The molybdenum blue reaction for the determination of orthophosphate revisited: Opening the black box.

The molybdenum blue reaction, used predominantly for the determination of orthophosphate in environmental waters, has been perpetually modified and re-optimised over the years, but this important reaction in analytical chemistry is usually treated as something of a 'black box' in the analytical literature. A large number of papers describe a wide variety of reaction conditions and apparently different products (as determined by UV-visible spectroscopy) but a discussion of the chemistry underlying this behaviour is often addressed superficially or not at all. This review aims to rationalise the findings of the many 'optimised' molybdenum blue methods in the literature, mainly for environmental waters, in terms of the underlying polyoxometallate chemistry and offers suggestions for the further enhancement of this time-honoured analytical reaction.

[1]  J. Poblet,et al.  Electronic Properties of Polyoxometalates: A DFT Study of α/β-[XM12O40]n- Relative Stability (M = W, Mo and X a Main Group Element) , 2001 .

[2]  P. Benes,et al.  The state and adsorption behaviour of traces of molybdenum(VI) in aqueous solutions , 1973 .

[3]  Michael J. Taylor,et al.  Molybdenum-95 nuclear magnetic resonance and vibrational spectroscopic studies of molybdenum(VI) species in aqueous solutions and solvent extracts from hydrochloric and hydrobromic acid: evidence for the complexes [Mo2O5(H2O)6]2+, [MoO2X2(H2O)2](X = Cl or Br), and [MoO2Cl4]2– , 1990 .

[4]  K. G. Falk,et al.  THE PRECIPITATION OF PHOSPHORUS AS AMMONIUM PHOSPHOMOLYBDATE IN THE PRESENCE OF SULFURIC ACID. , 1915 .

[5]  F. Cavani,et al.  Improved catalytic performance of Keggin-type polyoxometalates in the oxidation of isobutane to methacrylic acid under hydrocarbon-lean conditions using antimony-doped catalysts , 2001 .

[6]  S. R. Crouch,et al.  Kinetics of the formation and decomposition of 12-molybdophosphate , 1983 .

[7]  J. J. Cruywagen Potentiometric investigation of molybdenum(VI) equilibriums at 25.degree.C in 1 M sodium chloride medium , 1980 .

[8]  Peter J. Smith,et al.  Kinetics of α- and β-molybdosilicic acid formation , 1979 .

[9]  J. P. Riley,et al.  A Single-Solution Method for the Determination of Soluble Phosphate in Sea Water , 1958, Journal of the Marine Biological Association of the United Kingdom.

[10]  L. T. Kurtz Elimination of Fluoride Interference in Molybdenum Blue Reaction , 1942 .

[11]  T. Osakai,et al.  Voltammetric determination of sulphate ion through heteropoly blue formation , 1990 .

[12]  S. Eisenreich,et al.  Spectrophotometric studies of reduced molybdoantimonylphosphoric acid , 1974 .

[13]  R. I. Maksimovskaya Molybdophosphate heteropoly blues: Electron-transfer reactions in aqueous solutions as studied by NMR , 2013 .

[14]  C. Jing,et al.  A novel colorimetric method for field arsenic speciation analysis. , 2012, Journal of environmental sciences.

[15]  T. Han An improved phosphorus assay for oils without carcinogenic hydrazine sulfate , 1995 .

[16]  J. Poblet,et al.  Electronic properties of polyoxometalates: a DFT study of alpha/beta-[XM(12)O(40)](n-) relative stability (M=W, Mo and X a main group element). , 2001, Journal of the American Chemical Society.

[17]  Quan-min Li,et al.  Determination of thiamazole in pharmaceutical samples by phosphorus molybdenum blue spectrophotometry. , 2012, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[18]  Determination of Orthophosphate in Fresh , 2016 .

[19]  J. J. Cruywagen,et al.  Molybdenum(VI) equilibria at high perchloric acid concentration , 2000 .

[20]  K. Grudpan,et al.  Stopped-flow injection method for determination of phosphate in soils and fertilisers , 2008 .

