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.     

Atmospheric deposition and ionic interactions within a beech canopy in the Karkonosze Mountains

A method, of artificial foliage placed above rain collectors, which enables to estimate total atmospheric inputs of elements, was employed to study processes related to ionic flow through a tree canopy. The investigations were conducted within a beech forest in the Karkonosze Mountains, in 1996-1997. An analysis of net canopy exchange (throughfall flux-atmospheric input) revealed that NH4+, NO3-, H+ had been retained in the canopy, Ca2+, Na+, Cl-, SO(2-)4, PO(3-)4 flowed passively, whereas K+ and Mg2- had been removed from the tree foliage. Ammonium absorption was more efficient than that of NO3- ions, because NH4+ was taken up from rain-waters and aerosol-gaseous fraction of the atmospheric input, whereas NO3- ions were captured primarily from the latter source. Retention of H+ was also related exclusively to the aerosol-gaseous input. Leaching losses of K+ and Mg2+ did not result from exchange reactions of these ions with retained H+, but from ionic exchange between NH4+ and K+ + Mg2+. At the same time, neutralisation of H+ in the canopy has been attributed to NO3- absorption, resulting most likely from HNO3 vapour penetration into the plants.     

Acid neutralization of precipitation in Northern China

There is an increasing concern over the impact of human-related emissions on the acid precipitation in China. However, few measurements have been conducted so far to clarify the acid-neutralization of precipitation on a regional scale. Under a network of 10 sites across Northern China operated during a 3-year period from December 2007 to November 2010, a total of 1118 rain and snow samples were collected. Of this total, 28% was acid precipitation with pH < 5.6. Out of these acid samples, 53% were found heavily acidic with pH value below 5.0, indicating significantly high levels of acidification of precipitation. Most of the acidity of precipitation was caused by H2SO4 and HNO3, their relative contribution being 72% and 28%, respectively. However; the contribution of HNO3 to precipitation acidity will be enhanced due to the increasing NO(x) and stable SO2 emissions in future. Neutralization factors for K+, NH4+, Ca2+, Na+, and Mg2+ were estimated as 0.06, 0.71, 0.72, 0.15, and 0.13, respectively. The application of multiple regression analysis further quantified higher NH4+ and Ca2+ contribution to the neutralization process, but the dominant neutralizing agent varied from site to site. The neutralization was less pronounced in the rural than urban areas, probably due to different levels of alkaline species, which strongly buffered the acidity. Presence of high concentrations of basic ions was mainly responsible for high pH of precipitation with annual volume-weighted mean (VWM) values larger than 5.6 at several sites. It was estimated that in the absence of buffering ions, for the given concentration of SO4(2-) and NO3-, the annual VWM pH of precipitation would have been recorded around 3.5 across Northern China. This feature suggested that emissions of particles and gaseous NH3 played very important role in controlling the spatial variations of pH of precipitation in the target areas.     

Chemical composition and seasonal variation of acid deposition in Guangzhou, South China: comparison with precipitation in other major Chinese cities

With the aim of understanding the origin of acid rains in South China, we analyzed rainwaters collected from Guangzhou, China, between March 2005 and February 2006. The pH of rainwater collected during the monitoring period varied from 4.22 to 5.87; acid rain represented about 94% of total precipitation during this period. The rainwater was characterized by high concentrations of SO₄²⁻, NO₃⁻, Ca²⁺, and NH₄⁺. SO₄²⁻ and NO₃⁻, the main precursors of acid rain, were related to the combustion of coal and fertilizer use/traffic emissions, respectively. Ca²⁺ and NH₄⁺ act as neutralizers of acid, accounting for the decoupling between high SO₄²⁻ concentrations and relatively high pH in the Guangzhou precipitation. The acid rain in Guangzhou is most pronounced during spring and summer. A comparison with acid precipitation in other Chinese cities reveals a decreasing neutralization capacity from north to south, probably related to the role and origin of alkaline bases in precipitation.     

