Mechanisms of episodic acidification in low-order streams in Maine, USA

Five factors contribute to episodic depressions in pH and ANC during hydrologic events in low-order streams in Maine: (1) increases of up to 50 microeq litre(-1) NO3; (2) increases of up to 75 microeq litre(-1) organic acidity; (3) increases of as much as 0.3 in the anion fraction of SO4; (4) as much as 100 microeq litre(-1) acidity generated by the salt-effect in soils; and (5) typically < or = 40% dilution by increased discharge. In conjunction with increased discharge, factors 1, 2 or 4 appear necessary to depress pH to less than 5.0. The chemistry of individual precipitation events is irrelevant to the generation of acidic episodes, except those caused by high loading of neutral salts in coastal regions. Increases in discharge, but not necessarily in dilution of solutes, in combination with the chronically high SO4 from atmospheric deposition, provide the antecedent chemical conditions for episodic acidification. Differences in antecedent moisture conditions determine the processes that control output of either ANC or acidifying agents to aquatic systems.     

Hydrogen behaviour and ion concentrations in precipitation of Europe and the United States

Hydrogen ions in precipitation vary primarily with (SO4 + NO3) concentration. However the slope of the H: (SO4 + NO3) relation for high concentrations (0.60 and 0.61) is twice that at low concentrations (0.32 and 0.22) in European and US samples respectively. Sulphuric and nitric acid dominate precipitation in the US. Precipitation in Europe, although nearly equally acid, is dominated by NH4+, Ca2+, and Mg2+ salts at total ionic concentrations 2 and 3 times higher. Ion concentrations in precipitation, other than H, are proportional to their respective emission fluxes.     

Geographic distribution of selected elements in the livers of polar bears from Greenland, Canada and the United States

To assess geographic distributions of elements in the Arctic we compared essential and non-essential elements in the livers of polar bears (Ursus maritimus) collected from five regions within Canada in 2002, in Alaska between 1994 and 1999 and from the northwest and east coasts of Greenland between 1988 and 2000. As, Hg, Pb and Se varied with age, and Co and Zn with gender, which limited spatial comparisons across all populations to Cd, which was highest in Greenland bears. Collectively, geographic relationships appeared similar to past studies with little change in concentration over time in Canada and Greenland for most elements; Hg and Se were higher in some Canadian populations in 2002 as compared to 1982 and 1984. Concentrations of most elements in the polar bears did not exceed toxicity thresholds, although Cd and Hg exceeded levels correlated with the formation of hepatic lesions in laboratory animals.     

Water chemistry and fish community responses to episodic stream acidification in Pennsylvania, USA

Five streams were studied on the Northern Appalachian Plateau of Pennsylvania from October 1988 through June 1989 to determine chemical changes that occur during episodic storm run-off and the responses of fish to these events. These second-order streams flowed through undisturbed, wooded, sandstone bedrock catchments with surface areas ranging from 500 to 1000 hectares. Median pH of precipitations was about 4.2, and among streams it ranged from 5.0 to 6.2. During storm events, pH declined by as much as 1.2 units and peak concentrations of total monomeric Al ranged from < 0.01 to 0.75 mg litre(-1). Organically bound A1 was generally a minor component of total monomeric A1. Wild brook trout (Salvelinus fontinalis) were found in all streams, although only a remnant population existed in the most acidic stream. Sculpins (Cottus bairdi or C. cognatus) were collected only in the two streams with the least severe episodes. Mortality of brook trout and sculpins in in situ bioassays ranged from 0 to about 80% among streams during acidic episodes and was positively related to concentrations of total dissolved Al. Radio-tagged brook trout moved downstream during episodes when Al reached toxic concentrations. Some displaced trout were found near groundwater seeps, where pH was higher and dissolved Al was lower than in the main channel.     