[21]  P. Cannon Some electrometric measurements of heteropoly ion formation in aqueous systems , 1960 .

[22]  S. Pai,et al.  Effect of Heating on the Color Formation Reaction in the Murphy andRiley Method for the Determination of Phosphate in Natural Waters , 2015 .

[23]  Jia-Zhong Zhang,et al.  Neutral persulfate digestion at sub-boiling temperature in an oven for total dissolved phosphorus determination in natural waters. , 2009, Talanta.

[24]  Víctor Cerdà,et al.  Flow analysis techniques for phosphorus: an overview. , 2005, Talanta.

[25]  Alejandro Cifuentes,et al.  Determination of Critical Micelle Concentration Values Using Capillary Electrophoresis Instrumentation , 1997 .

[26]  J. Masini,et al.  Spectrophotometric determination of phosphate and silicate by sequential injection using molybdenum blue chemistry , 2000 .

[27]  M. Cindrić,et al.  Synthesis, structure and properties of molybdenum(VI) oxalate complexes of the types M2[Mo2O5(C2O4)2(H2O)2] and M2[MoO3(C2O4)] (M=Na, K, Rb, Cs) , 2000 .

[28]  E. Steckhan,et al.  Electrochemical Properties of Polyoxometalates as Electrocatalysts. , 1998, Chemical reviews.

[29]  P. S. Chen,et al.  Microdetermination of Phosphorus , 1956 .

[30]  A. Geen,et al.  A rapid colorimetric method for measuring arsenic concentrations in groundwater , 2004 .

[31]  A. Komura,et al.  Reactions of the Di-μ-oxo-bis[aquaoxalatooxomolybdate(V)] Ion , 1976 .

[32]  A. B. Bendtsen,et al.  Spectrophotometric determination of silicon in soil solutions by flow injection analysis: reduction of phosphate interference , 1994 .

[33]  L. G. Hargis,et al.  Spectrophotometric determination of cesium using 12-molybdophosphoric acid , 1967 .

[34]  E. Papaconstantinou Photochemistry of polyoxometallates of molybdenum and tungsten and/or vanadium , 1989 .

[35]  S. Tarapchak Soluble Reactive Phosphorus Measurements in Lake Water: Evidence for Molybdate-enhanced Hydrolysis , 1983 .

[36]  H. Levine,et al.  Molybdenum blue reaction and determination of phosphorus in waters containing arsenic, silicon, and germanium , 1955 .

[37]  J. J. Cruywagen,et al.  A potentiometric, spectrophotometric, and calorimetric investigation of molybdenum(VI)–oxalate complex formation , 1986 .

[38]  C. H. Fiske,et al.  THE COLORIMETRIC DETERMINATION OF PHOSPHORUS , 1925 .

[39]  S. R. Crouch,et al.  Kinetics of the formation of 12-molybdophosphate in perchloric, sulfuric, and nitric acid solutions , 1975 .

[40]  J. P. Riley,et al.  A modified single solution method for the determination of phosphate in natural waters , 1962 .

[41]  R. Clark,et al.  Structural and electronic properties of some polymolybdates reducible to molybdenum blues , 1985 .

[42]  T. Kiba,et al.  Studies on the formation and the extraction of molybdophosphoric acid , 1970 .

[43]  J. P. Riley,et al.  Effects of acidity and molybdate concentration on the kinetics of the formation of the phosphoantimonylmolybdenum blue complex , 1990 .

[44]  L. Lutwak,et al.  The catalytic effect of molybdate on the hydrolysis of organic phosphates. , 1953, Journal of Biological Chemistry.

[45]  P. L. Buldini,et al.  Rapid determination of dissolved silica in natural waters , 1985 .

[46]  R. Massart,et al.  Gradual reduction of molybdosilicates and related compounds , 1974 .

[47]  E. Diemann,et al.  Molybdenum Blue: A 200‐Year‐Old Mystery Unveiled. , 1996 .

