Unravelling organic matter and nutrient biogeochemistry in groundwater-fed rivers under baseflow conditions: controls on in situ analysis

Abstract:

In agricultural catchments diffuse fluxes of nutrients, mainly nitrogen (N) and phosphorus (P) from arable land and livestock are responsible for pollution of receiving waters and their eutrophication. Organic matter (OM) can play an important role in mediating a range of biogeochemical processes controlling diffuse pollution in streams and at their interface with surrounding land in the riparian and hyporheic zones. Thus, a holistic and simultaneous monitoring of N, P and OM fractions can help to improve our understanding of biogeochemical functioning of agricultural streams. In this study we build on intensive in situ monitoring of diffuse pollution in a small agricultural groundwater-fed stream in NW England carried out since 2009. We examine the variation in baseflow macronutrient and organic matter concentrations determined by automatic in situ (wet chemistry analyser, UV-Vis and fluorescence sensors) and automated grab sampling without instantaneous analysis using autosamplers. We evaluate and compare the performance of the automatic sampling techniques and their ability to capture typically low baseflow concentrations of highly reactive forms of nutrients and organic matter: total reactive phosphorus, nitrate nitrogen and tryptophan-like fluorescence which is an autochthonous fraction of OM. In particular, we examine the temperature effects on in situ automatic nutrient and organic matter determinations and autosampler storage effects for hourly samples retrieved daily for laboratory analyses. Understanding transformations and measurement variability in reactive forms of nutrients and organic matter associated with in situ analysis is of great importance for establishing robust monitoring protocols and creating future monitoring networks.