Acid pollutants in air and precipitaion/deposition at the Sudeten Mountains,Poland

The results of several separately performed field studies on air quality in south-western Poland (Black Triangle) are presented In the period 1988–1993 atmospheric aerosol measurement and precipitation/deposition samples were collected at three locations of mountain region (810–1490 m asl). Precipitation was monitored in forest ecosystem using a 24-gauge network was carried out during June–October 1992 and 1993. The occurence of cloud at ground level over hills is difficult to categorize and quantify in mountain terrain and has constituted a basic part of our studies. Precipitation/deposition samples (seven rain and three cloud collectors) in the Karkonosze Mountains were collected over the period 1994–1995 (four field campaigns were conducted) to examine aqueous chemical interactions between constituents in samples. Meteorological data measured at the site included temperature, humidity, wind speed and direction and the amount of precipitation.     

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.     

Acidic Precipitation and Large-Scale Transport of Air Pollutants Observed in Korea

Acid rain at a rural site in Chongwon (KHN), central Korea has been under observation since 1990. To substantiate the 10-year observations, rain samples from six other sites were also collected and analyzed. Results show that acid rain occurred frequently at all sites. At KHN, seasonal and annual variability of pH values had a 10-year VWM value of 4.67 and an arithmetic mean value of 5.09. In general, a high value of pH occurred during springtime when the occurrence of yellow sand (dust) was prevalent in East Asia; during summer, heavy rain usually contained neutral pH values. During other seasons, the degree of acidic precipitation usually coincided with certain air flows. Most frequently, air flows and cyclones coming from south and central China often resulted in precipitation with low pH values observed in Korea. Using daily satellite observations from 1996, we have also been monitoring the long-range and large-scale transport of air pollutants (LSTAP) over East Asia. Many samples of LSTAP were obtained when they were crossing the Yellow Sea and moving over the Korean Peninsula and to SW Japan. The width of the Yellow Sea is ca. 350～700 km and air pollutants take 1～2 days to cross it. Cases of acid rain in Korea clearly correlate wth the LSTAP from source regions in China.     

2006—2007年南昌市城郊地带的酸雨特征

为了解南昌地区酸雨现状,通过对南昌农区、郊区、市区布设观测点,根据有关监测数据资料,对2006—2007年酸雨pH值、酸雨频率、酸雨成分、空气污染状况进行了统计分析。结果表明,3个测点观测的南昌地区酸雨年均pH值处强酸性标准,3测点酸雨发生概率为88%～97%,9—4月酸雨较重、5—8月减弱,酸雨pH值与空气污染物浓度有极显著相关关系。酸雨呈硫酸性酸雨,主要阴离子为SO4^2-、NO3^-、Cl^-,阳离子为NH4＋、Ca^2＋、K^＋,且SO4^2-/NO3^-比值较小。农田保护区因处于城市及工业污染源下风向,降水总离子及SO24-浓度较高,酸雨强度不亚于城市。在新设工业园及迁出企业布局上,应考虑设于较小风频方位,以减轻南昌农田保护区及城市污染,建议选择城市西北、东南侧安排新设排放源。     

Multielement analysis of natural waters by neutron activation,group chemical separations,and gamma-ray spectrometric techniques

A multielement analytical technique of thermal neutron activation of frozen water samples has been developed and applied to the studies of natural waters. A rapid group chemical separation utilizing ion exchange resins and a precipitation step to reduce ²⁴Na and 42K interferences, followed by γ-ray analysis of the fractions with Ge (Li) and multiparameter NaI (TI) systems, permits the simultaneous measurement of a large number of trace constituents. Samples of river water, rain water, processed sewage water and Greenland ice were analyzed for 19 trace elements — Ag, As, Br, Cl, Co, Cs, Cr, Cu, Fe, Hg, K, Mn, Na, Rb, Sb, Se, Se, U, and Zn. These data have been used in studies of trace element concentration factors in aquatic biota, precipitation scavenging processes, and environmental pollution.     

