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Predicting watershed acidification under alternate rainfall conditions

The effect of alternate rainfall scenarios on acidification of a forested watershed subjected to chronic acidic deposition was assessed using the model of acidification of groundwater in catchments (MAGIC). The model was calibrated at the Panola Mountain Research Watershed, near Atlanta, Georgia, U.S.A. using measured soil properties, wet and dry deposition, and modeled hydrologic routing. Model forecast simulations were evaluated to compare alternate temporal averaging of rainfall inputs and variations in rainfall amount and seasonal distribution. Soil water alkalinity was predicted to decrease to substantially lower concentrations under lower rainfall compared with current or higher rainfall conditions. Soil water alkalinity was also predicted to decrease to lower levels when the majority of rainfall occurred during the growing season compared with other rainfall distributions. Changes in rainfall distribution that result in decreases in net soil water flux will temporarily delay acidification. Ultimately, however, decreased soil water flux will result in larger increases in soil- adsorbed sulfur and soil-water sulfate concentrations and decreases in alkalinity when compared to higher water flux conditions. Potential climate change resulting in significant changes in rainfall amounts, seasonal distribution of rainfall, or evapotranspiration will change net soil water flux and, consequently, will affect the dynamics of the acidification response to continued sulfate loading.

Water, Air, & Soil Pollution

Volatilization of ketones from water

The overall mass-transfer coefficients for the volatilization from water of acetone, 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-heptanone, and 2-octanone were measured simultaneously with the oxygen-absorption coefficient in a laboratory stirred water bath. The liquid-film and gas-film coefficients of the two-film model were determined for the ketones from the overall coefficients, and both film resistances were important for volatilization of the ketones. The liquid-film coefficients for the ketones varied with the 0.719 power of the molecular-diffusion coefficient, in agreement with the literature. The liquid-film coefficients showed a variable dependence on molecular weight, with the dependence ranging from the −0.263 power for acetone to the −0.378 power for 2-octanone. This is in contrast with the literature where a constant −0.500 power dependence on the molecular weight is assumed. The gas-film coefficients for the ketones showed no dependence on molecular weight, in contrast with the literature where a −0.500 power is assumed.

Water, Air, & Soil Pollution

Hydrologic pathways and chemical composition of runoff during snowmelt in Loch Vale Watershed, Rocky Mountain National Park, Colorado, USA

Intensive sampling of a stream draining an alpine-subalpine basin revealed that depressions in pH and acid neutralizing capacity (ANC) of surface water at the beginning of the spring snowmelt in 1987 and 1988 were not accompanied by increases in strong acid anions, and that surface waters did not become acidic (ANC<0). Samples of meltwater collected at the base of the snowpack in 1987 were acidic and exhibited distinct ‘pulses’ of nitrate and sulfate. Solutions collected with lysimeters in forest soils adjacent to the stream revealed high levels of dissolved organic carbon (DOC) and total Al. Peaks in concentration of DOC, Al, and nutrient species in the stream samples indicate a flush of soil solution into the surface water at the beginning of the melt. Infiltration of meltwater into soils and spatial heterogeneity in the timing of melting across the basin prevented stream and lake waters from becoming acidic.

Colorado

The association of water chemistry variables and fish condition in streams of Shenandoah National Park (USA)

As part of the “Shenandoah National Park: Fish in Sensitive Habitats” (SNP:FISH) project, the blacknose dace ( Rhinichthys atratulus ) was utilized as an indicator species to assess the susceptibility of the ichthyofaunal community of Shenandoah National Park (USA) to acidification. Water chemistry (ANC, conductivity, pH, and concentrations of Ca 2+ , Mg 2+ , Na + , K + , Cl − , NO 3 − , SO 4 2− , and SiO 2 ) was sampled every three months over the course of 3 1/4 years which represents the probable maximum lifetime of R atratulus. Condition factors (K=[g/mm 3 ] * 10 6 ) were calculated for samples of fish (age class 2+ yr; n=370) from nine montane, second/third order streams representing a range of ANCs. A principle components regression was performed on factor scores from a principle components analysis of the water chemistry variables and fish condition factor. Two factors, one associated with stream water ANC and ion concentrations, and another associated with SO 4 2− concentration, collectively explained 84% of the variance in condition factor. The influence of variables other than water chemistry upon R atratulus K is addressed. The results show that environmental chemistry is highly associated with the K of R atratulus.

