Pollution in the upland environment

As part of a study on the effects of pollutants on forests, a long-term monitoring programme has been operating at two sites (602 and 275 m above sea level (a.s.l.)) in Glentress Forest, south-east Scotland, since June 1987. At these sites, equipment has been recording 20-min data for weather parameters, and cloud and rain event frequency, duration and intensity. The chemical composition of bulk cloud and rainwater has been measured. Cloudwater detection and collection has been made using passive 'Harp wire' gauges (with a cross-sectional area of 0.047 m2) strung with polypropylene filament and having a typical collection efficiency of 29% when compared with independent measurements of windspeed and liquid water content. During 1988, the annual rainfall at the upper site was 1213 mm, occurring over 1776 h. The equivalent cloudwater deposition to a forest with a drag coefficient of 0.06 was estimated to be 375 mm over 1936 h. A 'typical cloud event' lasted 4.5 h and would deposit to forests at a rate of 0.2 mm h(-1). There were significantly higher loadings of suspended particulate material (> 0.2 microm) in cloudwater (mean 18.42, max. 94.5 mg litre(-1)) compared with rainwater (mean 2.6, max. 25.6 mg litre(-1)). There were similar differences in ion concentrations, e.g. for H+ in cloudwater (mean 163, max. 1259 microm) and in rainwater (mean 33, max. 262 microM). It is concluded that cloudwater deposition represents a major pathway for pollutant transfer to the upland environment, especially where the surface vegetation is efficient at capturing cloudwater, i.e. forests. The consequences of this increased pollutant loading to forests and water catchments are yet to be assessed.     

Measurements and modelling of cloudwater deposition to moorland and forests

The objective of the study was to measure the size dependence of cloudwater deposition and associated average ionic fluxes to vegetated surfaces. Measurements were made over a forest canopy at Dunslair heights in south Scotland and a moorland site, Great Dun Fell, in northern England. Measurements were made using the gradient and eddy correlation techniques. Eddy correlation measurements were made using an ultrasonic anemometer, a Knollenberg forward scattering spectrometer probe (to measure liquid water fluxes and fluxes of droplets in 1 microm size intervals) and a GSI particulate volume monitor (to measure liquid-water fluxes). Measurements were made at Great Dun Fell of the size dependence of droplet deposition velocity, using the gradient technique with two Knollenberg probes. Simultaneous gradient and eddy correlation measurements were also made at Great Dun Fell of average cloud-water fluxes, together with chemical analysis of cloud water composition, using a continuous analysis system. At Dunslair Heights, eddy correlation measurements were made using both the Knollenberg and Gerber Scientific Instruments (GSI) probes, while simultaneous gradient measurements using two GSI probes were also attempted. Samples of cloud water were collected at Dunslair Heights, using passive string collectors for chemical analysis by ion chromatography. The major findings of the study were: 1. The droplet deposition velocities measured by the two techniques were similar. 2. The deposition velocities were a strong function of droplet size. Considerable resistance to deposition was evident for droplets of less than 5 microm radius. Deposition velocities for particles from about 6 to 8 microm exceeded those for momentum. 3. Except when the droplets were very small or the winds very light, bulk cloud-water deposition velocities were about 80% or more of the momentum deposition velocities to forests.     

Air parcel model simulations of a convective cloud: Bacteria acting as immersion ice nuclei

The effects of bacteria acting as immersion ice nuclei were investigated in numerical sensitivity studies and compared to the efforts of other ice nuclei such as mineral dust and soot particles. An adiabatic air parcel model was employed simulating convective situations with different initial aerosol particle distributions. The maximum fractions of active ice nuclei were based on field measurements of the proportioning of atmospheric aerosol particle types in continental and marine air masses. Recent field measurements of bacteria concentrations in cloud water and in snow samples were used. From the concentrations in bulk samples the concentration in mean sized cloud droplets was estimated. Immersion freezing was described based on laboratory measurements to constrain the freezing fraction versus temperature. The results indicated that the effects of diminutive amounts of bacteria on ice formation in convective clouds, while being significantly less than the effects of mineral dust particles, might be comparable to the expected effects of soot particles acting as ice nuclei. It can be predicted that bacterial ice nuclei would have to be enriched by at least 10⁴ times reported concentrations in cloud water in order to equate to the impact of mineral dust ice nuclei present in 20–25% of all cloud droplets.     