Assessment of the potential for soil acidification in North India using the critical load approach and locally derived data for acidic and basic inputs

Major ions (Cl-, NO3(-), SO4(2-), Ca2+, Mg2+, Na+, K+ and NH4(+)) were analysed in wet and dry deposition samples collected for 2 years using a polyethylene bottle and funnel collector at Agra in India. The deposition of ionic components (Ca2+ and Mg2+) derived from natural sources i.e. soil were higher than those of anthropogenic origin. In rainwater samples, non-sea-salt fraction was found to be 60-90%. In both wet and dry deposition Ca2+ was found to be the dominant ion which may be due to its large particle diameter. Results suggest that most of the acidity, which occurs due to NO3(-), SO4(2-) and Cl- is neutralized by alkaline constituents, which originate from airborne local soil and dust transported from the Thar desert. Acid neutralizing capacity of soil has also been quantified and found to be 33 x 10(3) neqg(-1). Using deposition data, the critical load for acidity of soil with respect to Ashoka and Eucalyptus was evaluated. The present level of deposition of S and N was found to be much lower than critical loads calculated for S and N. Critical load of exceedance in terms of deposition acidity was also calculated and found to be negative. This indicates that with respect to these species, the ecosystem is protected at the current level of deposition.     

Relationship between precipitation chemistry and meteorological situations at a rural site in NE Spain

Bulk precipitation samples were collected at Montseny (Catalonia, NE Spain) from 1983 to 1994 and analysed for major cations and anions. The samples were classified for provenance based on meteorological synoptic maps and back trajectory analysis to identify the source areas of pollutants in precipitation. The meteorological classification was compared to an independent grouping based on multivariate data analysis (Clustering and Principal Component Analysis). Alkaline rain (mean pH=7.2) was associated to African trajectories. Local events produced neutral rains (mean pH=5.5). Acid rain was associated to rains of Atlantic origin (mean pH=4.8) and to European rains (mean pH=4.4), which also presented the highest mean concentrations of NH⁺₄ (57 μeq ℓ^-1), NO^-₃(49 μeq ℓ^-1) and SO^2-₄(103 μeq ℓ^-1). However, European events were only a small fraction of the total precipitation (10% of the cases). Marine rains accounted for 52% of the events, and African and Local for 20 and 18%, respectively. During the 11 year period there was a decreasing trend for the frequency of European events.     

Ions species size distribution in particulate matter associated with VOCs and meteorological conditions over an urban region

Airborne particulate matter (PM10, PM2.5, PM1) and volatile organic compounds (benzene, toluene, m,p-xylene, o-xylene) samples were collected during winter and summer seasons of 2005 at two sites, representing an urban and a suburban region of the Greater Athens Area. Urban site traffic emissions were the major contributor to the concentration of PM2.5, PM10, toluene, and xylenes, while benzene and PM1 concentrations were presented in significant spatial variations. K+, Na+, Mg2+, Ca2+, NO3-, Cl- and SO42- ions were analyzed for the chemical characterization of the collected PM samples. The results showed that Na+ cations and SO42- anions were the dominant species, during winter and summer, respectively, in both sites. The analysis of the synoptic scale and mesoscale atmospheric circulation during the experimental periods demonstrated that the meteorological conditions play a key role, not only in the variation but also in the distribution of the ionic concentrations at the three fractions of particulates and the dominant character (alkaline/acidic/neutral) of the particulates at the two sampling sites.     

