臭氧监测仪实验室校准及稳定性测试

以国内监测系统在用的臭氧校准仪为二级传递标准对臭氧监测仪开展了实验室校准,通过计算单次校准所得校准曲线的斜率和截距,符合中国相关标准中关于臭氧监测仪的校准指标:多点校准所得校准曲线的斜率为0.95~1.05,截距为-5~5 nmol/mol。进一步对2台臭氧监测仪进行了稳定性测试,12个月内臭氧监测仪的斜率变化为0.976 05~1.008 42,截距变化为-0.669 00~0.577 93 nmol/mol,臭氧监测仪的斜率、截距均符合臭氧监测仪校准指标的要求。稳定性测试表明,TF 49i型臭氧监测仪和EC 9810型臭氧监测仪经校准后均可用于实验室内臭氧标准传递比对工作。实验中臭氧监测仪更换臭氧涤除器、仪器零件后校准曲线的斜率均有明显变化,建议更换耗材后需采用高浓度臭氧对臭氧监测仪进行饱和并再次校准。     

校准曲线截距误差和检验方法

对环境监测样品的分析大部分采用校准曲线定量法,校准曲线拟合方程的质量对监测结果的可靠性影响很大。把测量信号值(ｙ)对标准物质含量(ｘ),用最小二乘法拟合校准曲线方程有两种方法,一种是直接拟合,一种是扣除空白信号值后再拟合,两种方法截距(ａ)的含义不同,这里论述的截距是指后者。1　截距误差产生的原因分析方法的依据是测量信号值与样品待测物质含量成某种确定的直线关系,空白信号估计值应是空白实际测定值。理论上校准曲线的截距应是0。非零截距是由截距误差产生的,其中包括随机误差、系统误差和过失误差。11　截距的随机误差以分光…     

校准曲线的运用

校准曲线的运用陈俊（江苏省滨海县环境监测站２２４５００）环境样品测定中，很多项目采用分光光度法分析。科学地运用校准曲线，有利于提高监测质量，节约分析操作时间和监测成本。结合工作实践，对校准曲线的运用作初步探讨。１斜率的稳定性及其运用根据斜率的稳定性，...     

在大气自动监测多 点线性校准中仪器示值误差的分析及控制

阐述了在大气自动监测多点线性校准中，气体流量对仪器示值误差的影响，分析了标准气流量影响仪器浓度示值的原因，以及控制低浓度校准气仪器示值误差的方法。通过比较相对固定标准气流量和崮定校准气流量两种校准方法，得出校准气(或零空气)流量大小对校准气浓度的准确性影响不显著，而标准气流量大小对校准气浓度的准确性影响显著，故在大气自动监测多点线性校准中，宜采用相对固定标准气流量的办法，以降低仪器示值的误差。     

二氧化氮标准物质校准氮氧化物分析仪的差异性

采用一氧化氮、二氧化氮标准物质对化学发光法的氮氧化物分析仪进行校准,并分析校准系统中零气源、连接管路、动态气体校准仪和标准物质对二氧化氮校准的影响,发现一氧化氮标准物质中的二氧化氮杂质会影响氮氧化物的校准结果,得出氮氧化物分析仪校准需要进行二氧化氮补偿的结论;同时,通过比较国产二氧化氮和进口二氧化氮标准物质产生的校准结果,得出进口二氧化氮标准物质较国产二氧化氮标准物质的稀释结果具有更好的稳定性和一致性。     

臭氧二级传递标准量值传递技术

臭氧(O_3)二级传递标准对O_3三级传递标准进行量值传递,开展了对分析类型、发生类型等不同类型O_3三级传递标准的量值传递实验。分析类型O_3三级传递标准6组校准斜率的相对标准偏差Sm为0.19%、截距的标准偏差SI为0.25 nmol/mol;发生类型O_3三级传递标准6组校准的Sm为0.67%、SI为0.20 nmol/mol,均符合美国环保局O_3二级传递标准量值传递的评价指标:6组多点校准斜率的相对标准偏差Sm≤3.7%,截距的标准偏差SI≤1.5 nmol/mol。进一步对分析类型、发生类型O_3三级传递标准分别进行了6个月的量值传递时间稳定性考察,O_3三级传递标准新的斜率与最近6组斜率均值的比值为0.965~1.037,且新计算的斜率的相对标准偏差Sm为0.37%~1.87%,截距的标准偏差SI为0.20~0.52 nmol/mol,均符合美国环保局量值传递评价指标的要求,建议至少每6个月采用O_3二级传递标准开展一次量值传递。     

环境监测部门标准变更和仪器校准后的确认方法

探讨了监测方法标准、污染物排放标准和环境质量标准变更后的确认方法及仪器设备校准后确认的要求及方法,分析了标准变更后和仪器校准后确认工作对环境监测质量控制的重要性。     

大气自动监测校准中气体流量对仪器示值误差的影响及控制

研究了大气自动监测系统中标准气、校准气以及零空气的流量大小引起仪器示值误差及时校准曲线质量的影响,提出了重点控制标气流量是减小仪器示值误差的关键,从而解决了低浓度校准点仪器示值偏低、误差大及校准曲线截距大的技术难点,提高了大气自动监测中多点校准质量和监测结果的准确性.     