The scavenging of atmospheric sulfate by arctic snow

Scavenging ratios for sulfate on the south-central Greenland Ice Sheet at Dye 3 have been computed for 1982–1984. The ratios are based on measured concentrations in snow and estimated concentrations in air. The snow data have been obtained from snowpit samples which were dated by comparing δ¹⁸O values with meteorological records. The airborne concentrations have been estimated from data collected at coastal Greenland sites. Scavenging ratios resulting from this process are found to be in the range ~ 100–200 in winter and ~ 200–400 in summer. The greater summer values are attributed to increased riming, resulting in scavenging of sulfate as condensation nuclei and possible oxidation of SO₂ in cloudwater droplets. Using the airborne and snowpit concentrations with assumed dry deposition velocities of 0.02–0.05 cms⁻, it is estimated that dry deposition is responsible for roughly 10–30% of the total sulfate deposition on a year-round basis at Dye 3. During portions of the Arctic winter, however, when the snow is unrimed and when there is less precipitation, dry deposition may be dominant.     

Acidity of raindrop by uptake of gases and aerosol pollutants

Below-cloud raindrops acidification simulated with a simple model incorporating gas–liquid equilibriums, gas-phase mass transfer, and catalyzed SO₂ oxidation in aqueous phase with uptake of gases and scavenging of particles. Ionic contents of various species in raindrops of different size and pH are computed using one-dimensional time-variant model. The model results are based on SO₂ and NH₃ absorption and collection of calcium aerosols by raindrops with various collection mechanisms. Aqueous concentrations of (SO₂)_l and (NH₃)_l and their ionic components in raindrops are found to be increased with the fall distance from cloud base and decrease of drop size. The overall magnitude of pH enhances with the increase in drop size and transient position of raindrops in the atmosphere below the cloud base. The elevated ionic calcium in raindrops by impaction of calcium aerosols of higher inertia neutralizes the acidic components. Acidic ion contents in smaller droplets are found to be significant and resulted pH of raindrop increases with the size and neutralizing potential of alkaline species. The pH values of rainwater contents of predominant size raindrops in bulk samples corresponding to various rainfall intensities are higher as against the individual non-evaporating smaller raindrops. Results are important in view of the impact of showers on earth surfaces during rain containing large number of smaller droplets as compared to the acidification studies of bulk rainwater.     

A multivariate statistical analysis of the composition of rainwater near Cubatão, SP, Brazil

With the aim of estimating the chemical composition of bulk precipitation (wet + dry) in Cubat?o, rainwater samples were collected at several localities in the Cubat?o region from May 1984 to October 1985. The levels of some inorganic ions (Na+, Ca2+, K+, Mg2+, Cl-, SO4(2-), NH4+, PO4(3-)) were measured by atomic absorption spectrophotometry, turbidimetry and titration analysis. Correlation and Fisher discrimination indices, principal component and varimax loading and scores were determined in the multivariate statistical data treatment. The results showed that ionic concentrations in rainwater from Vila Parisi are significantly higher than those of Cubat?o Centro, Santos and Serra do Mar. The ionic compositions of the Vila Parisi rainwater seem to be mainly determined by local anthropogenic activities (industrial pollution). Besides the influence of this factor on water quality, there is also a natural oceanic contribution involving Cl- and Na+ at the other locations.     