Shenandoah National Park

Metal concentration in the gill, gastrointestinal tract, and carcass of white suckers ( Catostomus commersoni ) in relation to lake acidity

Adult white suckers were collected from four lakes in Maine that ranged in pH from 7.0 to 5.4. The gastrointestinal tract and remainder of the carcass of fishes of similar age and size from each lake, and gills from additional fishes of similar size, were analyzed for Al, Cd, Pb, and Zn. Carcasses were also analyzed for Hg. Concentrations of Al, Cd, and Pb were highest in the gastrointestinal tract and lowest in the carcass; Zn concentration was highest in the gill. For carcass, all metals except Al differed significantly among lakes, for gill tissue Cd and Pb differed, and for gastrointestinal tract, only Cd differed among lakes. Where differences were significant, patterns among lakes were similar in each tissue analyzed. Concentrations of Cd, Hg, and Pb were negatively correlated with lake water pH, acid neutralizing capacity (ANC), Ca, and lake:watershed area, and positively correlated with lake water SO 4 , indicating that concentrations were higher in fish from more acidic lakes. Zinc concentrations in gills were unrelated to lake acidity, and carcass concentrations were higher in the less acidic lakes, which is the opposite of the pattern for the other metals studied. Zinc in gastrointestinal tract did not differ among lakes. Although the lakes we studied were located in undisturbed watersheds and did not receive any point source discharges, fish metal concentrations were comparable to or higher than those reported from waters receiving industrial discharges.

Water, Air, & Soil Pollution

Chemical characteristics and temporal trends in eight streams of the Catskill Mountains, New York

Discharge to concentration relationships for eight streams studied by the U.S. Geological Survey (USGS) as part of the U.S. Environmental Protection Agency's (U.S. EPA) Long-Term Monitoring Project (1983-89) indicate acidification of some streams by H2SO4 and HNO3 in atmospheric deposition and by organic acids in soils. Concentrations of major ions in precipitation were similar to those reported at other sites in the northeastern United States. Average concentrations of SO42- and NO3- were similar among streams, but base cation concentrations differed widely, and these differences paralleled the differences in acid neutralizing capacity (ANC). Baseflow ANC is not a reliable predictor of stream acidity at high flow; some streams with high baseflow ANC (> 150 ??eq L-1) declined to near zero ANC at high flow, and one stream with low baseflow ANC (< 50 ??eq L-1) did not approach zero ANC as flow increased. Episodic decreases in ANC and pH during peak flows were associated with increased concentrations of NO3- and dissolved organic carbon (DOC). Aluminum concentrations exceeding 300 ??g L-1 were observed during peak flows in headwater streams of the Neversink River and Rondout Creek. Seasonal Kendall Tau tests for temporal trends indicate that SO42- concentrations in streamwater generally decreased and NO3- concentrations increased during the period 1983-1989. Combined acid anion concentrations (SO42- + NO3-) were generally unchanged throughout the period of record, indicating both that the status of these streams with respect to acidic deposition is unchanged, and that NO3- is gradually replacing SO42- as the dominant acid anion in the Catskill streams.Discharge to concentration relationships for eight streams studied by the US Geological Survey (USGS) as part of the Environmental Protection Agency's (US EPA) Long-term monitoring project (19831-89) indicate acidification of some streams by H2SO4 and HNO3 in atmospheric deposition and by organic acids in soils. Concentrations of major ions in precipitations were similar to those reported at other sites in the northeastern United States. Average concentrations of SO42- and No3- were similar among streams, but base cation concentrations differed widely, and these differences parallelel the differences in acid neutralizing capacity (ANC).

