Electrospray ionization fourier transform ion cyclotron resonance mass spectrometry of dissolved organic phosphorus species in a treatment wetland after selective isolation and concentration.

Abstract

A method for the selective concentration of dissolved organic phosphorus (DOP) from complex surface water samples for the first time allows mass spectral characterization of individual DOP compounds in phosphorus-limited ecosystems. The entire dissolved organic matter (DOM) pool is first separated according to molecular weight by tangential cross-flow ultrafiltration (CFF). DOP is selectively isolated and concentrated from CFF fractions by a barium precipitation procedure. The DOP precipitate is then reconstituted in distilled water and excess barium, and other cations are removed with an ion-exchange resin. The DOP isolation/concentration step can provide up to 15-fold concentration and 300-fold concentration of high molecular weight DOP when combined with the inherent concentration provided by CFF. The procedure also removes cations and most of the background DOM, leaving DOP in a matrix suitable for electrospray ionization and mass spectral characterization. Model organic phosphate standards representative of DOP species expected in aquatic environments were used to evaluate the technique. It was then applied to a series of high molecular weight (>1000) CFF retentates isolated from sites within the Everglades Nutrient Removal (ENR) treatment wetland. The elemental compositions of several individual DOP compounds observed at different sites within the ENR were determined by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.