Precision farming aims at reduced environmental impacts with increased productivity. Soils are multi-functional media in which air, water and biota occur together and form an essential part of the landscape with a fundamental role in the environment. The requirement for herbicides and fertilizers can vary within a field in response to spatial differences in soil properties. Near infrared (NIR) spectroscopy is widely used today as a nondestructive analytical technique which is capable of determining a number of physio-chemical parameters. The objectives of this study were to develop optimal models to predict chemical properties of paddy soils by visible and NIR reflectance spectra. Total of 60 soil samples were collected in spring from 20 paddy fields within central regions in Korea. Reflectance spectra, moisture contents, pH, total nitrogen (N), organic matter, available phosphate ($P_2O_5$) of soil samples were measured. The reflectance spectra were measured in wavelength ranges of 400-2,500 nm with 2 nm interval. The method of partial least square (PLS) analysis was used to determine the soil properties. The PLS analyses showed good correlation between predicted and measured chemical properties of paddy soils in the wavelength range of 1,800-2,400 nm. Especially, it showed better performance than the previous results which used the entire wavelength range of the spectrophotometer, without considering the optimal wavelength of each soil properties.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
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pp.1526-1526
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2001
To improve the accuracy of sweetness sensor in automated sorting operations, it is necessary to clarify unevenness of the sugar content distribution within fruits. And it is expected that the technique to evaluate the content distribution in fruits contribute to the development of the near-infrared (NIR) imaging spectroscopy. Sugiyama (1999) had succeeded to visualize the distribution of the sugar content on the surface of a half-cut green fresh melon. However, this method cannot be applied to red flesh melons because it depends on information of the absorption band of chlorophyll (676 nm), which is affected by the color of the fresh. The objective of this study was to develop the universal visualization method depends on the absorption band of sugar, which can be applied to various kinds of melons and other fruits. The relationship between the sugar contents and absorption spectra of both green and red fresh melons were investigated by using a NIR spectrometer to determine the absorption band of sugar. The combination of 2$\^$nd/ derivative absorbances at 902 nm and 874 nm was highly correlated with the sugar contents. The wavelength of 902 nm is attributed to the absorption band of sugar. A cooled charge-coupled device (CCD) imaging camera which has 16 bit (65536 steps) A/D resolution was equipped with rotating band-pass filter wheel and used to capture the spectral absorption images of the flesh of a vertically half-cut red fresh melon. The advantage of the high A/D resolution in this research is that each pixel of the CCD is expected to function as a detector of the NIR spectrometer for quantitative analysis. Images at 846 nm, 874 nm, 902 nm and 930 nm were acquired using this CCD camera. Then the 2$\^$nd/ derivative absorbances at 902 nm and 874 nm at each pixel were calculated using these four images. On the other hand, parts of the same melon were extracted for capturing the images and squeezed for the measurement of sugar content. Then the calibration curve between the combination of 2$\^$nd/ derivative absorbances at 902 nm and 874 nm and sugar content was developed. The calibration method based on NIR spectroscopy techniques was applied to each pixel of the images to convert the 2$\^$nd/ derivative absorbances into the Brix sugar content. Mapping the sugar content value of each pixel with linear color scale, the distribution of the sugar content was visualized. As a result of the visualization, it was quantitatively confirmed that the Brix sugar contents are low at the near of the skin and become higher towards the seeds. This result suggests that the visualization technique by the NIR imaging spectroscopy could become a new useful method fer quality evaluation of melons.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
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pp.3112-3112
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2001
Near-Infrared Spectroscopy (NIRS) was investigated aiming at the identification of falsified drugs. The identification is based on comparison of the NIR spectrum of a sample with a typical spectra of an authentic drug using multivariate modelling and classification algorithms (PCA/SIMCA). Two spectrophotometers (Brimrose - Luminar 2000 and 2030), based on acoustic-optical filter (AOTF) technology, sharing the same controlling computer, software (Brimrose - Snap 2.03) and the data acquisition electronics, were employed. The Luminar 2000 scans the range 850 1800 nm and was employed for transmitance/absorbance measurements of liquids with a transflectance optical bundle probe with total optical path of 5 mm and a circular area of 0.5 $\textrm{cm}^2$. Model 2030 scans the rage 1100 2400 nm and was employed for reflectance measurement of solids drugs. 300 spectra, acquired in about 20 s, were averaged for each sample. Chemometric treatment of the spectral data, modelling and classification were performed by using the Unscrambler 7.5 software (CAMO Norway). This package provides the Principal Component Analysis (PCA) and SIMCA algorithms, used for modelling and classification, respectively. Initially, NIRS was evaluated for spectrum acquisition of various drugs, selected in order to accomplish the diversity of physico-chemical characteristics found among commercial products. Parameters which could affect the spectra of a given drug (especially if presented as solid tablets) were investigated and the results showed that the first derivative can minimize spectral changes associated with tablet geometry, physical differences in their faces and position in relation to the probe beam. The effect of ambient humidity and temperature were also investigated. The first factor needs to be controlled for model construction because the ambient humidity can cause spectral alterations that should cause the wrong classification of a real drug if the factor is not considered by the model.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