Local circulation and aerosol water-soluble ions--a case study in Taiwan during Mei-yu season

The Mei-yu (plum rain) season is a short but important period when the weather changes from spring to summer in Taiwan. In this study, size-segregated aerosols were collected alternately at 5 sampling sites in northwestern Taiwan from June 16 to 24, 1994. For the first time in Taiwan, this study revealed the aerosol mass spectra and water-soluble ions in the Mei-yu season. For all samples, a bi-modal aerosol mass spectra was found with modal diameters at 3.2 and 0.32 microm, respectively. The aerosol samples were able to be divided into different groups to show their mass and ion spectra according to the calculated 5-hr backward air trajectory. The utilization of enrichment factors showed that aerosol Cl-, Na+, and Mg2+ for all sizes, and super-micron SO4(2-) were related to the sea. Both the scheme of "chlorine loss" (Ohta and Okita, 1990) and a multivariate analysis (Thurston and Spengler, 1985) for categorizing water-soluble ions showed that sea-salts were major contributors in the prevalence of a sea breeze. In contrast, the secondary salts were significant for land breeze and a mix of land-sea breeze. In conclusion, the influence of local circulation on the distribution of aerosol mass and ionic species was found to be prominent.     

Chemical composition and hygroscopic properties of size-segregated aerosol particles collected at the Adriatic coast of Slovenia

The chemical composition as well as the water uptake characteristics of aerosols was determined in size-segregated samples collected during November 2002 on the Slovenian coast. Major ions, water-soluble organic compounds (WSOC), short-chain carboxylic acids and trace elements were determined in the water-soluble fraction of the aerosol. Total aerosol black carbon (BC) was measured from filter samples. Our results showed that the origin of air masses is an important factor that controls the variation in the size distribution of the main components. Very high concentrations of WSOC as well as higher concentrations of BC were found under mostly continental influence. Besides the main ionic species (SO4(2-), NH4(+), K+) in the finest size fraction (0.17-0.53 microm), the concentration of NO3(-) was also high. The difference between the two different air mass origins is particularly expressed for Cl-, Na+, Mg2+ and Ca2+ determined in particles larger than 1.6 microm. As expected, a very good correlation was found between Na+ and Cl-. A good correlation was found between sea salt elements and elements of crustal origin (Na+, Cl-, Mg2+, Ca2+, Sr). A good relationship between typical anthropogenic tracers (K, V and Pb) was also observed. The mass growth factors, for all size fractions of aerosols collected under continental influence were very low (maximum 2.23 at 94%, 1.6-5.1 microm), while under marine influence the mass growth factors increased significantly with the particle size. At 97% humidity, the mass growth factors were 6.95 for the size fraction 0.53-1.6 microm and 9.78 for larger particles (1.6-5.1 microm).     

The significance of water ionic strength on aluminium toxicity in brown trout (Salmo trutta L.)

The toxicity of aluminium to fish is related to interactions between aluminium and the gill surface. We investigated the possible effect of water ionic strength on this interaction. The mortality of brown trout (Salmo trutta L.) exposed to three different degrees of Al polymerisation was compared in water with increased ionic strength (mean 7.31 x 10(-4) M) after additions of the base cations Ca2+, Mg2+, Na+ or K+, and in water with no such addition (mean ionic strength 5.58 x 10(-4) M). Only a very slight ameliorating effect of increased ionic strength was observed, while the degree of Al polymerisation was of major importance in fish mortality. In addition, it was observed that smaller fish survived the Al exposures for a longer time than larger fish. We hypothesise that this is because larger fish are more susceptible to hypoxia than smaller fish.     

Precipitation chemistry in the coast of the Metropolitan Region of Rio de Janeiro, Brazil

Precipitation chemistry was studied in the Metropolitan Region of Rio de Janeiro (MRRJ). This study reveals that rainwater in the MRRJ is affected by emissions of air pollutants and provides essential data for future estimates of regional biogeochemical cycles and the impacts of acid deposition on tropical ecosystems. The volume-weighted mean (VWM) pH was 4.77, varying from 3.50 to 6.85. Sea-salt aerosols were the dominant sources of the Na+, Cl- and Mg2+. Excess SO4(2-), Ca2+ and K+ comprised 82, 91, and 87% of their total VWM concentrations, respectively. There were very strong correlations (r > 0.75, P > 0.01) for NO3- and H+, NO3- and excess(exc-)SO4(2-), NH4+ and exc-K+, and exc-SO4(2-) and exc-Ca2+, suggesting causal relationships between these ion pairs. The VWM concentrations of all major ions, except H+, were higher in the dry season, with dry to wet VWM concentration ratios varying from 1.1 (NH4+) to 4.7 (for total K+).     

