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Janet S. Herman

Publications and source records attributed to Janet S. Herman.

9 recordsLinked to original sources

Acidification of Earth: An assessment across mechanisms and scales

In this review article, anthropogenic activities that cause acidification of Earth’s air, waters, and soils are examined. Although there are many mechanisms of acidification, the focus is on the major ones, including emissions from combustion of fossil fuels and smelting of ores, mining of coal and metal ores, and application of nitrogen fertilizer to soils, by elucidating the underlying biogeochemical reactions as well as assessing the magnitude of the effects. These widespread activities have resulted in (1) increased CO 2 concentration in the atmosphere that acidifies the oceans; (2) acidic atmospheric deposition that acidifies soils and bodies of freshwater; (3) acid mine drainage that acidifies bodies of freshwater and groundwaters; and (4) nitrification that acidifies soils. Although natural geochemical reactions of mineral weathering and ion exchange work to buffer acidification, the slow reaction rates or the limited abundance of reactant phases are overwhelmed by the onslaught of anthropogenic acid loading. Relatively recent modifications of resource extraction and usage in some regions of the world have begun to ameliorate local acidification, but expanding use of resources in other regions is causing environmental acidification in previously unnoticed places. World maps of coal consumption, Cu mining and smelting, and N fertilizer application are presented to demonstrate the complex spatial heterogeneity of resource consumption as well as the overlap in acidifying potential derived from distinctly different phenomena. Projected population increase by country over the next four decades indicates areas with the highest potential for acidification, so enabling anticipation and planning to offset or mitigate the deleterious environmental effects associated with these global shifts in the consumption of energy, mineral, and food resources.

Applied Geochemistry

The mobilization of aluminum in a natural soil system: Effects of hydrologic pathways

A two-component soil water flow model was used in conjunction with an equilibrium speciation model WATEQF to study aluminum mobility in soils of a forested watershed, White Oak Run, in the Shenandoah National Park, Virginia. Soil solution samples, taken from the O, E, B, C 1 , and C 2 horizons, were collected from zero-tension lysimeters designed to collect faster gravitational macropore flow and tension lysimeters designed to collect slower capillary micropore flow. Dissolved aluminum was fractionated into acid-soluble, inorganic monomeric, and organic monomeric aluminum. Soil water aluminum concentrations decreased with depth indicating that the deep soil is a sink for aluminum. All waters contained significant concentrations of acid-soluble aluminum and exhibited a negative correlation between p H and the inorganic monomeric aluminum concentrations. Water in the shallow soil showed distinctly different chemical compositions for the two flow types, while C horizon micropore and macropore waters were more similar. Because of its shorter residence time, water flowing in deep soil macropores underwent less extensive neutralization and immobilization of aqueous aluminum than micropore water. The O horizon macropore waters were undersaturated for all hydroxide, silicate, and sulfate mineral phases considered. The C horizon samples from both flow types were near equilibrium with respect to kaolinite and synthetic gibbsite, indicating that mineral solubility controls water chemistry in the deep soil, while organic substances are the key control in the shallow macropore waters.

Water Resources Research

The chemical evolution of a travertine-depositing stream: Geochemical processes and mass transfer reactions

This field study focuses on quantitatively defining the chemical changes occurring in Falling Spring Creek, a travertine-depositing stream located in Alleghany County, Virginia. The processes of CO 2 outgassing and calcite precipitation or dissolution control the chemical evolution of the stream. The observed chemical composition of the water was used with the computerized geochemical model WATEQF to calculate aqueous speciation, saturation indices, and CO 2 partial pressure values. Mass balance calculations were performed to obtain mass transfers of CO 2 and calcite. Reaction times, estimated from stream discharge, were used with the mass transfer results to calculate rates of CO 2 , outgassing and calcite precipitation between consecutive sampling points. The stream, which is fed by a carbonate spring, is supersaturated with respect to CO 2 along the entire 5.2-km flow path. Outgassing of CO 2 drives the solution to high degrees of supersaturation with respect to calcite. Metabolic uptake of CO 2 by photosynthetic plants is insignificant, because the high supply rate of dissolved carbon dioxide and the extreme agitation of the stream at waterfalls and rapids causes a much greater amount of inorganic CO 2 outgassing to occur. Calcite precipitation is kinetically inhibited until near the crest of a 20-m vertical waterfall. Calcite precipitation rates then reach a maximum at the waterfall where greater water turbulence allows the most rapid escape of CO 2 . Physical evidence for calcite precipitation exists in the travertine deposits which are first observed immediately above the waterfall and extend for at least 1.0 km below the falls. Net calcite precipitation occurs at all times of the year but is greatest during low-flow conditions in the summer and early fall.

