pH and hydrogen ion deposition patterns in precipitation for the continental United States and Canada

Maps of both volume-weighted mean pH and mean H⁺ deposition in precipitation were developed for the continental United States and Canada using data from 12 precipitation chemistry monitoring networks. The maps were constructed using 1981–1982 laboratory pH data from approximately 130 monitoring sites. The area of greatest acidity (lowest pH/highest H⁺ deposition) is located in the northern Ohio Valley and southeastern Ontario, an area corresponding to high SO_x and NO_x emissions.     

Seasonal patterns in acidity of precipitation and their implications for forest stream ecosystems

Data collected since 1965 at a network of nine stations in the northeastern United States show that precipitation is most acid in the growing season (May-September) and least acid in winter (December-February). For the Hubbard Brook station in New Hampshire, where the mean hydrogen ion content of precipitation ranges between 46 peq 1^?1 in winter and 102 peq 1^?1 in summer, the seasonal pattern in acidity correlates closely with seasonal differences in S deposition from the atmosphere. As summer precipitation passes through the forest canopy, H ion concentrations are lowered by an average of 90%, primarily as a result of exchange with other cations. In winter the H ion content of incident precipitation is lowered from a mean of 50 peq 1^?1 to a mean of 25 peq l^?1 during storage in the snowpack.     

Acidic precipitation: Considerations for an air quality standard

Acidic precipitation, wet or frozen precipitation with a H⁺ concentration greater than 2.5 μeq l^?1, is a significant air pollution problem in the United States. The chief anions accounting for the H⁺ in rainfall are nitrate and sulfate. Agricultural systems may derive greater net nutritional benefits from increasing inputs of acidic rain than do forest systems when soils alone are considered. Agricultural soils may benefit because of the high N and S requirements of agricultural plants. Detrimental effects to forest soils may result if atmospheric H⁺ inputs significantly add to or exceed H⁺ production by soils. Acidification of fresh waters of southern Scandinavia, southwestern Scotland, southeastern Canada, and northeastern United States is caused by acid deposition. Areas of these regions in which this acidification occurs have in common, highly acidic precipitation with volume weighted mean annual H⁺ concentrations of 25 μeq l^?1 or higher and slow weathering of granitic or precambrian bedrock with thin soils deficient in minerals which would provide buffer capacity. Biological effects of acidification of fresh waters are detectable below pH 6.0. As lake and stream pH levels decrease below pH 6.0, many species of plants, invertebrates, and vertebrates are progressively eliminated. Generally, fisheries are severely impacted below pH 5.0 and are completely destroyed below pH 4.8. At the present time studies documenting effects of acidic precipitation on terrestrial vegetation are insufficient to establish an air quality standard. It must be demonstrated that current levels of precipitation acidity alone significantly injure terrestrial vegetation. For aquatic ecosystems, current research indicates that establishing a maximum permissible value for the volume weighted annual H⁺ concentration of precipitation at 25 μeq l^?1 may protect the most sensitive areas from permanent lake acidification. Such a standard would probably protect other systems as well.     

Investigation of Differences between Field and Laboratory pH Measurements of National Atmospheric Deposition Program/National Trends Network Precipitation Samples

A study was undertaken to investigate differences between laboratoryand field pH measurements for precipitation samples collected from 135 weekly precipitation-monitoring sites in the National Trends Network from 12/30/1986 to 12/28/1999. Differences in pH between field and laboratory measurements occurred for 96% of samples collected during this time period. Differences between the two measurements were evaluated for precipitation samples collected before and after January 1994, when modifications to sample-handling protocol and elimination of the contaminating bucket o-ring used in sample shipment occurred. Median hydrogen-ion and pH differences between field and laboratory measurements declined from 3. 9 μeq L^-1 or 0. 10 pH units before the 1994 protocol change to 1. 4 μeq L^-1 or 0. 04 pH units after the 1994 protocol change. Hydrogen-ion differences between field and laboratory measurements had a high correlation with the sample pH determined in the field. The largest pH differences between the two measurements occurred for high-pH samples (>5. 6), typical of precipitation collected in Western United States; however low-pH samples (<5. 0) displayed the highest variability in hydrogen-ion differences between field and laboratory analyses. Properly screened field pH measurements are a useful alternative to laboratory pH values for trend analysis, particularly before 1994 when laboratory pH values were influenced by sample-collection equipment.     

