Improvement of On-Site Sensor for Simultaneous Determination of Phosphate, Silicic Acid, Nitrate plus Nitrite in...

Accurate, on-site determinations of macronutrients (phosphate (PO₄^3-), nitrate (NO₃^-), and silicic acid (H₄SiO₄)) in seawater in real time are essential to obtain information on their distribution, flux, and role in marine biogeochemical cycles. The development of robust sensors for long-term on-site analysis of macronutrients in seawater is a great challenge. Here, we present improvements of a commercial automated sensor for nutrients (including PO₄^3-, H₄SiO₄, and NO₂^- plus NO₃^-), suitable for a variety of aquatic environments. The sensor uses the phosphomolybdate blue method for PO₄^3-, the silicomolybdate blue method for H₄SiO₄ and the Griess reagent method for NO₂^-, modified with vanadium chloride as reducing agent for the determination of NO₃^-. Here, we report the optimization of analytical conditions, including reaction time for PO₄^3- analysis, complexation time for H₄SiO₄ analysis, and analyte to reagent ratio for NO₃^- analysis. The instrument showed wide linear ranges, from 0.2 to 100 μM PO₄^3-, between 0.2 and 100 μM H₄SiO₄, from 0.5 to 100 μM NO₃^-, and between 0.4 and 100 μM NO₂^-, with detection limits of 0.18 μM, 0.15 μM, 0.45 μM, and 0.35 μM for PO₄^3-, H₄SiO₄, NO₃^-, and NO₂^-, respectively. The analyzer showed good precision with a relative standard deviation of 8.9% for PO₄^3-, 4.8% for H₄SiO₄, and 7.4% for NO₂^- plus NO₃^- during routine analysis of certified reference materials (KANSO, Japan). The analyzer performed well in the field during a 46-day deployment on a pontoon in the Kiel Fjord (located in the southwestern Baltic Sea), with a water supply from a depth of 1 m. The system successfully collected 443, 440, and 409 on-site data points for PO₄^3-, Σ(NO₃^- + NO₂^-), and H₄SiO₄, respectively. Time series data agreed well with data obtained from the analysis of discretely collected samples using standard reference laboratory procedures and showed clear correlations with key hydrographic parameters throughout the deployment period.