Atmospheric mercury in northern Wisconsin: Sources and species

The atmospheric chemistry, deposition and transport of mercury (Hg) in the Upper Great Lakes region is being investigated at a near-remote sampling location in northern Wisconsin. Intensive sampling over two years and various seasons has been completed. A multi-phase collection strategy (gas-, particle- and precipitation-phases) was employed to gain insight into the processes controlling concentrations and chemical/physical speciation of atmospheric Hg. Additional chemical and physical atmospheric determinations (e.g. ozone, particulate constituents, meteorology) were also made during these periods to aid in the interpretation of the Hg determinations. For example, correlations of Hg with ozone, sulfur dioxide and synopticscale meteorological features suggest a regionally discernible signal in Hg. Comparison to isosigma backward air parcel trajectories confirms this regionality and implicates the areas south, southeast and northwest of the site to be sources for Hg. Particle-phase Hg (Hg_p) was found to be approximately 40% in an oxidized form, or operationally defined as “reactive”. However, this was quite variable from year-to-year. Hg_p and other particle constituents (esp. sulfate) show significant correlation and similarity in behavior (concentration ratios in precipitation and in particles). These observations are part of the growing evidence to support the hypothesis that precipitation-phase Hg arises in large part from the scavenging of atmospheric particulates bearing Hg. Observed concentrations of rain and particle-Hg fit broadly the theoretical expectations for nucleation and below-cloud scavenging. Significant increases in the Hg/aerosol mass ratio appear to take place during transport. Enrichment of aerosols is taken as evidence of gas/particle conversion which could represent the step linking gas-phase Hg with rain. The refined budget indicates ca. 24% of total deposition is from summer particle dry deposition, and that this deposition also contributes ca. 24% of all reactive Hg deposition. Additionally, almost all (86%) deposition (wet and dry) occurs during the summer months.     

Interaction between simulated rain and barren rock surface

During the latter decades extensive fish kills have been observed in the mountainous areas of southernmost Norway. These kills have been attributed to the increased acidity of the river-water. The increased acidity is generally assumed to be caused by acid precipitation. However, the relationship between precipitation and runoff quality is very complex. The present paper is concerned with the relationship between chemical composition of simulated rain and that of runoff from bare granitic rock, partly covered by lichens. When supplying simulated rain with a pH value of approximately 5 the very first runoff had pH values between 4.1 and 4.3. However, the pH in the runoff increased rapidly and leveled out at values between 4.6 and 4.7. When supplying simulated rain with pH approximately 3.5, the pH in the first runoff varied between 3.8 and 3.6. The pH then gradually decreased to the same values as those in the simulated rain. Runoff from ‘rain’ with pH 4.3, obtained the same pH value as that of the ‘rain’. The pH of the runoff was dependent not only on the rain acidity, but also on its content of neutral salts.     

Long range transport of air pollutants in Europe and acid precipitation in Norway

Observations show that pollutants from large emission sources may cause significant air concentrations 500 to 1000 mi away. Very acid precipitation occurs in such periods. The scavenging is often intensified by the topography. Case studies will be presented with special emphasis on acid precipitation in Scandinavia. Large scale dispersion models have been developed recently in order to estimate the long range transport of air pollutants. The models take into account chemical transformations as well as deposition of pollutants. The calculations will be compared with observations from airplanes and surface stations. A simple model has been integrated over a long period of time in order to derive the best value for the decay rate of SO₂. This best value is based on a day-by-day comparison with surface observations.     