Modern and paleolimnological evidence for accelerated leaching and metal accumulation in soils in New England,caused by atmospheric deposition

Empirical field evidence for changing chemical processes in soils caused by atmospheric deposition of pollutants consists of: (1) Long-term water quality data including total dissolved solids, concentrations of specific metals (e.g. Ca), and conductivity; (2) Cation exchange capacity and base saturation values for soils located on precipitation pH gradients; (3) Lysimeter studies; and (4) Chemical analysis of organic soils on precipitation pH and metal gradients. For well-drained organic soils, as precipitation pH decreases, metals are differentially leached at an accelerated rate (Mn>Ca>Mg≥Zn>Cd and Na>Al). Experimental field and laboratory lysimeter studies on soil columns yield similar results, with increases in leaching rates for soil solutions with pH=3 up to 100 × values for soil solutions with pH=5. Nearly 100% of the Pb from precipitation is accumulating in the organic soil layer or sediments. Zn is accumulating in soils and sediments where the pH's of precipitation, soil solutions, and surface waters are generally above 5 to 5.5. At lower pH values Zn and other chemically similar elements are desorbed/leached (net) at an accelerated rate. Chemical analyses of dated sediment cores from high and low altitude lakes, with drainage basins relatively undisturbed for the last 200+ yr, reveal that increased deposition of metals on a regional scale started in the northeastern United States as early as 1880, consistent with increased fossil fuel consumption. This suggests acidified precipitation as early as 1880. Cores from historically acidified lakes (pH<≈5.3 to 5.5) indicate that, as acidification of surface waters occurs (caused by acidic deposition), concentrations of Zn, Mn, and Ca decrease in the sediment. Apparently the metals are leached from the detritus prior to sedimentation. This conclusion results from data from experimental acidification of sediment cores and the general observation that precipitation pH is generally ≥0.5 pH units lower than lake water pH. Accelerated leaching of soil in New England dates to earlier than 1900.     

Seasonal mass balance of major ions in three small watersheds in a maritime environment

Three watersheds (16.4, 544, and 83 ha) at distances of 0.5, 20, and 40 km from the Atlantic coast have been monitored for major ion chemistry of precipitation input and streamflow from May 1977 to November 1978. More than 200 precipitation and stramflow samples were analyzed for Na, K, Ca, Mg, chloride and sulphate, as well as pH, conductivity, alkalinity, and compared to similar studies at Hubbard Brook, New Hampshire, U.S.A., and Kejimkujik National Park, Nova Scotia. Major ion chemistry reflects proximity to Atlantic and Bay of Fundy coastal sources of marine aerosols. Evidence is presented implying biological reduction of H ⁺ and S04 to H₂S during summer months for two consecutive growing seasons. Weighted mean annual pH values of precipitation for the three watersheds in Nova Scotia range from 4.11 to 4.63. More than 50% of the H ⁺ in precipitation is retained in the watersheds (with the exception of the ombrotrophic Fink Cove ecosystem), principally at the expense of basic cations being leached from the watersheds. Acidic deposition of Nova Scotian precipitation is predominantly as sulphuric acid, in contrast to ammonium sulphate, characteristic of continental precipitation.     

Changes in the Chemistry of Precipitation in the United States, 1981–1998

Regulatory measures in the United States, such as Title IV of the Clean Air Act Amendments of 1990, have primarily restricted sulfur dioxide emissions as a way to control acidic deposition. These restrictions, coupled with increasing concentrations of NH₄ ⁺ in wet deposition in some regions of the U.S. and continued high emissions of nitrogen oxides have generated a significant shift in the chemistry of precipitation as measured at National Atmospheric Deposition Program/National Trends Network sites. Trends in precipitation chemistry at NADP/NTN sites were evaluated for statistical significance for the period 1981–1998 using a Seasonal Mann-Kendall Test, a robust non-parametric test for detection of monotonic trends. SO₄ ^2? declines were detected at 100 of the 147 sites examined while no sites exhibited increasing SO₄ ^2? trends. On average, SO₄ ^2? declined 35% over the period 1981–1998 with downward SO₄ ^2? trends being most pronounced in the north-eastern United States. In contrast, no consistent trends in NO₃ ^? concentrations were observed in precipitation in any major region of the United States. Although the majority of sites did not exhibit significant trends in NH₄ ⁺ concentration, 30 sites exhibited upward trends. For Ca²⁺ concentration in precipitation, 64 sites exhibited a significant decreasing trend and no sites exhibited an upward trend.     