Water, Air, & Soil Pollution

Soil-solution chemistry in a low-elevation spruce-fir ecosystem, Howland, Maine

Soil solutions were collected monthly by tension and zero-tension lysimeters in a low-elevation red spruce stand in east-central Maine from May 1987 through December 1992. Soil solutions collected by Oa tension lysimeters had higher concentrations of most constituents than the Oa zero-tension lysimeters. In Oa horizon soil solutions growing season concentrations for SO 4 , Ca, and Mg averaged 57, 43, and 30 μmol L −1 in tension lysimeters, and 43, 28, and 19 μmol L −1 in zero-tension lysimeters, respectively. Because tension lysimeters remove water held by the soil at tensions up to 10 kPa, solutions are assumed to have more time to react with the soil compared to freely draining solutions collected by zero-tension lysimeters. Solutions collected in the Bs horizon by both types of collectors were similar which was attributed to the frequency of time periods when the water table was above the Bs lysimeters. Concentrations of SO 4 and NO 3 at this site were lower than concentrations reported for most other eastern U.S. spruce-fir sites, but base cation concentrations fell in the same range. Aluminum concentrations in this study were also lower than reported for other sites in the eastern U.S. and Ca/Al ratios did not suggest inhibition of Ca uptake by roots. Concentrations of SO 4 , Ca, K, and Cl decreased significantly in both the Oa and Bs horizons over the 56-month sampling period, which could reflect decreasing deposition rates for sulfur and base cations, climatic influences, or natural variation. A longer record of measured fluxes will be needed to adequately define temporal trends in solution chemistry and their causes.

Maine

Occurrence of active and inactive herbicide ingredients at selected sites in Iowa

The objective of this study was to investigate the occurrence of herbicide active and inactive ingredients (primarily volatile organic compounds) at four selected sites in Iowa representing drain tiles, observation wells, or lysimeters. Water samples were collected monthly and bi-monthly before and after herbicide applications in 1991, respectively. They were analyzed for seven herbicides and 32 volatile organic compounds using methods recommended by the U.S. Environmental Protection Agency. Commercially available herbicide formulations also were obtained and analyzed for volatile organic compounds. Herbicides were detected in 50% of water samples, ranging from 78% of water samples from the Ames site to 25% from the Walnut Creek site. Among herbicides detected, listed in decreasing order of frequency, were atrazine > alachlor > cyanazine > metolachlor > metribuzin. Volatile organic compounds were detected in 11% of water samples. Among the compounds detected, listed in decreasing order of frequency, were xylene > toluene > acetone. One sample contained a detectable amount of aliphatic compound(s), with the empirical formula of C 8 H 18 . Results from the Deer Creek site showed that herbicides were detected primarily in the top layer (1.2 m), whereas xylene and other alkylbenzenes were detected at 2.1 m or deeper. Apparently, physico-chemical and other factors are separating herbicides and volatile organic compounds in the shallow unsaturated zone.

Iowa

Low cost limestone treatment of acid sensitive trout streams in the Appalachian Mountains of Virginia

The method of single point, single application liming has been studied as a means of mitigating anthropogenic acid in trout streams in Virginia. Three critically acid sensitive streams were dosed with a total of five applications of limestone sand and monitored before, during and after the treatments to assess changes in water chemistry and biota. Limestone treatments of 8 to 50 tons (particle sizes 150–1000 μ m), with the amounts based on sulfate deposition loading and existent stream water chemistry, were used to restore ‘lost’ acid neutralizing capacity (ANC). Contact time between the limestone bed in the stream bottom and the water was the limiting factor affecting the degree of treatment with bed length primarily controlled by the gradient of the stream at the dosing site. A single site application was able to restore approximately 2/3 of the ANC. Exponential fits of limestone consumption data were used to predict that treaments of similar streams would last from two five years before reliming was necessary. Both total and monomeric aluminum levels were reduced up to 50%, and aquatic biota increased below the treatment sites. Post-liming average values for the three streams were pH 6.66, 82.7 μ eq L −1 ANC and 2.63 mg L −1 Ca. The average ANC improvement suggests that some 88% of the native trout streams in Virginia, which average 29 μ eq L −1 ANC reduction from acid deposition, could be temporarily restored using single application liming.

Virginia

Dissolution of alkaline earth sulfates in the presence of montmorillonite

In a study of the effect of montmorillonite on the dissolution of BaSO4 (barite), SrSO4 (celestite), and 226Ra from U mill tailings, it was found that: (1) More of these substances dissolve in an aqueous system that contains montmorillonite than dissolve in a similar system without clay, due to the ion exchange properties of the clay; (2) Na-montmorillonite is more effective in aiding dissolution than is Ca-montmorillonite; (3) the amount of Ra that moves from mill tailings to an exchanger increases as solution sulfate activity decreases. Leaching experiments suggest that 226Ra from H2SO4-circuit U mill tailings from Edgemont, South Dakota, is not present as pure Ra sulfate or as an impurity in anhydrite or gypsum; it is less soluble, and probably occurs as a trace constituent in barite.

