Nitrate reduction in an unconfined sandy aquifer: Water chemistry, reduction processes, and geochemical modeling

Nitrate distribution and reduction processes were investigated in an unconfined sandy aquifer of Quaternary age. Groundwater chemistry was studied in a series of eight multilevel samplers along a flow line, deriving water from both arable and forested land. Results show that plumes of nitrate-contaminated groundwater emanate from the agricultural areas and spread through the aquifer.

The aquifer can be subdivided into an upper 10- to 15-m thick oxic zone that contains O2 and NO3-, and a lower anoxic zone characterized by Fe2+-rich waters. The redox boundary is very sharp, which suggests that reduction processes of O2 and NO3- occur at rates that are fast compared to the rate of downward water transport.

Nitrate-contaminated groundwater contains total contents of dissolved ions that are two to four times higher than in groundwater derived from the forested area. The persistence of the high content of total dissolved ions in the NO3- free anoxic zone indicates the downward migration of contaminants and that active nitrate reduction is taking place.

Nitrate is apparently reduced to N2 because both nitrite and ammonia are absent or found at very low concentrations. Possible electron donors in the reduced zone of the aquifer are organic matter, present as reworked brown coal fragments from the underlying Miocene, and small amounts of pyrite at an average concentration of 3.6 mmol/kg.

Electron balances across the redoxcline, based on concentrations of O2, NO3-, SO4(2-) and total inorganic carbon (TIC), indicate that pyrite is by far the dominant electron donor even though organic matter is much more abundant. Groundwater transport and chemical reactions were modeled using the code PHREEQM, which combines a chemical equilibrium model with a one-dimensional mixing cell transport model.

Only the vertical component of the water transport was modeled since, in contrast to rates along flow lines, the vertical rates are close to constant as required by the one-dimensional model. Average vertical transport rates of water in the saturated zone were obtained by tritium dating. The modeling process is a two-step procedure.

First the sediment column is initialized with natural water containing only oxygen as electron acceptor, and subsequently agricultural waters containing both oxygen and nitrate are fed into the column. The nitrate concentration of agricultural waters entering the saturated zone varies with time, and an input function was therefore constructed by linear mixing of natural waters and agricultural waters.

This input function was fed into the column initialized with natural water, and the model run forward in time to the year 1988 where field data are available. Comparison with field data shows that the variation in groundwater chemistry is well described by the model when reduction of oxygen and reduction of nitrate by pyrite oxidation are the only redox reactions occurring.

Finally, predictions are made for the distribution of water chemistry in the year 2003. Downward progression of the redoxcline is accelerated by a factor of five due to nitrate pollution of the aquifer, but absolute rates remain small, of the order of a few centimeters per year.