A recurring problem in watershed hydrology is the identification of flow paths along which water is routed in both surface and subsurface environments. In particular, the question of whether storm flow is composed primarily of water flowing over the land surface (overland flow) or beneath the land surface (subsurface flow) is significant, because the former flow path provides for little soil contact, while the latter allows for extensive interaction with subsurface materials. The Reedy Creek watershed (45.1 km 2) in the Virginia Coastal Plain has been the subject of field hydrogeological, hydrochemical, and hydrological studies since 1989. Results from chemical separation of six storm flow hydrographs indicate that saturation overland flow (including both direct precipitation onto and return flow to the surface) from saturated cor•tributing areas is the dominant storm flow generation mechanism in the watershed; new water composed 11-38% of creek discharge at the hydrograph peaks, and maximum 24-hour rainfall intensity explained 96% of the total variation in the peak new water contribution among the six events. Estimates of new water-contributing areas determined from the chemical separations were found to vary as a function of antecedent conditions and were also found to be consistent with estimates of areas of likely surface saturation (e.g., perennial channels, open water, and riparian wetland areas) based on field observations and topographic maps.

The importance of mineral weathering was assessed and compared for ®ve mid-Atlantic watersheds receiving similar atmospheric inputs but underlain by diering 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 diraction 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.

A field study of surface water and groundwater interactions during baseflow and stormflow conditions was performed at the Reedy Creek watershed in the Virginia Coastal Plain. Three estimates of the average saturated hydraulic conductivity (K,) of the unconfined aquifer were in reasonable agreement (ranging from 0.0033 to 0.010 cm/s), indicating that baseflow in the creek is entirely from the drainage of shallow groundwater from the relatively thin (1-6 m thick) unconfined aquifer. This relatively permeable surficial aquifer was found to be underlain by dark, olive grey, clay-silt and diatomaceous Miocene deposits of low permeability known as the Calvert Formation, which is believed to function as a confining bed in the area.A chemical hydrograph separation technique was used to resolve the contributions of 'old' (pre-event) and 'new' (event) water to stormflow. Results from a major rainstorm indicated that old water dominated the stormflow response of the watershed, although the new water contribution approached 40% at the hydrograph peak. Stormflow at Reedy Creek appears to result from saturation overland flow from variable source areas which include the stream channels and a significant part of the riparian wetland area. This response appears to be attributable to the transient dynamics of the shallow groundwater flow system and to the formation of localized groundwater mounds which raise the water-table to the wetland surface.

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.

The distribution of trace elements in New Jersey streambed sediments is described with respect to physiographic provinces and major drainage areas. Samples were collected during 1976-1993 at 295 sites distributed throughout New Jersey. Copper, chromium, lead, and zinc were detected with the greatest frequency and at the highest concentrations of the elements. Concentrations of most trace elements were significantly higher in streambed sediments from the New England (glaciated) and Piedmont physiographic provinces -the provinces with the lowest and highest percentages of urban land use, respectively -than in sediments from the other provinces. High trace-element concentrations in the New England (glaciated) province reflect previous mining of extensive magnetite deposits, whereas those in the Piedmont province most likely reflect urban land use. Significantly lower traceelement concentrations in streambed sediments from the Coastal Plain are attributable to the low pH of the streamwater, the lack of iron and manganese available to form coatings that scavenge trace elements, and the relatively low percentage of urban land use in the province. Trace-element concentrations were related to land use, population, or point sources in the drainage basin specific to the sampling location by using logistic regression. Results of this analysis indicate a relation between arsenic and agricultural land use; chromium and physiographic province; and copper, lead, and zinc and population density. (KEY TERMS: bed-sediment quality; trace elements; land use.)