Nondestructive Measurement of Acidity of Strawberry Using Vis/NIR Spectroscopy

Vis/Near infrared reflectance spectroscopy appears to be a rapid and convenient non-destructive technique that can measure the quality and compositional attributes of many substances. This paper assesses the ability of NIR reflectance spectroscopy to estimate the acidity of strawberry. Spectra were collected from 65 samples and data was expressed as absorbance, the logarithm of the reciprocal of reflectance (log1/R). The absorbance data was subsequently compressed using wavelet transformation. Two models to predict the acidity in strawberry were constructed. A prediction model based on wavelet transform (WT) combined with partial least squares (PLS) was found better with the r of 0.856, RMSEP of 0.026, and in the confidence lever 95%.     

Study of golden pompano (Trachinotus ovatus) freshness forecasting method by utilising Vis/NIR spectroscopy combined with electronic nose

Golden pompano (Trachinotus ovatus) quality forecasting method utilising Vis/NIR spectroscopy combined with electronic nose (EN) was investigated in this article. Responses of Vis/NIR spectroscopy and EN to pompanos stored at 4°C were measured for 6 days. Physical/chemical indexes including texture, total volatile basic nitrogen, pH, total viable counts, and human sensory evaluation were synchronously examined as quality references. Chemometric methods including principal component analysis (PCA) and stochastic resonance (SR) were employed for spectroscopic and EN data analysis. Physicochemical examination demonstrated that fish quality decreased rapidly during storage. PCA qualitatively classified freshness degree of pompano samples, while SR signal-to-noise ratio (SNR) spectrum using SNR maximum quantitatively characterised quality for all samples. Golden pompano quality predictive models were developed based on spectroscopy, EN, and spectroscopy combined with EN, respectively. Results demonstrated that the model developed based on spectroscopy combined with EN presented a forecasting accuracy of 93.3%.     

Non-destructive discrimination of paddy seeds of different storage age based on Vis/NIR spectroscopy

The potential of visible/near infrared reflectance (Vis/NIR) spectroscopy for non-destructive discrimination of paddy seeds of different storage age was examined based on Vis/NIR spectroscopy coupled with chemometrics. Data from 210 samples of paddy seed were collected from 325 to 1075 nm using a field spectroradiometer. The spectral data were processed and analyzed by chemometrics, which integrated the methods of wavelet transform (WT), principal component analysis (PCA) and artificial neural networks (ANN) modelling. The noise of spectral data was filtered and diagnostic information was extracted by the WT method. Then, diagnostic information from WT was visualized in principal components space, in which the structures with the storage period were discovered. Finally, the first eight principal components, which accounted for 99.94% of the raw spectral variables, were used as the input for the ANN model. A promising model was achieved with a high discrimination accuracy rate of 97.5%. Thus, an effective and non-destructive way to discriminate paddy seeds of different storage periods was put forward.     

哈姆林甜橙果实内在品质的可见-近红外光谱无损检测法

采用可见- 近红外漫反射光谱技术,结合偏最小二乘法,以不同时间采摘的哈姆林甜橙果实为样品建立其可溶性固形物、含酸量和VC 的无损检测数学模型,同时对不同光谱预处理方法和不同建模波段范围对模型的预测性能进行对比分析。结果表明：原始光谱在400～1000nm 波段的模型预测精度较高。经多元散射校正和5 点移动平均平滑预处理后,果实可溶性固形物含量的PLS 模型最好,校正集样品的相关系数为0.995RMSEC和RMSEP分别为0.026%、0.028%;预测集样品的相关系数为0.992。经多元散射校正和9 点移动平均平滑预处理后,果实含酸量的PLS 模型最好,校正集样品的相关系数为0.997,RMSEC 和RMSEP 分别为0.012%、0.013%;预测集样品的相关系数为0.997。经多元散射校正和9 点移动平均平滑预处理后,果实VC 含量的PLS 模型最好,校正集样品的相关系数为0.998,RMSEC 和RMSEP 分别为0.009%、0.009%;预测集样品的相关系数为0.999。可见由不同时间采摘的果实组成的样品集所建立的数学模型可以提高模型的预测精度,从而提高模型的适用范围。应用可见-近红外漫反射光谱检测哈姆林甜橙果实的内在品质可行。     

