Recent trends in the acid-base status of surface waters in Maine,USA

Data from the EPA Long Term Monitoring Program lakes at the Tunk Mountain Watershed, Maine, indicate that decreases of ≤1 Μeq L^?1 yr^?1 in SO₄, and increases of ≤2 Μeq L^?1 yr^?1 in ANC occurred in the 1980s. The sum of base cations also increased. These changes in aquatic chemistry were coincident with decreased concentrations of all solutes in precipitation during the 1980s. Other data on lakes and streams in Maine collected between the 1930s and 1990 generally confirm these trends and further indicate that larger increases in ANC may have occurred in some lowland lakes since 1940. Paleolimnologic studies indicate that decreases of 0.1 to 0.5 pH units occurred in a few small mountain lakes during the past 20 to 70 yr. However, ongoing acidification of lakes is indicated based on available data. Only lakes that were already at least marginally acidic (pH ≤5.8, ANC approximately 0) appear to have acidified.     

Chemical composition of hoarfrost,rime and snow during a winter inversion in Utah,U.S.A.

We present data on the chemical composition of hoarfrost, rime, and snow grains that accumulated during an eighteen-day long temperature inversion event in Salt Lake City, Utah in December 1985 and January 1986. Chemical analyses show that the precipitation formed during this inversion event was acidic (as low as pH 3.85) and had nitrate and sulfate contents up to 1680 and 1290 μeq · L^?1, respectively. Ammonia, nitrate, and sulfate deposition of 361, 615, and 792 μeq · m^?2, respectively, occurred in a six-day period due to the accumulation of snow grains during this inversion.     

Formiate and acetate in wet deposition at Pallanza (NW Italy) in relation to major ion concentrations

Weekly samples of wet deposition were collected at Pallanza (NW Italy) from January 1987 to December 1988. Their chemistry is characterized by high mineral acidity, with a median pH value of 4.26; only in 2 out of 62 samples was pH higher than 6.0. Sulphate, nitrate and ammonium are the main ions. Formiate and acetate showed a volume weighted average of 7 and 4 μeq L^?1, respectively; the values for the dissociated forms are 5 and 1 μeq L^?1, respectively. The contribution of formiate and acetate (dissociated form) to the total ionic concentration is about 2%, while the contribution to free hydrogenion is about 13%, mainly deriving from formic acid. Seasonal variations in concentration and the relationships between organic acid and other ions indicate that the photolysis of isoprenoid compounds released into the atmosphere from vegetation is a significant source for formic acid. In the case of acetic acid there is a contribution from anthropogenic emissions, more marked during the winter period.     

Acid precipitation and surface-water vulnerability on the western slope of the high colorado rockies

Precipitation and surface waters in a high-elevation watershed on the western slope of the Colorado Rockies were studied over a three-year period. The volume-weighted average pH for summer events was 4.61, for winter events was 5.11 and for the entire period was 4.91. Within the watershed, both low- and medium-alkalinity surface waters exist. Weekly alkalinity measurements ranged from 10 to 70 μeq L^?1 in the former and 100 to 900 μeq L^?1 in the latter.     

Response to a smelter closure in Cascade mountain lakes

A statistically significant decrease in sulfate was observed in high elevation Cascade lakes during 1983 through 1988. The total decrease averaged 2.2 μeq L^?1 in two slow-flush lakes and 4.2 μeq L^?1 in three fast-flush lakes for 1983–1985 vs 1986–1988, respectively. Coincident with these changes in sulfate concentrations were a sharp decrease of SO₂ emissions from the ASARCO smelter (100 km SE of the lakes), from 87 to 70 kt yr^?1 during 1983–1984 to 12 in 1985, the year of its closure, and a gradual change in SO₂ emissions from Mt. St. Helens, from 39 to 27 during 1983–1984 to 5 in 1988. The sharpest decreases occurred in non-marine sulfate in fast-flush lakes from 1984 to 1985 (about 2 μeq L^?1) and in slow-flush lakes from 1985 to 1986 (1 μeq L^?1, which point to the ASARCO closure as the sole cause. However, some of the more gradual decline in non-marine sulfate observed during 1983 through the 1988 sampling periods may have been due to a slow washout of sulfate enriched ash from the 1980 Mt. St. Helens' eruption. Sulfate concentrations in precipitation also declined significantly by about 2 μeq L^?1, but changes in volume-weighted sulfate content were not significant. Lake alkalinity did not show a consistent increase in response to decreased sulfate. This was probably due to either watershed neutralization of acidic deposition or the greater variability in alkalinity measurements caused by small changes in acidic deposition making it difficult to detect changes.     

