Protein and Apparent Amylose Contents of Milled Rice by NIR‐FT/Raman Spectroscopy

The chemometric calibration of near‐infrared Fourier‐transform Raman (NIR‐FT/Raman) spectroscopy was investigated for the purpose of providing a rigorous spectroscopic technique to analyze rice flour for protein and apparent amylose content. Ninety rice samples from a 1996 collection of short, medium, and long grain rice grown in four states of the United States, as well as Taiwan, Korea, and Australia were investigated. Milled rice flour samples were scanned in rotating cups with a 1,064 nm (NIR) excitation laser using 500 mW of power. Raman scatter was collected using a liquid N₂ cooled Ge detector over the Raman shift range of 175–3,600 cm^‐1. The spectral data was preprocessed using baseline correction with and without derivatives or with derivatives alone and normalization. Nearly equivalent results were obtained using all of the preprocessing methods with partial least squares (PLS) models. However, models using baseline correction and normalization of the entire spectrum, without derivatives, showed slightly better performance based on the criteria of highest r² and the lowest SEP with low bias. Calibration samples (n = 57) and validation samples (n = 33) were chosen to have similar respective distributions for protein and apparent amylose. The best model for protein was obtained using six factors giving r² = 0.992, SEP = 0.138%, and bias = ‐0.009%. The best model for apparent amylose was obtained using eight factors giving r² = 0.985, SEP = 1.05%, and bias = ‐0.006%.     

Rapid Variety Identification of Pure Rough Rice by Fourier‐Transform Near‐Infrared Spectroscopy

Rice variety is considered as an important factor influencing cooking and processing quality because of variations in size, shape, and constitution. Difficulty in management of rough rice with lower varietal purity becomes a significant problem in rice production and can result in the reduction of rice quality. Fourier‐transform near‐infrared (FT‐NIR) spectroscopy was used to identify the variety of rough rice through whole‐grain techniques. Moist rough rice samples (n = 259) comprising five varieties (Khao Dawk Mali 105 [KDML105], Pathum Thani 1, Suphan Buri 60, Chainat 1, and Pitsanulok 2) were gathered from different locations around Thailand and scanned in the NIR region of 9088–4000 cm^–1 in reflectance mode. Soft independent modeling of class analogies (SIMCA) and partial least squares discriminant analysis (PLSDA) methods were used for identification by utilizing preprocessed spectra. The highest identification accuracy achieved was 74.42% by the SIMCA model and 99.22% by the PLSDA model. The best PLSDA model demonstrated approximately 97% correct identification for KDML105 samples and 100% for the others. This study raises the possibility of applying FT‐NIR spectroscopy as a nondestructive technique for rapidly identifying moist rough rice varieties in routine quality assurance testing.     

Geographical classification of honey samples by near-infrared spectroscopy: a feasibility study

The potential of near-infrared (NIR) spectroscopy to determine the geographical origin of honey samples was evaluated. In total, 167 unfiltered honey samples (88 Irish, 54 Mexican, and 25 Spanish) and 125 filtered honey samples (25 Irish, 25 Argentinean, 50 Czech, and 25 Hungarian) were collected. Spectra were recorded in transflectance mode. Following preliminary examination by principal component analysis (PCA), modeling methods applied to the spectral data set were partial least-squares (PLS) regression and soft independent modeling of class analogy (SIMCA); various pretreatments were investigated. For unfiltered honey, best SIMCA models gave correct classification rates of 95.5, 94.4, and 96% for the Irish, Mexican, and Spanish samples, respectively; PLS2 discriminant analysis produced a 100% correct classification for each of these honey classes. In the case of filtered honey, best SIMCA models produced correct classification rates of 91.7, 100, 100, and 96% for the Argentinean, Czech, Hungarian, and Irish samples, respectively, using the standard normal variate (SNV) data pretreatment. PLS2 discriminant analysis produced 96, 100, 100, and 100% correct classifications for the Argentinean, Czech, Hungarian, and Irish honey samples, respectively, using a second-derivative data pretreatment. Overall, while both SIMCA and PLS gave encouraging results, better correct classification rates were found using PLS regression.     