Preliminary estimation of the rainfall chemical composition evaluated through the scavenging modeling for north-eastern Amazonian region (Amapá state,Brazil)

Numerical modeling of scavenging processes has been compared with data obtained for rainwater and aerosol chemistry at Serra do Navio, in the state of Amapá in the Brazilian Amazon region. Sulfate, nitrate and ammonium concentrations were determined in rainwater samples collected from May 1995 until June 1997. The levels of these same chemicals were also determined in aerosols for the same period and region. Scavenging processes have been evaluated on a rainfall event basis, via numerical modeling, in order to simulate the rainwater concentrations and compare them with the observed data. RAMS (Regional Atmospheric Modeling System) was used to simulate cloud structures. A model of below-cloud scavenging was evaluated, as well. The determinations made from the results of the scavenging model are the following: a) aerosol vertical profiles are quite important to rainwater concentrations; b) modeled sulfate in rainwater is a better fit to the observed data values than ammonium and nitrate; c) the obtained sulfate aerosol concentrations samples are similar to ones found in the literature, although the sulfate concentrations in rainwater are much lower than other studies in the literature; d) the in-cloud scavenging process dominates, e) our modeled results, using an input gas vertical profile extracted from the ABLE2B experimental data set, present a smaller ratio between gas and aerosol scavenging than found in other studies in the literature, other studies may have had larger rainfall times, which increase the importance of gas phase scavenging.     

Evaluation of trace elements contamination in cloud/fog water at an elevated mountain site in Northern China

Totally 117 cloud/fog water samples were collected at the summit of Mt. Tai (1534 m a.s.l.)—the highest mountain in the Northern China Plain. The results were investigated by a combination of techniques including back trajectory model, regional air quality and dust storm models, satellite observations and Principal Component Analysis. Elemental concentrations were determined by Inductively Coupled Plasma Mass Spectrometry, with stringent quality control measures. Higher elemental concentrations were found at Mt. Tai compared with those reported by other overseas studies. The larger proportions and higher concentrations of toxic elements such as Pb and As in cloud/fog water compared with those in rainwater at Mt. Tai suggests higher potential hazards of cloud/fog water as a source of contamination in polluted areas to the ecosystem. Peak concentrations of trace elements were frequently observed during the onset of cloud/fog events when liquid water contents of cloud/fog water were usually low and large amount of pollutants were accumulated in the ambient air. Inverse relationship between elemental concentrations and liquid water contents were only found in the samples with high electrical conductivities and liquid water contents lower than 0.3 g m⁻³. Affected mainly by the emissions of steel industries and mining activities, air masses transported from south/southwest of Mt. Tai were frequently associated with higher elemental concentrations. The element Mn is attributed to play an important role in the acidity of cloud/fog water. The composition of cloud/fog water influenced by an Asian dust storm event was reported, which was seldom found in the literature.     

Time study of trace elements and major ions during two cloud events at the Mt. Brocken

Cloud water investigations have been performed at the highest elevation of Central Germany in 1997. Results of extensive trace element measurements are presented. Besides conductivity, pH, liquid water content and major ions the data set includes 49 minor and trace elements. Estimation of crustal enrichment factors (EFs) provides an indication of the anthropogenic contributions to the cloud water concentrations. The variation of cloud composition with time has been illustrated for two selected events with different air mass origins. The chemical composition of the cloud condensation nuclei on which the droplets grow mainly determines the cloud water chemistry. For a cloud event in June 1997 the concentrations of the crustally derived elements Si, Al, Fe, Ti, Ce, La and Nd follow each other closely. The fact that SO₄²⁻, NO₃⁻ and NH₄⁺ are only moderately correlated with the particular pollutants with high enrichment factors such as Cd, Sb, Pb, Zn, Cu, As, Bi, Sn, Mo, Ni, Tl and V indicates that their source regions are more widespread. During an event in October 1997 the time trends for most minor and trace elements follow rather closely those for the major ions NH₄⁺, SO₄²⁻ and NO₃⁻. Back trajectories show that the transport from continental and marine European sources was the likely cause of the sample concentrations. EFs of trace elements in cloud water samples during the June and October event show a strong correlation with those obtained for urban particulate matter. Although both events are influenced by air masses of different origin, there is a good agreement between the EF signatures.     