多品种洋梨糖度近红外普适性模型的建立

目的 开发多品种洋梨糖度的普适性模型。方法 采用主成分得分空间距离将5个品种洋梨分为两组: 阿巴特 康佛伦斯 五九香(组1), 凯斯凯德 红考密斯(组2)。分别建立多品种洋梨SSC的普适性模型, 以Q值来评价模型综合性能。结果 组1和组2洋梨SSC的普适性模型具有较好性能, 其Q = 0.849、0.735(PLS)和0.875、0.749(MLR)。结论 多品种洋梨品质的MLR普适性模型可用于便携仪器, 实现现场洋梨SSC精确定量检测。     

Automatic freshness assessment of cod (Gadus morhua) fillets by Vis/Nir spectroscopy

VIS/NIR spectroscopy for differentiating between fresh and frozen-thawed cod fillets and for assessing the freshness as days on ice has been evaluated. Both a handheld interactance probe for doing quick measurements of single fillets and an imaging spectrometer for doing online analysis at industrial speed of one fillet per second, have been used. Results show that frozen-thawed cod fillets can be fully separated from fresh fillets using a small subset of wavelengths in the visible region. Freshness as days on ice can be determined with an accuracy of 1.6 days on individual fillets. The results indicate that oxidation of hemoglobin and myoglobin during freezing-thawing and cold storage on ice are explaining most of the variations seen in the visible region of the spectrum.     

可见/近红外光谱技术无损检测新鲜鸡蛋pH及蛋白质的研究

本文利用可见/近红外光谱技术检测新鲜鸡蛋p H和蛋白质。分别采集新鲜鸡蛋在400~1000 nm和900~1700 nm波长范围的漫反射光谱,使用多元散射矫正(MSC)、标准正态变量变换(SNV)等光谱预处理技术,选择最佳的预处理方法,使用偏最小二乘法(PLS)建立p H和蛋白质模型并对其进行评价。结果表明,基于900~1700 nm波长范围的光谱获得的p H模型较好,其校正集相关系数为0.948,预测集相关系数为0.855;基于400~1000 nm波长范围的光谱获得的蛋白质模型较好,其校正集相关系数为0.927,预测集相关系数为0.906。研究表明,可见/近红外光谱技术可以较好的预测新鲜鸡蛋的p H和蛋白质,为鸡蛋营养成分的快速无损检测提供新的思路和方法。      

A New Approach to Predict Acidity of Bayberry Juice by Using Vis/Near Infrared Spectroscopy

A total of 76 bayberry juices were collected and their spectra features were got by using a vis/NIR spectroscopy. One mixed algorithm was used to predict the acidity (pH) of bayberry juice with partial least squares (PLS) and artificial neural network (ANN). PLS was used to find some sensitive spectra actives to acidity in juice, before doing this, the influence of various spectral pretreatments (standard normal variate, multiplicative scatter correction, S.Golay first derivative, wavelet package transform) were compared. The PLS approach with WPT preprocessing spectra was found to provide the best results, and the spectral reflectivity corresponding to them were regarded as the input neurons of ANN. Remnant values by subtracting standard values and validation values, were regarded as the output neurons of ANN. The calibration equation developed from them was used to predict the constituent values for the independent spectra of 30 samples. The results indicated that the observed results using PLS-ANN (r_p = 0.943) were better than those obtained by PLS (r_p = 0.932). At the same time, the sensitive wavelengths corresponding to the acidity of bayberry juices or some element at a certain band were proposed on the basis of regression coefficients by PLS. It indicates that using vis/NIRS technique to fast and nondestructive detection the acidity of bayberry juices was feasible.     

可见/近红外光谱半透射法检测苹果中可溶性固形物含量

目的 检验自行搭建的半透射光谱采集平台检测水果中可溶性固形物含量的可行性, 并比较不同光谱采集方式对光谱模型的影响。方法 以红富士苹果为检测对象, 光谱采集平台中的USB2000 光谱仪采集半透射光谱数据, AntarisⅡ FT-NIR光谱仪采集漫反射光谱数据, 同标准法检测得到的苹果可溶性固形物含量建立偏最小二乘(PLS)模型, 并结合不同的预处理方式优化近红外光谱模型。结果 比较发现采用半透射的光谱采集方式优于漫反射方式。半透射光谱采用平滑处理后模型预测性能最佳, 对样本预测得到相关系数为0.937, 均方根误差为0.517。结论 自行搭建的光谱采集平台可行, 为今后检测水果的光谱采集方式提供参考。     