校准曲线斜率均值控制图及应用

在使用分光光度法进行样品分析时 ,通常采用标样或加标回收样来控制样品分析的准确度。但是 ,当缺少可靠的标准物质时 ,采用加标回收质控法 ,容易因系统误差而掩盖可能存在的质量问题。再者 ,由于样品分析工作的多样性和复杂性 ,往往缺少能适用于各种条件下的标准样品。多数标准样品一般只能一次性使用 ,保存期较短 ,将其用于频繁的日常例行监测分析 ,费用昂贵 ,基层站难以负担。为此 ,我们根据多年来的工作实践 ,总结了通过绘制校准曲线斜率均值控制图来确定和控制样品分析的准确度的方法 ,现以测定 Cr6 +的校准曲线为例进行讨论。1　斜率…     

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。     

Dealing with heterogeneous regression slopes in analysis of covariance: new methodology applied to environmental effects monitoring fish survey data

Analysis of covariance (ANCOVA) is a powerful statistical method which incorporates one or more covariates into the analysis to reduce error associated with measurement. ANCOVA (modeling response as a function of fish size) is frequently used to analyze environmental effects monitoring (EEM) fish survey data. In approximately 12% of fish survey data sets taken from cycles 1 to 3 of Environment Canada’s EEM database for pulp and paper mills, the standard assumption of parallel regression slopes is not met. For the first three cycles of the EEM program, these data sets were classified as indicating a mill effect, but for the most part were excluded from subsequent analyses aimed at quantifying the effect. We present two different methods for initially dealing with data sets that exhibit heterogeneous slopes so that they can be analyzed using the parallel slope model. The first method identifies data sets where heterogeneous slopes are forced by a few high-influence observations. The second approach identifies data sets where a model with heterogeneous slopes is statistically, but not practically, significant: with a high coefficient of determination for the parallel slope model. These new methodologies are applied to EEM pulp and paper data sets and about 55% of cases with heterogeneous slopes can be described by a parallel slope model. We also discuss a third method that can be used to describe mill effects when regression slopes remain heterogeneous even after applying the above two methods, enabling comparison with a critical effect size. These new methodologies could benefit the EEM program by enabling more data sets to be incorporated into meta-analyses and be used to make more equitable mill monitoring decisions in the future.     

External Contribution to Urban Air Pollution

Elevated particulate matter concentrations in urbanlocations have normally been associated with local trafficemissions. Recently it has been suggested that suchepisodes are influenced to a high degree by PM₁₀sources external to urban areas. To further corroboratethis hypothesis, linear regression was sought betweenPM₁₀ concentrations measured at eight urban sites inthe U.K., with particulate sulphate concentration measuredat two rural sites, for the years 1993–1997. Analysis ofthe slopes, intercepts and correlation coefficientsindicate a possible relationship between urban PM₁₀and rural sulphate concentrations. The influences of winddirection and of the distance of the urban from the ruralsites on the values of the three statistical parametersare also explored. The value of linear regression as ananalysis tool in such cases is discussed and it is shownthat an analysis of the sign of the rate of change of theurban PM₁₀ and rural sulphate concentrations providesa more realistic method of correlation. The resultsindicate a major influence on urban PM₁₀ concentrations from the eastern side of the UnitedKingdom. Linear correlation was also sought using PM₁₀ data from nine urban sites in London and nearby ruralRochester. Analysis of the magnitude of the gradients andintercepts together with episode correlation analysisbetween the two sites showed the effect of transportedPM₁₀ on the local London concentrations. This articlealso presents methods to estimate the influence of ruraland urban PM₁₀ sources on urban PM₁₀ concentrations and to obtain a rough estimate of thetransboundary contribution to urban air pollution from thePM₁₀ concentration data of the urban site.     