[48]  M. Ardon,et al.  Molybdenum(V) in aqueous solution , 1973 .

[49]  I. McKelvie,et al.  The nature of the salt error in the Sn(II)-reduced molybdenum blue reaction for determination of dissolved reactive phosphorus in saline waters. , 2015, Analytica chimica acta.

[50]  Y. Chow,et al.  Dimeric dioxomolybdenum(VI) and oxomolybdenum(V) complexes with citrate at very low pH and neutral conditions. , 2005, Inorganic chemistry.

[51]  J. Chi,et al.  Automated analysis of nanomolar concentrations of phosphate in natural waters with liquid waveguide. , 2002, Environmental science & technology.

[52]  J. D. Burton,et al.  Determination of soluble phosphate, and total phosphorus in sea-water and of total phosphorus in marine muds , 1956 .

[53]  Nanoscale assemblies of gigantic molecular {Mo154}-rings: (dimethyldioctadecylammonium)20[Mo154O462H8(H2O)70]. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[54]  M. T. Pope,et al.  Structure of a heteropoly blue. The four-electron reduced .beta.-12-molybdophosphate anion , 1985 .

[55]  H. W. Harvey The Estimation of Phosphate and of Total Phosphorus in Sea Waters , 1948, Journal of the Marine Biological Association of the United Kingdom.

[56]  N. Lingaiah,et al.  Acidity Constants of Supported Salts of Heteropoly Acids Using a Methodology Related to the Potentiometric Mass Titration Technique , 2006 .

[57]  A. G. Sinclair,et al.  Analytical applications of β-heteropoly acids : Part I. Determination of arsenic, germanium and silicon , 1965 .

[58]  P. Wakeley,et al.  Synthesis , 2013, The Role of Animals in Emerging Viral Diseases.

[59]  Peter A. Williams,et al.  N.m.r. studies of complexes of molybdenum(VI) with tartaric acid in aqueous solution , 1984 .

[60]  Fang Zhao-lun,et al.  Compensation of calibration graph curvature and interference in flow-injection spectrophotometry using gradient ratio calibration , 1990 .

[61]  K. Tytko,et al.  Equilibrium studies of aqueous polymolybdate solutions in 1 M sodium chloride medium at 25.degree.C , 1985 .

[62]  M. Pilson,et al.  Spectrophotometric determination of arsenite, arsenate, and phosphate in natural waters , 1972 .

[63]  William A. Maher,et al.  Determination of phosphorus in aqueous solution via formation of the phosphoantimonylmolybdenum blue complex re-examination of optimum conditions for the analysis of phosphate , 1995 .

[64]  Elias A.G. Zagatto,et al.  Flow analysis with spectrophotometric and luminometric detection , 2012 .

[65]  Y. Abe,et al.  Elucidation of molybdosilicate complexes in the molybdate yellow method by ESI-MS. , 2015, Talanta.

[66]  R. H. Bray,et al.  Colorimetric determination of phosphate. , 1940 .

[67]  J. Malý Beitrag zur Phosphorbestimmung im Klärschlamm , 1985 .

[68]  G. G. Stokes "J." , 1890, The New Yale Book of Quotations.

[69]  R. Cattrall,et al.  Pervaporation-flow injection determination of arsenic based on hydride generation and the molybdenum blue reaction , 2001 .

[70]  J. J. Cruywagen,et al.  Molybdenum(VI) complex formation—8. Equilibria and thermodynamic quantities for the reactions with citrate , 1995 .

[71]  Clara Bargamini Masquage des complexes du molybdne par l'lon fluorhydriquetude spectrophotomtrique , 1950 .

[72]  P. Worsfold,et al.  Determination of nanomolar concentrations of phosphate in natural waters using flow injection with a long path length liquid waveguide capillary cell and solid-state spectrophotometric detection. , 2007, Talanta.

[73]  D. F. Boltz,et al.  Determination of Phosphorus, Germanium, Silicon, and Arsenic , 1947 .