A computer modelling study of the chemistry occurring during cloud formation over hills

A model has been developed which describes the chemical processes occurring during the formation of hill cloud. This model has been applied to the study of four cases which should be typical of the chemical conditions which can exist during the formation of such cloud over hills in the N of England.The results show that a wide range of chemical behaviour is possible in cloud droplets, depending on the history of the airmass. The composition of the water-soluble aerosol is of importance in determining the chemical composition of cloud droplets, with most of the sulphate and large proportions of the other ions being derived from this source. Gas-phase chemistry is also important, not only because it dictates the initial concentrations of oxidants such as H₂O₂ and O₃ and of acidic gases such as HNO₃ at the onset of condensation, but also because of the chemical processes which occur concurrently with those in clouds. These are important sources of radicals, as well as of nitric acid, which continue to dissolve in solution. Gasphase HCl, HNO₃ and NH₃ are all of primary importance in describing the acidity of cloud droplets. The various oxidation mechanisms for SO₂ can all be important, with their relative contributions varying from case to case. H₂O₂ does not invariably dominate this process, especially in winter when its concentration may be low.The chemistry of hill clouds is far from trivial and oversimplification can result in a misunderstanding of the behaviour which occurs. There is a need, rather, to consider a wide range of reactions if the nature of the overall processes and the impact of manmade emissions on the environment via this route are to be understood.     

Mineral dust is a sink for chlorine in the marine boundary layer

Dust particles affect the budgets of important traces gases by providing a surface on which heterogeneous reactions can occur. The uptake of soluble species on dust alters the physical, chemical, and optical properties and the overall ability of dust to act as cloud condensation and ice nuclei. It is commonly assumed that all measured chloride in particulate filter samples is associated with sea-salt particles and any chloride in dust occurs as the result of internal mixtures of sea-salt and dust particles, formed by cloud processing. Here we show high temporal resolution data demonstrating the direct uptake of chlorine by dust via heterogeneous reaction with HCl(g). This reaction added significant amounts of chlorine to the dust particles during a major dust storm, representing 4–9% of the individual dust particle mass. Up to 65±4% of the dust particles contained chlorine due to this heterogeneous reaction during the dust front. Ignoring this process leads to an overestimation of sea-salt concentrations from bulk measurements, and an underestimation of the degree of sea-salt aging. The uptake of chloride will change the pH and hygroscopic properties of the dust and thus can influence the budgets of other reactive gases. Including this heterogeneous process in atmospheric measurements and chemical transport models will improve our ability to predict the atmosphere's composition and radiation budget with greater accuracy.     

Estrogenic and esterase-inhibiting potency in rainwater in relation to pesticide concentrations,sampling season and location

In a year-round monitoring program (1998), pesticide composition and toxic potency of the mix of pollutants present in rainwater were measured. The goal of the study was to relate atmospheric deposition of toxic potency and pesticide composition to each other and to sampling period and local agricultural activity. Rainwater was collected in 26 consecutive periods of 14 days in a background location (BACK) and in two locations representative for different agricultural practices, i.e. intensive greenhouse horticulture (HORT) and flower bulb culture (BULB). Samples were chemically analyzed for carbamate (CARB), organophosphate (OP) and organochlorine (OC) pesticides and metabolites. Esterase inhibiting potency of rainwater extracts was measured in a specially developed bio-assay with honeybee esterases and was expressed as an equivalent concentration of the model inhibitor dichlorvos. Estrogenic potency of the extracts was measured in the ER-CALUX reporter gene assay and was expressed as an equivalent concentration of estradiol. Multivariate principal component analysis (PCA) techniques proved to be valuable tools to analyze the numerous pesticide concentrations in relation to toxic potency, sampling location, and sampling season. Pesticide composition in rainwater depended much more on sampling season than on sampling location, but differences between and were mainly attributed to local differences in agricultural practice. On average, the esterase inhibiting potency exceeded the maximum permissible concentration set for dichlorvos in The Netherlands, and was significantly higher in than in and . Esterase inhibition correlated significantly with OP and CARB concentrations, as expected given the working mechanism of these insecticides. The estrogenic potency incidentally exceeded NOEC levels reported for aquatic organisms and was highest in . Although estrogenic potency of rainwater correlated with OC concentrations, the ER-CALUX responses could not be attributed to any particular pesticides. Besides, the contribution of non-analyzed xeno-estrogens as alkylphenol(-ethoxylates) and bisphenol-A to the estrogenic potency of rainwater could not be excluded. Further research should focus on the chemical identification of estrogenic compounds in rainwater. In addition, more attention should be given to the ecological consequences of atmospheric deposition of individual pesticides and of total toxic potencies that regularly exceed environmental criteria for Dutch surface waters and/or toxic threshold values for aquatic organisms.     