Cloudwater chemistry in the subcooled droplet regime at Mount Sonnblick (3106 M A.S.L., Salzburg,Austria)

Cloudwater and wet precipitation (snow) samples were collected at Mount Sonnblick during two field campaigns in May and November 1991. A newly designed active cloud water samples was used. Concentrations of major anions, cations and carboxylic acids were determined. Cloudwater and wet precipitation samples were generally more acidic in the warm season than in the cold season. Average cloudwater pH was 4.2 in May and 4.5 in November, average pH in snow was 4.4 in May and 5.1 in November. Average levels for sulfate (May: 96 μeq L^?1, November: 64 μeq L^?1) and nitrate (May: 27 μeq L^?1, November: 32 μeq L^?1) in cloudwater at SBO (3 km altitude) were considerably lower than at high mountain sites (0.9–2 km altitude) in the Eastern U.S.A. Cold season levels of sulfate in cloud water at SBO were as low as cloud water levels observed in Alaska. Equivalent concentrations of sulfate, nitrate and ammonium in snow precipitation were basically lower or equal compared to cloudwater but showed higher concentrations and stronger acidity in both phases in May than in November. Cloud to snow ratios for major ions were higher in November showing a wider spread than in May. Average cloud to snow ratios for sulfate were 2.4 in May and 3.5 in November. For nitrate the ratio was 1.7 in May and 2.1 in November. The lower cloud to snow ratios for nitrate are explained by the ability of the ice phase to scavenge nitric acid. Cloud to snow ratios were similar to measurements from the Swiss Alps and generally equal or lower than high elevation cloud to rain ratios from the U.S.A. Cloud to snow ratios for sulfate were used to reconstruct the mixing ratio of sublimation grown ice phase and cloud water droplets during the riming process of the ice particles in the seeder-feeder mechanism. The mixing ratio of ice phase and cloud droplets was estimated to be 1.4 in May and 2.5 in November. Sulfate to nitrate ratios were higher in cloud water than in snow and within the range of values found in North America. Generally, sulfate was more concentrated than nitrate at an equivalent basis for both cloudwater and rainwater. Total equivalent concentrations of acetate were generally higher than those of formate which is in contrast to measurements at remote high elevation sites in the U.S.A.     

Chemistry differences in two streams entering an acidic lake in the Adirondack Mountains,New York (U.S.A.)

Solution chemistry was measured in two major inlets, lake water column, lake outlet, and soils of the South Lake watershed in the Adirondack Mountains, New York. The east inlet had greater concentrations of H⁺, sulfate-S, and Al and smaller concentrations of base cations and silica than the west inlet (70, 116, 25, 90, 64 and 4, 99, 8, 228, 148 μeq L^?1 of H⁺ and sulfate-S, μmol L^?1 Al, μeq L^?1 total base cations and μmol L^?1 silica in east and west inlets, respectively). Concentrations of base cations in C horizon soil solutions (157 μeq L^?1 total base cations) were smaller and greater than west and east inlets, respectively. This suggests that water flowing into the west inlet contacted deeper mineral layers, whereas water reaching the east inlet did not. Lake and lake outlet concentrations were also intermediate between the two inlets, and the lake was acidic (pH 4.9 to 5.1) with relatively high total monomeric Al concentrations (8 to 9 μmol Al L^?1). The east inlet also had greater DOC concentrations than the west (0.38 and 0.24 μmol C L^?1, respectively), again indicating that soil solutions entering the east inlet passed through the forest floor but had more limited contact with deeper mineral layers in comparison with the west inlet. Differences between the streams are hypothesized to be related to contact of percolating solutions with mineral soil horizons and underlying glacial till, which provides neutralization of acidic solutions and releases base cations. This work indicates that processes controlling surface water acidification can be spatially quite variable over a small watershed.     

An Evaluation of In-Situ Measurements of Water Temperature, Specific Conductance, and pH in Low Ionic Strength Streams

The performance of minimonitors used by the U.S. Geological Survey for continuous measurement of water temperature, specific conductance, and pH in four low ionic strength streams in the Catskill Mountains of New York was evaluated through a calculation of their bias, precision, and accuracy and by comparison with laboratory measurements of specific conductance and pH on samples collected concurrently. Results indicate that the mini-monitor measurements of specific conductance and pH in an acidic stream (acid-neutralizing capacity always less than 0) agreed with laboratory measurements well enough that the minimonitors can be used to supplement laboratory measurements (mean difference in pH was 0.02 pH unit and mean difference in specific conductance was 0.72 μS cm^?1. This mean difference was 0.32 μS cm^?1 if the minimonitor data were adjusted by the bias). In less acidic streams (two streams in which the acid-neutralizing capacity was always greater than 0 and one in which the acid-neutralizing capacity was greater than 0 except during high flows), there was poor agreement between laboratory and minimonitor measurements of specific conductance at high flows and pH at all flows. The water-temperature probes measured with sufficiently small bias (–0.1 °C) and adequate precision (±0.70 °C) for use with most applications.     