Water Resources Research

Processes controlling the episodic streamwater transport of atrazine and other agrichemicals in an agricultural watershed

Episodic streamwater transport of atrazine (a common agricultural herbicide) and nutrients has been observed throughout agricultural watersheds in the United States and poses a serious threat to the quality of its water resources. Catchment-scale atrazine and nutrient transport processes after agricultural application are still poorly understood, and predicting episodic streamwater composition remains an elusive goal. We instrumented a 1.2-km 2 agricultural catchment near Harrisonburg, Virginia, and examined streamwater, overland flow, soil water, groundwater, and rainfall during the summer of 1998. Storm chemographs demonstrated different patterns for constituents derived primarily from weathering (silica and calcium), compared to constituents derived primarily from early spring land applications (nitrate, atrazine, DOC, potassium, chloride, and sulfate). During storms, the concentrations of silica and calcium decreased, the atrazine response was variable, and the concentrations of nitrate, DOC, potassium, chloride, and sulfate increased; the elevated nitrate signal lagged several hours behind the other elevated constituents. Graphical and statistical analyses indicated a relatively stable spring-fed baseflow was modified by a mixture of overland flow and soil water. A rapid, short-duration overland-flow pulse dominated the streamflow early in the event and contributed most of the potassium, DOC, chloride, suspended sediment, and atrazine. A longer-duration soil–water pulse dominated the streamflow later in the event and contributed the nitrate as well as additional potassium, DOC, sulfate, and atrazine. The contributions to the episodic streamflow were quantified using a flushing model in which overland-flow and soil–water concentrations decreased exponentially with time during an episode. Flushing time constants for the overland-flow and soil–water reservoirs were calculated on a storm-by-storm basis using separate tracers for each time-variable reservoir. Initial component concentrations were estimated through regression analyses. Mass-balance calculations were used for flow separations and to predict the observed streamwater composition. Model forecasts indicated that reduced fertilizer and pesticide application (rather than elimination of overland-flow or soil–water contributions) was necessary to improve the episodic streamwater composition. This study provides important additional understanding of the catchment-scale processes by which land-applied pesticides and nutrients can move through agricultural systems.

Virginia

Mobilization and transport of soil particles during infiltration experiments in an agricultural field, Shenandoah Valley, Virginia

Evidence that fine particles mobilized and transported in soils and aquifers can have a profound influence on contaminant migration has spawned much interest recently in understanding colloid transport in natural materials. Repeated infiltration experiments on an initially dry field soil were conducted to evaluate rates of mobilization of fine particles over time and to investigate the importance of transient-flow events on particle transport. Water flow was measured in zero-tension lysimeters at 25 cm depth. For repeated infiltration events and for all plots, water flow sharply increased shortly after initial ponding of water at the soil surface, maintained a relatively steady level during the period of ponding, and decreased gradually thereafter. Particle concentrations measured in the pan lysimeters ranged from 7 mg L - 1 to 265 mg L - 1 and were typically on the order of 10 to 100 mg L - 1 . Greatest particle mass flux was observed during the initial infiltration experiment on each plot. During four subsequent infiltration experiments, all conducted within 250 min of the first event, steady mass fluxes were observed that were approximately 70% of the average value seen in the first flush of water through a dry soil, indicating that the supply of mobile soil particles is only sparingly reduced over closely spaced infiltration events. All peak particle concentrations and mass fluxes occurred near either the rising limb or the falling limb of the water flux hydrograph, presumably reflecting the movement of air−water interfaces during imbibition and drainage.

Virginia

Alteration of reactive mineral surfaces by ground water

Two different investigations of shallow sandy aquifers inform our thinking about the role of reactive iron minerals in hydrogeological systems. Ground water in a number of settings has been described as having elevated concentrations of dissolved iron in anoxic portions of contaminant plumes (e.g. Baedecker et al., 1993; Lyngkilde and Christensen, 1992), and the coupling of microbial reduction of Fe(III) to the degradation of organic compounds links the study of the biogeochemistry of iron to our desire to understand processes influencing contaminated aquifers. Questions about the transport and fate of reactive constituents in ground water are linked to the study of iron through recognition of the importance of sorption processes on sesquioxide mineral surfaces common in sedimentary aquifers limiting the migration of metals, anions, and bacteria. We have been grappling with questions related to the stability of iron mineral phases in contaminated aquifers and the role of Fe(III)- bearing minerals and grain coatings as sorption substrates