广州市空气质量自动监测系统设计及建设

广州市空气质量自动监测系统分为子站系统和中心控制数据接收平台系统丽部分.子站系统利用串口通讯采集仪器数据及状态标识;为确保中心系统的数据接收,系统通讯采用ADSL宽带和无线通讯相结合的方式,并设立了发送和接收数据的协议;子站系统的可视化界面与远程控制软件结合,可随时对子站进行监控;采用SQL语言对数据库进行访问.完成每...     

Modified Grey Model and its application to groundwater flow analysis with limited hydrogeological data: a case study of the Nubian Sandstone, Kharga Oasis, Egypt

Groundwater flow at Kharga Oasis, located in the western desert of Egypt, was previously analyzed using numerical models; however, the lack of basic data often limits the implementation of these models, as well as introducing a problem for model calibration and validation. The Grey Model (GM) was used to overcome these difficulties of data limitation and uncertainty of hydrogeological conditions. However, no clear theories exist for selecting the number of input model trends and the most suitable values of input parameters. Therefore, in the current study, a modification of the GM is newly proposed and called the Modified Grey Model (MGM) in an attempt to determine a process for selecting the best input models' trends with the appropriate values of input parameters to achieve acceptable fitting to observations. The sensitivity analysis results showed that the MGM produced more stable results than the GM using a wide range of values for input parameters. Moreover, the MGM reduced the calculation time required for fitting the measured piezometric level trends by 99.8 %. Three development scenarios of groundwater withdrawal were proposed that involved either expanding the present extraction rate or redistributing the groundwater withdrawal over the recent working production wells (RWPWs). The results concluded that the groundwater table in the northern part of the oasis could be temporally recovered to an economical piezometric level; however, the table in the southern part is severely decreased. Therefore, new production wells are recommended to be constructed in the southern part far enough from the RWPWs.     

基于大数据分析的大气网格化监测质控技术研究

基于对现阶段中国环境空气的污染特征及监测手段进行分析,研究了如何采用传感器技术进行大气污染防治网格化监测。对标物校准、训化校准、自适应校准、传递校准等校准质控技术进行了充分研究并基于此建立了自主学习神经网络算法的校准体系。为解决传感器应用过程中零点漂移、温度和湿度漂移、时间漂移等问题,利用大数据、基因算法成功开发出了智能数据修正模型,实现了低成本、高稳定、具有相当精度且可自动化运行的网格化监测体系。     

Statistical analysis of the physico-chemical data on the coastal waters of Cochin

Measurements of temperature, salinity, dissolved oxygen, nitrogen as ammonia, nitrate and nitrite, and phosphate along with chlorophyll were carried out at three stations on the coastal waters of Cochin, south west India, at two-levels of the water column over a period of five years. The data set has been factorised using principal component analysis (PCA) for extracting linear relationships existing among a set of variables. A graphical display of the scores generated from the PCA was done by means of boxplots and biplots, which helped in the interpretation of the data. The major factors conditioning the system are related to the input of fresh water from the estuary of the Periyar river and the high organic load of the bottom sediment in the coastal area which results in a reducing environment, as reflected in the parameters of dissolved oxygen, ammoniacal-nitrogen and nitrite-nitrogen. Another factor which contributes to the variation in the system is related to the unloading activity in the port area. The present approach presents a logical way to interpret the complex data of the physico-chemical measurements.     

Use of pharmaceuticals and pesticides to constrain nutrient sources in coastal groundwater of northwestern Long Island, New York, USA

In developed, non-agricultural, unsewered areas, septic systems and fertilizer application to lawns and gardens represent two major sources of nitrogen to coastal groundwater, in addition to atmospheric input. This study was designed to distinguish between these two possible nitrogen sources by analyzing groundwater samples for pharmaceutical residuals, because fertilizers do not contain any of these pharmaceuticals, but domestic wastewater commonly does. In addition, several herbicides and insecticides used in lawn treatment were analyzed as indicators of nitrogen delivery to groundwater from fertilizers. Groundwater samples were taken through piezometres at shoreline sites in unsewered areas surrounding Northport Harbor and in sewered areas adjacent to Manhasset Bay (hereafter referred to as "Northport" and "Manhasset", respectively), both in northwestern Long Island, USA. Excessive nitrogen loading has led to reduced dissolved oxygen concentrations in Long Island Sound, and the groundwater contribution to the nitrogen budget is poorly constrained. The frequent detection of the anticonvulsant compound carbamazepine in groundwater samples of the Northport Harbor area (unsewered), together with the fact that few pesticides associated with lawn applications were detected, suggests that wastewater input and atmospheric input are the likely sources of nitrogen in the Northport groundwater. High concentrations of nitrogen were also detected in the Manhasset (sewered) groundwater. The low detection frequency and concentration of carbamazepine, however, suggest that the sewer system effectively intercepts nitrogen from wastewater there. The likely sources of nitrogen in the Manhasset groundwater are atmospheric deposition and lawn fertilizers, as this area is densely populated.     

