Sequential sampling and variability of acid precipitation in Hampton,Virginia

Rain samples were collected sequentially by amount (≈2.7 mm each) from individual events at a single, relatively isolated, suburban site from August 1977 to July 1980. Rain pH's for ≤ 3 mm samples closely fit a monomodal Gaussian distribution with a median of 4.50 and a standard deviation of 0.39. The variability in pH was primarily interevent as opposed to intraevent. The 3-yr volume-weighted pH was 4.35 ± 0.02 for 3.16 m collected; annual pH's were 4.31, 4.37, and 4.38, and cumulative H⁺ deposition was 141 mg H⁺ m^?2. Event-averaged rain pH and meteorological and air quality data were correlated. Low pH was associated with low rainfall volume and rate; rain after several dry days; rains with northeast surface winds; high SO₂, NO₂, and O₃ in the ambient atmosphere; and high, strongly correlated, SO₄ ⁼ and NO₃ ^? rainwater concentrations. The lowest 3-yr seasonal average pH (4.31) occurred during summer; values for other seasons were ≈4.37. Average intraevent H⁺ molarity (volume-weighted) was accurately characterized by 6.89 E^{?5 *}(mm ram)^?0.215. The relative merits of composite (e.g., whole event) and sequential sampling are examined.     

Acid and alkaline deposition in precipitation on the Western coast of Sardinia,Central Mediterranean (40° N, 8° E)

The ionic composition of 53 precipitation samples collected at a coastal site in western Sardinia (Torregrande) was measured in order to determine concentrations and fluxes of the major ions. Precipitation events were sampled over a two year period, Oct'92/Oct'93 and Oct'93/Oct'94. Despite the proximity to the African continent and the detection of Saharan inputs reflected in high pH values and high_nssCa fluxes, there is evidence for acidic rain with over 54% of the events having pH values <5.6. This would suggest long-range transport of anthropogenic inputs, as there is no obvious local source. Within the study period, a marked decrease in median pH is recorded at Torregrande in '93/'94, decreasing from 5.94 to 5.18. This is coupled with an increase in total annual flux of NO₃ from 27 to 63 μg/cm², making the average flux of NO₃ in the two years comparable with that at Capo Carbonara (48 μg/cm²). Particulate fluxes at Torregrande show a marked inter- as well as intra-annual variability, from 70 to 200 μg/cm². Variations of pH seems to be partially due to the total particulate as well as_nssCa fluxes. A statistic of Saharan enriched rain episodes of the two sites showed a peak transport season in April–May and October which is two times greater at Capo Carbonara. Rainfall on the west coast, therefore, appears to be less affected by Saharan dust than rainfall on the southern coast and therefore shows greater signs of acidification due to anthropogenic inputs.     

A rain acidity study in Brunei Darussalam

Fifty-three bulk deposition samples were collected at the campus of the University of Brunei Darussalam between April and November 1994 using a funnel-in bottle sampler. The pH and conductivity were determined immediately after collection on aliquots of the sample. Samples were refrigerated at 5 °C for subsequent chemical analysis. Analyses for Cl^?, NO₃ ^? and SO₄ ^2? were carried out by means of ion chromatography, while Na⁺, K⁺, Ca²⁺ and Mg²⁺ were determined by atomic spectroscopy. The recorded pH values were in the range of 4.35 to 6.59. Seventy-seven percent of the samples had pH values below 5.6, demonstrating the occurrence of acidic deposition. The range, mean and standard deviation of measured concentrations are reported. There was very little difference between measurements in filtered and unfiltered samples. Correlation coefficients between pairs of parameters are reported and discussed.     

Lysimeter study with a cambic Arenosol exposed to artificial acid rain: I. Concentrations of ions in leachate

The effects of artificial acid rain on soil leachate composition were studied in a lysimeter experiment. Cambic Arenosol (Typic Udipsamment) in monolith lysimeters was treated for 6 1/2 yr with 125 mm yr^?1 artificial rain in addition to natural precipitation. Artificial acid rain was produced from groundwater with H₂SO₄ added. pH levels of 6.1, 4 and 3 were used. Increasing content of H₂SO₄ in the artificial rain increased the concentration of Ca²⁺ and Mg²⁺ in the leachate significantly. The pH of the leachate was slightly reduced only by the most acidic treatment (pH 3). The H^+? retention was not accompanied by a proportionate increase in the Al ion concentration. A slight increase in the Al ion concentration was only observed in the leachate from the pH 3-treated lysimeter. We conclud that cation exchange and/or weathering were the main buffer mechanisms in the soil. The study supports conclusions from other acidification studies, that acidic precipitation is likely to increase the leaching of Ca²⁺ and Mg²⁺ from soils.     

