A numerical study of expected accuracy and precision in Calibration-Free Laser-Induced Breakdown Spectroscopy in the assumption of ideal analytical plasma

Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) has been proposed several years ago as an approach for quantitative analysis of Laser-Induced Breakdown Spectroscopy spectra. Recently developed refinement of the spectral processing method is described in the present work. Accurate quantitative results have been demonstrated for several metallic alloys. However, the degree of accuracy that can be achieved with Calibration-Free Laser-Induced Breakdown Spectroscopy analysis of generic samples still needs to be thoroughly investigated. The authors have undertaken a systematic study of errors and biasing factors affecting the calculation in the Calibration-Free Laser-Induced Breakdown Spectroscopy spectra processing. These factors may be classified in three main groups: 1) experimental aberrations (intensity fluctuations and inaccuracy in the correction for spectral efficiency of a detection system), 2) inaccuracy in theoretical parameters used for calculations (Stark broadening coefficients and partition functions) and 3) plasma non-ideality (departure from thermal equilibrium, spatial and temporal inhomogeneities, optical thickness, etc.). In this study, the effects of experimental aberrations and accuracy of spectral data were investigated, assuming that the analytical plasma is ideal. Departure of the plasma conditions from ideality will be the object of future work. The current study was based on numerical simulation. Two kinds of metallic alloys, iron-based and aluminum-based, were studied. The relative weight of the error contributions was found to depend on the sample composition. For the here-investigated samples, the experimental aberrations contribute to the overall uncertainty on the quantitative results more than theoretical parameters. The described simulation method can be applied to the Calibration-Free Laser-Induced Breakdown Spectroscopy analysis of any other kind of sample.     

Towards validating a method for two-dimensional electrophoresis/silver staining

Two-dimensional electrophoresis (2-DE) is a technique involving numerous steps, many of them to be performed manually. Hence, some operator dependency must be taken into account. An attempt to elucidate the reliability of 2-DE combined with silver staining is presented, employing the general practice to validate a method in pharmaceutical analysis. Most proteomic studies employing 2-DE aim at qualitative or quantitative differences in protein expression. One of the most sensitive and broadly applied staining techniques is silver staining. In order to gain information on accuracy, precision, linearity, and ruggedness of this technique, gels were run in replicates with different amounts of protein from a complex standard sample. In addition, sets of gels were repeated by two different operators in a second independent laboratory equipped with identical hardware and software. Our results show that reliable qualitative data on differential protein expression can be obtained by 2-DE, nevertheless replicate gels should be run and experimental conditions have to be kept stringently to a standardized protocol. Quantitative data are just achievable with spots, which are well-resolved, of high quality, with an optical density (OD) above a certain threshold (OD > 10), and which show a linear response. Quantitative differences occurring due to method-derived deviations may easily be misinterpreted as true changes in protein expression. After normalization, relative standard deviation (RSD) values of approximately 30% (n = 4) could be obtained, therefore minor changes (< 50%) should be critically reviewed.     

Comparison of several extraction procedures for the determination of biopesticides in soil samples by ultrahigh pressure LC-MS/MS

A new procedure has been proposed for the determination of biopesticides (nicotine, sabadine, veratridine, rotenone, azadirachtin, cevadine, deguelin, spynosad D, and pyrethrins) and piperonyl butoxide in agricultural soils. Several extraction procedures such as solid-liquid extraction using mechanical shaking, sonication, pressurized liquid extraction, and modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) have been tested, obtaining better results when QuEChERS procedure without further cleanup steps was applied. The determination of the compounds was carried out by ultra high pressure liquid chromatography coupled to tandem mass spectrometry, using methanol and aqueous solution of ammonium formate 5 mM as mobile phase. The method was validated for all compounds at concentrations ranging from 10 to 100 μg/kg and recoveries ranged from 68 to 116%, except for nicotine and sabadine, with recoveries lower than 50%. Precision was estimated through intra- and inter-day studies, obtaining intra-day precision lower than 20% for most of the compounds, and inter-day precision was lower than 25%. Limits of detection and quantification were also estimated, obtaining limits of quantification equal or lower than 10 μg/kg. Finally, the method was applied to the analysis of 20 real agricultural soil samples and no biopesticide residues were found over the limit of quantification.     

Monitoring of technical oils in supercritical CO(2) under continuous flow conditions by NIR spectroscopy and multivariate calibration

Metal parts and residues from machining processes are usually polluted with cutting or grinding oil and have to be cleaned before further use. Supercritical carbon dioxide can be used for extraction processes and precision cleaning of metal parts, as developed at Forschungszentrum Karlsruhe. For optimizing and efficiently conducting the extraction process, in-line analysis of oil concentration is desirable. Therefore, a monitoring method using fiber-optic NIR spectroscopy in combination with PLS calibration has been developed. In an earlier paper we have described the instrumental set-up and a calibration model using the model compound squalane in the spectral range of the CH combination bands from 4900 to 4200 cm⁻¹. With this model only poor prediction results were obtained if applied to technical oil samples in supercritical CO₂. In this paper we describe a new calibration model, which was set up for the squalane/carbon dioxide system covering the 323–353 K temperature and the 16–35.6 MPa pressure range. Here, calibration data in the spectral range from 6100 to 5030 cm⁻¹ have been used. This range includes the 5100 cm⁻¹ CO₂ band of the Fermi triad as well as the hydrocarbon 1st overtone CH stretching bands, where spectral features of oil compounds and squalane are more similar to each other.

