Études des transformations des formes du carbone, azote, phosphore, soufre et des principaux éléments minéraux au cours de la mesure de la demande totale en oxygene—III transformation des formes du soufre

Previous experiments carried out with the laboratory TOD meter Ionics 225 of the DOW Chèmical made it possible (after a high temperature catalytic action) to characterize the stable forms of organic and inorganic carbon and nitrogen (NH₄⁺, NO₂⁻, NO₃⁻), and the principal cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) in the course of the total oxygen demand (TOD) measurement.The object of this study is firstly to compare the oxidation capability of different techniques of organic pollution (particularly the COD and TOD) in relation to the constituent elements of the organic matter C, N, P, S, and to calculate the possible interferences of the inorganic compounds at the time of TOD test.These investigations warrant the application of this technique to measure the amount of organic pollution in relatively mineralized conditions (Industrial wastewater, sea-water…). The present publication is concerned more with the study of the transformation of the organic and inorganic sulphur forms (S²⁻, SO₃²⁻. SO₄²⁻) in the course of the TOD measurement.The study of the oxidizability of the organic sulphur compound type C_xH_yO_zS, made it possible to establish a specific relation with a ratio of 0–50 mg of organic sulphur l⁻¹, between the oxygen demand of this element TOD (S)] and its concentration (TOD (S) = 0.97 S]).These tests showed a partial oxidation of the sulphur to SO₂ and SO₃ as the literature claimed. On the other hand, the oxidation of the same compounds during the COD tests varies greatly and although it is not possible to establish a correlation between these two measurements, as applies in the case of organic nitrogen, nevertheless these experiments showed a greater reliability of the TOD compared with the COD in the oxidation of organic matter in general. We then carried out experiments on the different mineral forms of sulphur in order to distinguish the possible effects and to recommend simple improvements.A relative study on sulphate ions had been carried out with standard solutions which have the same TOD (the basic TOD is obtained using potassium phthalate acid) and the same increasing concentration of the salt M₂SO₄ type. The experiments showed that the basic TOD decreases when the concentration of sulphate ions is increased (Fig. 3). Therefore, the interference is negative and taking into consideration the specific oxygen demand of the cation, we can propose an evaluation of this interference (ΔTOD (SO₄²⁻) = 0.203 SO₄²⁻]). The same experiments have been conducted with a salt of M₂SO₃ type and similar results obtained (Fig. 5).The specific interference of the sulphite ion is negative and can be estimated by the following equation (ΔTOD (SO₃²⁻) = 0.132 SO₃²⁻]). In both cases, we have to note that the transformation of these inorganic anions occurs between those relative to the theoretical dissociation reaction corresponding to the appearance of the oxide SO₂ and SO₃. For sulphurous on the contrary, the interference is positive and therefore corresponds to an extra oxygen demand (Fig. 8).The experiments were conducted directly with the M₂S salts (M representing K or Na) in aqueous solution.The evaluation of this interference had been made in the consideration of two concentration ranges of the sulphurous ions (0–35 mg S²⁻ l⁻¹): TOD (S²⁻) = 0.4 S²⁻] and (35–100 mg S²⁻ l⁻¹): TOD (S²⁻) = 1.2 S²⁻] − 30.Therefore this study confirms a better oxidation of the organic matter by TOD test in comparison with COD test.But sulphate and sulfite have a negative interference in the TOD measurement, whereas sulphurous is positive.The evaluation model of these interferences allows a correction to be made of the TOD value or to verify TOD measurement of organic pollution obtained by this technique.