A.T. Abebe, J. Near Infrared Spectrosc. 14, 67–70 (2006) 67 Short communication Total sugar and maturity evaluation of intact watermelon using near infrared spectroscopy Ashenafi Tessema Abebe OMI Weighing Machine Inc., Higashi-yagura, 3-11-70, Kusatsu, Shiga, Japan. E-mail: [email protected] In this study, a near infrared spectroscopy (700–1100 nm) measurement technique was used to evaluate the internal quality of watermelons non-destructively. A spectrometer and near infrared ray emitting diode were designed and developed to evaluate the internal quality parameters such as total sugar content and maturity of intact watermelons. A relationship was found between the maturity of intact watermelon and the diffuse transmittance spectra. The total sugar content was calculated from the second derivative spectral values at four selected wavelengths. The verification correlation coefficient and standard error of prediction values were 0.81 and 0.42 Brix% respectively. Keywords: NIRRED, diffuse transmittance, maturity, total sugar Introduction destructive methods, such as extracting juice and chemical analysis of total sugar content. The internal qualities of agricultural products include moisture, starch, protein and fat content, and their maturity. The problem of watermelon maturity gained the attention of researchers as a direct result of difficulties growers and distributors face to solve the same problem based on external features such as colour, texture and conformity. The near infrared (NIR) diffuse transmittance method is becoming a promising tool for measuring internal quality of agricultural products such as watermelon. Non-destructive methods of evaluation have been used to determine papaya maturity,1 dry matter in onion,2 soluble solid content of intact cantaloupe,3 sugar content of intact peaches,4 acidity, soluble solids and firmness of Jonagold apples,5 optical methods for quality evaluation of fruits6 and nondestructive prediction of internal quality of heat-treated “Irwin” mango by near infrared spectroscopy.7 Other near infrared spectroscopic studies report versatile intact fruit spectroscopy,8 optical properties of selected fruits vs maturity,9 design of a high-speed, fibre-optic blueberry sorter10 and internal quality assessment of kiwifruit.11 Watermelons, compared to other fruit products, are larger in size and their internal quality, such as maturity and total sugar content, is commonly determined based on their external appearance including colour, texture and conformity and by using Objective The objective of this research was to examine the potential of the NIR diffuse transmittance method to estimate the total sugar and maturity parameters of intact watermelons. Materials and methods Samples Watermelons harvested from the Nagano, Akita and Nigata areas of Japan, specified in Table 1, were used for this particular study. Large numbers of samples were used at site to investigate the internal quality parameters of watermelon. Table 1. Watermelon sample specifications (n = 390). Watermelon Max. Min. Mean Weight (kg) 15 3.5 7 Rind size (mm) 15 9.5 10 © NIR Publications 2006, ISSN 0967-0335 68 Total Sugar and Maturity Evaluation of Intact Watermelon Instrumentaion Table 2. Spectrometer (Zeiss MCS-NIR) diode array specifications. In order to acquire the diffuse transmittance spectra for internal quality measurement, high-energy incident light is required. A high-energy monochromatic light source, such as halogen, was found inconvenient as it emits intense heat that affects measurement accuracy. In this study, a pre-fabricated array of NIR ray-emitting diodes (NIRRED) capable of emitting near infrared rays with a wavelength of 700–1100 nm was developed and used as a source of incident light. Spectral acqusition A watermelon sample was positioned in contact with the receptor urethane embedded fibre-optic and radiation from the near infrared emitting diodes, as shown in Figure 1. Radiation leaving the sample was scanned using a computer-controlled spectrometer from 700–1100 nm at 0.8 nm increments thus generating 512 data points per spectrum (Table 2). The standard spectrum was taken from a 15 cm (W × H × B) cubical Teflon block. The ratio of the watermelon spectral data to the standard produced a relative diffuse transmittance spectrum (T) for watermelon, which was converted to an optical density log (1/T) and the 2nd derivative was computed. Chemical analysis Watermelons were cut into approximately two haves and the edible portion was removed and juice samples were made with a juicer. The standard total sugar (Brix%) data was measured from the juice using a refractometer (Atago PR-101 model, Tokyo, Japan). Dark box Pixel size 25 × 2500 µm2 Maximum clock rate 2 MHz Diode array size 512 pixels Spectral distance 0.8 nm Temperature drift 0.005 nm °C–1 NIR imaging Watermelon samples were sectioned along the equator and the seeds and flesh colour were visually inspected. The juice off the edible portion of the upper half of the sample was used for the measurement of total sugar (Brix). Samples with light pink tissue, white seeds and sugar content less than 10% Brix were identified as immature and samples with light red