Comparing dissolved reactive phosphorus measured by DGT with ferrihydrite and titanium dioxide adsorbents: Anionic interferences, adsorbent capacity and deployment time

Abstract

Two adsorbents (Metsorb and ferrihydrite) used in binding layers with the diffusive gradients in a thin film technique were evaluated for the measurement of dissolved reactive phosphorous (DRP) in synthetic and natural waters. Possible interferences were investigated with Cl − (up to 1.35 mol L −1) and SO 4 2− (up to 0.056 mol L −1) having no affect on either DGT binding layer, and HCO 3 − (up to 5.7 mmol L −1) having no effect on Metsorb-DGT, over 4 days. However, HCO 3 − interfered with the ferrihydrite-DGT measurement at concentrations typical of many natural waters (≥0.7 mmol L −1) after a deployment period of 1–2 days. The capacity of the Metsorb binding phase for DGT response was ∼37,000 ng P, whereas the capacities of a low-mass (17.8 mg of adsorbent per DGT sampler) and high-mass (29.2 mg of adsorbent per DGT sampler) ferrihydrite binding phase were substantially lower (∼15,000 ng P and ∼25,000 ng P, low-mass and high-mass, respectively). Increasing the capacity of the ferrihydrite adsorbent allowed the ferrihydrite-DGT to be utilized for up to 3 days before interference by HCO 3 − was observed. Seawater deployments demonstrated that even high-capacity ferrihydrite-DGT devices underestimated the DRP concentration by 37%, whereas Metsorb-DGT measurements were accurate. The Metsorb-DGT is superior to the ferrihydrite-DGT for determining DRP over deployment times greater than 1 day and in waters with ≥0.7 mmol L −1 HCO 3 −. Based on the experience obtained from this detailed validation process, the authors propose a number of key requirements that need to be considered when developing new DGT binding layers, with testing the performance over longer deployment times being critical.