[74]  N A Zatar,et al.  Spectrophotometric determination of nitrite and nitrate using phosphomolybdenum blue complex. , 1999, Talanta.

[75]  J. Strickland The Preparation and Properties of Silicomolybdic Acid. III. The Combination of Silicate and Molybdate , 1952 .

[76]  A. R. Mcintyre,et al.  Inorganic Phosphates and Phosphate Esters in Tissue Extracts , 1951 .

[77]  C. Rabia,et al.  Preparation and characterization of mixed ammonium salts of Keggin phosphomolybdate , 2009 .

[78]  L. Öhman,et al.  Multicomponent polyanions. XXXV: A 31P NMR study of aqueous molybdophosphates , 1985 .

[79]  T. Ueda,et al.  Effects of Organic Solvents and Salts on the Isomerization Reaction (β→α) of Keggin-type 12-Molybdophosphate Anion , 2013, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[80]  O. H. Lowry,et al.  The determination of inorganic phosphate in the presence of labile phosphate esters. , 1946, The Journal of biological chemistry.

[81]  F. Lipmann,et al.  ACETYL PHOSPHATE: CHEMISTRY, DETERMINATION, AND SYNTHESIS , 1944 .

[82]  Jia-Zhong Zhang Distinction and quantification of carry-over and sample interaction in gas segmented continuous flow analysis , 1997, The Journal of automatic chemistry.

[83]  J. Keggin The Structure and Formula of 12-Phosphotungstic Acid , 1934 .

[84]  H. Kurokura,et al.  A problem in the spectrophotometric determination of dissolved total phosphorus in brackish anoxic waters , 1984 .

[85]  栄子 中村,et al.  ビスマス(III)イオン共存下のアスコルビン酸還元によるリンモリブデン青形成に基づくリンの吸光光度定量 , 2007 .

[86]  A. Hiskia,et al.  Photocatalytic oxidation of organic compounds by polyoxometalates of molybdenum and tungsten : catalyst regeneration by dioxygen , 1992 .

[87]  C. R. Chen,et al.  The effect of low-molecular-weight organic acids and inorganic phosphorus concentration on the determination of soil phosphorus by the molybdenum blue reaction , 2009, Biology and Fertility of Soils.

[88]  M. Mellon,et al.  Molybdenum Blue Reaction: A Spectrophotometric Study , 1941 .

[89]  Y. Chow,et al.  Crystalline and solution chemistry of tetrameric and dimeric molybdenum(VI) citrato complexes , 2013 .

[90]  S. Ikeda,et al.  Studies on polynuclear molybdates in the aqueous solution by laser Raman spectroscopy , 1983 .

[91]  S. Ikeda,et al.  A mechanistic investigation on the formation of molybdophosphate complexes in aqueous solution by the use of laser Raman spectroscopy , 1987 .

[92]  Hirokazu Kobayashi,et al.  Mechanism of salt error on the color development of phosphomolybdenum blue , 2004 .

[93]  K. Pettersson,et al.  Analytical determination of orthophosphate in water , 1988, Hydrobiologia.

[94]  D. Baldwin Reactive “organic” phosphorus revisited , 1998 .

[95]  Benjamin L Turner,et al.  Sampling, sample treatment and quality assurance issues for the determination of phosphorus species in natural waters and soils. , 2005, Talanta.

[96]  W. Harris,et al.  Determination of the phosphorus content of lipids , 1954 .

[97]  M. F. Iskander,et al.  Studies on some heteropoly blues—I the reduction of 12-molybdophosphoric acid with stannous chloride , 1973 .

[98]  I. Koshiishi,et al.  Study of the coloured substances in molybdenum blue using high-performance liquid chromatography , 1986 .

[99]  M. Baum,et al.  Determination of phosphate/arsenate by a modified molybdenum blue method and reduction of arsenate by S(2)O(4)(2-). , 2007, Talanta.

[100]  A. Ellern,et al.  Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study. , 2012, Dalton transactions.