On-line determination and control of fat content in batches of beef trimmings by NIR imaging spectroscopy

An NIR imaging scanner was calibrated for on-line determination of the fat content of beef trimmings. A good calibration model was obtained for fat in intact beef (R=0.98, RMSECV=3.0%). The developed model could be used on single pixels to get an image of the fat distribution, or on the average spectrum from each trimming/portion of trimmings passing under the scanner. The fat model gave a rather high prediction error (RMSEP=8.7%) and a correlation of 0.84 when applied to 45 single trimmings with average fat content ranging from 1.6 to 49.3% fat. Test measurements on streams of trimmings making up batches varying from 10 to 24 kg gave a much lower prediction error (RMSEP=1.33%). Simulations based on true measurements indicate that the RMSEP decreases with increasing batch size and, for the present case, reached about 0.6% for 100 kg batches. The NIR scanner was tested on six batches of intact trimmings varying from 145 to 210 kg and gave similar fat estimates as an established microwave system obtained on the ground batches. The proven concept should be applicable to on-line estimation of fat in trimmings in order to determine the batch fat content and also to control the production of batches to different target fat levels. A possible requirement for the concept to work properly is that the trimming or layer of trimmings on the belt is not too thick. In this study maximum thickness was about 8 cm. Thicker trimmings might be measured, but careful hardware adjustments are then required.     

Rapid and non-invasive analysis of deoxynivalenol in durum and common wheat by Fourier-Transform Near Infrared (FT-NIR) spectroscopy

Fourier transform near-infrared spectroscopy (FT-NIR) was used for rapid and non-invasive analysis of deoxynivalenol (DON) in durum and common wheat. The relevance of using ground wheat samples with a homogeneous particle size distribution to minimize measurement variations and avoid DON segregation among particles of different sizes was established. Calibration models for durum wheat, common wheat and durum + common wheat samples, with particle size <500 µm, were obtained by using partial least squares (PLS) regression with an external validation technique. Values of root mean square error of prediction (RMSEP, 306–379 µg kg^–1) were comparable and not too far from values of root mean square error of cross-validation (RMSECV, 470–555 µg kg^–1). Coefficients of determination (r ²) indicated an “approximate to good” level of prediction of the DON content by FT-NIR spectroscopy in the PLS calibration models (r ² = 0.71–0.83), and a “good” discrimination between low and high DON contents in the PLS validation models (r ² = 0.58–0.63). A “limited to good” practical utility of the models was ascertained by range error ratio (RER) values higher than 6. A qualitative model, based on 197 calibration samples, was developed to discriminate between blank and naturally contaminated wheat samples by setting a cut-off at 300 µg kg^–1 DON to separate the two classes. The model correctly classified 69% of the 65 validation samples with most misclassified samples (16 of 20) showing DON contamination levels quite close to the cut-off level. These findings suggest that FT-NIR analysis is suitable for the determination of DON in unprocessed wheat at levels far below the maximum permitted limits set by the European Commission.     

基于便携式高灵敏X射线荧光光谱技术快速检测小麦粉中砷、镉、铅含量的研究

目的 建立便携式高灵敏X射线荧光光谱法直接快速测定小麦粉中砷、镉、铅含量的分析方法。方法 取部分样品至进样杯中,然后直接将进样杯放入便携式高灵敏X射线荧光光谱仪进行检测,并对仪器检测时间、样品紧实度、检测厚度等条件进行优化,将最优条件应用于小麦粉的检测。结果 各元素的精密度的相对标准偏差（RSD,n=6）在0.6%～4.8%之间,基质中加标回收率为78.3%～120.4%,铅、镉、砷的检出限分别为0.06、0.06、0.05 mg/kg、定量限分别为0.19、0.19、0.17 mg/kg。对便携式高灵敏X射线荧光光谱法和电感耦合等离子体质谱法检测结果进行比较,相关系数大于0.98。结论 该方法精密度比较高,检出限与定量限良好,基本上能够满足小麦粉中多种重金属元素同时快速检测的要求。     

Non-destructive evaluation of maturity and quality parameters of pomegranate fruit by visible/near infrared spectroscopy