tissue, black seeds and sugar content greater than Brix 10% were identified as matured. The lower half of the sample was used for the NIR diffuse transmission test. The sample was positioned on a NIRRED light tray (100 × 100 mm) where the rind surface faced the lighting device and the edible surface faced the NIR camera (CCD type with spectral range 400–1000 nm and 768 × 498 pixel array) in a dark box. Figures 2, 3 and 4 are examples of watermelon tissue images taken using the NIR camera. Data analysis A step-forward linear regression analysis program was developed and used in the computation of correlation values of the 2nd derivative diffuse transmittance spectra of intact watermelon with the standard Brix values as SS = kx(λ) + C0 Watermelon where, SS = standard total sugar; Brix(%) Diffuse Transmittance Optical NIRRED Fibre Spectrometer PC No seed image Urethane Foam Figure 1. NIR ray emitting diode (NIRRED; with inner diameter = 50 mm and outer diameter = 110 mm) diffused transmittance system for watermelon internal quality measurement (optical fibre sensing diameter 600 µm). Figure 2. Example of image of distribution and intensity of NIRdiffuse transmittance of immature watermelon tissue. A.T. Abebe, J. Near Infrared Spectrosc. 14, 67–70 (2006) 69 Brix(%) = α1x(λ1) + α2x(λ2) + α3x(λ3) + α4x(λ4) + C0 where, α1, α2, α3, α4 = regression coefficients of selected wavelengths λ1, λ2, λ3, λ4 = selected wavelengths C0 = constant Seed Results and discussion Total sugar evaluation Results of the investigation of the relationship between spectral and chemical data of watermelons from three major production regions of Japan showed that NIRRED system based NIR spectroscopy gave good results in determining the total sugar content, as shown in Table 3 and Figure 5. Figure 3. Example of image of distribution and intensity of NIRdiffuse transmittance of matured watermelon tissue. Images and spectra of watermelon The images in Figures 2, 3 and 4 clearly show the difference in diffuse transmittance distribution for different maturity levels of watermelon samples. It was observed that immature watermelon transmitted less NIR light compared to mature watermelon and over mature watermelon. The transmitted light intensity around seeds for mature watermelons was greater than other parts of the tissue section. x(λ) = d2 log(1/Tλ) C0 = constant K = regression coefficient The wavelengths with higher correlations were selected and the calibration coefficients were computed using multiple linear regression (MLR) analysis as shown in Table 3. 14.0 Predicted NIR (%) 13.0 Seed 12.0 11.0 n= 10.0 9.0 8.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 Measured SS(Brix%) Figure 4. Example of image of distribution and intensity of NIRdiffuse transmittance of over matured watermelon tissue. Figure 5. Measured and predicted total sugar content of watermelon. Table 3. Statistical analysis for determining sugar content of watermelon. Selected wavelngth λ1 λ2 λ3 λ4 SEC Brix% SEP Brix% r2 Bias Brix% n 770 830 865 887 0.52 0.42 0.81 0.28 192 70 Total Sugar and Maturity Evaluation of Intact Watermelon 2.0 matured immature tissue seemed to have a light pink colour and the colour of the seeds was white, while matured watermelon tissue had a light red colour and the seed colour was black. Immature watermelon transmitted less light as compared to matured watermelon and over matured watermelon. 3. An exponential relationship was found between watermelon total sugar and optical density measurements of intact watermelon. The relationship showed that watermelon absorbance in the NIR region is a good indicator for the prediction of its maturity. overmatured log(1/T) 1.5 1.0 0.5 0.0 700 725 750 775 800 825 850 875 900 925 950 Wavelength (nm) Figure 6. Optical density curve of mature (12% Brix), immature (9.6% Brix) and over mature (13% Brix) watermelon. Figure 6 shows the optical density spectrum of immature, mature and over mature watermelon. The major difference in the absorption between mature and immature samples was observed in the wavelength range of 850–900 nm. This suggests the mean of the optical density spectrum in this range can be used to investigate watermelon maturity and total sugar content relationships. The total sugar and mean optical density at the peak wavelength range of 700–1110 nm gave a relationship expressed as: SS = 16.527e–0.4243A, R2 = 0.76 where, SS = total sugar content, A = absorption at mean diffuse transmittance Conclusion The above results indicate that: 1. internal quality evaluation of constituents such as total sugar of intact watermelons can be achieved using the NIRRED diffuse transmittance spectral analysis 2. the test for watermelons with known date of flowering indicated that the edible portion of immature watermelon References 1. G.S. Birth, G.G. Dull, J.B. Magee, H.T. Chan and C.G. Cavaletto, J. Am. Soc. Hort. Sci. 109, 62 (1984). 2. G.S. Birth, G.G. Dull, W.T. Renfroe and S.J. Kaya, J. Am. Soc. Hort. Sci. 110, 297 (1985). 3. G.G. Dull, G.S. Birth, D.A. Smittle and R.G. Leffler, J. Food Soc. Sci. 54, 393 (1989). 4. S. Kawano and S.H. Watanabe, J. Japan. Soc. Hort. Sci. 61(2), 445 (1992). 