[101]  S. Rabideau,et al.  THE APPLICATION OF HIGH-SPEED COMPUTERS TO THE LEAST SQUARES DETERMINATION OF THE FORMATION CONSTANTS OF THE CHLORO-COMPLEXES OF TIN(II)1 , 1961 .

[102]  I. McKelvie,et al.  On-line Removal of Sulfide Interference in Phosphate Determination by Flow Injection Analysis , 2006 .

[103]  Jia-Zhong Zhang,et al.  Optimization of performance and minimization of silicate interference in continuous flow phosphate analysis. , 1999, Talanta.

[104]  S. Himeno,et al.  Spectrophotometric investigation on the equilibration of monomeric forms of Mo(VI) in aqueous sulfuric acid , 1983 .

[105]  G. Hesse,et al.  Untersuchungen zur Phosphorbestimmung (Nukleotidphosphor) nach Hurst mit einem SnCl2/Hydrazinsulfatreagens , 1968 .

[106]  P. Pakalns,et al.  Effect of surfactants on the spectrophotometric determination of phosphate by direct and extraction procedures , 1976 .

[107]  Christopher J. Smith,et al.  The formation of molybdosilicic acids from mixed solutions of molybdate and silicate , 1975 .

[108]  P. Worsfold,et al.  Rapid determination of dissolved organic phosphorus in soil leachates and runoff waters by flow injection analysis with on-line photo-oxidation. , 1997, Talanta.

[109]  L. Kazansky,et al.  Infrared spectroscopic evidence of bipolaron delocalization in reduced heterododecamolybdates , 1994 .

[110]  G. Giester,et al.  Synthesis and structures of ammonium and tetraphenylphosphonium salts of μ-oxo-diaquadioxalatotetraoxodimolybdenum(VI). An interesting example of intramolecular hydrogen bonds within the dimeric anion , 2000 .

[111]  I. McKelvie,et al.  The use of on-line UV photoreduction in the flow analysis determination of dissolved reactive phosphate in natural waters. , 2015, Talanta.

[112]  Miho Tanaka,et al.  Analysis of Complex-formation Reaction in Molybdenum Blue Method by ESI-MS , 2012 .

[113]  J. J. Cruywagen,et al.  Spectrophotometric determination of the thermodynamic parameters for the first two protonation reactions of molybdate: An advanced undergraduate laboratory experiment , 1989 .

[114]  A. Draaijer,et al.  Molybdenum(VI) equilibria in different ionic media. Formation constants and thermodynamic quantities , 2002 .

[115]  Jia-Zhong Zhang Enhanced Sensitivity in Flow Injection Analysis Using a Long Pathlength Liquid Waveguide Capillary Flow Cell for Spectrophotometric Detection , 2006, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[116]  A. G. Sinclair,et al.  Analytical applications of β-heteropoly acids , 1965 .

[117]  G. Nürnberg Iron and hydrogen sulfide interference in the analysis of soluble reactive phosphorus in anoxic waters , 1984 .

[118]  J. J. Cruywagen,et al.  Molybdenum(VI) complex formation. Part 4. Equilibria and thermodynamic quantities for the reactions with tartrate in 1.0 mol dm-3 sodium chloride , 1990 .

[119]  S. Blomqvist,et al.  Interference from Arsenate, Fluoride and Silicate When Determining Phosphate in Water by the Phosphoantimonylmol Ybdenum Blue Method , 1993 .

[120]  H. Hahn,et al.  Über zwei reduzierte Formen der Molybdatophosphorsäure und deren Salze , 2004, Naturwissenschaften.

[121]  J. J. Cruywagen,et al.  Dimeric cations of molybdenum(VI) , 1978 .

[122]  Dimitrios K. Kampouris,et al.  Rapid and portable electrochemical quantification of phosphorus. , 2015, Analytical chemistry.

[123]  C. A. Emeis,et al.  On the identification of molybdophosphate complexes in aqueous solution , 1986 .