In this study, the potential of visible and near infrared spectroscopy was investigated to classify the maturity stage and to predict the quality attributes of pomegranate variety “Ashraf” such as total soluble solids content, pH, and titratable acidity during four distinct maturity stages between 88 and 143 days after full bloom. Principal component analysis was used to distinguish among different maturities. The prediction models of internal quality attributes of the pomegranate were developed by partial least squares regression. The transmission spectra of pomegranate were obtained in the wavelength range from 400 to 1100 nm. In this research several preprocessing methods were utilized including centering, smoothing (Savitzky–Golay algorithm, median filter), normalization (multiplicative scatter correction and standard normal variate) and differentiation (first derivative and second derivative). It concluded that different preprocessing techniques had effects on the classification performance of the model using the principal component analysis method. In general, standard normal variate and multiplicative scatter correction gave better results than the other pretreatments. The correlation coefficients (r), root mean square error of calibration and ratio performance deviation for the calibration models were calculated: r = 0.93, root mean square error of calibration = 0.22 °Brix and ratio performance deviation = 6.4 °Brix for total soluble solids; r = 0.84, root mean square error of calibration = 0.064 and ratio performance deviation = 4.95 for pH; r = 0.94, root mean square error of calibration = 0.25 and ratio performance deviation = 5.35 for titratable acidity.     

近红外光谱技术在南极磷虾粉水分、脂肪和蛋白质含量快速检测中的应用

利用傅里叶近红外光谱分析技术,以磷虾粉样品的实测值与模型预测值为基础,研究了采用最小二乘法建立磷虾粉原始样品与磷虾粉混合样品中水分、脂肪和蛋白含量近红外定标模型的可行性和准确性.结果表明,磷虾粉近红外图谱最佳预处理方式为:标准正态变换预处理+一阶导数+Norris导数滤波;以磷虾粉混合样品构建的近红外模型较磷虾粉原始样...     

A comparative study for the quantitative determination of soluble solids content,pH and firmness of pears by Vis/NIR spectroscopy

Visible and near infrared (Vis/NIR) spectroscopy was investigated to determine the soluble solids content (SSC), pH and firmness of different varieties of pears. Two-hundred forty samples (80 for each variety) were selected as sample set. Two-hundred ten pear samples (70 for each variety) were selected randomly for the calibration set, and the remaining 30 samples (10 for each variety) for the validation set. Partial least squares (PLS) and least squares-support vector machine (LS-SVM) with different spectral preprocessing techniques were implemented for calibration models. Different wavelength regions including Vis, NIR and Vis/NIR were compared. It indicated that Vis/NIR (400–1800 nm) was optimal for PLS and LS-SVM models. Then, LS-SVM models were developed with a grid search technique and RBF kernel function. All LS-SVM models outperformed PLS models. Next, effective wavelengths (EWs) were selected according to regression coefficients. The EW-LS-SVM models were developed and a good prediction precision and stability was achieved compared with PLS and LV-LS-SVM models. The correlation coefficient of prediction (r_p), root mean square error of prediction (RMSEP) and bias for the best prediction by EW-LS-SVM were 0.9164, 0.2506 and −0.0476 for SSC, 0.8809, 0.0579 and −0.0025 for pH, whereas 0.8912, 0.6247 and −0.2713 for firmness, respectively. The overall results indicated that the regression coefficient was an effective way for the selection of effective wavelengths. LS-SVM was superior to the conventional linear PLS method in predicting SSC, pH and firmness in pears. Therefore, non-linear models may be a better alternative to monitor internal quality of fruits. And the EW-LS-SVM could be very helpful for development of portable instrument or real-time monitoring of the quality of pears.     