Atmospheric Wet Deposition of Total Phosphorus in New Jersey

Wet deposition of total phosphorus has been measured as part of the New Jersey Atmospheric Deposition Network (NJADN). Precipitation samples were collected in 1999—2001, using automated wet-only precipitation collectors at four sites in New Jersey, representing different land-use regimes. Total phosphorus volume-weighted mean concentrations (VWM) and the wet depositional fluxes were estimated on seasonal and annual timescales. VWM concentrations (± standard error) of total phosphorus ranged from 4.1 ± 0.80 to 15 ± 8.8 μg L^-1 at all sites and were of similar magnitude across the region. The wet deposition flux estimates ranged from 3.9 to 14 mg m^-2 y^-1. VWM concentrations and fluxes were similar to those measured at other locations in the eastern United States.     

Estimating the atmospheric input of pollutants into a watershed

Estimating the atmospheric input of ions to a watershed has traditionally been accomplished through either the extrapolation of point measurements of deposition or the integration of model estimated deposition. This paper examines the characteristics of precipitation chemistry on the eastern seaboard of the United States where precipitation quality could conceivably affect fish habitats in estuaries. The measured values presented here have been extracted from the data base of the Utility Acid Precipitation Sampling Program (UAPSP) precipitation chemistry network. These data illustrate the nature of ionic deposition at four points on the eastern seabord. The deposition of H' (acidity) is shown to be dependent upon the amount of sulfate and, to a lesser degree, nitrate in the precipitation. It is also shown that the quantity of ionic deposition on a storm-by-storm basis was influenced by the amount of water deposition but the relationship was not very strong. Thus the use of water deposition as a surrogate for ionic deposition is not justified in these watersheds. Finally, it is shown that the deposition of H⁺, SO₄ ^2?, NO₃ ^?, and NH₄ ⁺ were not clearly seasonal. While a large percentage of total ionic deposition occurred in a small number of precipitation events, these exceptional events were not confined to a particular season.     

An analysis of spatial variability of the dominant ions in precipitation in the eastern United States

Data of the Multistate Atmospheric Power Production Pollution Study (MAP3S) and the National Atmospheric Deposition Program (NADP) were utilized to develop wet deposition spatial distribution patterns for the eastern United States for 1979. The ions of SO₄ ^?, NO₃ ^?, H⁺, and NH₄ ⁺ were selected for study since they are the most prominent ones found in precipitation. Total wet deposition for 1979 was normalized to one centimeter of precipitation and objectively analyzed using the Synagraphic Mapping System (SYMAP) technique. Gradients of SO₄ ^? and NO₃ ^? were found to be essentially uniform, both to the east and west of the major pollution regions. An increased gradient in normalized deposition for SO₄ ^?, NO₃ ^?, and H⁺ was found in the Appalachian Mountain region. Estimates of total wet deposition were obtained by using the normalized deposition values in conjunction with precipitation as reported by the National Climatic Center. SYMAP analyses of the estimated total wet deposition were localized in nature due to precipitation variations between sites.     

Historical deposition rates of mercury in scandinavia estimated by dating and measurement of mercury in cores of peat bogs

Historical deposition rates of Hg were determined in 7 ombrotrophic bogs located far from direct sources in Sweden and Norway. The peat bog cores were dated using ²¹⁰Pb. Based on the dating result 10 to 12 slices from each core were analyzed for Hg. In Southwestern Scandinavia (Rörvik) the deposition rate has increased from about 10 to about 30 μg Hg m^?2 yr^?1 since the beginning of this century. In Northwestern Norway (Överbygd) the deposition rate has increased from about 10 to about 35 μg Hg m^?2 yr^?1 since the 1960's. In Southeast Sweden (Aspvreten) the deposition rate decreased since the beginning of this century. There are no significant trends in the historical deposition rates at the two other stations in middle Scandinavia. A comparison between recent Hg deposition rates measured by peat bog analysis, wet precipitation and mosses shows good agreement at all stations except those in Northern Norway were local dry deposition of Hg may be an important source of Hg.     

Ozone,acidic precipitation,and soil Mg impacts on soil and loblolly pine seedling nutrient status after three growing seasons

Recent studies have suggested that the growth of loblolly pine (Pinus taeda L.) has declined in the southeastern United States, possibly due to acidic deposition and air pollutants, especially under conditions of low nutrient availability. Consequently, the potential for individual and synergistic impacts of O₃, acidic precipitation, and soil Mg status on the nutrient status of loblolly pine seedlings and soil was investigated over a 3 yr study period. Thirty-six open top chambers equipped with a rainfall exclusion/addition system were utilized to administer three levels of O₃ (subambient, ambient, or twice ambient) and two acidic precipitation treatments (pH 3.8 or 5.2) to seedlings growing in 24-L plastic pots containing soil having either 35 or 15 mg kg^?1 of exchangeable Mg. Each chamber contained 36 pots, and each treatment combination was replicated six times for a total of 1296 individual pots. After three seasons, throughfall and foliar nutrition data indicated that foliar leaching was not accelerated by increasing the acidity of precipitation from pH 5.2 to 3.8 and that increasing O₃ did not act to exacerbate foliar leaching. Further, foliar nutrient concentrations were not significantly affected by precipitation pH or O₃ treatments. Soil and soil solution data also indicate no accelerated soil leaching associated with chronic acidic precipitation. Differences in soil Mg treatments were reflected in soil solution and seedling Mg contents, but the 15 mg kg^?1 soil Mg treatment was not sufficiently low enough to induce Mg deficiency in the seedlings.     