[124]  Haoran Sun,et al.  Electrochemical and in-situ UV-visible-near-IR and FTIR spectroelectrochemical characterisation of the mixed-valence heteropolyanion PMo12O40n− (n=4, 5, 6, 7) in aprotic media , 1998 .

[125]  J. Harwood,et al.  A rapid method for orthophosphate analysis at high concentrations in water , 1969 .

[126]  J. Livage,et al.  Electron delocalization in mixed-valence molybdenum polyanions , 1982 .

[127]  N. Tanaka,et al.  Voltammetric and spectroelectrochemical studies of dodecamolybdophosphoric acid in aqueous and water-dioxane solutions at a gold-minigrid optically transparent thin-layer electrode , 1982 .

[128]  P. Worsfold,et al.  Determination of Dissolved Reactive Phosphorus in Estuarine Waters Using a Reversed Flow Injection Manifold , 1997 .

[129]  R. Ammon,et al.  Colorimetrische Phosphor- und Arsensäurebestimmung mit Ascorbinsäure. , 1936 .

[130]  T. Fontaine Spectrophotometric determination of phosphorus. , 1942 .

[131]  C. Serain,et al.  Soluble Molybdenum Blues — “des Pudels Kern” , 2000 .

[132]  Wolfhard Weidel Des Pudels Kern , 1964 .

[133]  T. Ueda,et al.  Formation and conversion of molybdophosphate and -arsenate complexes in aqueous solution , 1999 .

[134]  L. Cooper Salt Error in Determinations of Phosphate in Sea Water , 1938, Journal of the Marine Biological Association of the United Kingdom.

[135]  Subhash D. Katewa,et al.  A simplified method for inorganic phosphate determination and its application for phosphate analysis in enzyme assays. , 2003, Analytical biochemistry.

[136]  F. Cavani,et al.  Effect of Antimony on the Chemical–Physical Features and Reactivity in Isobutyric Acid Oxidehydrogenation of Keggin-Type Heteropolycompounds☆ , 1998 .

[137]  Jia-Zhong Zhang,et al.  Continuous Flow Analysis of Phosphate in Natural Waters Using Hydrazine as a Reductant , 2001 .

[138]  Theodore G. Towns,et al.  Determination of aqueous phosphate by ascorbic acid reduction of phosphomolybdic acid , 1986 .

[139]  J. J. Cruywagen,et al.  Coordination number of molybdenum(VI) in monomeric molybdic acid , 1975 .

[140]  L. Pettersson,et al.  Multicomponent polyanions. 39. Speciation in the aqueous hydrogen ion-molybdate(MoO42-)-hydrogenphosphate(HPO42-) system as deduced from a combined Emf-phosphorus-31 NMR study , 1986 .

[141]  A. E. Greenberg,et al.  Standard methods for the examination of water and wastewater : supplement to the sixteenth edition , 1988 .

[142]  S. Ikeda,et al.  Studies on yellow and colourless molybdophosphate complexes in the aqueous solution by laser raman spectroscopy , 1983 .

[143]  H. V. Malmstadt,et al.  Mechanistic investigation of molybdenum blue method for determination of phosphate , 1967 .

[144]  E. Baginski,et al.  Determination of phosphate: Study of labile organic phosphate interference , 1967 .

[145]  Eugenio Coronado,et al.  Mixed-valence polyoxometalate clusters. I. Delocalization of electronic pairs in dodecanuclear heteropoly blues with keggin structure , 1995 .

[146]  S. Eisenreich,et al.  Extraction of reduced molybdophosphoric and molybdoantimonylphosphoric acids with oxygenated solvents , 1974 .

[147]  I. McKelvie,et al.  Spectrophotometric determination of dissolved organic phosphorus in natural waters using in-line photo-oxidation and flow injection , 1989 .

[148]  J. P. Riley,et al.  The colorimetric determination of silicate with special reference to sea and natural waters , 1955 .

[149]  M. Z. Barakat,et al.  The microdetermination of ferrous iron , 1964 .

[150]  F. Taube,et al.  Molybdate speciation in systems related to the bleaching of kraft pulp , 2001 .

