Seasonal changes predominant over manure application in driving dissolved organic matter shifts in agricultural runoff

Abstract

Non-point source nutrient pollution can cause eutrophication, hypoxic events, and harmful algal blooms in surface waters. Surface water eutrophication is frequently attributed to agricultural runoff, a known source of inorganic and organic nutrients to surface and subsurface waters. Analysis of dissolved organic matter (DOM) using ultrahigh resolution mass spectrometry is an effective tool for characterizing diverse organic nitrogen and phosphorus components of DOM that may be mineralized and/or assimilated and ultimately contribute to eutrophication. An anion exchange resin was applied to extract DOM from surface and subsurface tile runoff from agricultural plots located within the Maumee River watershed (Ohio, USA) that received raw liquid manure, polymer-treated dewatered manure, or no manure (control). DOM extracts were analyzed using Fourier transform ion cyclotron resonance mass spectrometry prior to manure application and during three runoff events after manure application. Organic nitrogen compounds were predominant, making up 38–48% of the total assigned formulas. Principle coordinates analysis indicated clustering predominately by sample month and secondarily by treatment. These findings show that a large amount of variability in DOM in runoff was observed regardless of manure application, indicating the important role played by natural processes in driving transformation of the DOM pool during the growing season. Molecular ions unique to runoff from manure-applied plots were also identified that may be useful in source-tracking of non-point source nutrient pollution in waters draining to Lake Erie.