Some statistical and conceptual issues in the detection of low-level environmental pollutants

With increasing concern over chemicals that are potential health hazards at low levels, determination of limits of detection have undergone considerable scrutiny. Most traditional detection limit estimators suffer from extensive statistical and/or conceptual limitations. In this paper, traditional detection limit estimators are described and critically evaluated. Using the terminology of Currie (1968), methods are categorized into decision limits versus detection limits. The methods are further categorized into single concentration design versus calibration design methodologies. While the single concentration design methods are useful for fixing ideas and clarifying definitions, they are shown to be extremely limited in practice since dependence of variability on concentration can neither be estimated or incorporated. Calibration-based detection limit estimators are described, compared and contrasted. Generalizations to non-constant variance, multiple future detection decisions and simultaneous control of Type I and II errors are provided. The various calibration-based methods are illustrated using real data and experimental design issues for detection limit studies discussed.     

化学分析方法校准曲线有关问题的探讨

校准曲线的线性范围为测定下限与测定上限之间的浓度范围,测定上限应尽可能扩大,但要保证校准曲线呈线性,同时,最高点分析后不会对分析系统造成污染物残留。通常应根据分析方法原理、仪器的特点和样品基质情况来确定校准方式。对于线性校准曲线,除了相关系数外,还要根据不同情况,对校准曲线进行检验。校准曲线的合格判定,除考虑相关系数外,还需要用校准曲线重新计算校准点,对于线性校准,所有校准点计算结果拟合值与实际值的相对误差应在±30%以内,对于非线性二阶校准曲线,应进行最大值与最小值检验。     

Standardisation of Temperature Observed by Automatic Weather Stations

Daily mean, maximum and minimum surface airtemperature data were gathered from a network ofautomatic weather stations (AWS) within the Moor HouseNational Nature Reserve in northern England. Five AWSwere installed next to the official EnvironmentalChange Network weather station at Moor House. Datawere compared graphically and correction constantswere calculated to adjust data from each AWS to thestandard of the official station by optimising theconcordance correlation coefficient. Each correctedstation was re-located next to one of five in-situstations in and around the reserve, allowingcorrection of all temperature sensors to a commonstandard. The mean error associated with measureddaily mean, maximum and minimum temperature for eachsensor does not exceed ±0.2 K. The procedurequantifies a source of systematic measurement error,improving the identification of spatial temperaturedifferences between stations.     

Calibration and Validation of Far Field Dilution Models for Outfall at Worli, Mumbai

The city of Mumbai, India with a population of 15 million discharges about 2225 MLD of domestic wastewater after partial treatment to adjoining marine water body. Under the Mumbai Sewage Disposal Project Scheme, sewage is being disposed to the west coast at Worli and Bandra through 3.4 kms long submarine outfalls. A field study was conducted at recently commissioned outfall diffuser location at Worli, at the onset of neap flood tide to study the dispersion patterns and measure the far field dilutions using radio and dye tracers. Estimated dilutions using different tracers were compared with outputs from an empirical model (Brooks) and a 2D numerical model (DIVAST). Validation using parameters such as BOD and FC, indicated a good match for BOD in near field compared to FC. The radiotracer ⁸²Br and Rhodamine WT generally gave good correlation with Brooks' and DIVAST models for nearfield, however at further distances predictions were not accurate.     

Measurement Diagnostics by Analysis of Last Digits

Though measurement instruments and methods have their natural precision limits, long term monitoring, which is so importantfor environmental studies, requires to set up and maintaincertain standards regarding precision. The elementaryrequirement is to produce measurements with a prescribed numberof valid digits. If the technology further develops and allowsto increase the number of valid digits, the change should bedocumented. In this paper we discuss a simple procedure for validity assessment of the last digits of data in a data base.It may be useful for both calibration control of an instrumentas well as for preliminary data analysis in scientific studies.The procedure utilizes the assumption that, under normalconditions, the last digits of the observed data can usually beconsidered as uniformly distributed random numbers. Failures ordeliberate changes in the observation mechanism can be detectedif particular digits occur more frequently than the others. Thedecision about proper representations of the last digits is doneby means of the familiar chi-square statistics.     

