拉曼光谱法无损检测蜂蜜中的果糖和葡萄糖含量

应用拉曼光谱结合化学计量学方法对蜂蜜果糖和葡萄糖含量进行了定量分析。用自适应迭代重加权惩罚最小二乘(adaptive iteratively reweighted penalized least squares,airPLS)算法进行基线校正,用竞争性自适应重加权采样(competitive adaptive reweighted sampling,CARS)算法筛选变量,分别用线性的偏最小二乘(partial least squares,PLS)回归算法和非线性的支持向量机(support vector machines,SVM)回归算法建立定量校正模型,并进行预测。2种模型都有较好的预测结果。对果糖,SVM模型预测值与高效液相色谱法(high performance liquid chromatography,HPLC)测定值的相关系数(R)和预测均方根误差(root mean square error of prediction,RMSEP)分别为0.902和1.401,略优于PLS模型(R为0.892,RMSEP为1.604);对葡萄糖,PLS模型的R和RMSEP分别为0.968和0.669,优于SVM模型(R为0.933,RMSEP为1.410)。结果表明拉曼光谱结合化学计量学方法可快速无损测定蜂蜜果糖和葡萄糖含量。     

基于遗传算法的波长选择方法对土壤有机碳预测模型影响

以黑龙江农田黑土为研究对象,利用遗传算法(GA)波长选择结合偏最小二乘法(PLS)回归建立土壤有机碳(SOC)的预测模型。通过设定以下GA参数:波长选择数量上限k、初始种群大小P及迭代次数N,采用单点优化方式逐一确定各参数。结果表明,在主成份数为7的情况下,当GA的参数取N=300、P=300、k=50时,GA模型最优;模型的校正决定系数R2=0.922、校正均方根误差RMSEC=1.74、交叉检验均方根误差RMSECV=1.80;模型的预测决定系数R2=0.931、预测均方根误差RMSEP=1.84、预测相对误差RPD=3.81。与原始光谱的PLS模型相比,R2由0.900提升至0.922,RPD由3.38提升至3.81。结果表明,通过GA进行波长选择能够优化模型,提升模型稳定性以及预测精确性。     

北京典型耕作土壤养分的近红外光谱分析

为研究土壤养分含量分布信息,以从北京郊区一块试验田采集的72个土壤样品为试验材料,应用傅里叶变换近红外光谱技术分析了土样的全氮、全钾、有机质养分含量和pH值。采用偏最小二乘法(PLS)对光谱数据与土壤养分实测值进行回归分析,建立预测模型,以模型决定系数(R2)、校正标准差(RMSECV)、预测标准差(RMSEP)和相对分析误差(RPD)作为模型精度的评价指标。结果表明,利用该模型与光谱数据对土壤全氮、全钾、有机质养分含量和pH值进行预测,结果与实测数据具有较好的一致性,最高决定系数R2达到0.9544。偏最小二乘回归方法建立的养分预测模型能准确地对北京地区褐土土质全氮、有机质、全钾和pH值4种养分进行预测。     

基于小波去噪与SVR的小麦冠层含氮率高光谱测定

为改进小麦冠层含氮率的高光谱测定模型,以正交试验筛选出小波去噪的最优参数组合（小波类型取haar,分解层数为5,阈值方案选择Fixed form threshold,噪声结构定为Unscaled white noise）,并利用去噪后的小麦冠层光谱建立偏最小二乘回归（PLS）模型,对不同预处理方法进行比较分析。发现采用小波去噪结合一阶导数能最有效消除原始光谱的背景信息,此时PLS模型校正集均方根误差（RMSEC）为0.260,预测集均方根误差（RMSEP）为0.288。对经一阶导数结合小波去噪后的光谱用主成分分析（PCA）进行降维,以前6个主成份为输入变量,建立最小二乘支撑向量机回归模型（LS-SVR）,其RMSEC与RMSEP分别为0.154与0.259,具有比PLS模型更高的精度。结果表明：以小波去噪结合一阶导数去除小麦冠层反射光谱中的土壤背景信息以提高模型的精度是可行的,且LS-SVR是建模的优选方法。     