Detection and identification of bacteria in an isolated system with near-infrared spectroscopy and multivariate analysis

Near-infrared (NIR) transflectance spectra of Listeria innocua FH, Lactococcus lactis, Pseudomonas fluorescens, Pseudomonas mendocina, and Pseudomonas putida suspensions were collected and investigated for their potential use in the identification and classification of bacteria. Unmodified spectral data were transformed (first and second derivative) using the Savitzsky-Golay algorithm. Principal component analysis (PCA), partial least-squares discriminant analysis (PLS2-DA), and soft independent modeling of class analogy (SIMCA) were used in the analysis. Using either full cross-validation or separate calibration and prediction data sets, PLS2 regression classified the five bacterial suspensions with 100% accuracy at species level. At Pseudomonas genus level, PLS2 regression classified the three Pseudomonas species with 100% accuracy. In the case of SIMCA, prediction of an unknown sample set produced correct classification rates of 100% except for L. innocua FH (77%). At genus level, SIMCA produced correct classification rates of 96.7, 100, and 100% for P. fluorescens, P. mendocina, and P. putida, respectively. This successful investigation suggests that NIR spectroscopy can become a useful, rapid, and noninvasive tool for bacterial identification.     

Discrimination between Shiraz wines from different Australian regions: the role of spectroscopy and chemometrics

This study reports the use of UV-visible (UV-vis), near-infrared (NIR), and midinfrared (MIR) spectroscopy combined with chemometrics to discriminate among Shiraz wines produced in five Australian regions. In total, 98 commercial Shiraz samples (vintage 2006) were analyzed using UV-vis, NIR, and MIR wavelength regions. Spectral data were interpreted using principal component analysis (PCA), linear discriminant analysis (LDA), and soft independent model of class analogy (SIMCA) to classify the wine samples according to region. The results indicated that wine samples from Western Australia and Coonawarra can be separated from the other wines based on their MIR spectra. Classification results based on MIR spectra also indicated that LDA achieved 73% overall correct classification, while SIMCA 95.3%. This study demonstrated that IR spectroscopy combined with chemometric methods can be a useful tool for wine region discrimination.     

Discrimination of irradiated starch gels using FT-Raman spectroscopy and chemometrics

The effects of gamma-irradiation on starch gels were characterized at the molecular level by Fourier transform (FT) Raman spectroscopy. Starches from five different sources were gelatinized and irradiated at 3, 5, and 10 kGy using a Co60 gamma-irradiator. Gamma-irradiation effects on starch gels were noted by the C-H stretch (2800-3000 cm(-1)) and O-H stretch (3000-3600 cm(-1)) and bend (1600-1800 cm(-1)) regions of the FT-Raman spectra. FT-Raman molecular fingerprints obtained through spectral analyses were used for discrimination of the gels based on the extent of irradiation by means of two different pattern-recognition techniques: canonical variate analysis (CVA) and soft modeling of class analogy (SIMCA). A complete discrimination of irradiated starches was attained using a hybrid partial least-squares (PLS) and CVA model, using the spectral variations in the C-H stretch and O-H stretch and bend regions of FT-Raman spectra. Using the same spectral regions, SIMCA predicted 84% of samples correctly.     

Estimation of the Deoxynivalenol and Moisture Contents of Bulk Wheat Grain Samples by FT‐NIR Spectroscopy

