Karen C. Rice

Comparison of hydrochemical tracers to estimate source contributions to peak flow in a small, forested, headwater catchment

Three-component (throughfall, soil water, groundwater) hydrograph separations at peak flow were performed on 10 storms over a 2-year period in a small forested catchment in north-central Maryland using an iterative and an exact solution. Seven pairs of tracers (deuterium and oxygen 18, deuterium and chloride, deuterium and sodium, deuterium and silica, chloride and silica, chloride and sodium, and sodium and silica) were used for three-component hydrograph separation for each storm at peak flow to determine whether or not the assumptions of hydrograph separation routinely can be met, to assess the adequacy of some commonly used tracers, to identify patterns in hydrograph-separation results, and to develop conceptual models for the patterns observed. Results of the three-component separations were not always physically meaningful, suggesting that assumptions of hydrograph separation had been violated. Uncertainties in solutions to equations for hydrograph separations were large, partly as a result of violations of assumptions used in deriving the separation equations and partly as a result of improper identification of chemical compositions of end-members. Results of three-component separations using commonly used tracers were widely variable. Consistent patterns in the amount of subsurface water contributing to peak flow (45-100%) were observed, no matter which separation method or combination of tracers was used. A general conceptual model for the sequence of contributions from the three end-members could be developed for 9 of the 10 storms. Overall results indicated that hydrochemical and hydrometric measurements need to be coupled in order to perform meaningful hydrograph separations.

Seasonal cycles of dissolved constituents in streamwater in two forested catchments in the mid-Atlantic region of the eastern USA

Abstract Streamwater discharge and chemistry of two small catchments on Catoctin Mountain in north-central Maryland have been monitored since 1982. Repetitive seasonal cycles in stream-water chemistry have been observed each year, along with seasonal cycles in the volume of stream discharge and in groundwater levels. The hypothesis that the observed streamwater chemical cycles are related to seasonal changes in the hydrological flow paths that contribute to streamflow is examined using a combination of data on groundwater levels, shallow and deep groundwater chemistry, streamwater discharge, streamwater chemistry, soil-water chemistry, and estimates of water residence times. The concentrations of constituents derived from rock weathering, particularly bicarbonate and silica, increase in streamwater during the summer when the water table is below the regolith-bedrock interface and stream discharge consists primarily of deep groundwater from the fractured-bedrock aquifer. Conversely, the concentrations in streamwater of atmospherically derived components, particularly sulfate, increase in winter when the water table is above the regolith-bedrock interface and stream discharge consists primarily of shallow groundwater from the regolith. Tritium and chlorofluorocarbon (CFC) measurements suggest that the groundwater in these systems is young, with a residence time of less than several years. The results of this study have implications for the design of large-scale water-quality monitoring programs.

Comparison of episodic acidification of Mid-Atlantic Upland and Coastal Plain streams

Episodic acidification was examined in five mid-Atlantic watersheds representing three physiographic provinces: Coastal Plain, Valley and Ridge, and Blue Ridge. Each of the watersheds receives a similar loading of atmospheric pollutants (SO42− and NO3−) and is underlain by different bedrock type. The purpose of this research was to quantify and compare the episodic variability in storm flow chemistry in Reedy Creek, Virginia (Coastal Plain), Mill Run and Shelter Run, Virginia (Valley and Ridge), and Fishing Creek Tributary and Hunting Creek, Maryland (Blue Ridge). Because episodic responses were similar from storm to storm in each of the watersheds, a representative storm from each watershed was discussed. Acidification, defined as the loss of acid-neutralizing capacity (ANC), was observed in all streams except Mill Run. Mill Run chemistry showed little episodic variability. During storms in the other streams, pH decreased while SO42−, NO3−, and K+ concentrations increased. Concentrations of Mg2+ and Ca2+ increased in Reedy Creek and Fishing Creek Tributary, but decreased in Shelter Run and Hunting Creek. Therefore the net effect of episodic changes on the acid-base status differed among the streams. In general, greater losses of ANC were observed during storms at Shelter Run and Hunting Creek, watersheds underlain by reactive bedrock (carbonate, metabasalt); comparatively smaller losses in ANC were observed at Reedy Creek and Fishing Creek Tributary, watersheds underlain by quartzites and unconsolidated quartz sands and cobbles. Increased SO42− concentrations were most important during storms at Reedy Creek and Fishing Creek Tributary, but organic anions (inferred by anion deficit) were also a factor in causing the loss of ANC. Dilution of base cations was the most important factor in the loss of ANC at Shelter Run. Both increased sulfate and dilution of base flow were important in causing the episodic acidification at Hunting Creek. The role of SO42− in contributing to episodic acidification in these watersheds is similar to that documented in studies conducted in other regions of the United States, Scandinavia, Canada, and the United Kingdom. The importance of SO42− in mid-Atlantic United States streams contrasts with northeastern United States streams, in which increased NO3- derived from snowpack is more important in causing episodic acidification. Results support the importance of shallow subsurface processes in determining storm flow chemistry, regional climatic characteristics in determining the different sources of acidity during episodes, and the importance of bedrock geology in determining the amount of ANC loss.

Use of geochemical mass balance modelling to evaluate the role of weathering in determining stream chemistry in five mid-Atlantic watersheds on different lithologies

The importance of mineral weathering was assessed and compared for five mid-Atlantic watersheds receiving similar atmospheric inputs but underlain by differing bedrock. Annual solute mass balances and volume-weighted mean solute concentrations were calculated for each watershed for each year of record. In addition, primary and secondary mineralogy were determined for each of the watersheds through analysis of soil samples and thin sections using petrographic, scanning electron microscope, electron microprobe and X-ray diffraction techniques. Mineralogical data were also compiled from the literature. These data were input to NETPATH, a geochemical program that calculates the masses of minerals that react with precipitation to produce stream water chemistry. The feasibilities of the weathering scenarios calculated by NETPATH were evaluated based on relative abundances and reactivities of minerals in the watershed. In watersheds underlain by reactive bedrocks, weathering reactions explained the stream base cation loading. In the acid-sensitive watersheds on unreactive bedrock, calculated weathering scenarios were not consistent with the abundance of reactive minerals in the underlying bedrock, and alternative sources of base cations are discussed.