A winter study of air,cloud and precipitation chemistry in Ontario,Canada

During January and February 1984, a field project was conducted near North Bay, Ontario, Canada. The principal objective was to characterize the chemical and microphysical properties of the air masses, clouds and precipitation in this region of NE North America during the winter season. Two extensively instrumented aircraft with some newly designed cloudwater and snow collectors were used, as well as a surface station continuously monitoring pollutant concentrations and a precipitation event sampling network. Pollutant concentrations at the surface were found to vary with the airmass back trajectory with the highest concentrations observed for trajectories from the S and SW and the lowest from the N. Vertical profiles of aerosol particle (0.2−2 μm diameter) and NOx concentrations show similar trends with maxima of 1200 cm⁻³ and 7 ppb, respectively near ground level with air mass trajectories from the S, in comparison to values of 250 cm⁻³ and 1 ppb obtained with trajectories from the N. Cloudwater, aircraft precipitation and ground precipitation samples had a daily median pH of 3.6,4.6 and 4.2, respectively with the cloudwater having the highest sulphate and nitrate concentrations. The nitrate/sulphate equivalent concentration ratios in the cloudwater, aircraft precipitation and ground precipitation samples were 0.7,0.6 and 1.4, respectively. The data suggest that precipitation scavenging of nitric acid below cloud base is an important process during the winter season.     

Long-term study of cloud condensation nuclei (CCN) activation of the atmospheric aerosol in Vienna

During a total of 11 months, cloud condensation nuclei (CCN at super-saturation S 0.5%) and condensation nuclei (CN) concentrations were measured in the urban background aerosol of Vienna, Austria. For several months, number size distributions between 13.22?nm and 929?nm were also measured with a scanning mobility particle spectrometer (SMPS). Activation ratios (i.e. CCN/CN ratios) were calculated and apparent activation diameters obtained by integrating the SMPS size distributions. Variations in all CCN parameters (concentration, activation ratio, apparent activation diameter) are quite large on timescales of days to weeks. Passages of fronts influenced CCN parameters. Concentrations decreased with the passage of a front. No significant differences were found for fronts from different sectors (for Vienna mainly north to west and south to east). CCN concentrations at 0.5% S ranged from 160?cm(-3) to 3600?cm(-3) with a campaign average of 820?cm(-3). Activation ratios were quite low (0.02-0.47, average: 0.13) and comparable to activation ratios found in other polluted regions (e.g. Cubison et?al., 2008). Apparent activation diameters were found to be much larger (campaign average: 169?nm, range: (69-370) nm) than activation diameters for single-salt particles (around 50?nm depending on the salt). Contrary to CN concentrations, which are influenced by source patterns, CCN concentrations did not exhibit distinct diurnal patterns. Activation ratios showed diurnal variations counter-current to the variations of CN concentrations.     

Organic carbon,total nitrogen,and water-soluble ions in clouds from a tropical montane cloud forest in Puerto Rico

Chemical characterization to determine the organic and nitrogen fractions was performed on cloud water samples collected in a mountaintop site in Puerto Rico. Cloud water samples showed average concentrations of 1.09 mg L^?1 of total organic carbon (TOC), of 0.85 mg L^?1 for dissolved organic carbon (DOC) and of and 1.25 mg L^?1 for total nitrogen (TN). Concentrations of organic nitrogen (ON) changed with the origin of the air mass. Changes in their concentrations were observed during periods under the influence of African dust (AD). The ON/TN ratios were 0.26 for the clean and 0.35 for the AD periods. Average concentrations of all these species were similar to those found in remote environments with no anthropogenic contribution. In the AD period, for cloud water the concentrations of TOC were 4 times higher and TN were 3 times higher than during periods of clean air masses associated with the trade winds. These results suggest that a significant fraction of TOC and TN in cloud and rainwater is associated to airborne particulate matter present in dust. Functional groups were identified using proton nuclear magnetic resonance (¹H NMR) spectroscopy. This characterization led to the conclusion that water-soluble organic compounds in these samples are mainly aliphatic oxygenated compounds, with a small amount of aromatics. The ion chromatography results showed that the ionic species were predominantly of marine origin, for air masses with and without African dust influence, with cloud water concentrations of NO₃^? and NH₄⁺ much lower than from polluted areas in the US. An increase of such species as SO₄^2?, Cl^?, Mg²⁺, K⁺ and Ca²⁺ was seen when air masses originated from northwest Africa. The changes in the chemical composition and physical properties of clouds associated with these different types of aerosol particles could affect on cloud formation and processes.     