表面增强拉曼光谱检测脐橙果皮混合农药残留

为了研究果皮农药残留快速检测方法。该文以脐橙为例,混合农药(亚胺硫磷和乐果)为研究对象,选用银纳米线作为增强基底,利用共焦显微拉曼光谱仪对农药残留进行检测。通过表面增强拉曼光谱(surface enhanced Raman scattering,SERS)技术,采集脐橙表皮混合农药残留的SERS光谱。对混合农药定性分析,银纳米线对2种农药都有较好的增强效果。对采集的光谱进行预处理后,建立模型,进行定量分析,研究结果表明,经过二阶微分预处理后光谱数据结合偏最小二乘法(partial least squares,PLS)得到的模型预测效果最好,预测相关系数(R_p)为0.954,其预测均方根误差(root-mean-square prediction error,RMSEP)为4.822 mg/L。挑选两种农药特征峰的特征波段,混合农药中亚胺硫磷的特征波段经多元散射校正(multiplicative scatter correction,MSC)处理后,建模效果较好,其中R_p为0.898,RMSEP为6.621 mg/L;混合农药中乐果的特征波段经基线校正处理后,建模效果较好,其中R_p为0.911,RMSEP为7.369 mg/L。研究结果表明SERS技术是一种快速、可靠的检测混合农药残留的方法。     

衰减全反射-中红外光谱法定量测定小麦粉中的石灰类添加物

为了对市售小麦粉中的石灰类添加物进行现场快速检测,该文采用衰减全反射-中红外光谱(mid-infrared spectroscopy combined with attenuated total reflection,ATR-MIR)结合偏最小二乘算法建立了小麦粉中掺入氧化钙、氢氧化钙、碳酸钙、氧化钙+氢氧化钙以及石灰总量的定量校正模型,并采用外部验证集对各模型进行验证。结果表明,氧化钙、氢氧化钙、碳酸钙、氧化钙+氢氧化钙和石灰总量模型的决定系数均大于0.98;校正均方根误差(root mean square error of calibration,RMSEC)均小于0.3;交互验证均方根误差(root mean square error of cross validation,RMSECV)均小于0.5;外部验证的预测均方根误差(root mean square error of prediction,RMSEP)均小于0.95;各模型的相对预测性能(ratio performance deviation,RPD)均大于4.5,该模型具有较高的精度,可以满足小麦粉中石灰含量的现场快速检测要求。该研究可为市售小麦粉的快速质量安全筛查提供新的方法,对小麦粉市场质量监控具有重要意义,并且对小麦粉中其他违禁添加物的检测亦有参考价值。     

基于最小二乘支持向量回归的鹅肉弹性的可见-近红外光谱测定

为简化鹅肉弹性的可见-近红外光谱模型和提高预测精度,采用联合区间偏最小二乘法(synergyinterval partial least square algorithm,siPLS)结合遗传算法(Genetic algorithm,GA)提取可见-近红外光谱特征波长,用最小二乘支持向量回归(least square support vector for regression,LSSVR)建立鹅肉弹性的预测模型。试验以万能试验机获取恢复距离S作为鹅肉弹性实际值。在模型建立过程中,先利用sym8小波的2层分解对原始的可见-近红外光谱进行光谱预处理;然后用siPLS优选出4个特征光谱子区间(分别为第3、5、9、13子区间),在这4个特征光谱子区间内继续用GA优选出74个特征波长,并建立基于LSSVR的鹅肉弹性的预测模型。模型预测集的决定系数(R2)和预测均方根误差(root mean squarederror of prediction,RMSEP)分别为0.9096和0.0588。试验结果表明,siPLS结合GA法能够有效提取光谱中的鹅肉弹性对应的特征波长,有利于提高LSSVR模型预测鹅肉弹性的精度。     