Characterization of atmospheric PM10 and related chemical species in southern Taiwan during the episode days

The concentrations of atmospheric PM10 on days with episodes of pollution were examined at four different sampling sites (CC, DL, LY, and HK) in southern Taiwan. The related to particulates water-soluble ionic species (Na+, K+, Mg2+, Ca2+, NH4+, Cl-, NO3-, SO4(2-)), carbonaceous species (EC and OC) and metallic species (Zn, Ni, Pb, Fe, Mn, Al, Si, V) were also analyzed. On the episode days of this study, the PM10 mass concentration ranged from 155 to 210 microgm(-3), from 150 to 208 microgm(-3), from 182 to 249 microgm(-3), and from 166 to 228 microgm(-3) at CC, DL, LY, and HK, respectively. The results indicate that the dominant water-soluble species were SO4(2-), NO3-, NH4+, and Cl- at the four sampling sites on these days. Moreover, the high sulfate and nitrate conversion values (SOR and NOR) presented herein suggest that secondary formations from SO2 to SO4(2-) and from NO2 to NO3- are present in significant quantities in the atmosphere of southern Taiwan on episode days. In particular, high SOR and NOR verified that both SO4(2-) and NO3- dominated the increase of atmospheric PM10 concentration in southern Taiwan on episode days.     

The Impact of Urban and Industrial Emissions on Mesoscale Precipitation Quality

Results from an acid rain field study around the city of Philadelphia are presented. The study involved the sampling of wet deposition at a network of 40 sites within a distance of 60 km from the Delaware River. Emphasis was placed on event-type rain sampling of frontal and primarily nonconvective storms which are responsible for most of the Northeast’s wet deposition. For most storms, meteorological conditions contributed to a predominant southeasterly transport. Since most of the area’s urban and industrial emissions occur along the Delaware River, the Pennsylvania sector of the network was identified as the downwind (target) region; the New Jersey sector was the upwind (control) region. Local emissions appear to impact the deposition of nitrate (NO₃?) which may register increases greater than 200%. It appears that this impact grows with distance from the river suggesting peaks beyond the 60 km boundary of the network. Comparisons with estimates of NO _x emissions reveal that a substantial fraction may be deposited as NO₃? on the mesoscale. The impact of local emissions on total sulfur is less striking; for some storms the sulfur excess is only in the form of dissolved SO₂. Storm-to-storm variabilities in meteorological conditions, emissions, and oxidant availabilities are probable causes of the variability in the magnitude of the local impact.     

Acid rain and pollen germination in corn

The properties of an acid rain episode that could influence the germination of pollen in corn, Zea mays L., were evaluated by treating silks with a simulated acid rain and measuring the subsequent germination of pollen on the silks. The data indicated that acid rain creates an inhospitable environment for pollen germination on the silk surface. Reduced germination appeared directly related to the acidity of the rain, but not the sulphate concentration. Rinsing silks with a pH 5.6 rain after treatment with a pH 2.6 rain did not increase pollen germination above that on silks treated only with a pH 2.6 rain, suggesting the reduced germination was due to physical and/or chemical modifications of the silk surface and not to residual acid on the tissue. Pollen germination on silks was inhibited even when silk tissue was exposed to a simulated rain of pH 2.6 for <1.5min.     