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pp.1244-1244
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2001
In linear discriminant analysis there are two important properties concerning the effectiveness of discriminant function modeling. The first is the separability of the discriminant function for different classes. The separability reaches its optimum by maximizing the ratio of between-class to within-class variance. The second is the stability of the discriminant function against noises present in the measurement variables. One can optimize the stability by exploring the discriminant variates in a principal variation subspace, i. e., the directions that account for a majority of the total variation of the data. An unstable discriminant function will exhibit inflated variance in the prediction of future unclassified objects, exposed to a significantly increased risk of erroneous prediction. Therefore, an ideal discriminant function should not only separate different classes with a minimum misclassification rate for the training set, but also possess a good stability such that the prediction variance for unclassified objects can be as small as possible. In other words, an optimal classifier should find a balance between the separability and the stability. This is of special significance for multivariate spectroscopy-based classification where multicollinearity always leads to discriminant directions located in low-spread subspaces. A new regularized discriminant analysis technique, the principal discriminant variate (PDV) method, has been developed for handling effectively multicollinear data commonly encountered in multivariate spectroscopy-based classification. The motivation behind this method is to seek a sequence of discriminant directions that not only optimize the separability between different classes, but also account for a maximized variation present in the data. Three different formulations for the PDV methods are suggested, and an effective computing procedure is proposed for a PDV method. Near-infrared (NIR) spectra of blood plasma samples from mastitic and healthy cows have been used to evaluate the behavior of the PDV method in comparison with principal component analysis (PCA), discriminant partial least squares (DPLS), soft independent modeling of class analogies (SIMCA) and Fisher linear discriminant analysis (FLDA). Results obtained demonstrate that the PDV method exhibits improved stability in prediction without significant loss of separability. The NIR spectra of blood plasma samples from mastitic and healthy cows are clearly discriminated between by the PDV method. Moreover, the proposed method provides superior performance to PCA, DPLS, SIMCA and FLDA, indicating that PDV is a promising tool in discriminant analysis of spectra-characterized samples with only small compositional difference, thereby providing a useful means for spectroscopy-based clinic applications.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
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pp.1042-1042
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2001
In linear discriminant analysis there are two important properties concerning the effectiveness of discriminant function modeling. The first is the separability of the discriminant function for different classes. The separability reaches its optimum by maximizing the ratio of between-class to within-class variance. The second is the stability of the discriminant function against noises present in the measurement variables. One can optimize the stability by exploring the discriminant variates in a principal variation subspace, i. e., the directions that account for a majority of the total variation of the data. An unstable discriminant function will exhibit inflated variance in the prediction of future unclassified objects, exposed to a significantly increased risk of erroneous prediction. Therefore, an ideal discriminant function should not only separate different classes with a minimum misclassification rate for the training set, but also possess a good stability such that the prediction variance for unclassified objects can be as small as possible. In other words, an optimal classifier should find a balance between the separability and the stability. This is of special significance for multivariate spectroscopy-based classification where multicollinearity always leads to discriminant directions located in low-spread subspaces. A new regularized discriminant analysis technique, the principal discriminant variate (PDV) method, has been developed for handling effectively multicollinear data commonly encountered in multivariate spectroscopy-based classification. The motivation behind this method is to seek a sequence of discriminant directions that not only optimize the separability between different classes, but also account for a maximized variation present in the data. Three different formulations for the PDV methods are suggested, and an effective computing procedure is proposed for a PDV method. Near-infrared (NIR) spectra of blood plasma samples from daily monitoring of two Japanese cows have been used to evaluate the behavior of the PDV method in comparison with principal component analysis (PCA), discriminant partial least squares (DPLS), soft independent modeling of class analogies (SIMCA) and Fisher linear discriminant analysis (FLDA). Results obtained demonstrate that the PDV method exhibits improved stability in prediction without significant loss of separability. The NIR spectra of blood plasma samples from two cows are clearly discriminated between by the PDV method. Moreover, the proposed method provides superior performance to PCA, DPLS, SIMCA md FLDA, indicating that PDV is a promising tool in discriminant analysis of spectra-characterized samples with only small compositional difference.
