Inorganic phosphorous (as phosphate (PO43−), is one of the essential nutrients for all living forms, either terrestrial or marine. In oligotrophic seawaters, this macronutrient is limited (10−9 M) and its ratio with other elements (nitrogen or carbon) is denoting the health state of the marine environment; a small variation of its concentration can produce eutrophication. The gold standard method used for PO43− detection is based on colorimetric detection of phosphomolybdate. The colored complex is obtained by mixing water-soluble molybdenum salts (Mo(VI)) and reducing agents in acid media, along with the sample containing PO43−. Moreover, the kinetic of complex formation is slow, about 1 h is generally required for color to develop, exposing the assay to the drawbacks of interferences as those from silica. The detection is preferably performed in a controlled environment (i.e. in a laboratory) because several chemicals and steps of preparations are required as well as the optical instrumentation is not intended for in-field use. Electrochemical sensors offer portability and simplicity making them a practical option for on-site detection applications. To gain an analytical alternative in measuring low quantities of PO43− (10−9 M), and overcome some of the drawbacks of the classical approaches, we optimised a new easy way to produce a plastic electrode decorated with an alkyl Mo-polyoxometalate (Mo8O264−), that is soluble in organic solvents. This tetra-butyl-ammonium octamolybdate powder, [N (C4H9)4]4 Mo8O26, purposely synthetized was identified with FTIR, Raman, MS methods, and the electroactivity and reactivity with PO43− was confirmed in solution with cyclic voltammetry (CV). When the Mo-decorated electrode was in contact with PO43−, an electroactive phosphomolybdate aggregate formed at the electrode surface that was electrochemically detectable with square wave voltammetry (SWV). A remarkably low detection limit of 6.1 nM, to PO43−, as well as good stability and selectivity were obtained also in real samples. In fact, PO43− was measured in saline simulated and real seawater samples at nM concentrations in less than 5 min. The present investigation provides a new alternative to the current standard colorimetric methods to detect low phosphate concentrations, showing the potential to be used for monitoring nutrients in oligotrophic seawater.
Plastic electrode decorated with polyhedral anion tetrabutylammonium octamolybdate [N(C4H9)4]4 Mo8O26 for nM phosphate electrochemical detection / Figueredo, Federico; Girolametti, Federico; Aneggi, Eleonora; Lekka, Maria; Annibaldi, Anna; Susmel, Sabina. - In: ANALYTICA CHIMICA ACTA. - ISSN 0003-2670. - STAMPA. - 1161:(2021), p. 338469. [10.1016/j.aca.2021.338469]