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Application News No. O77 Total Nitrogen/Total Phosphorus Analysis Measurement of Total Nitrogen/Total Phosphorus in Wastewater by TNPC-4110 Plus As a measure to improve eutrophication of closed bodies of water, total pollutant load control regulations were implemented in Japan from 1979 to reduce the total load of organic contaminants discharged into such waters to a standard value or less. Beginning with the 5 th Total Pollutant Load Control regulations, total nitrogen and total phosphorus were added and designated to the object items. Many places of business which are subject to those regulations measure these substances with automatic measuring devices. In a recent model change, Shimadzu improved the performance and functions of its TNPC-4110 series online total nitrogen/phosphorus analyzer, which had been used since the 5 th Total Pollutant Load Control regulations were implemented, and now offers the new model as the TNPC-4110 Plus series. In the improved model, the thermal decomposition/ chemiluminescence method was adopted for measurement of total nitrogen. This method provides the same high oxidative decomposition capacity and enables detection with minimal interference as the previous model, and samples containing contaminants or sea water can be measured with virtually no interference effects. The reagent and measurement sequence were also improved in this series, and in total phosphorus measurement, the influence of contaminants was minimized as far as possible, enabling highly accurate measurement. This article introduces an example of measurement of samples containing seawater and minerals with the TNPC-4110 Plus. M. Tanaka Total Nitrogen (TN) Analysis Method The thermal decomposition/chemiluminescence method is used in measurement of total nitrogen (TN) in the TNPC-4110 Plus. This method enables measurement unaffected by metal ions and bromide ions, which are interference components in ultraviolet (UV) spectrophotometry. Therefore, measurement unaffected by coexistent substances is possible, even when the sample is contaminated with seawater. The sample used in this experiment was prepared by adding a nitrogen compound to a solution of diluted seawater (dilution rate: 2×) to obtain a concentration of 0.5 mgN/L (i.e., nitrogen concentration: 0.5 mg/L), and measurements were carried out by the summation method (manual analysis), ultraviolet spectrophotometry (manual analysis), and thermal decomposition/chemiluminescence method. Table 1 Total Nitrogen Measurement Conditions with TNPC-4110 Plus Analyzer : TNPC-4110 Plus total nitrogen/phosphorous analyzer Measured item : Total nitrogen (TN) Measurement method : Thermal decomposition/chemiluminescence Calibration : 2-point calibration using 0-2 mgN/L potassium nitrate aqueous solution (full scale (FS): 2 mgN/L) Sample : Liquid prepared by adding potassium nitrate to natural diluted seawater (dilution rate 2×) to a concentration of 0.5 mgN/L Total Nitrogen (TN) Analysis Results Table 2 shows the measurement results for each method. The column on the right shows the difference between the UV spectrophotometry/TNPC-4110 Plus results and the value measured by the summation method as a standard, calculated as the full scale ratio (%FS). UV spectrophotometry gave a large value, showing the interference effect of components contained in the seawater. On the other hand, the result by the TNPC-4110 Plus measurement was approximately the same as that by the summation method, demonstrating that measurement unaffected by seawater components is possible. Table 2 Total Nitrogen Measurement Results Analysis method Measurement principle Measurement results (mgN/L) Difference from summation method (%FS) Manual analysis Summation 0.59 — Manual analysis UV spectrophotometry 0.84 +12.5% TNPC-4110 Plus Thermal decomposition/ chemiluminescence 0.54 -2.5%
First Edition: Apr. 2020 For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country. The content of this publication shall not be reproduced, altered or sold for any commercial purpose without the written approval of Shimadzu. Shimadzu disclaims any proprietary interest in trademarks and trade names used in this publication other than its own. See http://www.shimadzu.com/about/trademarks/index.html for details. The information contained herein is provided to you "as is" without warranty of any kind including without limitation warranties as to its accuracy or completeness. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. This publication is based upon the information available to Shimadzu on or before the date of publication, and subject to change without notice. © Shimadzu Corporation, 2020 www.shimadzu.com/an/ Application News No. O77 Total Phosphorus (TP) Analysis Method Total phosphorus (TP) measurement by the TNPC-4110 Plus is based on molybdenum blue spectrophotometry, but uses an improved reagent and measurement sequence. Because abnormal coloring during spectrophotometric measurement due to metal ions or other contaminants in the sample is slight, accurate measurement is possible regardless of the sample properties. The sample for TP analysis was prepared by adding a phosphorus compound to groundwater containing silica to obtain a concentration of 0.5 mgP/L (phosphorus concentration: 0.5 mg/L), and measurements were conducted by potassium peroxodisulfate decomposition-molybdenum blue spectrophotometry (manual analysis), the conventional TNPC-4110 instrument, and the improved TNPC-4110 Plus. Table 3 Total Phosphorus Measurement Conditions with TNPC-4110 Plus Analyzer : TNPC-4110 Plus total nitrogen/phosphorous analyzer Measured item : Total phosphorus (TP) Measurement method : Ultraviolet oxidative decomposition – molybdenum blue spectrophotometry Calibration : 2-point calibration using 0-1 mgP/L potassium dihydrogen phosphate (FS: 1 mgP/L) Samples : ① Liquid prepared by adding potassium dihydrogen phosphate to groundwater containing potassium silicate with a silica concentration of 50 mgSi/L to obtain a potassium dihydrogen phosphate concentration of 0.5 mgP/L ② Liquid prepared by adding potassium dihydrogen phosphate to groundwater containing potassium silicate with a silica concentration of 30 mgSi/L to obtain a potassium dihydrogen phosphate concentration of 0.5 mgP/L Total Phosphorus (TP) Analysis Results Table 4 shows the results of the measurements by each method. Using the values measured by the potassium peroxodisulfate decomposition-molybdenum blue spectrophotometry (manual analysis) as a standard, the column below the measured values shows the difference between the measured results by that method and by the conventional TNPC-4110/improved TNPC- 4110 Plus, calculated as %FS of the analyzers. With the conventional TNPC-4110, the value was large, and the interference effect of contaminant components was apparent. However, the measured values obtained with the improved TNPC-4110 Plus were substantially the same as the manual analysis values, showing that measurement unaffected by contaminants is possible. Table 4 Total Phosphorus Measurement Results Analysis method FS error between measurement result (mgP/L) and manual analysis Sample ① Sample ② Manual analysis Molybdenum blue spectrophotometry 0.5069 (--) 0.5013 (--) Conventional TNPC-4110 Molybdenum blue spectrophotometry (conventional analyzer) 0.6575 (+15.1%) 0.5970 (+9.6%) TNPC-4110 Plus Molybdenum blue spectrophotometry (improved analyzer) 0.5114 (+0.45%) 0.5025 (+0.12%) Conclusion This experiment demonstrated that the TNPC-4110 Plus is resistant to the effects of contaminants in samples and can make more accurate measurements of both total nitrogen and total phosphorus than the conventional techniques. TNPC-4110 Plus Online Total Nitrogen/ Total Phosphorus Analyzer
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