5. J. Lammertyn, B. Nicolai, K. Ooms, V. De. Smedt and J. De Baerdemaeker, Trans. ASAE 41(4), 1089 (1998). 6. W I. Budiastra, unpublished PhD dissertation, Kyoto University, Kyoto, Japan (1998). 7. R. Hasbullah, T. Tanabe, M. Tanaka and T. Tanabe, J. SASJ. 33(3), 155 (2002). 8. T.A. Ashenafi and T. Suzuki, Proceedings of Japanese Food Engineering Conference, p. 133 (2003). 9. D.R. Bittner and K.H. Norris, Trans. ASAE 11(4), 534 (1968). 10. W.F. McClure, R.P. Rohrbach, L.J. Kushman and W.E. Bullinger, Trans. ASAE 18(3), 487 (1975). 11. D.C. Slaughter and C.H. Crisoto, Seminar in Food Analysis 3, pp. 131–140. Chapman & Hall, London, UK. (1998). Received: 5 April 2005 Revised: 4 November 2005 Accepted: 5 December 2005 Web Publication: 4 April 2006 G.D. Batten, J. Near Infrared Spectrosc. 14, vii–viii (2006) vii Book review Spectrochemical analysis using infrared multichannel detectors Graeme D Batten Seas Spec Pty Ltd, PO Box 487, Woolgoolga, NSW 2456, Australia. E-mail: [email protected] Spectrochemical analysis using infrared multichannel detectors, Edited by Rohit Bhargava and Ira W. Levin. Blackwell Publishing Ltd, published November 2005, 328 pp in hardback, ISBN: I 405125047 Price: £110.00, Available on-line from www.blackwellpublishing.com This smartly presented volume contains 13 chapters written by a total of 35 authors—26 based in the USA and nine in four other countries. It is a timely summary of the developments in, and current status of, infrared analyses and provides basic theory and many practical examples of the value and potential of multi-channel detectors. This text achieves its aim of capturing the advances made in imaging, which began over 50 years ago, when a spectrometer was interfaced with a microscope, attracted more interest in the 1970s and advanced rapidly along with improved instruments and computer power over the last ten years. The strengths of this publication lie in the clear descriptions of theory and basic concepts, the breadth of subjects included and the clear comparisons, aided by black and white illustrations and many full colour images. Chapter 1 is an overview of available Fourier transform and mid-infrared (MIR) instruments, the salient features of interferometers for data acquisition, evolution of microspectrometry and multi-channel detectors and data analysis techniques. Chapter 2 discusses the advantages of near infrared and MIR with interesting reports from the 1922 to 1945 era, which many of us have overlooked. There are some useful notes on available hardware, detectors and data processing. Chapter 3 gives an excellent introduction to synchrotron radiation as the source. The first hand experience of the authors is evident in their discussion on edge sharpness in regular and biological samples. Chapter 4 is an excellent review of data pre-processing and processing options for hyperspectral images and the examples given are practical and easy to follow. This topic is further discussed with reference to real time analysis in Chapters 7 and 10. Chapters 5–13 contain further basic information plus a wealth of experience with examples of practical applications of spectral imaging. In several examples, the authors mention the value of non-contact analysis of samples of variable shape and heterogeneous composition at competitive prices in real times. The text contains illustration and additional references to an extensive range of products including catalysts, polymers, industrial wastes, foods (including wheat, raw and processed meats and fruits), animal feeds (mixtures; soils v grasslands), contamination of foods by pathogens and insects, metal surfaces, fabrics, petroleum products, gemstones, biological samples, pharmaceuticals, monitoring patterns from aerosol sprays, movement of water, distribution of food flavourings, histology of bone, skin and cartilage and improved detection of cancerous cells. While the potential of spectral imaging is reported in a positive manner, the authors are careful to mention the limitations imposed by computer power and time per analysis relative to practical needs and mention alternative techniques where a comparison is appropriate. The volume has minimal typographical errors. As in many publications where different regions of the electromagnetic spectrum are discussed, it is difficult to standardise on terminology, such as wavelengths or wavenumber, but this is a minor criticism. A list of abbreviations and how to convert between units would be helpful to less experienced readers. © NIR Publications 2006, ISSN 0967-0335 viii The images in this text do more than boost its visual impact; they clearly demonstrate the potential, and in some cases, the pitfalls, of the technique for assessing chemical abundance, statistical analyses of component distribution and morphological analysis of discrete particles; these being valuable for inter and intra-sample comparisons. Book Review This neatly presented volume would make a valuable addition to the library of any spectroscopist. It is an essential primary source of information for students, researchers, process control managers and quality assurance technicians and contains references to more detailed information.
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