Turmeric powder (Curcuma longa L.) is valued both for its medicinal properties and for its popular culinary use, such as being a component in curry powder. Due to its high demand in international trade, turmeric powder has been subject to economically driven, hazardous chemical adulteration. This study utilized Fourier Transform-Raman (FT-Raman) and Fourier Transform-Infra Red (FT-IR) spectroscopy as separate but complementary methods for detecting metanil yellow adulteration of turmeric powder. Sample mixtures of turmeric powder and metanil yellow were prepared at concentrations of 30%, 25%, 20%, 15%, 10%, 5%, 1%, and 0.01% (w/w). FT-Raman and FT-IR spectra were acquired for these mixture samples as well as for pure samples of turmeric powder and metanil yellow. Spectral analysis showed that the FT-IR method in this study could detect the metanil yellow at the 5% concentration, while the FT-Raman method appeared to be more sensitive and could detect the metanil yellow at the 1% concentration. Relationships between metanil yellow spectral peak intensities and metanil yellow concentration were established using representative peaks at FT-Raman 1406 cm−1 and FT-IR 1140 cm−1 with correlation coefficients of 0.93 and 0.95, respectively.
Therapeutic and subtherapeutic use of veterinary drugs has increased the risk of residue contamination in animal food products. Antibiotics such as tetracycline are used for mastitis treatment of lactating cows. Milk expressed from treated cows before the withdrawal period has elapsed may contain tetracycline residue. This study developed a simple surface-enhanced Raman spectroscopic (SERS) method for on-site screening of tetracycline residue in milk and water. Six batches of silver colloid nanoparticles were prepared for surface enhancement measurement. Milk-tetracycline and water-tetracycline solutions were prepared at seven concentration levels (1000, 500, 100, 10, 1, 0.1, and 0.01 ppm) and spiked with silver colloid nanoparticles. A 785 nm Raman spectroscopic system was used for spectral measurement. Tetracycline vibrational modes were observed at 1285, 1317 and 1632 cm−1 in water-tetracycline solutions and 1322 and 1621 cm−1 (shifted from 1317 and 1632 cm−1, respectively) in milk-tetracycline solutions. Tetracycline residue concentration as low as 0.01 ppm was detected in both the solutions. The peak intensities at 1285 and 1322 cm−1 were used to estimate the tetracycline concentrations in water and milk with correlation coefficients of 0.92 for water and 0.88 for milk. Results indicate that this SERS method is a potential tool that can be used on-site at field production for qualitative and quantitative detection of tetracycline residues.
Yellow turmeric (Curcuma longa) is widely used for culinary and medicinal purposes, and as a dietary supplement. Due to the commercial popularity of C. longa, economic adulteration and contamination with botanical additives and chemical substances has increased. This study used FT-IR spectroscopy for identifying and estimating white turmeric (Curcuma zedoaria), and Sudan Red G dye mixed with yellow turmeric powder. Fifty replicates of yellow turmeric—Sudan Red mixed samples (1%, 5%, 10%, 15%, 20%, 25% Sudan Red, w/w) and fifty replicates of yellow turmeric—white turmeric mixed samples (10%, 20%, 30%, 40%, 50% white turmeric, w/w) were prepared. The IR spectra of the pure compounds and mixtures were analyzed. The 748 cm−1 Sudan Red peak and the 1078 cm−1 white turmeric peak were used as spectral fingerprints. A partial least square regression (PLSR) model was developed for each mixture type to estimate adulteration concentrations. The coefficient of determination (R2v) for the Sudan Red mixture model was 0.97 with a root mean square error of prediction (RMSEP) equal to 1.3%. R2v and RMSEP for the white turmeric model were 0.95 and 3.0%, respectively. Our results indicate that the method developed in this study can be used to identify and quantify yellow turmeric powder adulteration.
Curry powder is extensively used in Southeast Asian dishes. It has been subject to adulteration by azo dyes. This study used a newly developed 1064 nm dispersive point-scan Raman system for detection of metanil yellow and Sudan-I contamination in curry powder. Curry powder was mixed with metanil yellow and (separately) with Sudan-I, at concentration levels of 1%, 3%, 5%, 7%, and 10% (w/w). Each sample was packed into a nickel-plated sample container (25 mm × 25 mm × 1 mm). One Raman spectral image of each sample was acquired across the 25 mm × 25 mm surface area. Intensity threshold value was applied to the spectral images of Sudan-I mixtures (at 1593 cm−1) and metanil yellow mixtures (at 1147 cm−1) to obtain binary detection images. The results show that the number of detected adulterant pixels is linearly correlated with the sample concentration (R2 = 0.99). The Raman system was further used to obtain a Raman spectral image of a curry powder sample mixed together with Sudan-I and metanil yellow, with each contaminant at equal concentration of 5% (w/w). The multi-component spectra of the mixture sample were decomposed using self-modeling mixture analysis (SMA) to extract pure component spectra, which were then identified as matching those of Sudan-I and metanil yellow using spectral information divergence (SID) values. The results show that the 1064 nm dispersive Raman system is a potential tool for rapid and nondestructive detection of multiple chemical contaminants in the complex food matrix.
This study used Raman spectral imaging coupled with self-modeling mixture analysis (SMA) for identification of three components mixed into a complex food powder mixture. Vanillin, melamine, and sugar were mixed together at 10 different concentration level (1% to 10%, w/w) into powdered non-dairy creamer. SMA was used to decompose the complex multi-component spectra and extract the pure component spectra and corresponding contribution images. Spectral information divergence (SID) values of the extracted pure component spectra and reference component spectra were computed to identify the components corresponding to the extracted spectra. The contribution images obtained via SMA were used to create Raman chemical images of the mixtures samples, to which threshold values were applied to obtain binary detection images of the components at all concentration levels. The detected numbers of pixels of each component in the binary images was found to be strongly correlated with the actual sample concentrations (correlation coefficient of 0.99 for all components). The results show that this method can be used for simultaneous identification of different components and estimation of their concentrations for authentication or quantitative inspection purposes.
Non-destructive subsurface detection of encapsulated, coated, or seal-packaged foods and pharmaceuticals can help prevent distribution and consumption of counterfeit or hazardous products. This study used a Spatially Offset Raman Spectroscopy (SORS) method to detect and identify urea, ibuprofen, and acetaminophen powders contained within one or more (up to eight) layers of gelatin capsules to demonstrate subsurface chemical detection and identification. A 785-nm point-scan Raman spectroscopy system was used to acquire spatially offset Raman spectra for an offset range of 0 to 10 mm from the surfaces of 24 encapsulated samples, using a step size of 0.1 mm to obtain 101 spectral measurements per sample. As the offset distance was increased, the spectral contribution from the subsurface powder gradually outweighed that of the surface capsule layers, allowing for detection of the encapsulated powders. Containing mixed contributions from the powder and capsule, the SORS spectra for each sample were resolved into pure component spectra using self-modeling mixture analysis (SMA) and the corresponding components were identified using spectral information divergence values. As demonstrated here for detecting chemicals contained inside thick capsule layers, this SORS measurement technique coupled with SMA has the potential to be a reliable non-destructive method for subsurface inspection and authentication of foods, health supplements, and pharmaceutical products that are prepared or packaged with semi-transparent materials.