基于NIR高光谱成像技术的长枣虫眼无损检测

为了研究快速识别虫眼枣与正常枣的有效方法,利用特征波长主成分分析法结合波段比算法进行虫眼枣识别。首先,利用NIR高光谱成像系统采集130个长枣(50个正常、80个虫眼枣)图像,提取并分析不同类型长枣特征区域的平均光谱曲线,对970~1 670 nm范围内的光谱数据进行主成分分析,确定7个特征波长(990,1 028,1 109,1 160,1 231,1 285,1 464 nm)。然后,对长枣图像做主成分分析,选择PC2图像进行虫眼识别,虫眼与正常枣的识别率分别为67.5%、100%。为了进一步提高虫眼枣的识别率,采用波段比(R1231/R1109)对未识别的虫眼枣进行再次识别,识别率提高到90%。结果表明,基于NIR高光谱成像技术的检测方法对虫眼枣识别是可行的,同时也为多光谱成像技术应用于在线检测长枣品质提供了理论依据。     

Nondestructive discrimination of internal defects in jujube (Huizao) of Xinjiang based on visible and near-infrared spectroscopy

Abstract

During harvest and transport, defects are most likely to affect the interior of jujubes and thus shorten their storage period. This study applied visible and near-infrared transmission spectroscopy to detect such internal defects. Spectra were acquired on the equator area at 0, 90, 180, and 270 degrees of each sample, and a model was constructed to obtain three-dimensional damage and defect detection model. The first derivative, multiplicative scatter correction, standard normal variate, and median filtering were used for preprocessing. Modeling by mean spectra achieved a better effect than using unidirectional spectra. Then, naive Bayes classifier and support vector machine were employed for the model establishment at 600–950?nm and 680–950?nm bands, respectively, using mean spectra. Median filtering effectively improved the signal to noise ratio and the discrimination accuracy of the support vector machine model at 600–950?nm reached 96.77%, which was the best value among all models. This result indicates that the support vector machine model was the optimum model and 600–950?nm was a suitable data range for the detection of internal defects. This research confirms the feasibility of implementing visible and near-infrared spectroscopy for the detection of internal defects in jujubes.     

水源性病原菌光谱检测技术研究进展

水源性病原菌污染会引发多种疾病,严重危害人类健康和公共卫生安全。水源性病原菌检测对人类医疗保健、水安全保障和疾病诊断等具有重要的意义。常规水源性病原菌检测技术,如人工培养法、分子生物法和免疫学法,其测量结果准确、有效,但样品预处理繁琐且费时,不利于病原菌实时在线检测。光谱检测技术以非侵入式获取病原菌发射、散射或吸收光谱特征,能够确定病原菌性质、结构和含量等信息。由于该技术具有易于操作、快速、便携、无损和便于实时监测等优点,在环境监测、生物分析中具有广泛的应用前景。文章介绍了现有水源性病原菌检测技术及其优缺点,指出开展病原菌快速、高效检测的必要性;讨论了光谱检测技术原理及数据分析方法,重点综述了紫外可见光谱、荧光光谱、红外光谱、拉曼光谱和太赫兹光谱在水源性病原菌检测的工作原理和研究进展;最后总结了各技术的优缺点。提出了光谱技术在病原菌检测的实际应用中面临的挑战及应对策略,为进一步发展基于光谱技术的水源性病原菌的快速检测提供参考。     

光谱技术在草地土壤检测中的应用和展望

光谱技术检测具有、省时、成本低、可以无损伤、直接分析等特点,可以同时检测多种土壤成分、在野外检测具有实时性。文章对光谱技术应用于检测草地土壤水分含量、土壤有机质、各种营养元素、土壤质地等方面进行了总结,使用该技术可以及时快捷获取各种土壤数据,有效提高草地管理水平。当前需要解决的问题是对草地植物地下生物量的检测,这对于预测牧草生长状况具有重要作用。另外,能够应用于野外检测草地土壤的光谱仪器还不多,需要开发更多便携式、可野外使用的实时检测仪器。     

Interpreting technical evidence from spectral imaging of paintings by Édouard Manet in the Courtauld Gallery

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.     