Effect of the quantity and duration of application of simulated acid precipitation on nitrogen mineralization and nitrification in a forest soil

A study was conducted of the influence of the rate of application of simulated acid rain on N mineralization and nitrification in a forest soil. The rates were varied by applying different quantities of simulated rain for varying periods of time. The soil was exposed in the laboratory to simulated rain at pH 3.5, 4.1, or 5.6 at rates equivalent to 1.5, 2.3, 4.6, 7.1 or 15 times the average rate of precipitation in the field, and then mineralization of soil N or oxidation of added ammonium was determined. The rates of N mineralization were inhibited by precipitation at pH 3.5 or 4.1 when applied for 27 to 234 day at rates 1.5 times greater than that which occurs in nature. Nitrogen mineralization was not affected by simulated rain at pH 3.5 or 4.1 in soils exposed for 156 day at 2.3 times the natural rate of precipitation, for 27 or 81 day at 4.6 times the natural rate, for 54 day at 7.1 times the natural rate, or for 234 day at 15 times the natural rate. On the other hand, mineralization was fastest in soil exposed to pH 3.5 rain for 234 day at 4.6 times the natural rate of precipitation and for 81 day at 15 times the natural rate. Nitrate formation in soil amended with ammonium was inhibited by rain of pH 3.5 regardless of the intensity of rain or the duration of exposure. For a constant rate of rain application, the inhibition of nitrate formation in ammonium-amended soil generally increased with longer periods exposure. The data show that the use of different rates of additions of artificial rain or different periods of exposure to the simulated precipitation will lead to different conclusions on the influence of acid rain on N mineralization in soil.     

Activities and results of the terrestrial effects program: Acid precipitation in ontario study (APIOS)

Studies on the terrestrial effects of acidic precipitation in Ontario involve determining the effects on .soils, crops, forests, lichens, mosses and biogeochemical systems. In the soils program, a baseline study was started in 1980 to establish a reliable and uniform data base for soils across the province, in order to identify future trends. Soil sensitivity criteria are being derived for mapping purposes. Starting in 1982, a complex, sophisticated mobile rain exclusion canopy system was constructed outdoors for controlled acid rain studies to determine the dose-response relationships of field crops. In response to numerous complaints a program was designed to determine the role that acidic precipitation is playing in the decline of sugar maple trees in Ontario. At 8 sites, tree conditions were noted, samples of foliage, bark, roots and soil were collected for chemical analysis, and increment cores and discs (from felled trees) were taken for radial growth patterns. Results from this study indicated that acidic precipitation was an additional stress to insect outbreaks and spring droughts. Intensive surveys have been conducted in selected areas in Ontario to identify the current viability and distribution of common denominator lichens and mosses. Biogeochemical studies are being conducted at four watersheds in Ontario. The different watersheds are located in progessively decreasing atmospheric deposition loadings from east to west across the province. The studies are attempting to document the role of contrasting terrestrial ecosystems in the process of lake acidification by atmospheric deposition.     

南宁市酸雨污染现状及防治对策

本文对南宁市１９８９～１９９３年５年的降水情况进行分析，证明市区内酸雨污染日趋严重。影响酸雨的主要因子是二氧化硫，酸雨的防治主要是对二氧化硫的防治，并提出了相应的治理措施。     

The variability of pH in convective storms

The rainwater pH was measured in a total of 22 storms which occurred in 1972 and 1974 in the METROMEX (METROpolitan Meteorological EXperiment) rainwater sampling network. The network consists of 81 collectors in an area of 1800 kM² over and east of St. Louis, Missouri. The data set is composed of dry fallout samples as well as precipitation samples which have been analyzed independently. An analysis of the frequency distribution of these data shows the rainfall samples form a bimodal distribution of pH with relative frequency maxima at pH 7.0 and 4.0 while the dry samples are unimodal with the maximum frequency at pH 7.0. The areal distribution of precipitation weighted mean pH indicates a variability unrelated to total precipitation. However, the derived deposition of H+ is more similar to the areal rainfall pattern than to the pH. The dH is defined which incorporates both the rainfall and pH which is useful for climatological trend studies of acid rainfall. Examples of two individual storm events illustrate an inexplicable area-wide variation from nearly an all acid rain (pH ? 4.5) to an all alkaline rain (pH ? 5.5). These case studies indicate some of the meteorological as well as chemical problems which must be considered when attempting to characterize convective storm rainfall pH.     

