DETERMINATION OF ORTHOPHOSPHATE IN WATER BY SOLID-PHASE CHEMILUMINESCENT METHOD

G. Sumarokova, R. Linnik, О. Zaporozhets, L. Zinko
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Abstract

Phosphorus is one of the most important nutrients. Excessive content of its compounds in water objects leads to eutrophication, as well as reduces water quality. Methods based on the formation of molybdophosphate heteropolyacid (HPA) in an acidic medium with its subsequent reduction and spectrophotometric detection of the formed reduced "blue" HPA are most often used to determine phosphorus compounds. These methods are unsuitable for the analysis of waters with a phosphorus content <40 μg /L. The use of the chemiluminescent method (CL) makes it possible to increase the sensitivity of the determination, but CL detection in an acidic medium under the conditions of formation of HPA is limited by the existing indicator systems. To increase the selectivity of the method for determining the microquantities of phosphate relative to metal ions, we used an approach based on the adsorption removal of analyte with next determination using the CL method. Previous removal of phosphate from an aqueous solution in the form of reduced molybdostibiumphosphate HPA was released using batch technique in optimal conditions of its formation in the solution. Silica modified with cetyltrimethylammonium bromide was used as anion exchange adsorbent. Then the concentrate was processed with alkaline lucigenin solution and registration of the CL glow resulting from the reaction. Under optimal conditions of phosphate determination, the calibration curve is linear in the range from 3.7 to 147 μg PO43–/L with a detection limit of 0.8 μg PO43–/L. Cations K+, Na+, Fe(III), Mo(VI), NH4+ and anions Cl–, F–, HCO3–, С4Н4О62–, Asc–, NO2–, SO42–, as well as EDTA, do not interfere. Silicates (SiO32–) do not interfere with the determination of phosphate, even in 100-fold excess. Nitrates at concentrations below the average content in drinking water do not interfere with the determination. The developed technique was tested on a sample of pump room water. The technique is characterized by high sensitivity and a wide range of detectable concentrations. It is not inferior in sensitivity to flow methods using fluorescent or chemiluminescent detection.
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固相化学发光法测定水中正磷酸盐
磷是最重要的营养物质之一。其化合物在水中的过量含量会导致富营养化,并降低水质。基于磷酸钼杂多酸(HPA)在酸性介质中的形成及其随后的还原和形成的还原“蓝色”HPA的分光光度法检测的方法最常用于测定磷化合物。这些方法不适用于磷含量<40 μg /L的水质分析。化学发光法(CL)的使用使测定灵敏度的提高成为可能,但现有的指示剂体系限制了CL在酸性介质中形成HPA条件下的检测。为了提高该方法相对于金属离子测定微量磷酸盐的选择性,我们采用了一种基于吸附去除分析物的方法,并使用CL法进行下一次测定。在溶液中形成磷酸盐的最佳条件下,采用批处理技术以还原性磷酸钼铋HPA的形式从水溶液中去除磷酸盐。采用十六烷基三甲基溴化铵改性二氧化硅作为阴离子交换吸附剂。然后用碱性lucigenin溶液对浓缩物进行处理,记录反应产生的CL辉光。在最佳条件下,校准曲线在3.7 ~ 147 μg PO43 - /L范围内呈线性关系,检出限为0.8 μg PO43 - /L。阳离子K+、Na+、Fe(III)、Mo(VI)、NH4+和阴离子Cl -、F -、HCO3 -、С4Н4О62 -、Asc -、NO2 -、SO42 -以及EDTA不受干扰。硅酸盐(SiO32 -)不干扰磷酸盐的测定,即使超过100倍。低于饮用水中平均含量的硝酸盐浓度不会干扰测定。该技术已在某泵房水样品上进行了试验。该技术具有灵敏度高、检测浓度范围广的特点。它的灵敏度不低于使用荧光或化学发光检测的流动方法。
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