Annual anthropogenic pollutant emissions in the United States and Southern Canada east of the Rocky Mountains

Annual anthropogenic pollutant emissions of sulfur dioxide, nitrogen oxides, and hydrocarbons from point and area sources were apportioned to 80-km grid squares on a 35 × 30 grid network. The grid network was superimposed on a polar stereographic projection map true at 60°N. The domain of the network included southern Canada and the United States east of the Rocky Mountains, excluding southern Texas and northern New England.The emissions data were obtained from the 1977 United States Environmental Protection Agency's National Emissions Data System (NEDS) file as well as from data compiled by the Ontario Ministry of the Environment and Environment Canada. These emission inventories, the design of the gridding procedures, and the major source classifications responsible for much of the emissions are discussed.     

Modelling episodic acidification of surface waters: the state of science

Field studies of chemical changes in surface waters associated with rainfall and snowmelt events have provided evidence of episodic acidification of lakes and streams in Europe and North America. Modelling these chemical changes is particularly challenging because of the variability associated with hydrological transport and chemical transformation processes in catchments. This paper provides a review of mathematical models that have been applied to the problem of episodic acidification. Several empirical approaches, including regression models, mixing models and time series models, support a strong hydrological interpretation of episodic acidification. Regional application of several models has suggested that acidic episodes (in which the acid neutralizing capacity becomes negative) are relatively common in surface waters in several regions of the US that receive acid deposition. Results from physically based models have suggested a lack of understanding of hydrological flowpaths, hydraulic residence times and biogeochemical reactions, particularly those involving aluminum. The ability to better predict episodic chemical responses of surface waters is thus dependent upon elucidation of these and other physical and chemical processes.     

Source areas contributing to the episodic acidification of a forested headwater stream

A study was initiated on the Leading Ridge Experimental Watersheds in central Pennsylvania to investigate the extent to which episodic depressions of streamwater pH result from direct channel interception of acidified rainwaters and from rapid subsurface stormflow. During a 4.78-cm rainfall event on June 6, 1986, stream pH declined from 5.93 to 5.46. Analysis of the storm hydrograph indicated that direct channel interception accounted for only 2.8% of the total stormflow volume but contributed 40% of the total increase in the concentration of H⁺. At peak flow, channel interception accounted for 5.7% of the stormflow volume and 72% of H⁺. Large increases in the height of the saturated soil zone and coinciding increases in H⁺ concentrations in soilwater were measured at a number of soilwater observation wells. These fluctuations occurred almost simultaneously with measured fluctuations in both streamflow and streamwater H⁺ concentrations, indicating direct interactions between saturated soilwater and the storm discharge. These results indicate that cathcments in which soil macropores permit rapid subsurface flow could be especially susceptible to stream acidification.     

Application of four watershed acidification models to Batchawana Watershed, Canada

Four watershed acidification models (TMWAM, ETD, ILWAS, and RAINS) are reviewed and a comparison of model performance is presented for a common watershed. The models have been used to simulate the dynamics of water quantity and quality at Batchawana Watershed, Canada, a sub-basin of the Turkey Lakes Watershed. The computed results are compared with observed data for a four-year period (Jan. 1981-Dec. 1984). The models exhibit a significant range in the ability to simulate the daily, monthly and seasonal changes present in the observed data. Monthly watershed outflows and lake chemistry predictions are compared to observed data. pH and ANC are the only two chemical parameters common to all four models. Coefficient of efficiency (E), linear (r) and rank (R) correlation coefficients, and regression slope (s) are used to compare the goodness of fit of the simulated with the observed data. The ILWAS, TMWAM and RAINS models performed very well in predicting the monthly flows, with values of r and R of approximately 0.98. The ETD model also showed strong correlations with linear (r) and rank (R) correlation coefficients of 0.896 and 0.892, respectively. The results of the analyses showed that TMWAM provided the best simulation of pH (E=0.264, r=0.648), which is slightly better than ETD (E=0.240, r=0.549), and much better than ILWAS (E=-2.965, r=0.293), and RAINS (E=-4.004, r=0.473). ETD was found to be superior in predicting ANC (E=0.608, r=0.781) as compared to TMWAM (E=0.340, r=0.598), ILWAS (E=0.275, r=0.442), and RAINS (E=-1.048, r=0.356). The TMWAM model adequately simulated SO4 over the four-year period (E=0.423, r=0.682) but the ETD (E=-0.904, r=0.274), ILWAS (E=-4.314, r=0.488), and RAINS (E=-6.479, r=0.126) models all performed poorer than the benchmark model (mean observed value).     