Deoxynivalenol (DON) levels in harvested grain samples are used to evaluate the Fusarium head blight (FHB) resistance of wheat cultivars and breeding lines. Fourier transform near‐infrared (FT‐NIR) calibrations were developed to estimate the DON level and moisture content (MC) of bulk wheat grain samples harvested from FHB screening trials. Grains in a rotating glass petri dish were scanned in the 10,000–4,000 cm⁻¹ (1,000–2,500 nm) spectral range using a Perkin Elmer Spectrum 400 FT‐IR/FT‐NIR spectrometer. The DON calibration predicted the DON levels in test samples with R ² = 0.62 and root mean square error of prediction (RMSEP) = 8.01 ppm. When 5–25 ppm of DON was used as the cut‐off to classify samples into low‐ and high‐DON groups, 60.8–82.3% of the low‐DON samples were correctly classified, whereas the classification accuracy of the high‐DON group was 82.3–94.0%. The MC calibration predicted the MC in grain samples with R ² = 0.98 and RMSEP = 0.19%. Therefore, these FT‐NIR calibrations can be used to rapidly prescreen wheat lines to identify low‐DON lines for further evaluation using standard laboratory methods, thereby reducing the time and costs of analyzing samples from FHB screening trials.     

Influence of Soil Particle Size on the Measurement of Sodium by Near-Infrared Reflectance Spectroscopy

This study evaluates the effect of soil particle size (SPS) on the measurement of exchangeable sodium (Na) (EXC-Na) by near-infrared reflectance (NIR) spectroscopy. Three hundred thirty-two (n = 332) top soil samples (0–10 cm) were taken from different locations across Uruguay, analyzed by EXC-Na using emission spectrometry, and scanned in reflectance using a NIR spectrophotometer (1100–2500 nm). Partial least squares (PLS) and principal component regression (PCR) models between reference chemical data and NIR data were developed using cross validation (leaving one out). The coefficient of determination in calibration (R²) and the root mean square of the standard error of cross validation (RMSECV) for EXC-Na concentration were 0.44 (RMSECV: 0.12 mg kg^–1) for soil with small particle size (SPS-0.053) and 0.77 (RMSECV: 0.09 mg kg^–1) for soils with particle sizes greater than 0.212 mm (SPS-0.212), using the NIR region after second derivative as mathematical transformation. The R² and RMSECV for EXC-Na concentration using PCR were 0.54 (RMSECV: 0.07 mg kg^–1) and 0.80 (RMSECV: 0.03 mg kg^–1) for SPS-0.053 and SPS-0.212 samples, respectively.     

Can Near or Mid‐Infrared Diffuse Reflectance Spectroscopy Be Used to Determine Soil Carbon Pools?

Abstract

The objective of this study was to compare mid‐infrared (MIR) an near‐infrared (NIR) spectroscopy (MIRS and NIRS, respectively) not only to measure soil carbon content, but also to measure key soil organic C (SOC) fractions and the δ¹³C in a highly diverse set of soils while also assessing the feasibility of establishing regional diffuse reflectance calibrations for these fractions. Two hundred and thirty‐seven soil samples were collected from 14 sites in 10 western states (CO, IA, MN, MO, MT, ND, NE, NM, OK, TX). Two subsets of these were examined for a variety of C measures by conventional assays and NIRS and MIRS. Biomass C and N, soil inorganic C (SIC), SOC, total C, identifiable plant material (IPM) (20× magnifying glass), the ratio of SOC to the silt+clay content, and total N were available for 185 samples. Mineral‐associated C fraction, δ¹³C of the mineral associated C, δ¹³C of SOC, percentage C in the mineral‐associated C fraction, particulate organic matter, and percentage C in the particulate organic matter were available for 114 samples. NIR spectra (64 co‐added scans) from 400 to 2498 nm (10‐nm resolution with data collected every 2 nm) were obtained using a rotating sample cup and an NIRSystems model 6500 scanning monochromator. MIR diffuse reflectance spectra from 4000 to 400 cm^?1 (2500 to 25,000 nm) were obtained on non‐KBr diluted samples using a custom‐made sample transport and a Digilab FTS‐60 Fourier transform spectrometer (4‐cm^?1 resolution with 64 co‐added scans). Partial least squares regression was used with a one‐out cross validation to develop calibrations for the various analytes using NIR and MIR spectra. Results demonstrated that accurate calibrations for a wide variety of soil C measures, including measures of δ¹³C, are feasible using MIR spectra. Similar efforts using NIR spectra indicated that although NIR spectrometers may be capable of scanning larger amounts of samples, the results are generally not as good as achieved using MIR spectra.     