Lysimeter Study on the Effects of Different Rain Qualities on Element Fluxes from Shallow Mountain Soils in Southern Norway

This study focuses on fluxes of elements from, and changes in the soil properties of shallow organic material rich soil as a result of changes in precipitation acidity. Intact soil columns including natural vegetation from two areas (one exposed to acidic precipitation and one unpolluted) were used in a lysimeter experiment. The lysimeters were watered with simulated normal rain (pH 5.3) or simulated acidic rain (pH 4.3) for four years. Sulphuric acid and ammonium nitrate were used to regulate the quality of the simulated rain. Significantly more SO₄ ^2? was leached from lysimeters receiving acid rain. Rain acidity had no significant effect on NO₃ ^? leaching. Significantly more Mg²⁺ was leached from lysimeters receiving acid rain, but this only applied for the soils from the unpolluted area. Four years of treatment did not cause any significant effect on the soil acidity and the amounts of base cations in the soil. The more acidic rain did, however, cause a significant lower cation exchange capacity. For the soils from the polluted area the acid precipitation did cause a lowering of the exchangeable K⁺ in the upper 5 cm of the soil. Different quality of the soil organic material indicated by different vegetation types appeared to cause significant differences in the amount of components leached from the soil, but did not cause any difference in response to the different rain qualities.     

Stages in the History of China's Acid Rain Control Strategy in the Light of China-Japan Relations

We analyze the history of acid rain in China over the last three decades in the light of the relationship between China and Japan. China has been aware of the problem of acid rain and has been conducting scientific research since the late 1970s. However, little effort has been put into practical countermeasures. In the early 1990s, acid rain was re-evaluated as an international environmental problem. Meanwhile, Japan became concerned about trans-boundary air pollution from China. What is important is that Japan's concern strongly influences China's acid rain policy. In the context of growing international concern for environmental problems, China has taken remarkable steps to control acid rain. In this respect, dealing with acid rain is an issue of national pride for China.     

Acidity of atmospheric precipitation in Polish Tatra Mountains

A three-year (1991–93) study on atmospheric precipitation (bulk and throughfall) and stream chemistry was carried out in two — granitic (Waksmundzka Val.) and calcareous (Mietusia) valleys (Polish Tatra Mountains). It was found that both valleys were under acid rain influence — chemical analysis showed strong seasonal fluctuations of the studied elements. Chemistry of precipitation was dominated by sulphate ions, buffered more efficiently in Mietusia Val. than Waksmundzka Val. mainly by calcium and ammonium ions. In both valleys an increase of throughfall acidity compared to bulk precipitation was observed. There were also found differences between bulk and throughfall chemistry — amounts of hydrogen, calcium, potassium and ammonium ions in throughfall were higher whereas amounts of phosphate, copper and zinc ions were lower in throughfall than in bulk precipitation. In both valleys significant seasonal variation of most of the studied elements in bulk and throughfall was detected.     

EPISODIC NATURE OF WET DEPOSITION OF ACIDIC MATERIAL AT A SITE IN SOUTH-EAST ENGLAND

The causal factors for episodic deposition of acidic material in rainfall cannot be fully understood from conventional daily network data. A brief review of the meteorological conditions leading to episodes is given. A definition of ‘episodicity’ was considered and applied to a 6 month data set collected at high temporal resolution using a microprocessor based acid rain monitor at a site in south-east England. The deposition was highly episodic for all of the measured variables when data from individual rain events were considered. Combining the data into daily averages resulted in changes of episodicity classification for several chemical species. A large percentage of the total deposition recorded during the field experiment occurred in a 5 day period when there was an independent report of ecological damage at other locations in England. Nitrate deposition showed the highest degree of episodicity with 51% of the 6 month total occurring during the 5 day episode. Meteorological details of the transport and wet deposition processes during this period were examined. Back trajectory analysis indicated that the episode was the result of pollutant loading in eastern and central Europe of the air masses reaching the site together with an absence of upwind precipitation scavenging.     