Conference Paper

Geochemical heterogeneity of a gasoline-contaminated aquifer

The scale of biogeochemical reactions was studied in a physically and chemically heterogeneous surficial Coastal Plain aquifer contaminated by a gasoline spill. The physical heterogeneity of the aquifer is manifested in two hydrologic units, a shallow local aquifer of perched water and a regional sandy aquifer. Over the studied vertical interval of 21.3 ft (6.5 m), concentrations of reactive species varied by orders of magnitude, and the impact of biodegradation was expressed to widely varying degrees. A thin (3 ft thick) section of the perched-water zone was the most contaminated; total aromatic hydrocarbons were as high as 19.4 mg/l. Hydrocarbons were degraded by microbially mediated reactions that varied over short vertical distances and time. Anaerobic processes dominated within the low-permeability clay unit, whereas in the more permeable sandy layers nitrate reduction and aerobic degradation occurred. Hydrocarbons were more persistent over time in the low-permeability layer due to the limited availability of electron acceptors for degradation. The microbial degradation of hydrocarbons was linked to sulfate and iron reduction in the clay unit and led to alterations in the aquifer solids; electron microscopy revealed the presence of FeS minerals encrusting primary aquifer grains. High concentrations of Fe 2+ in groundwater, up to 34.5 mg/l, persist in kinetic disequilibrium in the presence of elevated H 2 S levels of 1.0 mg/l. Assessment of aquifer heterogeneities and groundwater contamination was possible due to sample discrimination at a scale of approximately 2 ft (∼0.6 m), a much finer resolution than is attempted in many remedial investigations of polluted aquifers. The information obtained in this type of study is essential to the development of models capable of estimating the fate of hydrocarbons at a site scale.

Journal of Contaminant Hydrology

Seasonal dynamics of groundwater-lake interactions at Doñana National Park, Spain

The hydrologic and solute budgets of a lake can be strongly influenced by transient groundwater flow. Several shallow interdunal lakes in southwest Spain are in close hydraulic connection with the shallow ground water. Two permanent lakes and one intermittent lake have chloride concentrations that differ by almost an order of magnitude. A two-dimensional solute-transport model, modified to simulate transient groundwater-lake interaction, suggests that the rising water table during the wet season leads to local flow reversals toward the lakes. Response of the individual lakes, however, varies depending on the lake's position in the regional flow system. The most dilute lake is a flow-through lake during the entire year; the through flow is driven by regional groundwater flow. The other permanent lake, which has a higher solute concentration, undergoes seasonal groundwater flow reversals at its downgradient end, resulting in complex seepage patterns and higher solute concentrations in the ground water near the lake. The solute concentration of the intermittent lake is influenced more strongly by the seasonal wetting and drying cycle than by the regional flow system. Although evaporation is the major process affecting the concentration of conservative solutes in the lakes, geochemical and biochemical reactions influence the concentration of nonconservative solutes. Probable reactions in the lakes include biological uptake of solutes and calcite precipitation; probable reactions as lake water seeps into the aquifer are sulfate reduction and calcite dissolution. Seepage reversals can result in water composition that appears inconsistent with predictions based on head measurements because, under transient flow conditions, the flow direction at any instant may not satisfactorily depict the source of the water. Understanding the dynamic nature of groundwater-lake interaction aids in the interpretation of hydrologic and chemical relations between the lakes and the ground water.

Journal of Hydrology

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

Rates of aqueous, abiotic pyrite oxidation were measured in oxygen-saturated and anaerobic Fe(III)-saturated solutions with initial pH from 2 to 9. These studies included analyses of sulfite, thiosulfate, polythionates and sulfate and procedures for cleaning oxidation products from pyrite surfaces were evaluated. Pyrite oxidation in oxygen-saturated solutions produced (1) rates that were only slightly dependent on initial pH, (2) linear increases in sulfoxy anions and (3) thiosulfate and polythionates at pH > 3.9. Intermediate sulfoxy anions were observed only at high stirring rates. In anaerobic Fe(III)-saturated solutions, no intermediates were observed except traces of sulfite at pH 9. The faster rate of oxidation in Fe(III)-saturated solutions supports a reaction mechanism in which Fe(III) is the direct oxidant of pyrite in both aerobic and anaerobic systems. The proposal of this mechanism is also supported by theoretical considerations regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic pyrite. Results from a study of sphalerite oxidation support the hypothesis that thiosulfate is a key intermediate in sulfate production, regardless of the bonding structure of the sulfide mineral.

Geochimica et Cosmochimica Acta