Water, Air, & Soil Pollution

The effect of membrane filtration on dissolved trace element concentrations

The almost universally accepted operational definition for dissolved constituents is based on processing The almost universally accepted operational definition for dissolved constituents is based on processing whole-water samples through a 0.45-μm membrane filter. Results from field and laboratory experiments indicate that a number of factors associated with filtration, other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample), can produce substantial variations in the ‘disolved’ concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. These variations result from the inclusion/exclusion of colloidally-associated trace elements. Thus, 'dissolved' concentrations quantitated by analyzing filtrates generated by processing whole-water through similar pore-sized membrane filters may not be equal/comparable. As such, simple filtration through a 0.45-μm membrane filter may no longer represent an acceptable operational definition for dissolved chemical constituents. This conclusion may have important implications for environmental studies and regulatory agencies.

Water, Air, & Soil Pollution

Predictive techniques for river channel evolution and maintenance

Predicting changes in alluvial channel morphology associated with anthropogenic and natural changes in flow and/or sediment supply is a critical part of the management of riverine systems. Over the past few years, advances in the understanding of the physics of sediment transport in conjunction with rapidly increasing capabilities in computational fluid dynamics have yielded now approaches to problems in river mechanics. Techniques appropriate for length scales ranging from reaches to bars and bedforms are described here. Examples of the use of these computational approaches are discussed for three cases: (1) the design of diversion scenarios that maintain channel morphology in steep cobble-bedded channels in Colorado, (2) determination of channel maintenance flows for the preservation of channel islands in the Snake River in Idaho, and (3) prediction of the temporal evolution of deposits in lateral separation zones for future assessment of the impacts of various dam release scenarios on lateral separation deposits in the Colorado River in Grand Canyon. With continued development of their scientific and technical components, the methodologies described here can provide powerful tools for the management of river environments in the future.

Water, Air, & Soil Pollution

Precision of a field method for determination of pH in dilute lakes

Replicate pH measurements in three dilute lakes made during extreme conditions indicate that pH can be measured in the field with a variance due to measurement error of 0.005 unit. Error of the field technique in measuring the pH of dilute solutions in the laboratory ranges from less than 0.01 unit in dilute strong-acid solutions to about 0.05 unit in air-saturated deionized water.

Water, Air, & Soil Pollution

Recent sedimentary history of Lake Monona, Wisconsin

Chemical analyses from two short cores in Lake Monona show that pronounced changes in chemical stratigraphy have occurred since white man moved into Madison and southern Wisconsin and began modifying the area. Since the mid to late 1800's, there has been an appreciable increase in P, Fe, Mn, Al, and K in the uppermost sediments. Maximum concentrations of P were observed near the turn of the century and in the most recent sediment layers.

Wisconsin

Mercury accumulation in Devils Lake, North Dakota effects of environmental variation in closed-basin lakes on mercury chronologies

Sediment cores were collected from lakes in the Devils Lake Basin in North Dakota to determine if mercury (Hg) accumulation chronologies from sediment-core data are good indicators of variations in Hg accumulation rates in saline lakes. Sediment cores from Creel Bay and Main Bay, Devils Lake were selected for detailed analysis and interpretation. The maximum Hg concentration in the Creel Bay core was 0.15 micrograms per gram at 8 to 9 centimeters. The maximum Hg concentration in the Main Bay core was 0.07 micrograms per gram at 5 to 7 centimeters. The general decreases in Hg concentrations with depth are attributed to historic variations in atmospheric Hg deposition rate. Hg stratigraphies combined with 210Pb and 137Cs dating analyses yield Hg chronologies that indicate a general increase in Hg accumulation rates in Devils Lake since the middle of the 19th century. Mean modern Hg accumulation rates in Creel Bay were 4.9 nanograms per square centimeter per year, and rates in Main Bay were 1.8 nanograms per square centimeter per year. Mean preindustrial Hg accumulation rates in Creel Bay were 1.2 nanograms per square centimeter per year, and rates in Main Bay were 1.6 nanograms per square centimeter per year. Relatively low Hg concentrations in recent sediments in the Devils Lake Basin, along with similarities in Hg accumulation rates between lakes in the Devils Lake Basin and other lakes in the northern interior of North America, indicate that local sources of Hg are not important sources of Hg. Results of the study indicate that accurate Hg chronologies are discernible in sediment cores collected from saline lakes. However, spatial and temporal variations in lake level and water chemistry common to saline lakes make interpretation of radioisotopic and geochemical chronologies difficult. Hg geochemistry in Devils Lake, and presumably in other saline lakes, is dynamic. The results of this study indicate that the absolute amount of sediment transported to Devils Lake, along with the associated Hg and total organic carbon, and the distribution of sedimentation patterns in Devils Lake may be affected by changing lake levels.

