Atmospheric deposition in acid sensitive areas of Ireland — The influence of wind direction and a new coal burning electricity generation station on precipitation quality

Greater acidity and substantially higher annual deposition of the major ions, were recorded in the precipitation at Glencree (Co. Wicklow) on the east coast of Ireland compared to those recorded at the west coast sampling stations. The daily average deposition of hydrogen ions, non-marine sulphate and oxidized nitrogen was higher at all sampling locations when associated with air masses arriving from the east compared with those from the west, particularly at Glencree. The impact of emissions from the coal-fired power station at Moneypoint (Co.Clare) on the precipitation was negligible at all sampling locations except at Gortglass, a point 19 km to its east. At this sampling point the higher concentrations and deposition for hydrogen ion and non-marine sulphate were associated with air masses expected to show the influence of the Moneypoint power station.     

Some Insights into Atmospheric Processes Involving Urban Sulphur and Nitrogen in and around Hong Kong,SAR

The representative mass ratio of the reactive airborne sulphur-to-nitrogen, S/N in the gas and aerosol phases, and in wet and dry deposition over the territory of Hong Kong, SAR,was determined, utilizing available data for the 12 yr period, 1986–1997. Using this information, the representative stoichiometric ratio values for sulphate-to-nitrate in aerosoland in wet and dry depositions were estimated. A limited supplementary data set on various canopy depositions was alsoutilized. This information collectively suggests several basicdifferences in photochemical processes between the urbanatmospheres in and around Hong Kong and the classical, smoggyLos Angeles. This is also supported by the typical diurnal variation of nitrogen oxides in Hong Kong, which suggests a moreefficient photo-oxidation of NO to NO₂ within the territoryand in nearby areas upwind, as compared to further oxidation tothe NO₃ (or nitrate) stage. On the other hand, the relatively low gas-to-particle ratio value estimated for S (～3) relative to N (～26) suggests that the advectedfraction of non-sea salt aerosol sulphate in the territory couldbe considerably greater than the corresponding fraction for nitrate. Finally, significant losses (probably related to sampling) of NH₄-NH₃ in dry deposition could be inferred, while for SO₄ in wet deposition, a moderate enrichment factor of ～2 is observed in relation to SO₄ in aerosol.     

Chemical deposition to a high elevation red spruce forest

A preliminary analysis of O₃, SO₂, SO _inf4 ^sup2? , and total NO _inf3 ^sup? deposition to the red spruce forest on the summit of Whitetop Mountain, Virginia, illustrates uncertainties in analysis methodologies, establishes the relative importance of three deposition pathways, and suggests areas for further research. Results are presented here for an analysis of the dry, wet (precipitation), and cloud water deposition pathways for the four chemical species during a 26-day period in April and May 1986. Dry and cloud water depositions are estimated using available models along with air and cloud water chemistry measurements made at the summit. For water soluble species, depositions by precipitation and cloud interception are found to be comparable in magnitude, while dry deposition appears to be about an order of magnitude less. High levels of atmospheric O₃ lead to a large estimate of 03 deposition (on a mass flux basis) when compared to the estimated deposition of gaseous SO₂. This is in spite of the fact that computed SO₂ dry deposition velocities exceed those for O₃. Model uncertainties are large for both dry deposition velocity and cloud water flux computations, and some bias in computations probably exists because of the application of the models to a complex terrain situation. Field evaluation of the cloud water deposition model is of greatest priority because of the apparent relative importance of that deposition pathway.     

Concentration and deposition of trace metals in Ontario-1982

Results of trace metal concentrations in air and precipitation and the corresponding wet and dry deposition in Ontario in 1982 arc reported. In terms of the spatial patterns, in general, there was a decreasing gradient from south-to-north in both concentration and deposition. Patterns differed with each parameter although certain groups of metals (e.g., Fe and Al; Pb, Zn, and Mn) displayed similar patterns. In general, wet deposition was greater than dry deposition at all sites. Geographically, the variability in the wet to dry deposition ratio for coarse particles (MMD > 2.5 μm) was small. However, it increased from the south to the north for fine particles (MMD < 2.5 μm), being higher away from the source areas. Scavenging ratios (W) have been derived from the precipitation and air concentrations of trace metals. The scatter in W is quite large for all trace metals, up to 2 orders of magnitude. There was little seasonal variability in W for fine particles (Pb, Mn, Zn, and Cd). However, coarse particles (Fe, Al, and Cu) were more efficiently scavenged by snow than by rain.     

Meteorological characteristics of large acidic deposition events at Kejimkujik,Nova Scotia

The characteristics of acidic deposition at Kejimkujik National Park, a rural site in south-central Nova Scotia, were determined for the period from May 1979 to December 1983. The acidifying pollutants investigated were H⁺, sulphate ion and nitrate ion. Thirty per cent of the total annual amount of acidifying pollutants deposited by precipitation at Kejimkujik was deposited by only about 8% of the precipitation events during the year. These occasions of large deposition are referred to as episodes and occurred, on average, about five times per year, usually between March and November. The precipitation events that produced episodes were almost always rain events. The major meteorological feature producing deposition episodes at Kejimkujik is the sequence of a large high pressure area from mid-continent moving south of Nova Scotia, producing a prolonged southwesterly to westerly flow over the site, and then a weak frontal system, usually from south of the Great Lakes region, bringing moderate amounts of precipitation to the site. Since deposition episodes were almost always preceded by the above sequence of events, the ability to predict episodes was investigated. The results indicate that many “false alarms” could be anticipated because this sequence also occurs for non-episodes.