可见-近红外光谱联合随机蛙跳算法检测生物柴油含水量

生物柴油是一种优质清洁柴油,可从各种生物质中提炼,其特有的优势受到越来越广泛的关注。该文应用可见-近红外光谱技术原理对生物柴油的含水率进行了检测。配置含水率分别为0、2.5%、5.0%、7.5%和10.0%的试验样品并获取可见-近红外光谱,进行主成分分析,观察不同含水率生物柴油的聚类性,并采用Random Frog算法进行特征波段的提取,最后采用随机蛙跳算法(Random Frog)挑选出的特征波段作为偏最小二乘回归(partial least squares regression,PLSR)和最小二乘支持向量机(least squares-support vector machine,LS-SVM)模型的输入量,建立生物柴油含水量的预测模型。结果发现:采用Random Frog提取出的8条特征波段(563、560、642、565、562、493、559和779 nm)所建立非线性模型LS-SVM所得到的结果较好,其中Random Frog-LS-SVM的结果中R均大于0.95,校正集均方根误差RMSEC=0.722,预测集均方根误差RMSEP=0.520。结果表明采用Random Frog-LS-SVM模型可以准确的预测生物柴油的含水量,为实际应用提供参考。     

蜂蜜还原能力的电化学传感器检测

为了实现蜂蜜抗氧化物还原能力的快速检测,该文提出了一种用电化学传感器来检测3种不同蜜源蜂蜜的还原能力的新方法。试验采用循环伏安法采集蜂蜜样本的电化学响应信号,提取12个特征值进行归一化预处理,然后利用偏最小二乘法（PLS）建立模型进行检测。校正集的相关系数r和交互验证均方根误差（RMSECV）分别为0.9425和0.0433;预测集的相关系数r和预测均方根误差（RMSEP）分别为0.9392和0.0417。研究结果表明,电化学传感器结合偏最小二乘法检测蜂蜜的还原能力的思路是可行的。     

近红外光谱快速检测食用油必需脂肪酸

为了建立食用油必需脂肪酸快速检测的方法,该研究提出了基于近红外光谱技术检测食用油中α-亚麻酸和亚油酸含量的快速测定方法。对光谱信息分别采用偏最小二乘回归方法(PLS)和最小二乘支持向量机(LS-SVM)建立模型。比较了多种光谱预处理方法对模型预测能力的影响。结果表明对于亚油酸含量的预测,采用Savitzky-Golay平滑法结合多元散射校正(MSC)的光谱预处理所建立的LS-SVM模型最优。预测集的决定系数(R2)、预测均方根误差(RMSEP)和剩余预测偏差(RPD)分别达到了0.989,0.0161和9.4783。对于α-亚麻酸含量的预测,采用Savitzky-Golay平滑法结合标准正态变换(SNV)的光谱预处理所建立的LS-SVM模型最优。α-亚麻酸含量预测结果的R2、RMSEP和RPD为0.972,0.0036和6.0561,据此表明,应用近红外光谱技术能够检测食用油中α-亚麻酸和亚油酸的含量,为快速检测食用油的必需脂肪酸提供了参考。     

基于可见/近红外光谱技术的土壤总磷分析研究

Overabundance of phosphorus (P) in soils and water is of great concern and has received much attention in Florida, USA. Therefore, it is essential to analyze and predict the distribution of P in soils across large areas. This study was undertaken to model the variation of soil total phosphorus (TP) in Florida. A total of 448 soil samples were collected from different soil types. Soil samples were analyzed by chemical reference method and scanned in the visible/near-infrared (VNIR) region of 350--2 500 nm. Partial least squares regression (PLSR) calibration model was developed between chemical reference values and VNIR values. The coefficient of determination (R²) and the root mean squares error (RMSE) of calibration and validation sets, and the residual prediction deviation (RPD) were used to evaluate the models. The R² in calibration and validation for log-transformed TP (log TP) were 0.69 and 0.65, respectively, indicating that VNIR calibration obtained in this study accounted for at least 65% of the variance in log TP using only VNIR spectra, and the high RPD of 2.82 obtained suggested that the spectral model derived in this study was suitable and robust to predict TP in a wide range of soil types, being representative of Florida soil conditions.     