Water, Air, & Soil Pollution

Effects of coal-bed methane discharge waters on the vegetation and soil ecosystem in Powder River Basin, Wyoming

Coal-bed methane (CBM) co-produced discharge waters in the Powder River Basin of Wyoming, resulting from extraction of methane from coal seams, have become a priority for chemical, hydrological and biological research during the last few years. Soil and vegetation samples were taken from affected and reference sites (upland elevations and wetted gully) in Juniper Draw to investigate the effects of CBM discharge waters on soil physical and chemical properties and on native and introduced vegetation density and diversity. Results indicate an increase of salinity and sodicity within local soil ecosystems at sites directly exposed to CBM discharge waters. Elevated concentrations of sodium in the soil are correlated with consistent exposure to CBM waters. Clay-loam soils in the study area have a much larger specific surface area than the sandy soils and facilitate a greater sodium adsorption. However, there was no significant relation between increasing water sodium adsorption ratio (SAR) values and increasing sediment SAR values downstream; however, soils exposed to the CBM water ranged from the moderate to severe SAR hazard index. Native vegetation species density was highest at the reference (upland and gully) and CBM affected upland sites. The affected gully had the greatest percent composition of introduced vegetation species. Salt-tolerant species had the greatest richness at the affected gully, implying a potential threat of invasion and competition to established native vegetation. These findings suggest that CBM waters could affect agricultural production operations and long-term water quality.

Wyoming

Part 1: Vadose-zone column studies of toluene (enhanced bioremediation) in a shallow unconfined aquifer

The objectives of the laboratory study described in this paper were (1) to determine the effectiveness of four nutrient solutions and a control in stimulating the microbial degradation of toluene in the unsaturated zone as an alternative to bioremediation methodologies such as air sparging, in situ vitrification, or others (Part I), and (2) to compare the effectiveness of the addition of the most effective nutrient solution from Part I (modified Hoagland type, nitrate-rich) and hydrogen peroxide (H 2 O 2 ) on microbial degradation of toluene for repeated, simulated spills in the unsaturated zone (Part II). For Part 1, fifteen columns (30-cm diameter by 150-cm height), packed with air-dried, 0.25-mm, medium-fine sand, were prepared to simulate shallow unconfined aquifer conditions. Toluene (10 mL) was added to the surface of each column, and soil solution and soil gas samples were collected from the columns every third day for 21 days. On day 21, a second application of toluene (10 mL) was made, and the experiment was run for another 21 days. Solution 4 was the most effective for microbial degradation in Part I. For Part II, three columns were designated nutrient-rich 3-day toluene columns and received toluene injections every 3 days; three columns were designated as nutrient-rich 7-day columns and received toluene injections every 7 days; and two columns were used as controls to which no nutrient was added. As measured by CO 2 respiration, the initial benefits for aerobic organisms from the O 2 enhancement were sustained by the bacteria for only a short period of time (about 8 days). Degradation benefits from the nutrient solution were sustained throughout the experiment. The O 2 and nutrient-enhanced columns degraded significantly more toluene than the control columns when simulating repeated spills onto the unsaturated zone, and demonstrated a potentially effective in situ bioremediation technology when used immediately or within days after a spill. The combined usage of H 2 O 2 and nitrate-rich nutrients served to effectively maximize natural aerobic and anaerobic metabolic processes that biodegrade hydrocarbons in petroleum-contaminated media. Applications of this technology in the field may offer economical advantages to other, more intrusive abatement technologies.

Water, Air, & Soil Pollution