Mobility of major and trace elements in a coupled groundwater-surface water system: Merced River, CA

Trace element transport in coupled surface water/groundwater systems is controlled not only by advective flow, but also by redox reactions that affect the partitioning of various elements between mobile and immobile phases. These processes have been examined in the context of a field project conducted by the U.S. Geological Survey (USGS) as part of the National Water-Quality Assessment (NAWQA) program. The Merced River flows out of Yosemite National Park and the Sierra Nevada foothills and into California's Central Valley, where it joins the San Joaquin River. Our field site is approximately twenty river kilometers from the confluence with the San Joaquin River. This deep alluvial plain has minimal topography. Agricultural development characterizes the land surrounding this reach of river; consequently, the hydrology is heavily influenced by irrigation. Riverbed groundwater samples were collected from ten wells aligned in two transects across the river located approximately 100 m apart. The wells were sampled from depths of 0.5 m, 1 m, and 3 m below the sediment-water interface. Groundwater flowpath samples were taken from wells positioned on a path perpendicular to the river and located 100 m, 500 m, and 1000 m from the river. The saturated groundwater system exists from 7 to 40 m below the surface and is confined below by a clay layer. Each well location samples from 3-5 depths in this surface aquifer. Samples were collected in December 2003, March-April, June-July, and October 2004. This served to provide an evenly-spaced sampling frequency over the course of a year, and also to allow observation of trends coinciding with the onset of winter, the spring runoff, and early and late summer irrigation. An initial survey of the elements in the riverbed samples was conducted using Inductively-Coupled Plasma Mass Spectrometry (ICP-MS). Elements for further study were selected based on variability in this survey, either with respect to depth or location, as well as to cover a range of expected geochemical behaviors. Further ICP-MS measurements focused on eight elements: strontium, barium, uranium, molybdenum, manganese, iron, phosphorus, and bromine. Bromine is a conservative tracer. Molybdenum, manganese, and iron will precipitate when oxidized, and uranium will precipitate when reduced. Strontium and barium are not redox-active but may be affected by dissolution-precipitation and sorption reactions. Phosphorus is a nutrient that will cycle actively in areas of biological productivity. Generally, these elements appear to behave as expected based on physical waterflow and assumed redox conditions. The two transects of wells across the river bracket a zone of known denitrification, which implies that sediment conditions favor oxidation upriver and reduction downriver. This trend is borne out both by the redox-sensitive elements at each transect, and by the strontium and barium, which bind to precipitated iron and manganese oxides in oxidizing conditions and are released into the dissolved state in reducing conditions. The flowpath samples appear to be enriched in strontium, phosphorus, and bromine when compared to the riverbed samples, and they are depleted in manganese and iron.