Neutralization of Acid Droplets on Plant Leaf Surfaces

Sulfuric acid mist exposure of bush bean leaves at a low rate of precipitation suggested that acid on the leaf surface was neutralized by cations leached from leaf tissues and that Ca-S compounds were accumulated on the leaf surface (Kohno, 1994). This report summarizes visual observations of the neutralization process of acid on leaf surfaces as determined by a pH-imaging microscope. Small droplets of sulfuric acid were placed on the adaxial leaf surface and allowed to air dry under laboratory conditions. Droplets (0.1 µl) of sulfuric acid took about 7–8 minutes to dry. Leaf samples were cut at various times after the acid droplets dried. The adaxial leaf surface was placed on the pH-adjusted agar film layer on the pH-imaging sensor of the microscope. Hydrogen ions dispersed into the film layer and resulting pH distributions were visualized as pH distribution patterns. The size of the acidic area generated became smaller with time after the acid was added and allowed to dry. Results indicate that leaves could neutralize the surface acid probably by ion exchange with cations from their surface tissues and could recover from strong temporary acid stress imposed by acid rain or acid fog in a relatively short period of time. Our findings indicate that acidic precipitation at current acidity levels does not pose a direct threat to plants.     

Fractionation of soil humic acids by preparative polyacrylamide gel electrophoresis in the presence of concentrated urea

To separate soil humic acids (HAs) into their constituents and characterize them, polyacrylamide gel electrophoresis (PAGE) was carried out in the presence of 7 M urea using a preparative electrophoresis system. Two types of soil HAs were fractionated into nine fractions by PAGE. The dark-colored constituents were recovered from the electrophoretic fractions by precipitation on acidification, and the brown-colored constituents dissolved in the acidic solution of fast-moving fractions were recovered by adsorption onto DAX-8 resin. High-performance size-exclusion chromatography (HPSEC) confirmed that the constituents of the HAs were separated based on their molecular size by PAGE. The dark-colored constituents exhibited higher degrees of humification than did the corresponding unfractionated HAs, except for the constituents remaining in the electrophoretic gels at the end of electrophoresis. Diffuse reflectance infrared spectroscopy revealed that the chemical properties of the dark-colored constituents changed regularly: the content of carboxyl groups decreased and the proportions of proteinous, aliphatic and polysaccharide moieties increased with increasing molecular size. The humification degrees of the constituents adsorbed onto DAX-8 resin were considerably lower than those of the corresponding unfractionated HAs. The chemical properties of the DAX-8-adsorbed constituents were different from those of the dark-colored constituents. Observation of electrophoretic fractions under blue light (470 nm) and HPSEC with fluorescence detection at an excitation wavelength of 460 nm and an emission wavelength of 520 nm showed that green fluorescent substances were largely concentrated in the smallest molecular size fractions and were partitioned into both the dark-colored precipitates and DAX-8-adsorbed fractions. The proportion of organic carbon recovered by precipitation and adsorption onto DAX-8 resin was 45–63%, indicating that substantial parts of the HA constituents were missing. The unrecovered constituents were considered to be acid-soluble, nearly colorless substances. The dissociation of the acid-soluble constituents from the acid-insoluble dark-colored constituents during the preparative PAGE of soil HAs was ascribed to disruption of hydrogen bonding and hydrophobic interactions caused by concentrated urea.     

Measurement of acid precipitation in Norway

Since January 1972, chemical analysis of daily precipitation samples from about 20 background stations in Norway has been carried out on a routine basis. Air monitoring is carried out at six stations. The chemical analysis program is: sulphate, pH and acidity in precipitation, sulphates and SO₂ in air. In addition, more detailed chemical analysis of aerosol and precipitation has been carried out at selected stations. Some results for the measurement period 1972 to 1974 are presented. Comparison of air and precipitation concentrations of S compounds show that the precipitation scavenging efficiency is very high under the conditions in southern Norway.