基于近红外光谱的土壤全氮含量估算模型

土壤全氮是诊断土壤肥力水平和指导作物精确施肥所需的重要信息,建立土壤全氮的近红外光谱估测模型并对建模波段进行优化选择对于土壤养分信息快速获取和精确农业发展具有重要意义。该研究以中国中、东部地区5种主要类型土壤为研究对象,利用近红外光谱仪采集土壤样品的光谱信息,结合近红外区域分子振动特点选取全谱、合频、一倍频、二倍频和N-H基团及其组合的8个波段,采用多元散射校正等多种预处理方法组合进行处理,结合偏最小二乘法(PLS)对每个波谱区域进行定标建模。结果表明,利用4000～5500cm-1波谱区域结合附加散射校正处理过的原始光谱建立的模型精度表现最好,其内部互验证决定系数达到0.90,均方根误差为0.16。经不同类型土壤的观测资料检验,模型验证决定系数为0.91,均方根误差为0.15,相对分析误差RPD为3.40,表明模型具有极好的预测能力。因此,利用近红外光谱可以实现土壤全氮的快速估测,且以合频波段(4000～5500cm-1)为建模区域可以得到更好的预测效果。     

Transferability and scalability of soil total carbon prediction models in Florida, USA

The applicability, transferability, and scalability of visible/near-infrared (VNIR)-derived soil total carbon (TC) models are still poorly understood. The objectives of this study were to: i) compare models of three multivariate statistical methods, partial least squares regression (PLSR), support vector machine (SVM), and random forest methods, to predict soil logarithm-transformed TC (logTC) using five fields (local scale) and a pooled (regional-scale) VNIR spectral dataset (a total of 560 TC spectral datasets), ii) assess the model transferability among fields, and iii) evaluate their up- and downscaling behaviors in Florida, USA. The transferability and up- and downscaling of the models were limited by the following factors: i) the spectral data domain, ii) soil attribute domain, iii) methods that describe the internal model structure of VNIR-TC relationships, and iv) environmental domain space of attributes that control soil carbon dynamics. All soil logTC models showed excellent performance based on all three methods with R² > 0.86, bias < 0.01%, root mean squared error (RMSE) = 0.09%, residual predication deviation (RPD) > 2.70%, and ratio of prediction error to interquartile range (RPIQ) > 4.54. The PLSR method performed substantially better than the SVM method to scale and transfer the TC models. This could be attributed to the tendency of SVM to overfit models, while the asset of the PLSR method was its robustness when the models were validated with independent datasets, transferred, and/or scaled. The upscaled soil TC models performed somewhat better in terms of model fit (R²), RPD, and RPIQ, whereas the downscaled models showed less bias and smaller RMSE based on PLSR. We found no universal trend indicating which of the four limiting factors mentioned above had the most impact that constrained the transferability and scalability of the models. Given that several factors can impinge on the empirically derived soil spectral prediction models, as demonstrated by this study, more focus on their applicability and scalability is needed.     

基于高光谱数据的土壤全氮含量估测模型对比研究

构建基于高光谱数据的土壤全氮含量估测模型,为快速、准确监测农田土壤全氮含量,判断作物生长发育情况和评价土地质量提供新的技术和方法.以新疆南疆地区主要类型土壤为研究对象,于室内测定土壤全氮含量和光谱反射率数据,利用偏最小二乘回归(PLSR)、支持向量机回归(SVM)、随机森林回归(RF)与光谱反射率(R)及其4种数学变换...     

高光谱图像技术快速预测发酵醋醅总酸分布

固态发酵是镇江香醋生产的重要环节之一,直接决定着成品醋的风味和品质。但目前固态发酵的生产控制主要依赖人工经验,难以有效保障镇江香醋的品质。该文分析了总酸（total acid content,TAC）、pH值、含水率在不同阶段的变化规律;采用高光谱图像技术结合联合区间偏最小二乘法（synergy interval partial least squares,siPLS）快速预测固态发酵基质（醋醅）的TAC、pH值和含水率,其最佳模型的相关系数R分别为0.8316、0.9455和0.8503;同时利用主成分分析和逐步多元线性回归模型（stepwise multiple linear regression,SMLR）对醋醅高光谱图像进行分析,研究了总酸在醋醅中的分布情况,以此来快速判断醋醅发酵的均匀性。研究表明,利用高光谱图像技术快速预测醋醅的理化参数及其分布的方法是可行的,结果可为镇江香醋固态发酵的工艺控制提供基础数据和技术手段。     