Measurement of Phosphorus in Soils by Near Infrared Reflectance Spectroscopy: Effect of Reference Method on Calibration

Abstract

The use of ultraviolet (UV), visible (VIS), near infrared reflectance (NIR), and midinfrared (MIR) spectroscopy techniques have been found to be successful in determining the concentration of several chemical properties in soils. The aim of this study was to evaluate the effect of two reference methods, namely Bray and Resins, on the VIS and NIR calibrations to predict phosphorus in soil samples. Two hundred (n=200) soil samples were taken in different years from different locations across Uruguay with different physical and chemical characteristics due to different soil types and management. Soil samples were analyzed by two reference methods (Bray and Resins) and scanned using an NIR spectrophotometer (NIRSystems 6500). Partial least square (PLS) calibration models between reference data and NIR data were developed using cross‐validation. The coefficient of determination in calibration (R²) and the root mean square of the cross validation (RMSECV) were 0.58 (RMSECV: 3.78 mg kg^?1) and 0.61 (RMSECV: 2.01 mg kg^?1) for phosphorus (P) analyzed by Bray and Resins methods, respectively, using the VIS and NIR regions. The R² and RMSECV for P using the NIR region were 0.50 (RMSECV: 3.78 mg kg^?1) and 0.58 (RMSECV: 2.01 mg kg^?1). This study suggested that differences in accuracy and prediction depend on the method of reference used to develop an NIR calibration for the measurement of P in soil.     

Environmental Effects on Developing Wheat as Sensed by Near‐Infrared Reflectance of Mature Grains

For 30 years, near‐infrared (NIR) spectroscopy has routinely been applied to the cereal grains for the purpose of rapidly measuring concentrations of constituents such as protein and moisture. The research described herein examined the ability of NIR reflectance spectroscopy on harvested wheat to determine weather‐related, quality‐determining properties that occurred during plant development. Twenty commercial cultivars or advanced breeding lines of hard red winter and hard white wheat (Triticum aestivum L.) were grown in 10 geographical locations under prevailing natural conditions of the U.S. Great Plains. Diffuse reflectance spectra (1,100–2,498 nm) of ground wheat from these samples were modeled by partial least squares one (PLS1) and multiple linear regression algorithms for the following properties: SDS sedimentation volume, amount of time during grain fill in which the temperature or relative humidity exceeded or was less than a threshold level (i.e., >30, >32, >35, <24°C; >80%, <40% rh). Rainfall values associated with four pre‐ and post‐planting stages also were examined heuristically by PLS2 analysis. Partial correlation analysis was used to statistically remove the contribution of protein content from the quantitative NIR models. PLS1 models of 9–11 factors on scatter‐corrected and (second order) derivatized spectra produced models whose dimensionless error (RPD, ratio of standard deviation of the property in a test set to the model standard error for that property) ranged from 2.0 to 3.3. Multiple linear regression models, involving the sum of four second‐derivative terms with coefficients, produced models of slightly higher error compared with PLS models. For both modeling approaches, partial correlation analysis demonstrated that model success extends beyond an intercorrelation between property and protein content, a constituent that is well‐modeled by NIR spectroscopy. With refinement, these types of NIR models may have the potential to provide grain handlers, millers, and bakers a tool for identifying the cultural environment under which the purchased grain was produced.     

