废水急性毒性测定及评价中的不确定性研究及其改进方法
Uncertainty Studies in Determination and Assessment of Acute Toxicity of Wastewater and Its Improvement Method
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摘要: 目前，我国针对废水处理及排放的环境影响评估体系逐渐向生物毒性综合指标完善，然而传统的评价方法可能存在错误的接受和错误的拒绝2种风险，根据“检测和校准实验室能力认可准则”(CNAS-CL01: 2018)的要求，实验室在进行合格判定时，应考虑相关的风险水平。为研究分析废水急性毒性评价中存在的风险，采用发光细菌法测试废水急性毒性，选取接近排放限值的制药废水样品，进行测量不确定度评定，并依据“产品几何量技术规范(GPS) 工件的测量检验和测量设备 第1部分：按规范检验一致性或不一致性的判定规则”(ISO 14253-1: 2017)有关合格判定的思路，对废水急性毒性评价中的合格区、不确定区和不合格区进行研究。结果表明，废水急性毒性评价中，合格区、不确定区及不合格区会随着标准曲线|r|值和测量精密度的变化而变化，随着|r|值的降低或精密度的降低，合格区会变小，不确定区会变大，这导致了无法通过设置“保护带”的方法降低误判风险，对废水急性毒性评价的准确性造成了极大的影响。为准确开展废水急性毒性的测试与评价，可采用双样本t检验，通过比较废水样品的相对发光度与0.07 mg·L-1氯化汞溶液的相对发光度来判断废水急性毒性是否合格，当废水样品的相对发光度≥0.07 mg·L-1氯化汞溶液的相对发光度时，废水急性毒性合格，否则不合格。本研究通过开展方法的不确定度研究，阐明了现行国标分析方法及废水急性毒性评价方法存在的局限性，并提出了改进方案，为废水急性毒性的科学评判提供了重要依据。Abstract: Comprehensive biotoxicity indicators have been considered into environmental impact assessment system of wastewater treatment and discharge in China. However, the traditional methods of biotoxicity assessment face two risks of incorrect acceptance and incorrect rejection. According to Accreditation Criteria for the Competence of Testing and Calibration Laboratories (CNAS-CL01: 2018), laboratories should consider the risks when making conformity assessment. This study investigated the uncertainty evaluation of the luminescent bacteria test for the acute toxicity of wastewater, involving its conformance, uncertainty, and non-conformance zones (Geometrical Product Specifications (GPS)—Inspection by Measurement of Workpieces and Measuring Equipment—Part 1: Decision Rules for Verifying Conformity or Nonconformity with Specifications (ISO 14253-1: 2017)), using the pharmaceutical wastewater sample close to the discharge limits. The results show that the conformance, uncertainty, and non-conformance zones varied depending on the r-value of the standard curve and the precision of the measurement. The conformance zone decreased and uncertainty zone increased with the |r|-value or the precision decreased, which made it impossible to reduce the risk of incorrectly decision by setting a “guard band”, and greatly affected the accuracy of the acute toxicity assessment. To solve this problem, a Welch's t-test was introduced to assess whether the acute toxicity of wastewater was conformance by comparing the relative luminosity of the wastewater with that of the 0.07 mg·L-1 HgCl2 solution. If the relative luminosity of the wastewater was higher than that of the 0.07 mg·L-1 HgCl2 solution, the acute toxicity of the wastewater was conformance, otherwise the acute toxicity of the wastewater was non-conformance. This study clarifies the limitations of the national standard method and the acute toxicity assessment by carrying out the uncertainty study, and proposes an improvement, which provide an important basis for the scientific assessment of the acute toxicity of wastewater.
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