Phosphorus orthophosphate

The chemical form of phosphorus in the water column available for uptake by biota is important. The biologically available phosphorus is usually taken to be soluble reactive phosphorus (orthophosphate) , i.e. which, upon acidification of a water sample, reacts with added molybdate to yield molybdophosphoric acid, which is then reduced with SnCl2 to the intensely-coloured molybdenum blue complex and is determined spectrophotometrically (Imax = 882 nm). Reduction in inputs of phosphate, for example from point sources or by creating water meadows and buffer strips to contain diffuse runoff, has obviously been one of the major approaches to stemming eutrophication trends and... 

Phosphorus is the eleventh element in order of abundance in crustal rocks of the earth and it occurs there to the extent of 1120 ppm (cf. H 1520 ppm, Mn 1060 ppm). All its known terrestrial minerals are orthophosphates though the reduced phosphide mineral schrieber-site (Fe,Ni)3P occurs in most iron meteorites. Some 200 crystalline phosphate minerals have been described, but by far the major amount of P occurs in a single mineral family, the apatites, and these are the only ones of industrial importance, the others being rare curiosities. Apatites (p. 523) have the idealized general formula 3Ca3(P04)2.CaX2, that is Caio(P04)6X2, and common members are fluorapatite Ca5(P04)3p, chloroapatite Ca5(P04)3Cl, and hydroxyapatite Ca5(P04)3(0H). In addition, there are vast deposits of amorphous phosphate rock, phosphorite, which approximates in composition to fluoroapatite. " These deposits are widely... 

Phosphorus from organophosphorus compounds, which are combusted to give mainly orthophosphate, can be absorbed by either sulphuric acid or nitric acid and readily determined spectrophotometrically either by the molybdenum blue method or as the phosphovanadomolybdate (Section 17.39). 

The method can be applied to the determination of phosphorus in a wide variety of materials, e.g. phosphate rock, phosphatic fertilisers and metals, and is suitable for use in conjunction with the oxygen-flask procedure (Section 3.31). In all cases it is essential to ensure that the material is so treated that the phosphorus is converted to orthophosphate this may usually be done by dissolution in an oxidising medium such as concentrated nitric acid or in 60 per cent perchloric acid. 

The analysis of phosphates and phosphonates is a considerably complex task due to the great variety of possible molecular structures. Phosphorus-containing anionics are nearly always available as mixtures dependent on the kind of synthesis carried out. For analytical separation the total amount of phosphorus in the molecule has to be ascertained. Thus, the organic and inorganic phosphorus is transformed to orthophosphoric acid by oxidation. The fusion of the substance is performed by the addition of 2 ml of concentrated sulfuric acid to — 100 mg of the substance. The black residue is then oxidized by a mixture of nitric acid and perchloric acid. The resulting orthophosphate can be determined at 8000 K by atom emission spectroscopy. The thermally excited phosphorus atoms emit a characteristic line at a wavelength of 178.23 nm. The extensity of the radiation is used for quantitative determination of the phosphorus content. 

Phosphorus forms a wide variety of oxoanions, which outnumber those formed by any other element except silicon [ 1 ]. Many of these anionic hgands are of industrial importance and their derivatives are essential components of numerous biological processes. Some of the more common examples include orthophosphate PO " (1), phosphite HPO " (2) and metaphosphate PO3 (3). 

The simultaneous analysis of orthophosphate, glycerol phosphates, and inositol phosphates has been achieved by spectrophotometric analysis of the molybdovanadate complexes. Also, a sensitive and selective chemiluminescent molecular emission method for the estimation of phosphorus and sulphur is described, which is based on passing solutions into a cool, reducing, nitrogen-hydrogen diffusion flame. For organic compounds it was usually necessary to prepare test solutions by an oxygen-flask combustion technique. 

In the malachite green procedure, 10 ml of the sample solution containing up to 0.7 xg phosphorus as orthophosphate was transferred into a 25 ml test tube. To this solution was added 1 ml each of 4.5 M sulfuric acid and the reagent solution. The solution was shaken with 5 ml of a 1 3 v/v mixture of toluene and 4-methylpentan-2-one for 5 min. After phase separation, the absorbance of the organic phase was measured at 630 nm against a reagent blank in 1 cm cells. 

Eberlein and Kattner [194] described an automated method for the determination of orthophosphate and total dissolved phosphorus in the marine environment. Separate aliquots of filtered seawater samples were used for the determination orthophosphate and total dissolved phosphorus in the concentration range 0.01-5 xg/l phosphorus. The digestion mixture for total dissolved phosphorus consisted of sodium hydroxide (1.5 g), potassium peroxidisulfate (5 g) and boric acid (3 g) dissolved in doubly distilled water (100 ml). Seawater samples (50 ml) were mixed with the digestion reagent, heated under pressure at 115-120 °C for 2 h, cooled, and stored before determination in the autoanalyser system. For total phosphorus, extra ascorbic acid was added to the aerosol water of the autoanalyser manifold before the reagents used for the molybdenum blue reaction were added. For measurement of orthophosphate, a phosphate working reagent composed of sulfuric acid, ammonium molyb-... 

