Approaches to Evaluate Water Quality Model Parameter Uncertainty for Adaptive TMDL Implementation1

Abstract: The National Research Council recommended Adaptive Total Maximum Daily Load implementation with the recognition that the predictive uncertainty of water quality models can be high. Quantifying predictive uncertainty provides important information for model selection and decision‐making. We review five methods that have been used with water quality models to evaluate model parameter and predictive uncertainty. These methods (1) Regionalized Sensitivity Analysis, (2) Generalized Likelihood Uncertainty Estimation, (3) Bayesian Monte Carlo, (4) Importance Sampling, and (5) Markov Chain Monte Carlo (MCMC) are based on similar concepts; their development over time was facilitated by the increasing availability of fast, cheap computers. Using a Streeter‐Phelps model as an example we show that, applied consistently, these methods give compatible results. Thus, all of these methods can, in principle, provide useful sets of parameter values that can be used to evaluate model predictive uncertainty, though, in practice, some are quickly limited by the “curse of dimensionality” or may have difficulty evaluating irregularly shaped parameter spaces. Adaptive implementation invites model updating, as new data become available reflecting water‐body responses to pollutant load reductions, and a Bayesian approach using MCMC is particularly handy for that task.     

自配标准溶液不确定度的评定

测量不确定度（uncertainty of measurement）是表征合理地赋予被测量之值的分散性,与测量结果相联系的参数。不确定度一词指可疑程度,广义而言,测量不确定度是对测量结果正确性的可疑程度。标准溶液作为一种标准物质,有许多优点,比如使用方便、溶液均匀、量值准确等。在环境监测分析中经常要使用标准溶液,在配制过程产生不确定度,而标准溶液的不确定度直接影响检测结果的不确定度,因此,对自配标准溶液的测量不确定度进行合理评定,显得尤为重要。配制标准溶液时的合成不确定度与称量的溶质质量、物质的纯度、配制体积、环境温度的不确定度等有关,充分分析不确定度的来源上,得出其扩展不确定度。并以亚硝酸盐标准溶液为例,全面分析了影响标准溶液不确定度的因素,给出了不确定度评定的具体过程和方法。     

Uncertainties in stormwater runoff data collection from a small urban catchment, Southeast China

Monitoring data are often used to identify stormwater runoff characteristics and in stormwater runoff modelling without consideration of their inherent uncertainties. Integrated with discrete sample analysis and error propagation analysis, this study attempted to quantify the uncertainties of discrete chemical oxygen demand (COD), total suspended solids (TSS) concentration, stormwater flowrate, stormwater event volumes, COD event mean concentration (EMC), and COD event loads in terms of flow measurement, sample collection, storage and laboratory analysis. The results showed that the uncertainties due to sample collection, storage and laboratory analysis of COD from stormwater runoff are 13.99%, 19.48% and 12.28%. Meanwhile, flow measurement uncertainty was 12.82%, and the sample collection uncertainty of TSS from stormwater runoff was 31.63%. Based on the law of propagation of uncertainties, the uncertainties regarding event flow volume, COD EMC and COD event loads were quantified as 7.03%, 10.26% and 18.47%.     

基于CMAQ模型的随机响应曲面不确定性传递分析方法实现与评价

针对蒙特卡洛法在复杂环境模型进行不确定性传递分析时对计算机和时间资源需求巨大的缺点,本文引进快速高效的随机响应曲面法,并将其成功应用于CMAQ区域空气质量模型的不确定性传递分析,建立了基于CMAQ区域空气质量模型的不确定性分析概念框架.采用2阶和3阶随机响应曲面法,研究了排放清单不确定性对臭氧模拟结果的影响,并与1000次蒙特卡洛模拟结果进行对比.结果表明:3种模拟情景下臭氧浓度的均值几乎相同,模拟结果的概率分布曲线也基本一致,而采用随机响应曲面法可以极大节省模拟所需时间,提高计算效率,显示随机响应曲面法具有在复杂大气环境模型中进行不确定性传递分析的潜在价值.     

分光光度法测定地下水中六价铬的不确定度评定

对二苯碳酰二肼分光光度法测地下水中六价铬的不确定度来源进行分析、计算和合成,标准曲线的不确定度采用线性双误差拟合。地下水样品测定结果表明,影响测定结果的不确定度因素主要来源于六价铬标准系列溶液配制和样品的重复测定,对地下水样品中六价铬测定的不确定度作了评估。     

中国人为源VOC排放清单不确定性研究

针对采用"排放因子法"构建的中国人为源VOC排放清单,开展了不确定性研究工作.基于排放清单输入信息的准确性和可靠性,构建了活动水平和排放因子的不确定度评估系统,获得了清单输入信息概率密度分布函数.利用Monte Carlo模型将输入信息的不确定度传递到清单的输出值,计算了2005年我国人为源VOC排放概率密度分布函数....     

水样中氯化物测量不确定度的评定

目的对硝酸银滴定法测定水中氯化物含量的不确定度的来源及其对测量不确定度的影响进行分析。方法根据《测量不确定度评定与表示》JJF1059-1999对《生活饮用水标准检验方法》(GB/T 5750-2006)中氯化物测定的硝酸银滴定法的测量不确定度进行分析评定。结果按数学模型计算水样中氯化物浓度为25.2mg/L,水样中氯化物测定结果的扩展不确定度为0.6mg/L,结果表达为(25.2±0.6)mg/L。结论水样中氯化物含量测定的测量不确定度影响中,以分析滴定中消耗硝酸银标准溶液的体积引入的不确定度最大,其次为配制NaC l标准使用溶液引入的不确定度。     

吹扫捕集-气相色谱-质谱法测定水中环氧氯丙烷的不确定度评定

依照《测量不确定度评定与表示》,对吹扫捕集-气相色谱-质谱法测定水中环氧氯丙烷的结果进行不确定度评定。通过评定可知标准曲线配制过程所引入的相对不确定度最大,吹扫捕集-气相色谱-质谱法测定模拟水样中环氧氯丙烷结果为（78±21）μg/L。     

钼酸铵分光光度法测定废水中总磷的不确定度评定

测量不确定度是表征被测定值的分散性,并与测量结果相联系的参数,钼酸铵分光光度法是测定水质总磷主要方法之一,根据其分析过程的操作步骤确定了其影响因素.在此评定了该方法测定水质中总磷的不确定度,依照分析方法建立数学模型,并根据数学模型把不确定度分解为各不确定度,对影响测量结果的各个分量进行了分析评定和计算,最终给出结果报告和评定结果分析,提出校准实验和多次重复性测量是影响样品分析误差的重要因素.     

火焰原子吸收法测定水中铜的不确定度评定

详细叙述了火焰原子吸收法测定水中铜含量的操作步骤及标准曲线绘制的操作步骤,根据操作步骤建立火焰原子吸收法测定水中铜含量不确定度的数学模型,分别对配制标准使用液、取样过程、样品重复性测定、绘制标准曲线引入的不确定度分量进行了详细的分析和计算,得出扩展不确定度。通过不确定度的计算分析得出绘制标准曲线引入的不确定度分量和样品测量重复性引入的不确定度分量对测量结果产生主要影响,因此,提高方法的灵敏度和准确度的关键步骤是提高操作技能,增加标准曲线测量次数和被测样品测量次数。