基于中红外光谱的规模化奶牛场粪水总氮快速预测方法

为建立适用于规模化奶牛场粪水中总氮含量的快速预测方法,以天津市23家种养结合型规模化奶牛场粪水治理全过程环节的样品为研究对象,探讨了基于中红外衰减全反射光谱技术快速预测粪水总氮含量的可行性。以偏最小二乘法分别建立了同一奶牛场粪水总氮含量的全程定标模型和不同奶牛场粪水总氮含量的全局定标模型,并采用独立的预测集验证了模型有效性。结果表明:全程模型总氮预测含量与实测含量的线性拟合相关系数为0.98,预测均方根误差RMSEP为130.18 mg/L,剩余预测偏差为4.97,可用于某一奶牛场粪水运移全过程环节总氮含量的快速预测;全局模型总氮预测含量与实测含量的线性拟合相关系数为0.97,预测均方根误差RMSEP为191.66 mg/L,剩余预测偏差为3.83,可用于不同奶牛场多元因素条件下总氮含量的快速预测。研究表明,基于中红外衰减全反射光谱可以实现对不同类型规模化奶牛场粪水治理全过程环节样品总氮含量的即时监测和跟踪。     

不同利用方式下土壤有机质和全磷的可见近红外高光谱反演

以太湖流域直湖港小流域稻田、桃园和菜地的土壤样本为研究对象,研究了不同光谱建模方法和土地利用方式对土壤有机质和全磷高光谱反演的影响。结果表明:(1)偏最小二乘回归分析(Partial least squarer egression,PLSR)模型的建模和预测精度较高且稳定;人工神经网络中广义回归神经网络(Generalized regression neural network,GRNN)网络预测精度较高但易出现过拟合现象,反向传播神经网络(Back propagation neural network,BPNN)网络比较稳健但精度略低;偏最小二乘与人工神经网络相结合则可综合两者优点,改善复杂样本下的预测精度。(2)土壤有机质的光谱反演结果优于全磷。3种土地利用方式中,稻田的预测效果总体优于桃园和菜地。在当前研究区域内土地利用方式对土壤有机质光谱反演影响不大,但对全磷反演影响较大。今后利用光谱对土壤全磷反演时需分土地利用方式对模型进行校准。     

Evaluating a low‐cost portable NIR spectrometer for the prediction of soil organic and total carbon using different calibration models

This study aims to assess the performance of a low‐cost, micro‐electromechanical system‐based, near infrared spectrometer for soil organic carbon (OC) and total carbon (TC) estimation. TC was measured on 151 soil profiles up to the depth of 1 m in NSW, Australia, and from which a subset of 24 soil profiles were measured for OC. Two commercial spectrometers including the AgriSpec^TM (ASD) and NeoSpectra^TM (Neospectra) with spectral wavelength ranges of 350–2,500 and 1,300–2,500 nm, respectively, were used to scan the soil samples, according to the standard contact probe protocol. Savitzky–Golay smoothing filter and standard normal variate (SNV) transformation were performed on the spectral data for noise reduction and baseline correction. Three calibration models, including Cubist tree model, partial least squares regression (PLSR) and support vector machine (SVM), were assessed for the prediction of soil OC and TC using spectral data. A 10‐fold cross‐validation analysis was performed for evaluation of the models and devices accuracies. Results showed that Cubist model predicts OC and TC more accurately than PLSR and SVM. For OC prediction, Cubist showed R² = 0.89 (RMSE = 0.12%) and R² = 0.78 (RMSE = 0.16%) using ASD and NeoSpectra, respectively. For TC prediction, Cubist produced R² = 0.75 (RMSE = 0.45%) and R² = 0.70 (RMSE = 0.50%) using ASD and NeoSpectra, respectively. ASD performed better than NeoSpectra. However, the low‐cost NeoSpectra predictions were comparable to the ASD. These finding can be helpful for more efficient future spectroscopic prediction of soil OC and TC with less costly devices.