Matrix effect on the performance of headspace solid phase microextraction method for the analysis of target volatile organic compounds (VOCs) in environmental samples

Solid phase microextraction (SPME) is a fast, cheap and solvent free methodology widely used for environmental analysis. A SPME methodology has been optimized for the analysis of VOCs in a range of matrices covering different soils of varying textures, organic matrices from manures and composts from different origins, and biochars. The performance of the technique was compared for the different matrices spiked with a multicomponent VOC mixture, selected to cover different VOC groups of environmental relevance (ketone, terpene, alcohol, aliphatic hydrocarbons and alkylbenzenes). VOC recovery was dependent on the nature itself of the VOC and the matrix characteristics. The SPME analysis of non-polar compounds, such as alkylbenzenes, terpenes and aliphatic hydrocarbons, was markedly affected by the type of matrix as a consequence of the competition for the adsorption sites in the SPME fiber. These non-polar compounds were strongly retained in the biochar surfaces limiting the use of SPME for this type of matrices. However, this adsorption capacity was not evident when biochar had undergone a weathering/aging process through composting. Polar compounds (alcohol and ketone) showed a similar behavior in all matrices, as a consequence of the hydrophilic characteristics, affected by water content in the matrix. SPME showed a good performance for soils and organic matrices especially for non-polar compounds, achieving a limit of detection (LD) and limit of quantification (LQ) of 0.02 and 0.03 ng g⁻¹ for non-polar compounds and poor extraction for more hydrophilic and polar compounds (LD and LQ higher 310 and 490 ng g⁻¹). The characteristics of the matrix, especially pH and organic matter, had a marked impact on SPME, due to the competition of the analytes for active sites in the fiber, but VOC biodegradation should not be discarded in matrices with active microbial biomass.     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

碱式硫酸铝溶液中SO42-的测定

建立了以铬黑T为指示剂,乙二胺四乙酸二钠反滴定过量BaCl₂的碱式硫酸铝溶液中SO₄^2-的测定方法。实验确定的操作条件为：待测试样稀释后ρ（SO_4^2-）为0.025 ~0.100 g/L,BaCl₂过量率为25%~100%,并且在加入BaCl₂前将试样煮沸,三乙醇胺加入量为0.10 L/L。该法回收率在98.90%~100.72%,相对标准偏差小于1%。测定方法准确,可靠,且操作简便、快速。     

中国区域能源效率发展演变趋势的R/S分形分析

改革开放以来中国能源效率不断地提高,但是在某些年份存在波动现象.采用非线性分形理论及分形分析R/S方法,科学定量地描述了中国以及各个地区能源效率的演变趋势.首先采用分形理论对1978-2008年的中国能源效率时间序列数据进行研究,结果显示,中国能源效率发展演变存在Hurst现象,具有明显的分形特征.并依照“五年计划”来划分时间序列样本为研究区间,结合“五年计划”详尽地解释说明了中国能源效率变动的原因.然后将数据扩大为样本期为1995-2008年29地区的面板数据,采用面板变系数模型进一步对各个地区的能源效率进行分析,发现除海南外其他地区的能源效率演变过程中具有明显的持续性规律,各个地区能源效率将继续保持增长.西部6个地区以及东北三省的能源效率演变趋势高于全国水平,说明“西部大开发”战略和“振兴东北”战略都已经显效.     

光学检测法用于工业气体检测的研究

开展基于特定物质吸收光谱及其谐波检测技术的气体检测装置的实验研究.检测装置采用频率稳定措施,使激光频率始终控制在待测气体的吸收谱线上,对环境的抗干扰能力强,不会产生误判.不需要经常标定,不需要采样.     

太阳活动与四川盆地气候资源波动

本文应用四川省气象局提供的气候资料,借助于电子计算机,统计分析了太阳黑子位相与四川盆地热量资源、降水资源波动的关系;采用文献[2]的公式,计算了太阳黑子相对数年均值与热量、降水资源的同期及延后相关系数,并进行了周期分析,进而分析其演变趋势及其对农业生产的影响和应采取的对策。     

CONFLICTING PERSPECTWES ABOUT DETECTION LIMITS AND ABOUT THE CENSORING OF ENVIRONMENTAL DATA1

ABSTRACT: Current conventions for reporting analytical results from environmental samples brings the objectives of laboratory scientists into conflict with those of environmental scientists. The objective of chemical analyses is to provide estimates of the true composition of samples. Reported results must reflect the analytical uncertainty. Current conventions require left-censoring of those results below the Limit of Detection. The objective of statistical interpretation of environmental data is to provide estimates of the characteristics of ecosystems. Such statistical analyses are often confounded by left-censoring of analytical results. We review the different points of view and propose a compromise which recognizes these conflicting perspectives.     

A TAU-LIKE TEST FOR TREND IN THE PRESENCE OF MULTIPLE CENSORING POINTS1

ABSTRACT: A common problem arises in testing for trends in water quality when observations are reported as “less than detection limit.” If a single detection limit is used for the entire study, existing non-parametric statistical methods, modified for ties, are applicable. If, however, the detection limit varies during the course of the study, resulting in multiple detection limits, then the commonly used trend detection methods are not appropriate. A statistic similar to Kendall's tau, but based on expected ranks, is proposed. Monte Carlo simulations show that the normal approximation to the distribution of this statistic is quite good, even for small samples and a large proportion of censored observations. The statistic is also shown to have greater power than the ad-hoc method of treating all observations less than the target censored observation as tied.     

NONPARAMETRIC TESTS FOR TREND DETECTION IN WATER QUALITY TIME SERIES1

ABSTRACT: A review of nonparametric tests for trend leads to the conclusion that Mann-Whitney, Spearman, and Kendall tests are the best choice for trend detection in water quality time series. Recently these tests have been adapted to account for dependence and seasonality in such series (Lettenmaier, 1976; Hirsch, et al., 1972; Hirsch and Slack, 1984). For monotonic trends, a procedure allowing to select the pertinent tests considering the characteristics of time series is proposed and the practical limitations of the tests are also brought out. This procedure has been applied to identify the appropriate trend detection test for the time series of nine water quality parameters at Lake Laflamme (Québec). When a time series can be tested with the Mann-Whitney, Kendall, Spearman, or Lettenmaier (1976) test, the number of observations required to detect trends of a given magnitude, for selected significance and power levels can be calculated with the power function of the t test. When the test proposed by Hirsch, et al. (1984), Hirsch and Slack (1984), or Farrell (1980) need to be used, the number of observations can only be estimated approximately from the results of empirical power studies.     

大空间室内火灾早期自动探测与定位研究

本文在深入研究早期火灾一般燃烧火焰在彩色影像上所呈现的光谱及运动特性基础上，首次提出利用彩色影像实时探测室内火灾的新方法，通过物方坐标与像方坐标的直接线性变换，实现了早期火灾的自动探测与空间定位，实验证明了该方法的有效性与稳健性，且具有巨大的应用前景。