模拟酸雨对氧化锰吸附砷(Ⅲ)的解吸行为研究

以合成的氧化锰为吸附剂研究了酸雨pH值、酸雨离子强度、解吸时间和解吸次数等因素对模拟酸雨解吸砷(Ⅲ)的影响。实验结果表明:氧化锰对砷(Ⅲ)吸附容量较大,等温平衡吸附量为:48.38 mg/g。模拟酸雨的pH值与离子强度对砷(Ⅲ)的解吸影响不大;解吸反应在90 min后基本达到平衡,平衡解吸量为2.69×10-2mg/g;随解吸次数的增加解吸量变化不大。氧化锰对砷(Ⅲ)的吸附主要是专性的配位吸附,吸附砷(Ⅲ)后难以被模拟酸雨解吸。     

Acidic and alkaline precipitation components in the mesoscale range under the aspect of meteorological factors and the emissions

At two sites in the north of the G.D.R. 80–100 km distant from industry rain from individual precipitation events was collected by automatic samplers and relevant ionic species were analyzed. The sampler is described.The cloud routes at the 850 hPa level were traced back 1 day and then seven sectors were formed for each collection site taking into consideration geographical aspects and features of the emission pattern for the rea concerned.Investigating the precipitation components as a function of the emission pattern knowledge of meteorological input parameters are required. The influence of these parameters is reported.Contrary to the combustion of other fossil fuels, in the case of brown coal combustion a considerable emission of neutralizing components (especially CaO) occurs, counteracting the formation of “acid rain”. This effect is clearly proven by means of individual examples and average considerations, i.e. the formation of acid rain does not only depend on the SO₂ and NO_x emissions.The wet deposition of all types of ions at the measuring site for every emission sector was calculated by means of precipitation statistics. Using these investigations reference points with regard to border crossing transport are given.     

HCI in Rocket Exhaust Clouds: Atmospheric Dispersion,Acid Aerosol Characteristics,and Acid Rain Deposition

NASA is examining Space Shuttle launch impacts. Solid rocket exhaust includes ?60 tons HCL and ?87 tons alumina particles emitted below 2.5 km, of which 50-80% forms an altitude stabilized exhaust cloud (EC). Several 60% smaller Titan-Ill EC were sampled by aircraft for this study. Three distinct features are presented: (a) An analysis of HCL (gaseous plus aqueous) data traces. Total range of peak HCL was 25-0.5 ppm (3-300 min) for 8 EC. Power-law decays of peak HCL applied. Calculated HCL dispersions for 7 standard meteorologies are also shown, (b) An analysis of simultaneous HCL (g), HCL (g + aq) data for 2 EC. Vapor-liquid HCL/H₂O equilibria were calculated for a flat surface aqueous aerosol. HCL partitioning varied with EC dilution and H₂O content. HCL (aq) and aqueous mass fraction maximized early at >3 molal and >0.1 mg/g air. Calculated H₂O (g + aq) compared favorably with independent EC measurements, (c) An analysis of wet deposition after EC interception at ?30 min by a convective storm. A 28 km² acid chloride (1 < pH < 3) footprint was defined. In conclusion, (a) HCL dispersion in large EC tends to follow power-law decay, but HCL concentration may vary widely (100 times after 1 h) with meteorology, (b) HCL (g/aq) and H₂O (g/aq) partitioning is consistent with equilibrated acid aerosol compositions, and (c) localized deposition of highly acidic rain may occur sometimes.     

Effects of temperature and pH on conjugal transfer of zinc-resistant plasmids residing in Gram-negative bacteria isolated from industrial effluents