Determination of Total Petroleum Hydrocarbon (TPH) and Polycyclic Aromatic Hydrocarbon (PAH) in Soils: A Review of Spectroscopic and Nonspectroscopic Techniques

Abstract: In the analysis of petroleum hydrocarbon–contaminated soils for total petroleum hydrocarbons (TPHs) and polycyclic aromatic hydrocarbons (PAHs), the roles of spectroscopic and nonspectroscopic techniques are inseparable. Therefore, spectroscopic techniques cannot be discussed in isolation. In this report, spectroscopic techniques including Raman, fluorescence, infrared, and visible and near-infrared (Vis-NIR) spectroscopies, as well as mass spectroscopy (coupled to a gas chromatograph) and nonspectroscopic techniques such as gravimetry, immunoassay, and gas chromatography with flame ionization detection are reviewed. To bridge the perceived gap in coverage of the quantitative applications of Vis-NIR spectroscopy in the rapid determination of TPHs and PAHs in soils, a detailed review of studies from the period 1999–2012 are presented. This report also highlights the strengths and limitations of these techniques and evaluates their performance from the perspective of their attributes of general applicability, namely economic portability, operational time, accuracy, and occupational health and safety considerations. Overall, the fluorescence spectroscopic technique had the best performance (85% total score) in comparison to the others, and the gravimetric technique performed the least (60% total score). Method-specific solutions geared toward performance improvement are also suggested.     

空间分辨光谱和可见/近红外光谱的番茄颜色等级判别

比较分析空间分辨光谱和单点可见/近红外光谱（可见/短波近红外光谱和中波近红外光谱）对番茄颜色的识别能力。根据番茄表面和内部颜色将600个样品分为6个等级（green, breaker, turning, pink, light red和red）。分别利用新型空间分辨光谱系统（550~1 650 nm）,可见/短波近红外光谱仪（400~1 100 nm）和中波近红外光谱仪（900~1 700 nm）采集番茄的空间分辨（spatially-resolved, SR）光谱和单点可见/近红外（SP Vis/NIR）光谱,建立番茄等级的偏最小二乘判别（PLSDA）模型,比较其对番茄颜色等级的预测效果。结果表明, SR光谱组合可在最佳单一SR光谱基础上进一步提高番茄颜色的识别能力,对番茄表面颜色和内部颜色的识别率可分别达到98.8%和84.6%。光源-检测器距离较近的SR光谱对番茄表面颜色的识别有帮助,而光源-检测器距离较远的SR光谱能较好的判别番茄内部颜色。SP NIR光谱在对番茄表面颜色判别中与SR光谱具有一定可比性,其分类准确率可达到95%,但SP Vis/NIR光谱在对番茄内部颜色识别中具有较低的分类准确率,分类结果远不如SR光谱,说明SR光谱比SP Vis/NIR光谱对番茄颜色的判别更具潜力。     

基于植物油可见吸收光谱的相关系数鉴别特级初榨橄榄油

目前市场上的橄榄油品牌很多,质量参差不齐,亟需完善橄榄油的等级分类检测和特级初榨橄榄油的鉴别方法。可见吸收光谱光谱法可在不直接接触样品的情况下对样品进行无添加试剂的探测,因此为实现特级初榨橄榄油的鉴别,采用可见吸收光谱法对不同种类植物油进行了光谱测量。实验结果发现特级初榨橄榄油在500~780 nm波段内具有4个明显的吸收峰,而其他种类植物油在此波段内吸光度较弱或无吸收峰,且同种植物油不同品牌之间的光谱特征极其相似。采用相关系数比对不同种类植物油可见吸收光谱,分别计算了四个不同波长范围内植物油的可见吸收光谱的相关系数,实验发现不同波长范围内的植物油可见光谱相关系数差别较大。在520～700 nm范围内,特级初榨橄榄油间的光谱相关系数在0.999 6以上,特级初榨橄榄油与其他种类植物油的光谱相关系数均低于0.267 8,特级初榨橄榄油与其他等级橄榄油的光谱相关系数在0.194 6～0.835 8之间。研究结果表明可见吸收光谱相关系数法是一种快速非接触式鉴别特级初榨橄榄油的可行性方法。建立了一种特级初榨橄榄油快速鉴别方法,即可见吸收光谱相关系数法。该方法在特级初榨橄榄油的实际鉴别中具有一定的应用价值。     