Effects of acidity in precipitation on terrestrial vegetation

Over the last several decades rain in the Northeastern United States has become more acidic presumably as a result of anthropogenic inputs of SO_x and NO_x to the atmosphere and their conversion to H₂SO₄ and HNO₃. Present experimental results suggest that acidic precipitation would initially affect organisms on leaf surfaces and epidermal cells of leaves of higher plants. More internal cell layers would be affected with increasing duration or frequency of exposure. Differences in responses of plant foliage among plant species to acidic precipitation appear to be due to the degree of leaf wetting and differences in responses of leaf cells to low pH rain. Moreover, within the same plant, particular structures or cell types may be more sensitive than others. If the United States is to utilize coal reserves for electric power generation that might increase rainfall acidity in the future, an assessment of the impact that acidic rain might have on terrestrial vegetation is necessary. In one experiment, field-grown soybeans were exposed to short duration rainfalls of either pH 4.0, 3.1, 2.7, or 2.3 to provide inputs of 50, 397, 998, or 2506 μeq of H⁺, respectively, above ambient levels throughout the growing season. Control plots received only ambient rainfalls. These additional H⁺ decreased seed yield, 2.6, 6.5, 11.4, and 9.5%, respectively. A treatment response function determined between H⁺ treatments and seed yield wasy=21.06?1.01 logx had a correlation coefficient of ?0.90. Researchers must design additional experiments with adequate experimental controls to assess the impact that acidic rain, at the present pH levels of 3.0 to 4.0 or at anticipated worst-case levels, that could occur if the acidity of rain should increase. Only a holistic view of the impacts that acid precipitation may have on vegetation will enable optimal energy and environmental policy decisions to be made.     

Acid rain deposition patterns in the continental United States

Acid rain has become a major environmental concern, the current extent of which is illustrated in this paper. Maps of both pH and H⁺ deposition in precipitation have been developed for the continental United States by analyzing laboratory pH data from nine precipitation chemistry networks and two single stations spread across the continental United States and southern Canada during the late 1970's. Average laboratory pH values were obtained or calculated for approximately 100 stations, and isopleths of weighted mean pH and mean annual H+ deposition in precipitation were drawn. Results of this analysis show that in spite of a wide variety of collection methods and sampling intervals, there is remarkable uniformity in the average pH among the various stations. The northeastern United States continues to exhibit the most acidic precipitation, with remaining portions of the eastern United States, states along the western coastline and a pocket in central Colorado also experiencing acid precipitation.     

The influence of organic acidity on the acid-base chemistry of surface waters in Maine,USA

Results from surveys of low-ANC lakes (high elevation, and seepage lakes), and of surface waters in dystrophic, acidic bogs, indicate that acidic precipitation and organic acidity are each generally necessary, but not solely sufficient, for chronically acidic status in Maine lakes. Acidic, low DOC (ANC < 0; DOC < 5 mg L^-1) lakes of all hydrologic types are acidic due largely to acidic deposition; high DOC (DOC > 30 mg L^-1) acidic seepage lakes are acidic due largely to organic acidity, and high DOC drainage lakes are acidic due to a combination of both factors. No low DOC drainage lakes are known with pH less than about 5.0, suggesting that organic acidity is necessary to depress lake pH values to below 5 in Maine at current deposition loadings,The dominant anion of low DOC, acidic waters is sulfate. Acidic waters with intermediate concentrations of DOC (5 to 30 mg L^-1), may be dominated by S04 and/or organic acidity. Seepage-input lakes were the only group to include both organically-dominated (37% of the acidic lakes) and S0₄-dominated members (63% of the acidic lakes). High DOC systems are typically low pH bogs, and are all organic acid-dominated.     

Acidic precipitation in Western North America: Trends,sources, and altitude effects in New Mexico 1979–1985

Volume-weighted pH values in central New Mexico have averaged 3.8 to 5.1 during the period 1979–1985. Samples collected at a high altitude site (3200m) have lower pH values than found for low altitude samples (1400m). Both dry deposition and event-averaged pH values have been higher than the volume-weighted averages due to neutralization by terrestrial material. During the period 1980–1984, changes in pH values and wet sulfate loading have correlated to S0₂ emissions from regional non-ferrous smelters. Sulfur isotope analyses of sulfate extracted from regional rain samples yielded a δ³⁴S_CD(%) of + 3.91 ± 1.1, indicating very little regional differentiation which, in turn, suggests that the regional atmospheric sulfate scavenged by precipitation is well-mixed and relatively homogeneous.     