Two zinc (Zn)-resistant strains, AnZn-1 and AnZn-2, which were resistant to ZnSO4 up to 12.5 mg ml(-1) were isolated from industrial effluents. Both were Gram-negative with motile cells. They exhibited tolerance to Ba2+, Ni+, Co2+, Mn2+, Cu2+, Fe2+, Ni2+, Cd2+, kanamycin, chloramphenicol, ampillicin and tetracycline, but were sensitive to Hg2+ and streptomycin. For AnZn-1 and AnZn-2, the optimum pH for growth was 7. Both were facultative anaerobes and had cytochrome oxidase and urease enzymes, while catalase was present only in AnZn-2. Both strains had the ability to hydrolyse gelatin, reduce nitrate, and yield acid from arabinose and rhamnose. The two strains shared maximum characters with Vibrionaceae. Each strain carries a single Zn-resistant conjugative plasmid. The plasmid residing in AnZn-1 (pSH1211) displayed a lower level of resistance than the plasmid of AnZn-2 (pSH1212). Both required a minimum of 24 h for mating and showed highest transfer frequency at 25 degrees C. pSH1211 preferred pH 7 and pSH1212 pH 8.5 for their transfer. Both plasmids, when allowed to mate with Escherichia coli at 25 degrees C, alkaline pH values of 8-8.5 (pSH1211) of pH 7.5 (pSH1212), showed increased transfer frequency.     

Contribution of transboundary air pollution to ionic concentrations in fog in the Kinki Region of Japan

To estimate the contribution of transboundary transported air pollutants from other Asian countries to Japan in ionic concentrations in fog water in March 2005, the Community Multiscale Air Quality (CMAQ) modeling system was utilized with meteorological fields produced by the 5th generation Mesoscale Model (MM5). For meteorological predictions, the model well reproduced the surface meteorological variables, particularly temperature and humidity, and generally captured fog occurrence. For chemical predictions, most of the model-predicted monthly mean concentrations were approximately within a factor of 2 of the observations, indicating that the model well simulated the long-range atmospheric transport from the Asian Continent to Japan. For SO₄^2?, NO₃^? and NH₄⁺, the contribution rates of the transboundary air pollution in the Kinki Region of Japan ranged from 69 to 82% for aerosols, from 47 to 87% for ionic concentrations in rain, and from 55 to 79% for ionic concentrations in fog. The study found that the transboundary air pollution also affected ionic concentrations in fog as well as aerosol concentrations and ionic concentrations in rain.     

Chemical climatology of high elevation spruce-fir forests in the southern Appalachian mountains

The physical and chemical climatology of high elevation (> 1500 m) spruce-fir forests in the southern Appalachian mountains was studied by establishing a weather and atmospheric chemical observatory at Mt Mitchell State Park in North Carolina (35 degrees 44' 05" N, 82 degrees 17' 15"W). Data collected during the summer and autumn (May-October) of 1986, 1987, and 1988 are reported. All measurements were made on or near a 16.5 m walk-up tower extending 10 m above the forest canopy on Mt Gibbes (2006 m msl), which is located approximately 2 km SW of Mt Mitchell. The tower was equipped with standard meteorological instrumentation, a passive cloud water collector, and gas pollutant sensors for O3, SO2, NOx. The tower and nearby forest canopy were immersed in clouds 25 to 40% of the time. Non-precipitating clouds were very acidic (pH 2.5-4.5). Precipitating clouds were less acidic (pH 3.5-5.5). The dominant wind directions were WNW and ESE. Clouds from the most common wind direction (WNW) were more acidic (mean pH 3.5) than those from the next most common wind direction (ESE, mean pH 5.5). Cloud water acidity was related to the concentration of SO4(2-), and NO3- ions. Mean concentration of H+, NH4+, SO4(2-), and NO3- ions in the cloud water varied from 330-340, 150-200, 190-200 and 120-140 micromol litre(-1) respectively. The average and range of O3 were 50 (25-100) ppbv (109) in 1986, 51 (26-102) ppbv in 1987, and 66 (30-140) during the 1988 field seasons, respectively. The daily maximum, 1-h average, and 24-h average concentrations were all greatest during June through mid-August, suggesting a correlation with the seasonal temperature and solar intensity. Throughfall collectors near the tower were used to obtain a useful estimate of deposition to the forest canopy. Between 50-60% of the total deposition of SO4(2-) was due to cloud impact.