The root mean-squared error of prediction obtained with this model is 4 mg cm⁻³ for carbon dioxide and 0.4 mg cm⁻³ for squalane, respectively. The utilizability of the newly developed PLS calibration model for predicting the oil concentration and CO₂ density of solutions of technical oils in supercritical carbon dioxide has been tested. Three types of “real world” cutting and grinding oil formulations were used in these experiments. The calibration proved to be suitable for determining the technical oil concentration with an error of 1.1 mg cm⁻³ and the CO₂ density with an error of 6 mg cm⁻³. Therefore, it seems possible to apply this in-line analytical approach on the basis of a cost-effective and time-saving model compound calibration for the surveillance of real world de-oiling and other extraction process based on supercritical carbon dioxide, and furthermore to establish an automated process termination criterion based on this technique.     

农田土壤水分含量的激光诱导荧光光谱表征

通过实验探讨了植物的激光诱导叶绿素荧光光谱与土壤水分间的关系。实验利用Y-形光纤探头获取了植物在450 nm LED光源照射下所发出的叶绿素荧光光谱,同时利用TDR传感器测量土壤湿度。实验以水稻为研究对象,研究了在持续水分胁迫和间歇水分胁迫下,叶绿素荧光光谱743 nm附近波峰的变化,结果发现,波峰强度与土壤水分含量具有相关性。最后,利用Lorentzian方程,将持续水分胁迫下的土壤含水量与叶绿素荧光强度进行建模,发现所建的模型具有较高的决定系数,说明该方法可以应用于农业生产中对土壤水分的测量。     

靶丸表面轮廓形貌AFM精密测量及特性评价

 建立了由改造的原子力显微镜(AFM)、精密回转气浮轴系、辅助转位轴系等组成的靶丸表面形貌精密测量系统,气浮轴系的回转精度达0.049 μm,实现了对激光核聚变靶丸3个正交方向上完整圆周迹线的测量。对选定靶丸的测量数据进行了球度、表面粗糙度及功率谱分析。结果表明：其球度值为0.42 μm;模数范围为2~10,11~50,51~100及101~1 000对应的表面粗糙度值平均为105.7, 12.2, 6.2, 18.25 nm;并得出了平均1维功率谱-模数关系曲线。     

限制容差关系下的集对变精度粗糙集模型

不完备信息系统中目前有多种扩充,如基于容差关系的扩充、基于相似关系的扩充等等,但是这些扩充都各自存在局限性。针对这些局限性,引入相对分类错误率的概念,提出了一种基于限制容差关系下的集对变精度粗糙集模型。这就将经典的粗糙集模型和限制容差关系下的集对粗糙集模型进行了推广。然后,讨论了该模型上、下近似算子的一些性质。最后,通过一个具体例子,说明了该模型在不完备信息系统中处理模糊和不确定性知识是可行、有效的。     

BP神经网络在农机总动力预测中的应用

准确的预测黑龙江省农机总动力,可为黑龙江省的农业机械化发展趋势和农机产品市场分析提供理论指导,为制定黑龙江省农业机械化发展规划和预测近阶段农业机械化发展水平提供参考依据.利用黑龙江省1980-2007年农机总动力数据,运用标准BP神经网络和改进BP神经网络模型进行预测,预测结果表明,改进BP神经网络模型比标准BP神经网络模型在预测精度、运行时间、学习次数等方面更具优越性.     

安徽省农业经济增长影响因素的通径分析

本以1991～2001年安徽省农业统计资料为样本，运用多元统计的通径分析方法对安徽省农业经济增长因素进行分析，利用通径分析将相关系数进行分解，以期从方法上为安徽省农业经济增长问题的研究提供一个新视角。     

Broadening and shifting of the 321-, 325- and 380-GHz lines of water vapor by pressure of atmospheric gases

Three spectral lines of the main water molecule isotope in the ground vibrational state located near 321, 325 and 380 GHz were studied at low pressures and room temperature using spectrometer with radio-acoustic detection of absorption. Self-, N₂- and O₂-pressure broadening and shifting parameters of these lines have been precisely measured. A number of parameters, in particular pressure shifts, were obtained for the first time. Complementary study of the 325-GHz line by resonator spectrometer at atmospheric pressure validated the low pressure experiment data and allowed measurement of the 325-GHz line intensity. Obtained results are discussed in comparison with previous experimental and theoretical data.