Dynamic modelling of recovery from acidification of lakes in Killarney Park,Ontario, Canada

During much of the 1900s, the lakes in Killarney Provincial Park have been exposed to high levels of acid deposition due to sulfur emissions from the nearby metal smelters in Sudbury. The sulfur emissions from this large point source have decreased to about 10% of what they were in the 1960s. Lake water quality in Killarney Park has greatly changed in response to reduced emissions, with noticeable declines in sulfate, aluminum and calcium concentrations. Here we apply the dynamic acidification model MAGIC to 3 lakes in Killarney Park. The lakes, which have different buffering capacities and response times, were selected to represent fast, intermediate and slow recovery from acidification. The model was calibrated to match observed data for the lakes and 4 different forecast scenarios for future sulfur deposition reductions were applied. The results indicate that there is still a large potential for improvement in the water quality in Killarney. The recovery time for the different lakes varies greatly. For the lake having the slowest response time several decades are needed for the chemistry to stabilize after implementation of deposition reductions.     

Influence of atmospheric dispersion and new particle formation events on ambient particle number concentration in Rochester, United States, and Toronto, Canada

Continuous measurements of particle number concentrations were performed in Rochester, NY, and Toronto, Ontario, Canada during the 2003 calendar year. Strong seasonal dependency in particle number concentration was observed at two sites. The average number concentration of ambient particles was 9670 +/- 6960 cm(-3) in Rochester, whereas in Toronto the average number of particles was 28,010 +/- 13,350 cm(-3). The particle number concentrations were higher in winter months than in summer months by a factor of 1.5 in Rochester and 1.6 in Toronto. In general, there were also distinct diurnal variations of aerosol number concentration. The highest weekdays/weekends ratio of number concentration was typically observed during the rush-hour period in winter months with a ratio of 2.1 in Rochester and 2.0 in Toronto. The correlation in the total particle number concentrations between the two urban sites was stronger in winter because of the common urban traffic patterns, but weaker in summer because of local sulfur dioxide (SO2)-related particle formation events in Rochester in the summer. Strong morning particle formation events were frequently observed during colder winter months. Good correlations between particle number and carbon monoxide (CO) as well as temperature suggested that motorvehicle emissions lead to the formation of new particles as the exhaust mixes with the cold air. Regional nucleation and growth events frequently occurred in April. Local SO2-related particle formation events most frequently occurred in August. SO2 and UV-B were highly correlated with particle concentration, suggesting a high association of photochemical processes with these local events. A high directionality in a northerly direction was observed for particle number and SO2, indicating the influence of point sources located north of Rochester.     

Persistent episodic acidification of streams linked to acid rain effects on soil

Episodic acidification of streams, identified in the late 1980s as one of the most significant environmental problems caused by acidic deposition, had not been evaluated since the early 1990s despite decreasing levels of acidic deposition over the past decade. This analysis indicates that episodic acidification of streams in upland regions in the northeastern United States persists, and is likely to be much more widespread than chronic acidification. Depletion of exchangeable Ca in the mineral soil has decreased the neutralization capacity of soils and increased the role of the surface organic horizon in the neutralization of acidic soil water during episodes. Increased accumulation of N and S in the forest floor from decades of acidic deposition will delay the recovery of soil base status, and therefore, the elimination of acidic episodes, which is anticipated from decreasing emissions.     