Precipitation and streamwater chemistry from undisturbed watersheds in the cascade mountains of Oregon

Long-term records of precipitation and streamwater chemistry are rare; such records from forested watersheds relatively free of acidic deposition are even rarer. Precipitation and streamwater chemistry have been measured on two undisturbed forested watersheds at the H. J. Andrews Experimental Forest located on the western slopes of the Cascade Mountains of Oregon. Data from one watershed spans the period 1973–1985, the other 1969–1985. The mean annual pH of precipitation was 5.5 with a range of 4.7 to 6.0. HCO₃ ^? was the dominant anion; Ca²⁺ and Na⁺ were the dominant cations. The mean annual pH of streamwater was 7.3, and was dominated by HCO₃ ^? and Ca²⁺. These data contrast sharply with data from other calibrated watersheds in the north Cascade Mountains of Washington and British Columbia, and with data from New Hampshire and North Carolina where pH of precipitation averages 4.14 and 4.43, respectively, with SO₄ ^2? the dominant anion.     

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.     

Finnish lake survey: the role of organic and anthropogenic acidity

A lake survey consisting of 987 randomly selected lakes was conducted in Finland in autumn 1987. The survey covered the whole country, and the water quality of the lakes can be considered as representative of the approximately 56 000 lakes larger than 0.01 km² in Finland. The median TOC concentration is 12 mg L^-1 and the median pH 6.3. The proportion of lakes with TOC concentrations > 5 mg L^-1 in the whole country is 91 %. Organic anion is the main anion in the full data set (median 89 μeq L^-1). The high organic matter concentrations in Finnish lakes are associated with catchment areas containing large proportions of peatlands and acid organic soils under coniferous forest. The survey demonstrated that organic matter strongly affects the acidity of lakes in Finland. The decreasing effect of organic matter on the pH values was demonstrated by both regression analysis and ion balances. At current deposition levels of ^*SO₄ the pH of humic lakes in Finland is determined to a greater extent by high TOC concentrations than by ^*SO₄ in most areas. In lakes with pH values lower than 5.5 the average organic anion contribution is 56 % and non-marine sulfate contribution 39 %. However, in the southern parts of the country, where the acidic deposition is highest, the minerogenic acidity commonly exceeds the catchment derived organic acidity.     

Effects of sulphuric acid and acidifying ammonium deposition on water quality and vegetation of simulated soft water ecosystems

In a greenhouse, seven identical mini-ecosystems, simulating soft water ponds, were exposed to different types of artificial rain water. The effects of rain water containing H₂SO₄ and nitrate, and rain water containing ammonium sulphate on water quality and vegetation were studied and compared. Causal relations were established between rain water quality, water chemistry and changes in floristic composition. Ammonium sulphate deposition, particularly, strongly affected water quality and vegetation development. Although ammonium sulphate deposition was only slightly acid, due to nitrification it acted as an important acid source, causing acidification to pH=3.8. Under acidified conditions, ammonium sulphate deposition lead to a luxuriant growth ofJuncus bulbosus andAgrostis canina. In the mini-ecosystems, H₂SO₄ deposition with a pH of 3.5 only decreased the pH of the water to 5.1 within 1 yr. The acidification of water appeared to be coupled with changes in alkalinity, sulphate, Al, Cd, Ca, Mg, K and inorganic-N. It is concluded that in NH₃-affected regions in The Netherlands, the high atmospheric deposition of ammonium sulphate probably contributes to a large extent in the acidification, eutrophication and floristic changes of oligotrophic soft waters.     