基于近红外反射光谱的外来入侵植物的辨识

提出了一种利用可见一近红外反射光谱技术对婆婆纳、波斯婆婆纳、直立婆婆纳等3种入侵植物和本地杂草宝盖草的植物辨别方法,可以对外表相似度极高的这4种植物进行有效鉴别.研究在对光谱曲线进行预处理和聚类分析后,随机采用30×4个样本作为建模样本,其余的20×4个样本作为预测样本,应用独立软模式法SIMCA(soft independent models of class analogy)进行分类,在显著性水平为5%下,其预测分辨率为78.75%,去除婆婆纳后的预测分辨率为90%.根据变量建模能力(modeling power)值,找到敏感波段496～521,589～626和789～926 nm,并将相应的波段的光谱值作为最小二乘的支持向量机LS-SVM(least squares support vector machine)的输入,进行建模预测,并以预测结果作为目标函数值,进行遗传算法GA(genetic algorithm)优化,结果发现,预测分辨率达95.35%,辨识效果好,能快速正确区分外来入侵植物.     

近红外光谱-BP神经网络-PLS法用于橄榄油掺杂分析

橄榄油兼有食用和保健的作用,价值与价格远远高于其他食用油,所以橄榄油中以劣充好的现象十分普遍。可采用近红外光谱法测定初榨橄榄油中掺杂芝麻油、大豆油和葵花籽油的光谱数据,运用改进的BP算法——Levenberg-Marquardt方法,建立PCA-BP人工神经网络方法对其进行定性判别。同时采用偏最小二乘法(PLS)建立了初榨橄榄油中芝麻油、大豆油、葵花籽油含量的近红外光谱定标模型,用交互验证法进行验证。结果表明,BP人工神经网络有很好的定性鉴别能力,PLS建立的芝麻油、大豆油、葵花籽油定标模型的相关系数分别为98.77,99.37,99.44,交叉验证的均方根误差分别为1.3,1.1,1.04。该方法无损、快速、简便,为橄榄油掺杂的检测提供了一种新的途径。     

涩柿可溶性单宁的可见/近红外漫反射光谱无损检测研究

旨在建立可见/近红外漫反射光谱与涩柿内部可溶性单宁之间的关系,以评价可见/近红外漫反射光谱在测量涩柿内部指标可溶性单宁的应用价值.在可见/近红外光谱区域(570～1848 nm),实验对比分析了不同数学建模算法、不同导数处理方法和不同散射及标准化处理的涩柿可溶性单宁定标模型.结果表明,应用改进偏最小二乘回归算法、一阶导处理和去散射处理所建涩柿可溶性单宁定标模型的预测性能较优,其定标交互验证相关系数(Rcv)和预测相关系数(Rp2)分别为0.722 7和0.678 5,定标交互验证均方根误差(RMSECV)和预测均方根误差(RMSEP)分别为0.148 4和0.176 3.研究表明,可见/近红外漫反射光谱对涩柿可溶性单宁的快速无损检测具有一定的可行性,但模型精度有待提高.     

基于二维相关光谱的壶瓶枣室温贮藏硬度动力学模型研究

为了实现鲜枣常温贮藏期的硬度实时监测并对贮藏时间进行预测,建立了室温下壶瓶枣贮藏期的近红外光谱硬度动力学模型。基于二维相关光谱技术,分析综合浓度影响下的壶瓶枣敏感波段,优选的敏感波段为904,980,1 072,1 200,1 630,1 941和2 215 nm。分析不同贮藏天数的壶瓶枣果肉平均硬度,并拟合出零级反应方程,模型的相关系数为0.991 3,标准误差为6.116×10-4。鲜枣的贮藏过程中,由于复杂的生理化学反应,主要物质的含量发生变化,并通过宏观的信息光谱特征和硬度得以体现。将敏感波段下的光谱信息和贮藏期的硬度指标进行信息耦合,建立壶瓶枣果肉硬度的偏最小二乘模型(partial least square, PLS),模型的预测精度R_P为0.942 7,RMSEP为0.021 0。进而以敏感波段的吸光度为自变量,壶瓶枣果肉硬度指标为应变量,进行多元回归定量分析,建立近红外光谱硬度动力学模型,模型的拟合优度即相关系数为0.983 9,标准误差为0.024 9,并在此基础上建立壶瓶枣贮藏时间与近红外光谱的线性回归关系。研究表明,基于二维相关光谱的硬度动力学模型可以实现对壶瓶枣果肉硬度指标的快速、无损检测并实现其贮藏时间的预测。     

Application of transcutaneous diffuse reflectance spectroscopy in the measurement of blood glucose concentration