近红外与表面增强拉曼光谱融合技术快速检测花生油中黄曲霉毒素B1

目的 在近红外光谱(near infrared spectroscopy, NIR)与表面增强拉曼光谱(surface-enhanced Raman spectroscopy, SERS)特征层数据融合的基础上构建偏最小二乘回归模型(partial least squares regression, PLSR)实现花生油中黄曲霉毒素B1 (aflatoxin B1, AFB1)含量的快速检测。方法 首先,分别采集待测样本的NIR与SERS光谱。其次,将采集的NIR与SERS光谱分别进行光谱预处理。然后,采用基于希尔伯特-施密特独立准则的变量空间迭代优化算法(Hilbert-Schmidt independence criterion based variable space iterative optimization, HSIC-VSIO)分别筛选NIR与SERS光谱的特征变量。最后,将筛选的特征变量进行融合并构建PLSR模型用于定量检测花生油中AFB1含量。结果 与NIR光谱数据、SERS光谱数据以及NIR与SERS光谱直接融合数据构建的PLSR模型相比,NIR与SERS光谱特征层融合数据构建的PLSR模型具有最佳的预测性能：校正集均方根误差(root mean squared error of calibration set, RMSEC)为0.1569,校正集决定系数(coefficient of determination of calibration set, )为0.9908,预测集均方根误差(root mean squared error of prediction set, RMSEP)为0.1827,预测集决定系数(coefficient of determination of prediction set, )为0.9854,性能偏差比(ratio of performance to deviation, RPD)为8.2761。将本方法与标准方法分别检测真实含有AFB1的花生油样本,结果表明两者的检测性能无显著性差异(P=0.84>0.05)。结论 本方法可实现花生油中AFB1含量的快速、高精度定量检测,也验证了NIR与SERS光谱融合的可行性与有效性。     

Application of principal component analysis to the prediction of lucerne forage protein content and in vitro dry matter digestibility by NIR spectroscopy

Application of principal component regression (PCR) was proposed for the development of a prediction equation of forage composition by near infra-red spectroscopy. PCR involves two steps: (a) the creation of new synthetic variables by principal component analysis (PCA) of spectral data, and (b) multiple linear regression with these new variables. Results obtained by this procedure have been compared with those generated by the conventional application of multiple linear regression (MLR) on spectral data. The comparison used the determination of protein content and in vitro dry matter digestibility (IVDMD) in 345 samples of lucerne forages. For protein determination, results of both procedures were quite similar (correlation coefficients: 0.978 and 0.980; standard errors of calibration: 0.86 and 0.84% DM; standard errors of prediction: 0.81 and 0.80% DM respectively for MLR and PCR prediction equations). The same was observed for IVDMD determination (correlation coefficients: 0.942 and 0.951; standard errors of calibration: 1.89 and 1.71% DM; standard errors of prediction: 2.22 and 2.22% DM, respectively). A large number of PCA variables were necessary for an accurate prediction of both constituents. The influence of the number of regression terms introduced in the PCR equation has been studied. The criterion for stopping the introduction of new terms in PCR did not seem as critical as in MLR.     

Non-destructive analysis of anthocyanins in cherries by means of Lambert-Beer and multivariate regression based on spectroscopy and scatter correction using time-resolved analysis

In high-value sweet cherry (Prunus avium), the red coloration - determined by the anthocyanins content - is correlated with the fruit ripeness stage and market value. Non-destructive spectroscopy has been introduced in practice and may be utilized as a tool to assess the fruit pigments in the supply chain processes. From the fruit spectrum in the visible (Vis) wavelength range, the pigment contents are analyzed separately at their specific absorbance wavelengths.A drawback of the method is the need for re-calibration due to varying optical properties of the fruit tissue. In order to correct for the scattering differences, most often the spectral intensity in the visible spectrum is normalized by wavelengths in the near infrared (NIR) range, or pre-processing methods are applied in multivariate calibrations.In the present study, the influence of the fruit scattering properties on the Vis/NIR fruit spectrum were corrected by the effective pathlength in the fruit tissue obtained from time-resolved readings of the distribution of time-of-flight (DTOF). Pigment analysis was carried out according to Lambert-Beer law, considering fruit spectral intensities, effective pathlength, and refractive index. Results were compared to commonly applied linear color and multivariate partial least squares (PLS) regression analysis. The approaches were validated on fruits at different ripeness stages, providing variation in the scattering coefficient and refractive index exceeding the calibration sample set.In the validation, the measuring uncertainty of non-destructively analyzing fruits with Vis/NIR spectra by means of PLS or Lambert-Beer in comparison with combined application of Vis/NIR spectroscopy and DTOF measurements showed a dramatic bias reduction as well as enhanced coefficients of determination when using both, the spectral intensities and apparent information on the scattering influence by means of DTOF readings. Corrections for the refractive index did not render improved results.