Determination of Nitrate Nitrogen and Nitrite Nitrogen in Brackish and Saline Waters by Flow Injection Analysis
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摘要:
咸水、半咸水资源广布，是干旱、半干旱地区重要的替代水资源和锂、钾盐等国家战略性矿产资源的重要来源。对咸水、半咸水中硝酸盐和亚硝酸盐等关键指标进行监控，是实现水资源综合利用的重要前提。流动注射法集采样、富集、分离、检测于一体，能够实现在线检测分析，近年来被广泛应用于淡水和海水分析，但对盐度更高的咸水类样品，该法尚未开展深入研究。本文利用全自动流动注射分析仪，建立了适用于咸水和半咸水中硝酸盐氮和亚硝酸盐氮的分析测定方法。通过仪器工作参数、显色剂浓度和介质、缓冲溶液中氯化铵浓度和pH值等实验条件优化，确定了方法最佳试验参数。用纯水作载流，可以实现盐度为0～5%范围水样中硝酸盐氮和亚硝酸盐氮的准确测定。对于盐度大于5%的卤水样品，需采用载流盐度匹配的方式改善样品回收率，使该法对盐度的耐受范围扩展至24%左右。本法对硝酸盐氮和亚硝酸盐氮的检出限分别为0.002mg/L、0.001mg/L，测定范围分别为0～2.00mg/L、0～1.00mg/L。通过国家标准物质和实际样品分析表明，该法具有良好的精密度和正确度，自动化程度高，分析周期短，适用于大批量样品的分析测试。
Abstract:BACKGROUND Saline water and brackish water resources are widely distributed, which are important alternative water resources in arid and semi-arid areas. They are also important sources of national strategic mineral resources such as lithium and potassium salts. Monitoring the key indicators such as nitrate and nitrite in saline water and brackish water is an important prerequisite for the comprehensive utilization of water resources. There are various methods for determining nitrates and nitrites, including spectrophotometry, fluorescence, chemiluminescence, electrochemistry, chromatography, and flow injection analysis. Among them, chromatography and electrochemistry require expensive and complex instruments or reagent; while spectrophotometry, although using simple equipment, has complex manual operation. Flow injection analysis is an analytical method that integrates sampling, enrichment, separation, and detection and can be used to achieve online detection and analysis. It has been widely used in freshwater and seawater analysis, but for saline water samples with higher salinity, the method has not been studied in depth.
OBJECTIVES To establish an analytical method for the determination of nitrate nitrogen and nitrite nitrogen in saline water and brackish water using a fully automatic flow injection analyzer to expand the scope of application of the instrument and achieve simultaneous determination of nitrate nitrogen and nitrite nitrogen in saline water, brackish water and freshwater.
METHOD An analytical method suitable for the determination of nitrate nitrogen and nitrite nitrogen in saline and brackish water was established using a fully automatic flow injection analyzer after optimizing experimental conditions such as instrument working parameters, the affection of sulfonamide and N-(1-naphthyl) ethylenediamine concentration, the ammonium chloride concentration and pH value in buffer solution.
RESULTS The optimal instrumental operating conditions were selected through condition optimization experiments. The effects of chromogenic agent concentration and medium were investigated, as well as the buffer solution concentration and its pH value. Finally, sulfanilamide concentration was selected as 40g/L, hydrochloric acid-naphthyl ethylenediamine dihydrochloride concentration was selected as 1.0g/L as the optimal chromogenic concentration. Ammonium chloride concentration was selected as 60g/L, and the pH value was set to 8.5 to configure buffer solution. Under this condition, cadmium column had a reduction rate of more than 95% for nitrate nitrogen. Using pure water as carrier flow, this method can be used to accurately determine the content of nitrate nitrogen and nitrite nitrogen in water samples with salinity ranging from 0 to 5%. When the carrier flow was configured to have the same salinity as the sample to be tested, it effectively improved the recovery efficiency of high-salinity samples and extended the tolerance range of this method to about 24% salinity. The detection limits of nitrate nitrogen and nitrite nitrogen were 0.002mg/L and 0.001mg/L, respectively, with measurement ranges of 0-2.00mg/L and 0-1.00mg/L. The analysis results of national standard substances and actual samples show that this method has good precision and accuracy, as well as a high degree of automation and short analysis cycle, which are suitable for the analysis of large quantities of samples.
CONCLUSION A method for the determination of nitrate nitrogen and nitrite nitrogen in saline water and brackish water samples was established. This method can be used to accurately determine the content of nitrate nitrogen and nitrite nitrogen in brackish water and saline water to achieve efficient online automation analysis.
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Key words:
- saline water /
- brackish water /
- flow injection analysis /
- nitrate nitrogen /
- nitrite nitrogen
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表 1 流动注射分析仪工作参数
Table 1. Working parameters of flow injection analyzer.