In this paper, the propagation characteristics of near-infrared (NIR) light in the palm tissue are analyzed,and the principle and feasibility of using transcutaneous diffuse reflectance spectroscopy for non-invasive blood glucose detection are presented. An optical probe suitable for measuring the diffuse reflectance spectrum of human palm and a non-invasive blood glucose detection system using NIR spectroscopy are designed. Based on this system, oral glucose tolerance tests are performed to measure the blood glucose concentrations of two young healthy volunteers. The partial least square calibration model is then constructed by all individual experimental data. The final result shows that correlation coefficients of the two experiments between the predicted blood glucose concentrations and the reference blood glucose concentrations are 0.9870 and 0.9854, respectively. The root mean square errors of prediction of full cross validation are 0.54 and 0.52 mmol/1, respectively.     

Recent Trends on the Use of Infrared Spectroscopy to Trace and Authenticate Natural and Agricultural Food Products

Abstract: Verification of the authenticity of natural and agricultural foods has become a potential application of spectroscopic methods such as ultraviolet (UV), visible (VIS), near infrared (NIR), and mid-infrared (MIR). Adulteration can take many forms, including the addition of sugars, acids, volatile oils, overdilution of concentrate, addition of juices of other fruits, use of concentrate in a fresh product, and use of low-quality product recovered from what are normally waste products of manufacture. Food adulteration has been practiced since ancient times but has become more sophisticated in the recent past. Foods or ingredients most likely to be targets for adulteration include those that are of high value or subject to the vagaries of weather during their growth or harvest. The practice of adulteration commonly arises for two main reasons: firstly, it can be profitable, and secondly, adulterants can be easily mixed and are subsequently difficult to detect. To counter this problem, manufacturers subject their raw material and by-products to a series of quality controls, including high-performance liquid chromatography (HPLC), thin-layer chromatography (TLC), enzymatic tests, and physical tests. This mini-review highlights recent applications on the use of NIR and MIR spectroscopy to trace and authenticate natural and agricultural products.     

Spectral Analysis of a Hardening Medium Based on I‐20A Oil

Chemical conversions occurring in a hardening medium based on I20A mineral oil through its servicelife are investigated by spectroscopy methods in the IR, visible, and UV regions and by luminescence, massspectroscopy, and elemental analysis methods. The possible reasons leading to deterioration of its cooling properties are established. IR spectroscopic techniques of quantitative determination of the content of compounds in a hardening medium that negatively and positively influence its cooling ability are suggested.     

Photonic sensing of the atmosphere by absorption spectroscopy

Chemically reactive atmospheric species play a crucial role in tropospheric processes which affect regional air quality and global climate change. Contrary to long-lived species such as greenhouse gases, interference-free accurate and precise concentration assessments of strongly reactive short-lived species represent a real challenge. In this paper, we report on the recent progress in spectroscopic instrumental developments for monitoring of OH, NO₃, HONO and NO₂ by using modern photonic sources (Quantum Cascade Laser, distributed feedback diode laser, light emitting diode) in conjunction with high-sensitivity spectroscopic measurement techniques such as multi-pass cell based long optical path length absorption spectroscopy, wavelength-modulation enhanced off-axis integrated cavity output spectroscopy, Faraday rotation spectroscopy, incoherent broadband cavity enhanced absorption spectroscopy. The main techniques available for routine atmospheric measurements of OH, NO₃ and HONO are overviewed, in comparison with the emerging modern photonic spectroscopy techniques.     

Ultrasensitive laser spectroscopy for breath analysis

At present there are many reasons for seeking new methods and technologies that aim to develop new and more perfect sensors for different chemical compounds. However, the main reasons are safety ensuring and health care. In the paper, recent advances in the human breath analysis by the use of different techniques are presented. We have selected non-invasive ones ensuring detection of pathogenic changes at a molecular level. The presence of certain molecules in the human breath is used as an indicator of a specific disease. Thus, the analysis of the human breath is very useful for health monitoring. We have shown some examples of diseases’ biomarkers and various methods capable of detecting them. Described methods have been divided into non-optical and optical methods. The former ones are the following: gas chromatography, flame ionization detection, mass spectrometry, ion mobility spectrometry, proton transfer reaction mass spectrometry, selected ion flow tube mass spectrometry. In recent twenty years, the optical methods have become more popular, especially the laser techniques. They have a great potential for detection and monitoring of the components in the gas phase. These methods are characterized by high sensitivity and good selectivity. The spectroscopic sensors provide the opportunity to detect specific gases and to measure their concentration either in a sampling place or a remote one. Multipass spectroscopy, cavity ring-down spectroscopy, and photo-acoustic spectroscopy were characterised in the paper as well.     