On-line phosphate measurement is more often limited to orthophosphates, the total phosphorus measurement needing a mineralization step that is difficult to carry out on site. However, some recent works have been published [27, 28] based on the use of a biosensor or of UV spectrophotometry (after reagent addition). The limit of detection is rather high for this analyte (0.5 mg L 1 or higher). 

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Dietary phosphorus also affects calcium metabolism. Polyphosphate decreases calcium absorption in young men while orthophosphate supplement does not (26J. However, in the rat all forms of phosphate decrease calcium absorption about equally (31). However, widely divergent dietary calcium phosphorus ratios do not seem to affect calcium utilization by people as long as there is adequate phosphorus intake (32). In general phosphorus stimulates calcium retention in man (3277... 

Increasing both dietary Ca and P causes a decrease in PTH-mediated bone resorption polyphosphates and phosphorus in food cause greater reductions than does inorganic orthophosphate, as these sources are slowly released in digestion. 

We have conducted two human metabolic studies (5,6) to compare the effects of increasing phosphorus intake on calcium utilization in healthy young adults maintained at low (ca. 400 mg/day) and high (ca. 1200 mg/day) levels of calcium intake. Increasing dietary phosphorus, as orthophosphate, caused a slight reduction in fecal calcium and a substantial reduction in urinary calcium losses (Table III). 

Table V. Absorption, Excretion, and Retention of Phosphorus as Affected by Calcium and Orthophosphates...

Condensed (poly) phosphates may exert different effects on calcium utilization than the aforementioned effects of simple (ortho-) phosphates. Polyphosphates have a much greater affinity for calcium than do orthophosphates, and soluble calcium-polyphosphate complexes are readily formed in the gastric and intestinal environments. In addition, polyphosphates must be hydrolyzed by an intestinal alkaline phosphatase (27) prior to absorption. We have found polyphosphates to be incompletely (80.5%) hydrolyzed to orthophosphate during the digestive process in young adult males when calcium intake was low only 56% of a 1 g phosphorus supplement was absorbed from a polyphosphate sources as compared to 71% from an orthophosphate source (5). 

All subjects were in negative calcium balance when consuming the basal low calcium, low phosphorus diet (Table VII), the mean calcium loss being 110 mg/day. The orthophosphate supplement significantly reduced this loss to 29 mg/day, due to decreases in both urinary and fecal calcium losses. The polyphosphate supplement, however, caused... 

It is noteworthy that although phosphorus absorption was lower on the high calcium, high polyphosphate diet than on the high calcium, high orthophosphate diet, there was no significant difference between... 

Table VIII. Phosphorus Excretion and Retention as Affected by Orthophosphate, Hexametaphosphate (Polyphosphate), and Calcium...

Organic phosphorus is determined by the difference in phosphorus content of the 1M hydrochloric acid extract measured before and after ignition of the dry sediments at 550°C. In all instances the orthophosphate is determined by using standard Technicon AutoAnalyzer II techniques. Silica does not interfere. 

The determination of the orthophosphate was carried out by using the automated systems described by the Technicon Instruments Corporation. The manifolds used are shown in Fig. 12.3. The procedures referred to below as methods I and II are Technicon industrial methods Nos. 94-70W and 155-71W, respectively. Method I includes ascorbic acid alone for the reduction of the molybdophosphoric acid whereas in method II the mixed reagents ascorbic acid, sulphuric acid, ammonium molybdate and antimony potassium tartrate are used. Method I is intended for use for high levels of phosphorus (up to lOpg ml4) and method II for low levels (less than 0.5pg ml4). The wetting agent (Levor IV) used in order to obtain a smooth bubble pattern, is present in the ascorbic acid reagent line for method I whereas it is added externally Fig. 12.3) in the water line (0.5pg ml4 of Levor) in method II. 

Determination of total phosphorus in lake sediments by ignition of samples in a muffle furnace at 550°C, boiling of the residue from ignition in lmol L 1 hydrochloric acid, and subsequent determination of orthophosphate gave approximately the same values as the perchloric acid digestion. 

The whole column, apart from a small portion of the sediment, is sam pled in this way. The chemical checks were carried out every 15 days, determining pH, Conductivity, C.O.D., Ammoniacal Nitrogen, Orthophosphate Phosphorus and, furthermore, each month Total phosphorus, Total Kjeldahl Nitrogen, Total Solids and Volatile Solids. The methods utilized are those indicated in the Standard Methods (A.P.H.A., 1980). The amount of matter particles sedimented in the tanks was estimated with the use ol appropriate sampling devices located at the bottom of the tanks and withdrawn after a variable permanence of 40 to 60 days. 

Phosphorus is a common component of additives and appears most commonly as a zinc dialkyl dithiophosphate or triaryl phosphate ester, but other forms also occur. Two wet chemical methods are available, one of which (ASTM D1091) describes an oxidation procedure that converts phosphorus to aqueous orthophosphate anion. This is then determined by mass as magnesium pyrophosphate or photochemically as molybdivanadophosphoric acid. In an alternative test (ASTM D4047), samples are oxidized to phosphate with zinc oxide, dissolved in acid, precipitated as quinoline phosphomolybdate, treated with excess standard alkali, and back-titrated with standard acid. Both of these methods are used primarily for referee samples. Phosphorus is most commonly determined using x-ray fluorescence (ASTM D4927) or ICP (ASTM D4951). 

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