Towards a model of acidification effects on waterfowl in Eastern Canada

Data from 212 lakes in central Ontario were used to examine the relationship between presence of breeding waterfowl and loons and the following lake characteristics: pH, presence of fish, lake area, dissolved organic carbon (DOC) and total phosphorus (TP) concentration. In univariate analyses, the two fish-eating species preferred large, high pH lakes with fish, while insectivorous species showed little consistent pattern of lake association. Logistic regression analyses confirmed that large lake size and presence of fish were important determinants of presence of piscivores, though the residual effect of pH differed between the two species. Broods of three of the four insectivorous species avoided lakes with fish, and independently showed a positive response to pH. By calculating the probability that fish will be present on a lake of given area and pH, it is possible to estimate the net effect of pH change on these waterfowl. Relationships such as those presented here can, with some assumptions, be linked to models of lake acidification to estimate response of waterfowl to predicted changes in acidic deposition.     

Ozone in the urban southeastern United States

Ozone measurements (daily maximum values) from the Aerometric Information Retrieval System database are analyzed for selected sites, during 1980 to 1988, in southeastern USA. Frequency distributions, for most sites during most years, show a typical bell-shaped curve with the higher frequency around the yearly daily maximum ozone mean of about 100 to about 110 microg m(-3) (50-55 ppbv). Abnormal years in ozone concentration may skew the distribution as the mean shifts. A correlation of daily maximum ozone concentrations above 140 microg m(-3) (70 ppbv) between sites shows a division between the sites in the northern protion of the region and those in the southern portion of the region. Variations in ozone levels are well correlated over distances of several hundred kilometers, suggesting that high values are associated with synoptic scale episodes. An ozone exposure analysis also shows higher ozone exposures (250-300 ppm days) in the northerly sites as compared to the southerly sites (150-170 ppm days).     

Rural ozone in the southeastern United States

Ozone measurements are reported for five rural sites in the Tennessee Valley region of the southeastern U.S. for periods ranging from 18 to 83 months during the years 1977 through 1984. Rural ozone (O₃) levels were found to equal or exceed urban values for the same region. The daily maximum 1-h average concentration was found to peak during the summer months, while the 24-h average concentrations were greatest in the spring. The annual cycle of daily maximum concentrations is related to the seasonal photochemical cycle. The annual cycle in 24-h average concentrations is best explained by the combined effects of the annual cycles in solar intensity and noctural O₃ depletion. There was no indication that stratospheric intrusions exhibited a significant influence on the annual O₃ cycles. Evidence was found for elevated O₃ levels during touchdown of plumes from large power plants. No long-term trend in rural O₃ concentrations, either daily maxima or means, was discernible.     

A Comparison of Measured and Simulated Ozone Concentrations in the Rural Areas of the Eastern United States during Summer 1995

ABSTRACT

The recent regulatory actions toward a longer-term (i.e., 8-hr) average ozone standard have brought forth the potential for many rural areas in the eastern United States to be in noncompliance. However, since a majority of these rural areas have generally few sources of anthropogenic emissions, the measured ozone levels primarily reflect the effects of the transport of ozone and its precursor pollutants and natural emissions. While photochemical grid models have been applied to urban areas to develop ozone mitigation measures, these efforts have been limited to high ozone episode events only and do not adequately cover rural regions. In this study, we applied a photochemical modeling system, RAMS/UAM-V, to the eastern United States from June 1-August 31, 1995. The purpose of the study is to examine the predictive ability of the modeling system at rural monitoring stations that are part of the Clean Air Status Trends Network (CASTNet) and the Gaseous Pollutant Monitoring Program (GPMP).

The results show that the measured daily 1-hr ozone maxima and the seasonal average of the daily 1-hr ozone maxima are in better agreement with the predictions of the modeling system than those for the daily 8-hr ozone maxima. Also, the response of the modeling system in reproducing the measured range of ozone levels over the diurnal cycle is poor, suggesting the need for improvement in the treatment of the physical and chemical processes of the modeling system during the nighttime and morning hours if it is to be used to address the 8-hr ozone standard.     