化学镀铜天然高分子材料表面特征的近红外光谱分析

通过对天然高分子材料木材进行化学镀的方法制成的木质电磁屏蔽材料既可以保留木材的一些优良特性,又能有效改善木材导电、 导热和电磁屏蔽性,不仅为木材的增值利用开辟了新道路,还为电磁屏蔽材料的加工利用拓宽了领域。本研究利用近红外光谱结合主成分分析法对化学镀铜处理前后样品进行了分析研究,旨在探讨利用近红外光谱技术研究该材料表面特性的可行性。结果表明：(1)化学镀铜前后样品表面的近红外光谱在形状和吸收强度上存在显著差异,而不同镀铜时间的样品之间也存在差异,尤其是反应未充分的样品。(2)经过主成分分析后,镀铜前后样品沿PC1轴、 PC2轴大致分成了6类,其中未处理样品、 活化处理样品性质较接近,镀铜时间25和40 min样品因反应充分,性质也比较类似,说明近红外光谱中包含反映材料处理前后的重要特征信息。(3)比较近红外区域和可见光区域光谱的主成分分析效果,发现近红外光谱区比可见光光谱区对镀铜处理前后样品的分类效果好,可见光光谱在突出样品的表面颜色特征信息方面表现更好,这说明两者结合运用更有利于样品表面特征信息的表征。     

Variation in luminescence behavior of Yb3+ doped GdAlO3 phosphor with gradual increase in Yb3+ concentration

The present paper reports the combustion synthesis of Yb³⁺ doped GdAlO₃ phosphors. The structural characterization and luminescence spectra of Yb³⁺ doped GdAlO₃ phosphors have been discussed. The effects of variable concentration of Yb³⁺ on Photoluminescence (PL) behavior were studied. The structural characterization was done by X-ray diffraction (XRD) and Transmission electron microscope technique (TEM). The good connectivity with grains and the semi-sphere line structure was found by TEM. The functional group analysis was carried out by Fourier transform infrared (FTIR) spectroscopic techniques. The prepared phosphor gives emission spectra in visible as well as NIR region. Both emissions were studied as a function of Yb³⁺ concentration. The emission intensity variation with Yb³⁺ ion concentration for visible and NIR region were discussed separately. The NIR emission luminescence of GdAlO₃:Yb³⁺ phosphor luminescence continuously increases with increasing Yb³⁺ ion concentration.     

基于近红外光谱油分检测的玉米单倍体鉴别方法研究

目前,在单倍体育种技术中,可先使用低场核磁共振方法定量测得玉米单倍体与二倍体的油分,再依据二者油分差异鉴别单倍体,该方法在实际育种工作中已取得初步应用,但核磁共振鉴别单倍体方法存在速度慢、价格贵、维护难等缺点,难以获得大范围应用。近红外光谱技术有诸多优点并在各领域取得广泛应用,相关研究也表明该技术可用于玉米单倍体的定性鉴别,但是目前该方法用于鉴别单倍体实验研究时涉及的玉米品种相对较少,对于某些品种识别效果较差,且内部机理类似于黑盒,难以指明单倍体、二倍体两类种子是依据何种物质的差别进行区分,有时难以获得农业领域专家认可。根据花粉直感效应的原理,玉米单倍体与二倍体存在明显的油分区别,通过油分鉴别单倍体原理直观明白,易于被业内专家接受。因此,提出了一种先定量得到油分,再依据定量分析所得油分进行分类的方法,即首先使用玉米单籽粒的近红外光谱定量回归分析得到各籽粒的油分含量,再利用定量分析所得的油分值,并使用最小平方误差方法对单倍体、二倍体混合籽粒进行定性分类。实验结果表明近红外定量分析方法的识别精度与核磁共振方法相当,与几种定性分析方法比较,在训练集规模相同时,近红外定量分析方法所得识别率优于几种定性分析方法,进一步表明近红外定量分析方法鉴别单倍体具有一定优势,可满足育种行业精度要求,能够为尽快实现单倍体工程化育种提供保障。