亚硝酸盐氮 硝酸盐氮 工作参数 设定值 工作参数 设定值 镉柱开关 关闭 镉柱开关 打开 测定波长 540nm 测定波长 540nm 洗针时间 10s 洗针时间 10s 出峰时间 10s 出峰时间 26s 进样时间 35s 进样时间 35s 峰宽 20s 峰宽 45s 进载流时间 20s 进载流时间 20s 到达阀时间 45s 到达阀时间 30s 积分时长 20s 积分时长 40s 注射时间 35s 注射时间 10s 蠕动泵转速 35r/min 蠕动泵转速 35r/min 样品周期时间 60s 样品周期时间 60s 
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表 2 镉柱对硝酸盐氮还原率的测试结果
Table 2. Reduction efficiency of Cd column for nitrate nitrogen.
测定参数 硝酸盐氮
峰面积亚硝酸盐氮
峰面积还原率
（%）测定平均值 285.6 297.6 96.0 标准偏差 1.34 1.11 / RSD（%） 0.47 0.37 /
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表 3 载流盐度匹配后卤水样品中硝酸盐氮和亚硝酸盐氮测定结果
Table 3. Analytical results of nitrate nitrogen and nitrite nitrogen after matching the same salinity with the carrier stream.
样品编号 盐度
（%）硝酸盐氮 亚硝酸盐氮 本底值
（mg/L）加标量
（mg/L）测定值
（mg/L）回收率
（%）本底值
（mg/L）加标量
（mg/L）测定值
（mg/L）回收率
（%）卤水1 7.2 0.030 0.10 0.133 103.9 0.083 0.05 0.136 106.8 卤水2 10.6 0.150 0.10 0.256 106.1 0.075 0.05 0.121 92.6 卤水3 13.8 0.027 0.10 0.129 102.7 0.067 0.05 0.117 101.0 卤水4 18.2 0.023 0.10 0.125 101.6 0.043 0.05 0.092 97.4 卤水5 24.1 0.041 0.10 0.146 105.3 0.058 0.05 0.103 91.0 卤水6 27.8 0.001 0.10 0.032 31.0 0.060 0.05 0.104 87.8
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表 4 硝酸盐氮和亚硝酸盐氮的线性关系和方法检出限
Table 4. Regression analysis of calibration curves and quantification limits for nitrate nitrogen and nitrite nitrogen.
检测项目 线性关系 相关系数
（R2）方法检出限
（mg/L）线性范围
（mg/L）硝酸盐氮 y=0.0007x−0.0013 0.9999 0.002 0～2.00 亚硝酸盐氮 y=0.0007x+0.0007 0.9998 0.001 0～1.00
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表 5 国家标准物质中硝酸盐氮和亚硝酸盐氮分析结果
Table 5. Analytical results of of nitrate nitrogen and nitrite nitrogen in the national standard substances.
样品类型 标准物质编号 标准值
（mg/L）测定平均值
（mg/L）RSD
（%）硝酸盐氮
标准物质GBW08636 0.140 0.141 1.19 GBW08637 0.210 0.212 0.97 GSB07-3166—2014（批次号200848） 0.900 0.917 0.30 亚硝酸盐氮
标准物质GBW08641 0.056 0.056 0.49 GBW08640 0.028 0.028 0.61 GSB07-3165—2014（批次号200641） 0.178 0.180 0.28 GSB07-3165—2014（批次号200639） 0.345 0.350 0.78
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表 6 实际水样中硝酸盐氮和亚硝酸盐氮分析结果
Table 6. Analytical results of nitrate nitrogen and nitrite nitrogen in water samples.
实际水样 硝酸盐氮 亚硝酸盐氮 本底值
（mg/L）加标量
（mg/L）测定值
（mg/L）回收率
（%）本底值
（mg/L）加标量
（mg/L）测定值
（mg/L）回收率
（%）威海海水1 0.600 0.5 1.120 103.3 0.014 0.05 0.068 108.0 威海海水2 0.573 0.5 1.087 102.5 0.030 0.05 0.084 108.2 威海海水3 0.584 0.5 1.088 100.8 0.028 0.05 0.082 108.4 秦皇岛海水4 0.096 0.5 0.602 101.3 0.046 0.05 0.100 107.2 秦皇岛海水5 0.312 0.5 0.811 99.8 0.047 0.05 0.100 106.6 青岛海水6 0.308 0.5 0.829 104.2 0.079 0.05 0.132 106.6 青岛海水7 0.317 0.5 0.839 104.6 0.081 0.05 0.135 109.0 西藏卤水8 0.454 0.5 0.922 93.6 0.030 0.05 0.079 98.8 西藏卤水9 12.41 10.0 21.98 95.7 0.055 0.05 0.108 106.6 青海卤水10 0.283 0.5 0.773 98.0 0.029 0.05 0.078 98.8 青海卤水11 0.098 0.5 0.581 96.6 0.030 0.05 0.084 106.6
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