Summertime study of acid deposition in the Detroit area

A comprehensive acid-deposition measuring station has been set up at the General Motors Technical Center site in Warren, Michigan. A second station is also being operated at a rural site near Lapeer, Michigan, which is approximately 54 km north of the Warren site. This report presents the results of this study for the June-September 1981 period. The rain composition was similar at both sites with the pH averaging 4.1 and the SO₄ ⁼/NO₃ ^? equivalence ratio averaging 2.1:1. This similarity suggests that local sources, i.e., relatively high emissions near the Warren site, and low emissions near the Lapeer site, have little effect on rain composition. The SO₄ ⁼/NO₃ ^? ratio for individual rain events in Warren reflected the SO₂/NO_x emission ratio in the area from which the event had come. Thus, the highest SO₄ ⁼/NO₃ ^? ratios were observed for rains that arrived from the southeast and the lowest ratios for rains from the southwest. No rain events arrived from a northwesterly direction during this sampling period. Measurements were carried out at both sites to estimate the relative contribution of dry deposition. The ambient particulate was acidic about half the time and basic half the time. The acidity in the particulate was due to acid SO₄ ⁼ and the basicity was due to soil-related materials. Gaseous HNO₃ averaged 2.0 μg m^?3while the basic gas, NH₃, averaged 0.83 μg m^?3. Based on these measurements, it was estimated that dry deposition of particles and HNO₃ contributed less than 10% of the total deposition of acidity during this study period.     

A method for evaluation of acidic sulfate and nitrate in precipitation

A simple method is presented and used to estimate the portions of SO _inf4 ^sup2? and NO _inf? ^sup3 that contribute to the strong acidity in weekly precipitation samples collected at three NADP sites in the eastern United States. The method assumes that, in general, the difference between SO _inf4 ^sup2? and NH _inf+ ^sup4 represents acidic sulfate and the difference between NO _inf? ^sup3 and soil-derived materials (the sum of Ca²⁺, Mg²⁺, and K⁺) represents acidic nitrate. Acidic sulfate and nitrate are considered to be the predominant source of H⁺ (determined from laboratory pH) in the weekly precipitation samples. Most of the acidity for all three sites was attributed to acidic sulfate. The highest fraction of acidic SO _inf4 ^sup2? to H⁺ wet deposition values was for the east-central Tennessee site (0.95) and the northeastern Illinois site (0.90), and the lowest fraction occurred at the central Pennsylvania site (0.75). The Tennessee site had the greatest acidic fraction of sulfate (0.84) and the Pennsylvania site had the greatest acidic fraction of nitrate (0.59).     

Acid deposition and lake chemistry in southwest China

A water quality survey has been performed on selected lakes and streams in southwest China. The purpose of the study was to measure the concentrations of acidic deposition and surface water chemistry in a region of severe air pollution, forest decline, and relatively sensitive geology to acidic deposition. We show that, although there are some high elevation lakes of low acid neutralizing capacity (ANC<150μeq L^?1, acidification of lakes has not occurred in southwest China due to production of base cations in soil and dry deposition of dust that serves to neutralize acidic deposition. Water chemistry is buffered by high base cation concentrations (Ca²⁺, Mg²⁺, Na⁺, and K⁺ greater than 300μeq L^?1, and pH values are always greater than 6.5.     

Studies of Soils, Soil Water and Stream Water at a Small Catchment near Guiyang, China

Acid deposition is considered to be a major environmental problem in China, but information about effects on soils and waters is scarce. To contribute to increased knowledge about the problem a small catchment (about 7 ha) in the outskirts of Guiyang, the provincial capital of Guizhou in south-western China, was instrumented for collection of precipitation, throughfall, soil water and stream water. In addition soil samples have been collected and analyzed for key properties. Median pH in the precipitation is 4.40 (quartiles: 4.19 and 4.77) and the median sulfate concentration 228 µeq/L (quartiles: 147 and 334 µeq/L). The dry deposition of both SO₂ and alkaline dust is considerable. The sum of wet deposition of sulfate and dry deposition of SO₂ has been estimated to about 8.5 gSm^-2yr^-1. The total S-deposition may be somewhat higher due to dry deposition of sulfate and occult deposition. In soil water, SO₄ ^2- is the major anion, generally ranging from 300 to 2500 µeq/L in the different plots. Calcium is an important cation, but there is also a considerable contribution of aluminum from the soil. In some of the plots the concentrations of inorganic monomeric aluminum (Ali) are typically between 200 and 400 µm. Potential harmful levels of aluminum and/or high Ali/(Ca²⁺ + Mg²⁺) molar ratios occur in the catchment, but damages to vegetation have not yet been reported. In most cases exchangeable aluminum accounts for between 75 and 95% of the total effective cation exchange capacity (CEC_E) in the mineral soils. The aluminum chemistry cannot easily be explained by conventional models as the Gaines-Thomas ion-exchange equation or equilibrium with an Al(OH)₃ mineral phase. The stream water is generally less acidic and has considerably lower concentrations of aluminum than the soil water, even though quite acid events have been observed (pH < 4.4). The median pH values are 4.9 and 5.0 in the two first order streams and 6.3 in the dam at the lower boarder of the catchment.     