Nowadays, medical diagnostics is efficiently supported by clinical chemistry and near infrared spectroscopy is becoming a new dimension, which has shown high potential to provide valuable information for diagnosis. The investigation was carried out to study the influence of mammary gland inflammation, called mastitis, on cow´s milk spectra and milk composition measured by near infrared spectroscopy (NIRS). Milk somatic cell counts (SCC) in milk were used as a measure of mammary gland inflammation. Naturally occurred variations with milk composition within lactation and in the process of milking were included in the experimental design of this study. Time series of unhomogenized, raw milk spectral data were collected from 3 cow along morning and evening milking, for 5 consecutive months, within their second lactation. In the time of the trial, the investigated cows had periods with mammary gland inflammation. Transmittance spectra of 258 milk samples were obtained by NIRSystem 6500 spectrophotometer in 1100-2400 nm region. Calibration equations for the examined milk components were developed by PLS regression using 3 different sets of samples: samples with low somatic cell count (SCC), samples with high SCC and combined data set. The NIR calibration and prediction of individual cow´s milk fat, protein, and lactose were highly influenced by the presence of mil samples from animals with mammary gland inflammation in the data set. The best accuracy of prediction (i.e. the lower SEP and the higher correlation coefficient) for fat, protein and lactose was obtained for equations, developed when using only “healthy” samples, with low SCC. The standard error of prediction increased and correlation coefficient decreased significantly when equations for low SCC milk were used to predict examined components in “mastitis” samples with high SCC, and vice versa. Combined data set that included samples from healthy and mastitis animals could be used to build up regression models for screening. Further use of separate model for healthy samples improved milk composition measurement. Regression vectors for NIR mild protein measurement obtained for “healthy” and “mastitic” group were compared and revealed differences in 1390-1450 nm, 1500-1740 nm and 1900-2200 nm regions and thus illustrated post-secretory breakdown of milk proteins by hydrolytic enzymes that occurred with mastitis. For the first time it has been found that monitoring the spectral differences in water bands at 1440 nm and 1912 nm could provide valuable information for inflammation diagnosis.
Identifying the components of residues that are not completely burned at the sites of fires site can provide valuable information for tracing the causes of fires. In order to clarify the types of plastic combustion residues found at the scenes of fires, we studied the residue formed after the combustion of polyethylene (PE) and acrylonitrile butadiene styrene (ABS). Plastic samples were burned at 200, 300, 350, 400, and $500^{\circ}C$ for 3 min using a cone calorimeter, and the changes in weight and combustion products were observed. The powder products obtained by lyophilization and pulverization of the combustion products obtained at each temperature were analyzed by a Fourier transform-near infrared (FT-NIR) spectrometer. When the PE samples were burned, the weight did not change up to $350^{\circ}C$, however a significant change in the weight could be measured above $400^{\circ}C$. The principal component analysis (PCA) of the FT-NIR spectra of the PE and ABS samples obtained at each temperature confirmed that the combustion residues at each temperature were PE and ABS, respectively. Therefore, the types of unburned plastics found at the sites of fires can be confirmed rapidly by near infrared spectroscopy.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
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pp.1181-1181
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2001
Robinson with ${coworkers}^{1}$ have introduced two-state outer-neighbor bonding model to explain the anomalies of water. The studies on the properties of water as a function of temperature and pressure revealed that, unlike other ideas, all $H_2O$ molecules in liquid are tetrabonded. On the average they are forming two different bonding types. One type is the regular tetrahedral water-water bonding similar to that found in the ordinary ice Ih, whereas the other is a more dense nonregular tetrahedral bonding similar to that appearing in the ice II. The transformation between these two bonding forms is evidenced by FT-NIR experiment. The FT-NIR measurements were done for liquid water in the temperature range from $20^{\circ}C$ up to $80^{\circ}C$ in a wide extent of frequencies: 12 000 - 4000 $cm^{-1}$ /. Temperature dependent variations in the volume fraction of these two structures are directly related to the spectral changes. The absorbance variations are explored by means of the two-dimensional correlation spectroscopy (2DCOS), principal component analysis (PCA), curve fitting and second derivatives. The presence of the isosbestic points in a range of the combination and overtone transitions indicates that the experimental spectra are a superposition of two temperature independent components. One component of diminishing intensity with temperature increase, is assigned to a stronger hydrogen bonds occurred in the Ih type, whereas the second component showing an opposite behavior, one can attribute to a weaker H-bonds characteristic for the II type. The understanding of the hydrogen bonding network in the liquid water is very important in interpretation of the interaction between water and protein chain. The two-state model of water surrounding the protein surface could advance an understanding of the hydration process.