[151]  S. Rubio,et al.  Simultaneous determination of arsenate and phosphate by use of the kinetic wavelength-pair method , 1993 .

[152]  Jia-Zhong Zhang,et al.  Abundance and Chemical Speciation of Phosphorus in Sediments of the Mackenzie River Delta, the Chukchi Sea and the Bering Sea: Importance of Detrital Apatite , 2010 .

[153]  P. Sipos,et al.  The standard electrode potential of the Sn4+/Sn2+ couple revisited , 2009 .

[154]  T. Seward,et al.  Spectrophotometric determination of the stability of thallium (I) chloride complexes in aqueous solution up to 200°C , 1998 .

[155]  I. McKelvie,et al.  Determination of total phosphorus in waters and wastewaters by on-line UV/thermal induced digestion and flow injection analysis , 1996 .

[156]  R. Stauffer Determination of arsenic and phosphous compounds in groundwater with reduced molybdenum blue , 1983 .

[157]  R. Thomas,et al.  Communicaton. Automated method for determining and removing silica interference in determination of soluble phosphorus in lake and stream waters , 1970 .

[158]  S. Himeno,et al.  Spectrophotometric studies on the monomer-monomer equilibration of Mo(VI) in hydrochloric acid solutions , 1983 .

[159]  Jia-Zhong Zhang,et al.  Kinetic spectrophotometric determination of submicromolar orthophosphate by molybdate reduction , 2008 .

[160]  V. N. Jonge,et al.  Interference of sulphide in inorganic phosphate determination in natural waters , 1980 .

[161]  R. Massart,et al.  Electronic spectra of mixed valence reduced heteropolyanions , 1976 .

[162]  T. Osakai,et al.  A voltammetric study of Keggin-type heteropolymolybdate anions , 1994 .

[163]  Paul J. Worsfold,et al.  Analytical perspective. Techniques for the quantification and speciation of phosphorus in natural waters , 1995 .

[164]  Á. Molina,et al.  Reversible surface two-electron transfer reactions in square wave voltcoulommetry: application to the study of the reduction of polyoxometalate [PMo12O40]3- immobilized at a boron doped diamond electrode. , 2013, Analytical chemistry.

[165]  H. V. Malmstadt,et al.  Investigations of formation of 12-molybdophosphoric acid utilizing rapid reaction-rate measurements , 1968 .

[166]  N. K. Pandey,et al.  Spectrophotometric determination of trace amounts of phosphate in water and soil. , 2012, Water science and technology : a journal of the International Association on Water Pollution Research.

[167]  D. C. Martens,et al.  Determination of soluble phosphorus in the presence of organic ligands or fluoride , 1998 .

[168]  Paul J. Worsfold,et al.  Environmental applications of liquid-waveguide-capillary cells coupled with spectroscopic detection , 2007 .

[169]  M. T. Pope,et al.  182tungsten Mössbauer spectroscopy of heteropolytungstates. , 2009, Dalton transactions.

[170]  M. Valcárcel,et al.  Flow injection analysis of binary and ternary mixtures if arsenite, arsenate, and phosphate , 1986 .

[171]  P. Worsfold,et al.  Elimination of the Schlieren effect in the determination of reactive phosphorus in estuarine waters by flow injection analysis , 1997 .

[172]  M. Mellon,et al.  Indirect Absorptiometric Method for Determination of Boron , 1960 .

[173]  S. R. Crouch,et al.  Determination of formation constants of molybdophosphates in strong acid solutions , 1982 .

[174]  I. McKelvie,et al.  The use of a polymer inclusion membrane for separation and preconcentration of orthophosphate in flow analysis. , 2013, Analytica chimica acta.

[175]  S. Blomqvist,et al.  Influence of phosphate concentration and reaction temperature when using the molybdenum blue method for determination of phosphate in water , 1997 .

[176]  J. Strickland The Preparation and Properties of Silicomolybdic Acid. II. The Preparation and Properties of β-Silicomolybdic Acid , 1952 .