Entwicklung der Niederschlags-Deposition von Schwermetallen in West-Deutschland. 1. Blei und Cadmium

Development of heavy-metal deposition by precipitation in West Germany. 1. Lead and cadmium Between 1984 and 1993 the deposition of Pb and Cd with bulk precipitation was measured on 25 open field sites in 4 German federal states. The absolute amount of Pb and Cd deposition varies according to field sites and annual precipitation. In all studied areas, however, Pb deposition via bulk precipitation decreased significantly during the observation period. Considering all research areas under study, the average Pb deposition with bulk precipitation fell from 142 g ha^?1 in 1984 to 31 g ha^?1 in 1993 (r = ?0.934***). This decrease in Pb deposition correlates with the prognosticated decline in Pb emissions that occurred in Germany during the same time period owing to the introduction of unleaded motor fuels in 1984. Average Cd deposition on all research stations fell from 3.4 g ha^?1 in 1984 to 2.0 g ha^?1 in 1993 (r = ?0.900***). However, in contrast to Pb, the reduction of Cd deposition was significant only at 11 of 25 research stations. The reduction in Cd deposition with precipitation is substantially lower than the reduction in Cd emissions prognosticated.     

Urban wet deposition nitrate: A comparison to non-urban deposition

The concentration of nitrate in both wet and dry deposition has both increased historically and currently, and recently parallels emissions in NO_x. Since NO_x is produced in amounts comparable to SO₂, it is an important contributor to acid deposition, and is produced in higher amounts in urban areas due to concentrated sources. Prior to this study, national acid deposition monitoring networks in the United States have been and remain established in non-urban areas. This research study consisted of a comparison of precipitation sampling and analysis of wet deposition nitrate and pH for each deposition event in each of two urban sites over a 15 mo period. Also, a comparison of urban data and data generated at a nearby non-urban NADP site was made by examination of both monthly and seasonal data. This research suggests that national monitoring programs should consider inclusion of urban and non-urban monitoring sites in order to achieve a more representative regional assessment.     

Temporal variation in aluminum speciation and concentration during snowmelt

Precipitation samples in Alberta were collected and analyzed monthly from six Alberta Environment stations. Samples were collected with Sangamo samplers and analyzed for the major ions, pH and acidity. The data were tabulated and analyzed for spatial distribution, seasonal variation, temporal trends, ionic character and wet sulphate deposition. The major ionic species in Alberta precipitation are Ca²⁺, SO _inf4 ^sup2? , NH _inf4 ^sup+ and N0 _inf3 ^sup? . The spatial distribution shows a slight decrease in pH from southern Alberta (pH 6.0) to northern Alberta (pH 5.4). The seasonal variation shows higher hydrogen ion content in the summer months (pH 5.4 in summer and pH 5.8 in winter). Temporal trends are not apparent over the five year period investigated. The five year average wet sulphate deposition rate in Alberta is 9.1 kg ha^?1 yr^?1.     

Episodicity of Sulphate Deposition in Finland

A characteristic of daily acid deposition data, in particular at remote sites, is the occurrence of some extreme peaks above the base level of moderate values. A large proportion of the annual acid deposition is accumulated in a few days: 5 worst days at the Finnish background stations can bring 20–30 % of the annual bulk sulphate load. The aim of this study was to determine whether there is a difference between stations in the number of extreme daily bulk acid depositions. The bulk deposition of sulphate in the 1990's at five Finnish monitoring stations was used as a reference. Days on which the deposition value exceeded the annual median value of the station by a factor of 10 were counted as episode days. The number of episode days in central and northern Finland differed significantly (p<0.05) from the number in the south, when tested with the non-parametric Kruskal-Wallis test. The episodes cannot be completely explained by high precipitation amounts: the mean sulphate concentration in episodic rain was higher than the annual mean concentration. The episodes were mostly imported: the air mass arriving at the station had passed over areas with high emissions outside Finland. A more exact knowledge of the episodicity benefits an examination of the ecological stress caused by acid deposition as well as a study of the critical load and the crossing of this threshold.     