Blanco, Jose A.;Alomar, Daniel J.;Fuchslocher, Rita I.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
/
pp.1266-1266
/
2001
Pasture composition, an important attribute determining sward condition and value, is normally assessed by hand separation, drying and measuring weight contribution of each species in the mixture. This is a tedious, time and labour consuming procedure. NIRS has demonstrated the potential for predicting botanical composition of swards, but most of the work has been carried out on dry samples. The aim of this work was to evaluate the feasibility of developing NIR models for predicting the white clover and ryegrass content in fresh or dry mixtures artificially prepared from pure samples of both species. Mixtures from pure stands of white clover(Trifolium repens) and perennial ryegrass (Lolium perenne) were prepared with different proportions (0 to 100%) of each species (fresh weight). A total of 55 samples were made (11 mixtures,5 cuts). Spectra (400 to 2500 nm) were taken from fresh chopped (rectangular cuvettes, transport sample module) samples, in a NIR Systems 6500 scanning monochromator controlled by the software NIRS 3 (Infrasoft International), which was also utilized for calibration development. Different math treatments (derivative order, subtraction gap and smooth segment) and a scatter correction treatment of the spectra (SNV and Detrend) were tested. Equations were developed by modified partial least squares. Prediction accuracy evaluated by cross-validation, showed that percentage of clover or ryegrass, as contribution in dry weight, can be successfully percentage of clover or ryegrass, as contribution in dry weight, can be successfully predicted either on fresh or dried samples, with equations developed by different math treatments. Best equations for fresh samples were developed including a first, second, or third derivative, whereas for dry samples best equations included a second or third derivative. Standard errors of ross validation were about 6% for fresh and 3.6% for dry samples, Coefficient of determination of cross validation (1-VR) were over 0.95 times the value of SECV for fresh samples and over 8 times the value of SECV for dry samples. Scatter correction (SNV and Detrend) in general improved prediction accuracy. It is concluded more precise on dried and ground samples, it can be used with an acceptable error level and less time and labour, on fresh samples.
Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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2001.06a
/
pp.1528-1528
/
2001
Ginseng cultivated in different country or growing condition has generally different components such as saponin and protein, and it relates to efficacy and action. Protein content assumes by nitrogen content in ginseng radix. Nitrogen content could be determined by chemical analysis such as kjeldahl or extraction methods. However, these methods require long analysis time and result environmental pollution and sample damage. In this work we investigated possibility of non-destructive determination of nitrogen content in ginseng radix using near-infrared spectroscopy. Ginseng radix, root of Panax ginseng C. A. Meyer, was studied. Total 120 samples were used in this study and it was consisted of 6 sample sets, 4, 5 and 6-year-old Korea ginseng and 7, 8 and 9-year-old China ginseng, respectively. Each sample set has 20 sample. Nigrogen content was measured by electronic analysis. NIR reflectance spectra were collected over the 1100 to 2500 nm spectral region with a InfraAlyzer 500C (Bran+Luebbe, Germany) equipped with a halogen lapmp and PbS detector and data were collected every 2 nm data point intervals. The calibration models were carried out by multiple linear regression (MLR) and partial least squares (PLS) analysis using IDAS and SESAME software. Result of electronic analysis, Korean ginseng were different mean value in nitrogen content of China ginseng. Ginseng tend to generally decrease the nitrogen content according as cultivation year is over 6 years. The MLR calibration model with 8 wavelengths using IDAS software accurately predicted nitrogen contents with correlation coefficient (R) and standard error of prediction of 0.985 and 0.855%, respectively. In case of SESAME software, the MLR calibration with 9 wavelength was selected the best calibration, R and SEP were 0.972 and 0.596%, respectively. The PLSR calibration model result in 0.969 of R and 0.630 of RMSEP. This study shows the NIR spectroscopy could be applied to determine the nitrogen content in ginseng radix with high accuracy.
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