A Preliminary Assessment of Wet Deposition and Episodic Transport of Total and Methyl Mercury from Low Order Blue Ridge Watersheds,S.E. U.S.A.

Results from a preliminary sampling program designed to investigate total (THg) and methyl Hg (MeHg) deposition, cycling and transport at the Coweeta Hydrologic Laboratory western North Carolina are presented. Wet deposition samples were collected in June and July 1994 and throughfall, seep and streamwaters were intensively collected during and after a rainfall event in June 1994. All water samples were collected using ultra clean trace sampling protocol. Low elevation Watershed 18 streamwater THg concentrations peaked with discharge, increasing 6 fold to 9 ng L^-1. High elevation Watershed 27 which received less than one half the precipitation Watershed 18 received during the event, exhibited THg concentrations only 1.3 times over base flow conditions. Methyl Hg concentrations remained near detection limits (≤ 0.025 ng L^-1) in both streams. Dissolved MeHg concentrations were higher in shallow seep (0.097 ng L^-1), throughfall (0.135 ng L^-1) and precipitation (0.16 – 0.035 ng L^-1) than streamwaters. Initial estimates of annual THg and MeHg deposition and transport indicate >90% retention of Thg and a >80% retention or demethylation of wet deposition MeHg is occurring in these low order watersheds.     

Acidity status of surface waters in Massachusetts

The Massachusetts Acid Rain Monitoring project surveyed 80.5% of the state's 5294 named water bodies between 1983 and 1985. PH and acid neutralizing capacity (ANC) were measured monthly the first 14 mo and semi-annually afterwards. Sample collection and analysis were performed by volunteers. The majority of surface waters in Massachusetts were found to be sensitive to possible long term acidification, with 63% exhibiting ANC less than 200 μeq L^?1 and 22% with ANC less than 40 μeq L^?1. Seasonal patterns in ANC were observed, the median ANC being 384 μeq L^?1 in summer/fall and 134 μeq L^?1 in winter/spring. Geographical differences were also found across the state: the streams and lakes with lowest pH and ANC were located in the southeastern and north-central parts of the state, while the most alkaline surface waters were found in the western-most part of the state, which is the only area of the state with significant limestone deposits.     

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.     

Effects of liming on nutrient limitation of epilithic algae in an acid lake

The processes of lake acidification and lake restoration frequently involve major changes in DIC and DIN, both of which may potentially limit algal growth. We evaluate nutrient limitation of benthic algal biomass and species abundances during summers 1987 and 1989, before and after the liming of Lake Earnest (NE Pennsylvania) in November 1988. Limestone addition caused immediate increases in pH from 4.7 to 7.2. Alkalinity was ?34 μeq L^?1 in summer 1987, but rose to 620 μeq L^?1 in summer 1989, whereas DIN declined from 10.7 μmol L^?1 to 1.1 μmol L^?1 The algae were sampled after 45 to 46 d from clay flower pot substrates diffusing combinations of N, P and C. Algal biomass was strongly C-limited in 1987, but NP-limited in 1989. Mougeotia sp., which comprised >99% of total algal biovolume prior to liming, declined to < 1% of the community on control substrates, while Oedogonium sp. increased to 43% of total biovolume in 1989. The stimulation of chlorophyll-a accrual with C-enrichment during 1987 was consistent with the later increase in chlorophyll-a on control substrates following liming. Species enhanced by the diffused nutrients, however, generally differed from those which dominated the natural community.     

Temporal and Elevation-Related Variability in Precipitation Chemistry from 1993 to 2002, Eastern Erzgebirge, Germany