Potential effects of acid precipitation on soils in the humid temperate zone

Unmanaged soils in the northeast United States generally tend toward increasing acidity which results from several natural processes in the soil. Possible effects of acid precipitation on these processes may be caused by hydrogen ions associated with excess anions in the precipitation and, in addition, the anions may also have specific effects. This is especially true for N and S both of which have important biological implications. It is likely that direct effects of the H ion will be modest. As an example, the acidity in 114 cm of rainfall per year (Connecticut's average) with a pH of 4.3 would require 28.5 kg ha ^?1 of limestone for neutralization. By contrast agronomic practice in Connecticut frequently dictates limestone additions as high as several thousand kg ha^?1 to neutralize acidity generated by a combination of natural processes and fertilizer amendments. Studies of rainfall composition in Connecticut from 1929 to 1948 showed no clear trends with time and indicated levels of sulfate and nitrate in rainwater similar to those reported today. In a 10 yr lysimeter study in Connecticut in which tobacco was grown using conventional fertilization techniques, soil pH decreased from 5.4 to 5.0 and both gains and losses of soil cations were recorded. Thus it appears that changes in unmanaged soils induced by acid precipitation alone will be modest and subtle and probably cannot be expressed completely by measuring changes in soil pH value.     

Factors influencing atmospheric deposition,stream export,and landscape accumulation of trace metals in forested watersheds

Wet and dry deposition inputs and streamflow output of Cd, Mn, Pb, Zn, and Al were measured intermittently at four deciduous forested watersheds in the southeastern United States between 1976 and 1982. Atmospheric inputs to each site were similar, varying by factors of 1.1 to 2.2 for the different metals. Metal levels in precipitation indicate that these sites are representative of rural, continental areas. Metals in rain exhibit significant temporal and spatial trends, with concentrations generally higher during summer than winter at all sites and generally lowest at the more remote site. The concentrations of Cd and Pb in both wet and dry deposition decreased between the period 1976 to 1977 and 1981 to 1982. Ion ratios and enrichment factors suggest that Mn is largely soil derived in atmospheric samples while Cd, Pb, and Zn are enriched over typical soil levels. Factor analysis indicates that soil components influence both Al and Mn while fine aerosol components influence Cd in wet and dry deposition. Both components influence the behavior of Pb. Dry deposition dominated the input of Mn and Al to each site, while wet deposition was the major input process for the other metals (54 to 85% of total). On an annual basis, deposited Cd, Pb, and Zn are strongly retained in each watershed: 2% of the Pb, 8 to 29% of the Cd, and 8 to 34% of the Zn inputs were transported in stream flow. Deposited Mn and Al are retained to a lesser degree and show a net loss from two sites. Metal export is controlled by stream pH, organic carbon, bedrock geology, and hydrologic characteristics of each site.     

On the use of scavenging ratios for the inference of surface-level concentrations and subsequent dry deposition of Ca2+, Mg2+, Na+ and K+

An inference technique is developed that allows estimation of the annual and monthly dry deposition of Ca²⁺, Mg²⁺, Na⁺, and K⁺. Conceptually, this technique is based on the premise that precipitation efficiently scavenges aerosols, resulting in a strong correlation between concentrations within precipitation and the surface-level air. Empirically, it is based on the linear relationship exhibited between the measured surface-level air and precipitation concentrations at 23 stations in Ontario, Canada, for the period 1983–1985. Correlations ranged from 0.513 for K⁺ to 0.946 for Mg²⁺. Because of the stochastic nature of such an approach, the assumptions inherent to the concept of scavenging ratios, and therefore this inference technique, must be carefully considered. Under such considerations, annual and monthly dry deposition of alkaline aerosols can be estimated at many locations across North America where precipitation concentrations are routinely measured.     

Temporal chemical variability in acid sensitive high elevation lakes

Chemical indicators suggest that slight, but discernable acidification occurs during smowmelt in some highly sensitive Cascade Mountain Lakes (mean alkalinity 20 ueq L^?1). Although some SO₄ in the lakes (mean 13 μeq L^?1 ) comes from local geologic sources, several considerations suggest that some also comes from atmospheric deposition and anthropogenic sources. If sampling is stratified, the relatively low lake-to-lake and year-to-year variability in chemical constituents demonstrates that these highly sensitive lakes represent excellent indicators of acidification. The contention that precipitation pH >4.6 is needed for protection of sensitive lakes is supported. However, the slight but temporary acidification effect currently detectable during snowmelt, suggests that for adequate protection of these highly sensitive lakes, precipitation pH should be >4.7 to 4.8.