Analysis of Long-term Measurements of Airborne Concentrations of Sulphur Dioxide and SO42- in the Rural United Kingdom

During the last two decades, the importance of sulphur dioxide as a pollutant has moved away from its association with suspended particulate matter, to it being a precursor of SO ₄ ^2- aerosol (acidic e.g. sulphuric acid, or neutralised e.g. ammonium sulphate). Co-located concentration data of sulphur dioxide and SO ₄ ^2- , at nine monitoring sites situated in predominantly rural areas in the United Kingdom, collected over the time period 1979–1995, have been analysed. The time series for both species are discussed for the sites. Further analysis has shown that there is a degree of correlation between sulphur dioxide and SO ₄ ^2- for most of the sites considered. This correlation is of approximately the same level for most of the sites taken independently and together, and in most cases the slopes and intercepts associated with the simple empirical model equations arising from the correlation analysis, are of the same order of magnitude. The implementation of these site-dependent model equations within dispersion models for the prediction of the concentration of airborne sulphate aerosol from knowledge of sulphur dioxide concentration is discussed. Furthermore, the correlation analysis revealed the influence of transported sulphate aerosol on the local concentration, especially during high concentration episodes.     

Distribution behavior and carcinogenic level of some polycyclic aromatic hydrocarbons in roadside soil at major traffic intercepts within a developing city of India

A study of polycyclic aromatic hydrocarbons (PAHs) pollution in roadside soil was conducted at a developing city locations of Jalandhar (Punjab), India in winter season to ascertain the contamination levels and their distribution behavior in roadside soil. PAHs concentration level of ten locations was measured at 1, 2, and 3 m distances from roadside soil covering all the major traffic intercepts within a city. Samples were extracted in acetone and dichloromethane (1:1) using soxhlet extraction. The extracts were filtered on a silica gel micro column to remove impurities and eluate was subjected to GC-FID. The total average PAHs concentration (city average) was found to be 4.04 μg g(-1), whereas the concentration of 16 individual PAHs was found to vary between 0.008 and 28.4 μg g(-1). The average concentration of noncarcinogenic and carcinogenic PAHs in all the samples was 2.17 and 6.41 μg g(-1) (ratio 1:2.95). The concentration of five ringed PAHs was found to be 45% to 60%, whereas two ringed PAHs were found to be in the range from 0.28% to 0.56% in all most all locations. The average highest PAHs concentration for any individual location was found as 12.23 μg g(-1) at DAV Chowk at 1 m distance and minimum concentration was 0.98 μg g(-1) at Maqsuda Chowk at 1 m distance from roadside. DiB (ah) A was the individual PAHs found in highest concentration in all the intercepts ranging between 1.26 and 28 μg g(-1). At most of the city intercepts, total carcinogenic PAHs concentration was found to range from 60% to 80% in comparison to noncarcinogenic PAHs (20%-40%) at most of the intercepts. The pollution level our study was compared with other cities of India/worldwide.     

Serial Correlation and Inter-annual Variability in Relation to the Statistical Power of Monitoring Schemes to Detect Trends in Fish Populations

We studied the effects of inter-annual variability and serial correlation on the statistical power of monitoring schemes to detect trends in biomass of bream (Abramis brama) in Lake Veluwemeer (The Netherlands). In order to distinguish between 'true' system variability and sampling variability we simulated the development of the bream population, using estimates for population structure and growth, and compared the resulting inter-annual variabilities and serial correlations with those from field data. In all cases the inter-annual variability in the field data was larger than in simulated data (e.g. for total biomass of all assessed bream sigma = 0.45 in field data, and sigma = 0.03-0.14 in simulated data) indicating that sampling variability decreased statistical power for detecting trends. Moreover, sampling variability obscured the inter-annual dependency (and thus the serial correlation) of biomass, which was expected because in this long-lived population biomass changes are buffered by the many year classes present. We did find the expected serial correlation in our simulation results and concluded that good survey data of long-lived fish populations should show low sampling variability and considerable inter-annual serial correlation. Since serial correlation decreases the power for detecting trends, this means that even when sampling variability would be greatly reduced, the number of sampling years to detect a change of 15%.year(-1) in bream populations (corresponding to a halving or doubling in a six-year period) would in most cases be more than six. This would imply that the six-year reporting periods that are required by the Water Framework Directive of the European Union are too short for the existing fish monitoring schemes.