The geographical distribution and temporal variations of acidic deposition in Eastern North America

Data from two national precipitation chemistry monitoring networks, and several regional air and precipitation chemistry networks are used to describe some broad-scale features of acidic deposition in eastern North America. In northeastern North America, the coefficient of variation is shown to increase from 10–16% for annual averages to nearly 100% for daily values. There is a strong annual cycle in H⁺, SO _inf4 ^sup= and NH _inf4 ^sup+ deposition and some of the other ions although these cycles are not all in phase. The wet NO _inf3 ^sup? deposition contributes relatively more than SO _inf4 ^sup= to the acidity of snow as compared to rain. Wet deposition is highly “episodic” with about 50% to 70% of the total annual deposition of SO _inf4 ^sup= and NO _inf3 ^sup? accumulating in the highest 20% of the days. Estimates made in various ways indicate that, over eastern North America as a whole, dry deposition is approximately equal to wet for both SO _inf4 ^sup= and NO _inf3 ^sup? . Dry may exceed wet in the high emissions zone but drops to about 20% of the total deposition in more remote areas. Deposition via fog or low cloud impaction is an important input to high elevation forests, but more data are required to quantify the magnitude and regional extent of this.     

Effect of sulphur dioxide on precipitation and on the sulphur content and acidity of soils in Alberta,Canada

Rain and snow in Alberta are seldom acid. The S content of snow is so low that the snow pack gives a deposition of less than 1 kg S ha^?1, even downwind from large SO₂ emission sources. Rainfall contributes at the most 4 kg S ha^?1 yearly near SO₂ sources, and only about 1 kg S ha^?1 in clean areas. However, rain intercepted by forest trees exposed to SO₂ emission becomes acid (pH 3.5 to 4.5) and has a S content of 3 to 4 times greater than rain. Soils absorb large amounts of S from emissions (up to 50 kg S ha ^?1 annually) but much of the S is found in non-sulphate form. Soils are slowly acidified by the SO₂ at a rate estimated at 1 pH unit in 10 to 20 yr. Water surfaces will absorb SO₂ emissions at a rate of about 4 to 15 kg S ha^?1 annually. Particulates deposit 3 to 4 times as much S as is deposited by rainfall.     

Human exposure to mercury may decrease as acidic deposition increases

It has been hypothesized that human mercury (Hg) exposure via fish consumption will increase with increasing acidic deposition. Specifically, acidic deposition leads to reduced lake pH and alkalinity, and increased sulphate ion concentration ([SO₄ ^2?]), which in turn should cause increased Hg levels in fish, ultimately resulting in increased human Hg exposure via fish consumption. Our empirical test of this hypothesis found it to be false. We specifically examined Hg levels in the hair of Ontario Amerindians, who are known consumers of fish from lakes across the province, and observed a weak negative association with increasing sulphate deposition. An examination of Hg levels in lake trout, northern pike and walleye, three freshwater fish species commonly consumed by Ontario Amerindians, found a similar weak negative association with increasing sulphate deposition. Further analysis of these fish data found that fish [Hg] was most significantly (positively) associated with lake water concentrations of dissolved organic carbon (DOC), not pH, alkalinity or [SO₄ ^2?]. Lake DOC levels are lower in regions of greater acidic deposition. We propose an alternate hypothesis whereby human Hg exposure declines with increasing acidic deposition. In particular, we propose that increasing sulphate deposition leads to reduced lake DOC levels, which in turn leads to lower Hg in fish, ultimately reducing human Hg exposure via fish consumption.     

Pattern and cause of acidic deposition in the Chongqing region,Sichuan Province,China

The Chongqing region located in Sichuan Province of China, comprises a large city, many small towns and rural areas. The region relies heavily on high-sulfur coal for energy production. Atmospheric pollution by sulfur oxides and other compounds from coal burning has become a major issue. Acid rain is observed throughout the region; volume weighted average pH is about 4.30. Average total S deposition for the region is estimated to be about 8 g S m^?2 yr^?1. In this paper we report concentrations of major ions in rain, fog, dew and clouds, of SO₂ in air and of airborne particles as well as dustfall. The emissions and interactions between important chemical species in air and water droplets are discussed.