荧光法生物气溶胶监测仪标准物质研制及校准方法研究

生物气溶胶监测仪是利用激光或紫外光诱导生物粒子发射荧光,从而实现对空气中的生物气溶胶进行监测的仪器.目前,国内尚无生物气溶胶监测仪校准用标准物质和评价方法.以聚苯乙烯微球为核,通过Friedel-Crafts酰基化反应,研制出能够自身受激发产生荧光的聚苯乙烯(PS-PB)微球.PS-PB微球粒径分布的相对标准偏差为1....     

改进GC/FID法连续观测大气中CO浓度

改进装配有氢火焰离子化检测器(即FID)的气相色谱仪(GC),可连续监测大气中痕量气体CO浓度.本系统采用单阀双柱反吹进样技术,优选前置柱能更有效地剔除杂质,提高了分析柱效率,保持色谱基线平稳,提高分辨率和定量分析的准确率.优化后的气路设计与色谱柱的改进,使GC/FID对CO的最低检出限达到10×10-9、精密度误差小于2%,准确度在±2%之内.将气相色谱与动态气体稀释仪耦合使系统能够自动进行工作曲线校准,系统自动采样、分析和标定,无需人员职守.对北京大气CO连续观测结果表明,北京大气CO浓度变化受气象要素与排放源双重控制.     

生物营养物去除(BNR)工艺模型参数校正与验证方法

研究了结合活性污泥系统物料平衡的生物营养物去除(BNR)工艺模型参数校正与验证方法.首先采用代尔夫特理工大学开发的TUD模型及其参数缺省值进行初步模拟,并将模拟结果与实测数据进行对比以明确模拟偏差.同时,对原始运行数据进行物料平衡衡算,以消除测量误差并获得TP排放量、反硝化量及氧的净消耗量等平衡计算值,为模型校正提供依据.初步模拟结果显示,TP排放量(3913mg·d-1,以P计)和反硝化量(16170mg·d-1,以N计)均超出了平衡计算值的误差范围(分别为(3762.0±43.1)mg·d-1和(14150±237)mg·d-1),且沿程溶解性COD(SCOD)、PO43--P、NH4+-N、NO3--N不能完全与实测数据吻合,表明工艺模型参数的默认值需得到必要的校正.结合TP平衡,先修正污泥龄(SRT)的计算误差;应用平衡后的运行数据,将SRT由初始值10.3d调整为10d.SRT调整后,再次模拟得出的TP排放量为3750mg·d-1,已在平衡计算结果的范围之内,TP平衡得到了闭合.将发酵过程最大反应速率常数qfe从3d-1提高到15d-1后,沿程及PO43--P拟合结果同时得到了显著改善.通过调整DO及NH4+-N的亲和系数KNH4(从1mg·L-1至0.2mg·L-1),沿程NH4+-N得到了拟合.出水及沿程NO3--N的拟合通过调整氧的亲和系数KO2从0.7至0.1mg·L-1)得以实现.最后校核反硝化负荷及氧的净消耗量,模拟计算的反硝化负荷为14090mg·d-1,氧的净消耗量为126900mg·d-1,均在平衡计算值的误差范围之内(分别为(14150±237)mg·d-1和(129700±2910)mg·d-1),说明校正过程合理、可靠.     

14C年代校正曲线中“哈尔施塔特平台期”与新疆早期铁器时代遗址年代问题

在对14C测年数据进行校正时,由于大气14C本身波动的原因,其校正曲线出现反复波动,从而形成可持续上百年的放射性碳平台.其中\"哈尔施塔特平台期\"发生在800—400 BC,占据了考古学文化中早期铁器时代的大部分时段.该平台的存在使得这一时期的14C数据校正误差达到数百年,并且无法单纯地通过增加样本量获得更精确的遗址年代信息.全球很多地区在当时尚无可靠的文字记录可依赖,因此在这种情况下,这些地区的早期铁器时代遗址难以做进一步的分期.本文以新疆早期铁器时代遗存为例,分别介绍树轮交叉定年、14C摇摆匹配、贝叶斯模型及地磁测年的原理和适用范围等,并讨论了应用上述方法对于改善新疆早期铁器时代遗址年代问题的可行性.结合新疆早期铁器时代遗存的特性,提出在具体研究中应视材料的保存情况和研究的需求选择合适的方法.