The Erzgebirge, part of the so-called former “Black Triangle”, used to represent the strongest regional air pollution of Central Europe. To test the hypothesis of deposition enhancement with height, an altitudinal gradient along a N-S transect from the Elbe river lowlands to the Erzgebirge summit was chosen to investigate chemical composition, elevation-related variability, temporal changes, and seasonal patterns of ion concentrations from 1993 to 2002. The following questions were to be answered: (1) Which role does orography play on the composition of precipitation?, (2) Does fog occurrence overrule the orographic influence?, (3) Are there changes in the past 10 years, and if so, why?, (4) Do relevant seasonal changes occur and why? Air streams from westerly and to a lesser degree south-easterly directions prevail. The average precipitation was ion-poor (23 μS cm^?1 and acidic (pH 4.5). Sulphate still was the dominant anion (52.3–59.9 μeq L^?1, while NH⁺ ₄ determined the cations (41.9–62.2 μeq L^?1. Ion concentrations decreased with altitude to about 735 m a.s.l. and subsequently increased. The seeder-feeder effect largely explains the chemical composition of precipitation; enhanced in winter through snow crystals. Sub-cloud scavenging does not explain the observed patterns. Fog occurrence enhanced the observed effects at higher altitudes. Deposition amounts doubled from the lowlands to the Erzgebirge summit. From 1993 to 2002, acidity decreased by about 50%, mainly due to reduced SO₂ -emissions.     

The contribution of stone cover to biological activity in the Negev desert,Israel

Ancient valley agriculture in the northern Negev highlands was based on the principle of directed collection of water and eroded material from the slopes and their consequent flow towards the valleys. The stones on these slopes were therefore removed and/or collected into piles known as ‘grape mounds’. The aim of this study was to understand the contribution of stone cover and slope‐facing to biological activity in soil. Soil samples from a depth of 0–5 mm from the soil surface were collected during the study period (December 1994–March 1996) from northern and southern hill slopes, from under limestones and between stones. Soil moisture, organic matter, chlorophyll‐a and soil respiration were determined. The results obtained in field and laboratory studies demonstrated differences between the northern and southern slopes. The stone cover on the northern slope made up 33 per cent and in the southern slope 23 per cent, stone size ranging from 15–50 cm² and 15–35 cm², respectively. Soil moisture content varied from 12 per cent in December 1994 on both slopes to one‐quarter of the initial value during the dry period. Organic matter content reached a maximal level of 14 per cent and 16 per cent on the northern and southern slopes, respectively. Values of chlorophyll‐a on both the northern and southern slopes were 0.38 μg g⁻¹ dry soil during the wet season, decreasing to 0.05 μg g⁻¹ dry soil during the dry period. Soil samples from under the stones on both slopes produced high levels of CO₂, ranging between 50 and 100 μg CO₂ g;⁻¹ dry soil h⁻¹, whereas in the control samples the levels ranged between 30 and 70 μg CO₂ g⁻¹ dry soil h⁻¹. In conclusion, the stone cover apparently plays an important role in the maintenance of biological activity through its contribution to slope biotope stability. Copyright © 2001 John Wiley & Sons, Ltd.     

Behavior of Iodine in a Forest Plot,an Upland Field and a Paddy Field in the Upland Area of Tsukuba,Japan. Iodine Concentration in Precipitation,Irrigation Water,Ponding Water and Soil Water to a Depth of 2.5 m

In the course of a series of studies conducted to investigate the long-term behavior of ¹²⁹I (which has a half-life of 16 million years) in the environment, the concentration of stable iodine (¹²⁷I) in precipitation, irrigation water and soil water to a depth of 2.5 m in a forest plot, an upland field and a paddy field in the upland area of Tsukuba, Japan, was determined. In the forest plot, the mean iodine concentrations in soil water at all the depths ranged from 0.13 to 0.21 μg L^?1, about one-tenth of the values recorded in precipitation (weighted mean 2.1 μg L^?1). This finding suggests that the major part of iodine in precipitation was sorbed onto the surface soil horizon under oxidative conditions. In the upland field, the mean iodine concentration in soil water was 2.2 μg L^?1 at a depth of 0.2 m and it decreased to 0.34–0.44 μg L^?1 at a depth of 0.5 m or more; these concentrations were about one-fifth of that in precipitation. This suggested that the major part of the iodine derived from precipitation was sorbed onto the subsurface soil horizon (at depths between 0.2 and 0.5 m). In the paddy field, during the non-irrigation period, the mean iodine concentrations in soil water at all the depths ranged from 1.8 to 4.8 μg L^?1, almost the same values as those recorded in precipitation. During the irrigation period, the mean iodine concentrations at depths of 0.2 and 0.5 m were 18.8 and 16.7 μg L^?1, values higher than the 10.9 μg L^?1 value recorded in irrigation water and the 11.8 μg L^?1 value recorded in ponding water. However, at a depth of 1.0 m or more, the mean iodine concentrations in soil water rapidly decreased from 7.3 to 1.8 μg L^?1. These data suggested that a significant amount of iodine flowed out from the paddy field by surface runoff and a considerable amount of iodine that leached to a depth of 0.5 m was retained onto the mildly oxidative soil horizon (2Bw) that lay at depths between 0.5 and 1.0 m. At a depth of 2.5 m in the paddy field, the mean iodine concentration in soil water decreased to 1.8 μg L^?1, but this level was much higher than those in the forest plot and upland field at the same depth, which suggested that a significant amount of iodine had leached into the groundwater-bearing layer. There was a negative correlation (r=-0.889) between the E_h of soil and the iodine concentration in soil water (0.2 m depth) of the paddy field. Particularly, when the E_h of soil fell below approximately 150 mV, the iodine concentration rapidly increased to above 10μg L^?1. As for the chemical forms of iodine in precipitation, irrigation water, ponding water and soil water during the winter irrigation period in the paddy field with oxidative conditions, 58–82% of iodine consisted of IO^? ₃ and 17–42% of iodine consisted of I^?. In the soil water during the summer irrigation period in the paddy field under reductive conditions, 52–58% of iodine consisted of I^?, and 42–47% consisted of IO^? ₃.     