Application of diffuse reflectance FT-IR spectroscopy and partial least-squares regression to predict NMR properties of soil organic matter

Carbon 13 nuclear magnetic resonance spectroscopy (¹³C NMR) is a powerful technique for studying the structure and turnover of soil organic matter, but is time consuming and expensive. It is therefore worth seeking swifter and cheaper methods. Diffuse reflectance FT‐IR spectroscopy (DRIFT), along with partial least squares (PLS) algorithms, provides statistical models to quantify soil properties, such as contents of C, N and clay. I have applied DRIFT?PLS to quantify soil organic C species, as measured by solid state ¹³C NMR spectroscopy, for several bulk soils and physical soil fractions. Calibration and prediction models for organic C and for particular NMR regions, namely alkyl C, O?alkyl C and carboxyl C, attained R² values of between 0.94 and 0.98 (calibration) and 0.70–0.93 (cross‐validation). The prediction of unknown soil samples, after pre‐selection by statistical indices, confirmed the applicability of DRIFT?PLS. The prediction of aromatic C failed, probably because of superimposition of aromatic bands by signals from minerals. Results from fractions of particulate organic matter suggest that the chemical homogeneity of the material hampers the quantification of its constituting C species by DRIFT?PLS. For alkyl C, prediction of carbon species by DRIFT?PLS was better than direct peak‐area quantification in the IR spectra, but advantageous in parts only compared with a linear model correlating C species with soil C contents. In conclusion, DRIFT?PLS calibrated with NMR data provides quantitative information on the composition of soil organic matter and can therefore complement structural studies by its application to large numbers of samples. However, it cannot replace the information provided by more specific methods. The actual potential of DRIFT?PLS lies in its capacity to predict unknown samples, which is helpful for classification and identification of environmental outliers or benchmarks.     

On-line multisensor monitoring of yogurt and filmjölk fermentations on production scale

Near-infrared (NIR) spectrometry and electronic nose (EN) data were used for on-line monitoring of yogurt and filmj?lk (a Swedish yogurt-like sour milk) fermentations under industrial conditions. The NIR and EN signals were selected by evaluation of principal component analysis loading vectors and further analyzed by studying the variability of the selected principal components. First principal components for the NIR and the EN signals were used for on-line generation of a process trajectory plot visualizing the actual state of fermentation. The NIR signals were also used to set up empirical partial least-squares (PLS) models for prediction of the cultures' pH and titratable acidity (expressed as Thorner degrees, degrees T). By using five or six PLS factors the models yielded acceptable predictions that could be further improved by increasing the number of reliable and precise calibration data. The presented results demonstrate that the fusion of the NIR and EN signals has a potential for rapid on-line monitoring and assessment of process quality of yogurt fermentation.     

Near-Infrared Spectroscopy Coupled with Chemometrics Tools: A Rapid and Non-Destructive Alternative on Soil Evaluation

Near-infrared (NIR) spectroscopy is a rapid, non-destructive and accurate technique for analyzing a wide variety of samples, thus, the growing interest of using this technique in soil science. The objective of this study was to evaluate the potential of NIR spectroscopy to predict organic carbon (OC), total nitrogen (TN), available phosphorus (P) and available potassium (K) in the soil. NIR spectra from 20 cm³ of soil samples were acquired on the range of 750 to 2500 nm in diffuse reflectance mode, resolution of 16 cm^?1 and 64 scans. Eight models of calibration/validation were constructed. Calibration and validation models showed that the predictive potential of NIR varied with the specific soil property (OC, TN, P and K) under evaluation and according to the methodology employed in the model construction (cross-validation or test set). Good prediction models were obtained for OC and TN content based on the statistical parameters. Test set methodology was able to predict soil OC, TN, P, and K better than cross-validation methodology.     

White Pan Bread and Sugar‐Snap Cookies Containing Wheat Starch Phosphate,A Cross‐Linked Resistant Starch