The Evolution of Visibility Deterioration and Aerosol Spectra in the St. Louis Urban Plume

Under the auspices of Project METROMEX, studies of visibility de-teoration downwind of St. Louis were conducted during July-August 1974-1975. Estimates of horizontal visual range, standard meteorological data, and aerosol characteristics within the mixing layer were acquired upwind, over, and downwind of the metropolitan area by means of airborne transects. Aerosol number, surface, and volume distributions for particles between 0.025-2.5 µm were generated from the airborne measurement of Aitken nucleus concentrations, cloud condensation nuclei, and aerosols detected in situ with optical probes. Visibility reduction amounting to 50% of prevailing regional upwind visibilities consistently occurs at a distance corresponding to 2-3 hours travel time downwind for an air parcel moving with the mean transport wind. The regions of visibility minimum do not coincide with locations of maximum Aitken nucleus concentrations, but rather correspond in space and time to increased values of cloud condensation nuclei and increased numbers of particles in the 0.1-2.5 µm diameter range. Comparisons of observed aerosol evolution with similar laboratory studies suggest that most of the light scattering aerosols are of secondary origin.     

Characterization of size segregated particles collected over Alaska and the CAnadian high Arctic,AGASP-II flights 204–206

Ten aircraft-collected cascade impactor samples from the North American Arctic were analyzed using analytical electron microscopy. Morphological, mineralogical and elemental information were obtained from individual particles, as well as compositional data and size distribution estimates of the bulk aerosol. Categorization of carbonaceous material into organic-type and combustion-type carbon particles was performed in this study. This was accomplished through the use of a new ultra-thin window X-ray spectrometer, which can directly detect carbon X-rays emitted from particles, and through interpretation of morphological and electron diffraction data. Verification of graphite as a specific carbon mineral phase present in Arctic soot particles was performed in this manner.Several classes of particles were present in most of the aerosol samples and size fractions. These included liquid H₂SO₄ droplets, which were always present in the highest numbers, and crustal-type and composite SO₄⁻² particles. A small fraction (0–30%) of a random sampling of SO²⁻₄particles from all impactor stages were found to contain detectable nitrogen, suggesting that partial neutralization by NH₃ may have occurred in this minority of the SO²⁻₄ droplets. Particles rich in non-combustion carbon and thought to be composed of organic material were also observed in most samples. Haze samples collected off the coast of Alert, NWT, show moderate loadings of H₂SO₄ droplets. Judging from these loadings and those from higher-altitude samples, ambient aerosol particle concentrations must have been considerably higher in the haze. The extent to which local activity at Alert has influenced these haze samples is not known, although a major contribution is not expected. Stratospheric samples did not contain several classes of particles thought to have major anthropogenic source inputs to the Arctic, such as black carbon and coal-fired combustion spheres. The lightest particle loadings in any samples were collected in the upper troposphere near the tropopause, where condensation nuclei counts during sampling fell to as low as 10 cm⁻³.     

On the possible role of the biosphere in the control of atmospheric clouds and precipitation

It is well documented that atmospheric sulfate particles constitute the major class of cloud condensation nuclei. Under natural conditions, not disturbed by human activities, sulfate particles form from gaseous precursors released by the biosphere. In this way the biosphere plays an important role in the control of the cloud cover and consequently of the albedo of the Earth-atmosphere system. On the other hand, cloud condensation nuclei of biospheric origin make the redistribution of water on the Earth surface possible which is of crucial importance for the existence of living species.