The Gas Supply Situation in the United States

The body of information presented in this paper is directed to those individuals who require information on the present natural gas supply and demand relationship and the prospects for future changes, including individuals concerned with air quality control and the use of natural gas for combating air pollution.

If natural gas could continue to capture large shares of the energy market, as in the past when supply was not a growth inhibiting factor, annual demand for gas is projected to increase to 34.5 and 46.4 trillion cubic feet in 1980 and 1990, respectively. Annual production levels which could be supported by presently proven reserves and anticipated future reserve additions are estimated to peak in the mid-1970’s and decline to about 18 trillion cubic feet in 1990.

When viewed from the perspective of anticipated indigenous supply deficiencies, the acquisition of supplemental sources of gas becomes of paramount importance. Pipeline imports, the only substantive supplemental source presently available, could almost double by 1980 and be about 2 trillion cubic feet annually in 1990.

Available volumes of gas from Alaska could be 0.7 trillion cubic feet in 1980 and could increase to 2.3 trillion cubic feet annually by 1990. Actual initial deliveries of gas are inextricably related to construction of an oil pipeline from Prudhoe Bay. Construction delays postpone initial delivery dates for gas as well as oil.

Advancements in cryogenic transportation and storage technologies have made the heretofore largely untapped supplies of gas from several countries with limited internal markets available to the United States as LNG. Annual LNG imports could be about 0.3 trillion cubic feet in 1975 and perhaps 2 and 4 trillion cubic feet by 1980 and 1990, respectively.

Pipeline quality gas from coal presents the prospect for a supplemental source of gaseous fuel independent of foreign sources and free from balance of payments problems. The first pipeline quality gas from coal may be expected by 1976, and by 1980 perhaps 0.3 trillion cubic feet could be provided annually from this source; in 1990, 3.3 trillion cubic feet might be available. An additional, but presently unqualified, source of synthetic gas will be the conversion of liquid hydrocarbons.

In the aggregate, supplemental gas supplies are anticipated to total about 4.6 and 11.5 trillion cubic feet annually by 1980 and 1990, respectively. While demand for gas is anticipated to increase, domestic conventional gas production is projected to peak in the mid-1970’s and decrease somewhat thereafter. As a consequence, a continuing gas supply-demand imbalance is anticipated.     

Spatial and temporal trends of precipitation chemistry in the United States, 1985-2002

A Seasonal Kendall Trend (SKT) test was applied to precipitation-weighted concentration data from 164 National Atmospheric Deposition Program National Trends Network (NADP/NTN) sites operational from 1985 to 2002. Analyses were performed on concentrations of ammonium, sulfate, nitrate, dissolved inorganic nitrogen (DIN, sum of nitrogen from nitrate and ammonium), and earth crustal cations (ECC, sum of calcium, magnesium, and potassium). Over the 18-year period, statistically significant (p< or =0.10) increases in ammonium concentrations occurred at 93 sites (58%), while just three sites had statistically significant ammonium decreases. Central and northern Midwestern states had the largest ammonium increases. The generally higher ammonium concentrations were accompanied by significant sulfate decreases (139 sites, 85%), and only one significant increase which occurred in Texas. In the west central United States there were significant nitrate increases (45 sites, 27%), while in the northeastern United States there were significant decreases (25 sites, 15%). Significant DIN decreases were observed in the northeastern United States (11 sites, 7%); elsewhere there were significant increases at 75 sites (46%). ECC decreased significantly at 65 sites (40%), predominantly in the central and southern United States, and increased at 11 sites (7%). The concentrations of sulfate, nitrate, and ammonium in precipitation have changed markedly over the time period studied. Such trends indicate changes in the mix of gases and particles scavenged by precipitation, possibly reflecting changes in emissions, atmospheric chemical transformations, and weather patterns.