Chloride cycling in two forested lake watersheds in the west-central adirondack mountains,New York,U.S.A.

The chemistry of precipitation, throughfall, soil water, ground water, and surface water was evaluated in two forested lake-watersheds over a 4-yr period to assess factors controlling Cl^? cycling. Results indicate that Cl^? cycling in these watersheds is more complex than the generally held view of the rapid transport of atmospherically derived Cl^? through the excosystem. The annual throughfall Cl^? flux for individual species in the northern hardwood forest was 2 to 5 times that of precipitation (56 eq ha^?1), whereas the Na⁺ throughfall flux, in general, was similar to the precipitation flux. Concentrations of soil-water Cl^? sampled from ceramic tension lysimeters at 20 cm below land surface generally exceeded the Na⁺ concentrations and averaged 31 μeq L^?1, the highest of any waters sampled in the watersheds, except throughfall under red spruce which averaged 34 μeq L^?1. Chloride was concentrated prior to storms and mobilized rapidly during storms as suggested by increases in streamwater Cl^? concentrations with increasing flow. Major sources of Cl^? in both watersheds are the forest floor and hornblende weathering in the soils and till. In the Panther Lake watershed, which contains mainly thick deposits of till (>3 m), hornblende weathering results in a net Cl^? flux 3 times greater than that in the Woods Lake watershed, which contains mainly thin deposits of till. The estimated accumulation rate of Cl^? in the biomass of the two watersheds was comparable to the precipitation Cl^? flux.     

Mechanisms of deposition of methylmercury and mercury to coniferous forests

Deposition of methylmercury (MeHg) and mercury (Hg) to a coniferous forest have been investigated using field measurements. Samples of open field (OF) wet deposition, throughfall (TF) and litterfall (LF) have been collected and analyzed for MeHg and Hg during the period November 1991 to April 1994. Average concentrations in TF were 22.8 and 0.38 ng L^?1, for Hg and MeHg, respectively. Concentrations in OF precipitation were 11.9 and 0.37 ng L^?1, for Hg and MeHg, respectively, during the same period. Considerable differences were found for Hg in TF and OF which was attributed to a dry deposition of Hg. Hg in LF contributes a deposition of equal size as in TF. The relations between OF, TF and total Hg deposition were approximately 1∶1,5∶3. A decrease in OF Hg was found over the three year period studied. MeHg deposition in OF was also found to decrease during the same period whereas the TF MeHg showed a slight increase. Dry deposition of MeHg is also an important process in a coniferous forest although the flux to the forest floor is not via TF but rather as MeHg in LF.     

Precipitation chemistry at sinhagad-a hill station in India

The chemistry of precipitation in remote sites such as mountain tops is of interest in the study of atmospheric pollution and acid rain. The chemical composition measured at mountain site which is away from industrial and urban areas is useful as a reference level and it allows to determine the extent of anthropogenic contamination. Hence, rain water samples were collected at Sinhagad (18°21N, 73°45E, 1450 m asl during the monsoon season (June-September) of 1992 and were analysed for major ions. The precipitation samples collected at Sinhagad were alkaline in nature and pH values ranged between 5.9 to 6.76. The ionic composition was dominated by soil dust The concentration of Ca²⁺ was highest among all the ions. The concentrations of excess SO₃ ^2– and NO₄ ^– were small (23.8 and 15.2 eq l^–1 respectively) compared to the values of polluted regions in India. The correlation coefficient between the ions and pH values was calculated and it was found to be maximum in case of Ca²⁺. Precipitation samples collected at Sinhagad were alkaline owing to higher concentration of Ca²⁺ and lower levels of acidic pollutants (SO₄ ^2– and NO₃ ^–).     

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.