Assessing the sources and magnitude of diurnal nitrate variability in the San Joaquin River (California) with an <i>in situ</i> optical nitrate sensor and dual nitrate isotopes

Abstract

Summary 1. We investigated diurnal nitrate (NO 3 − ) concentration variability in the San Joaquin River using an in situ optical NO 3 − sensor and discrete sampling during a 5‐day summer period characterized by high algal productivity. Dual NO 3 − isotopes (δ 15 N NO3 and δ 18 O NO3 ) and dissolved oxygen isotopes (δ 18 O DO ) were measured over 2 days to assess NO 3 − sources and biogeochemical controls over diurnal time‐scales. 2. Concerted temporal patterns of dissolved oxygen (DO) concentrations and δ 18 O DO were consistent with photosynthesis, respiration and atmospheric O 2 exchange, providing evidence of diurnal biological processes independent of river discharge. 3. Surface water NO 3 − concentrations varied by up to 22% over a single diurnal cycle and up to 31% over the 5‐day study, but did not reveal concerted diurnal patterns at a frequency comparable to DO concentrations. The decoupling of δ 15 N NO3 and δ 18 O NO3 isotopes suggests that algal assimilation and denitrification are not major processes controlling diurnal NO 3 − variability in the San Joaquin River during the study. The lack of a clear explanation for NO 3 − variability likely reflects a combination of riverine biological processes and time‐varying physical transport of NO 3 − from upstream agricultural drains to the mainstem San Joaquin River. 4. The application of an in situ optical NO 3 − sensor along with discrete samples provides a view into the fine temporal structure of hydrochemical data and may allow for greater accuracy in pollution assessment.