Pup‐loaf bread was made with 10, 30, and 50% substitution of flour with wheat starch phosphate, a cross‐linked resistant starch (XL‐RS4), while maintaining flour protein level at 11.0% (14% mb) by adding vital wheat gluten. Bread with 30% replacement of flour with laboratory‐prepared XL‐RS4 gave a specific volume of 5.9 cm³/g compared with 6.3 g/cm³ for negative control bread (no added wheat starch), and its crumb was 53% more firm than the control bread after 1 day at 25°C, but 13% more firm after 7 days. Total dietary fiber (TDF) in one‐day‐old bread made with commercial XL‐RS4 at 30% flour substitution increased 3–4% (db) in the control to 19.2% (db) in the test bread, while the sum of slowly digestible starch (SDS) plus resistant starch (RS), determined by a modified Englyst method, increased from 24.3 to 41.8% (db). The reference amount (50 g, as‐is) of that test bread would provide 5.5 g of dietary fiber with 10% fewer calories than control bread. Sugar‐snap cookies were made at 30 and 50% flour replacement with laboratory‐prepared XL‐RS4, potato starch, high‐amylose (70%) corn starch, and commercial heat‐moisture‐treated high‐amylose (70%) corn starch. The shape of cookies was affected by the added starches except for XL‐RS4. The reference amount (30 g, as‐is) of cookies made with commercial XL‐RS4 at 30% flour replacement contained 4.3 g (db) TDF and 3.4 g (db) RS, whereas the negative control contained 0.4 g TDF and 0.6 g RS. The retention of TDF in the baked foods containing added XL‐RS4 was calculated to be >80% for bread and 100% for cookies, while the retention of RS was 35–54% for bread and 106–113% for cookies.     

Soil properties prediction of western Mediterranean islands with similar climatic environments by means of mid‐infrared diffuse reflectance spectroscopy

This study investigated the suitability of mid‐infrared diffuse reflectance Fourier transform (MIR‐DRIFT) spectroscopy, with partial least squares (PLS) regression, for the determination of variations in soil properties typical of Italian Mediterranean off‐shore environments. Pianosa, Elba and Sardinia are typical of islands from this environment, but developed on different geological substrates. Principal components analysis (PCA) showed that spectra could be grouped according to the soil composition of the islands. PLS full cross‐validation of soil property predictions was assessed by the coefficient of determination (R²), the root mean square error of cross‐validation and prediction (RMSECV and RMSEP), the standard error (SECV for cross‐validation and SEP for prediction), and the residual predictive deviation (RPD). Although full cross‐validation appeared to be the most accurate (R² = 0.95 for organic carbon (OC), 0.96 for inorganic carbon (IC), 0.87 for CEC, 0.72 for pH and 0.74 for clay; RPD = 4.4, 6.0, 2.7, 1.9 and 2.0, respectively), the prediction errors were considered to be optimistic and so alternative calibrations considered to be more similar to ‘true’ predictions were tested. Predictions using individual calibrations from each island were the least efficient, while predictions using calibration selection based on a Euclidian distance ranking method, using as few as 10 samples selected from each island, were almost as accurate as full cross‐validation for OC and IC (R² = 0.93 for OC and 0.96 for IC; RPD = 3.9 and 4.7, respectively). Prediction accuracy for CEC, pH and clay was less accurate than expected, especially for clay (R² = 0.73 for CEC, 0.50 for pH and 0.41 for clay; RPD = 1.8, 1.5 and 1.4, respectively). This study confirmed that the DRIFT PLS method was suitable for characterizing important properties for soils typical of islands in a Mediterranean environment and capable of discriminating between the variations in soil properties from different parent materials.     

Rice Quality by Spectroscopic Analysis: Precision of Three Spectral Regions

Three types of spectroscopy were used to examine rice quality: near infrared (NIR), Raman, and proton nuclear magnetic resonance (¹H NMR). Samples from 96 rice cultivars were tested. Protein, amylose, transparency, alkali spreading values, whiteness, and degree of milling were measured by standard techniques and the values were regressed against NIR and Raman spectra data. The NMR spectra were used for a qualitative or semiquantitative assessment of the amylose/amylopectin ratio by determining the 1–4 to 1–6 ratio for glucans. Protein can be measured by almost any instrument in any configuration because of the strong relationship between the spectral response and the precision of the reference method. Amylose has an equally strong relationship to the vibrational spectra, but its determination by any reference method is far less precise, resulting in a 10× increase in the standard error of cross‐validation (SECv) or standard error of performance (SEP) with R ² values equal to that of the protein measurement.