Discrimination of wild and cultured european sea bass (Dicentrarchus labrax) using chemical and isotopic analyses

Recent legislation in the European Union (EC/2065/2001) requires that seafood must provide the consumer with information that describes geographical origin and production method. The present studies aimed to establish methods, based on chemical and stable isotopic analysis, that could reliably differentiate between wild and farmed European sea bass (Dicentrarchus labrax). The study measured fatty acid and isotopic compositions (delta13C and delta18O) of total flesh oil, delta15N of the glycerol/choline fraction, and compound-specific analysis of fatty acids (delta13C) by isotope ratio mass spectrometry. The sample set comprised 10 wild and 10 farmed sea bass from England (wild) and Scotland or Greece (farmed). Discrimination was achieved using fatty acid composition with 18:0, 18:2n-6, 20:4n-6, and 22:6n-3 providing the highest contributions for discrimination. Principal component analysis of the data set provided good discrimination between farmed and wild sea bass where factor 1 and factor 2 accounted for 60% of the variation in the data.     

High-pressure effects on the proteolytic enzymes of sea bass (Dicentrarchus labrax L.) fillets

High-pressure processing is a nonthermal technique ensuring food product safety and enabling a longer shelf life. The purpose of this experiment was to evaluate the effect of high pressure on the main proteolytic enzymes involved in fish muscle degradation during storage. Enzymes were extracted with sarcoplasmic proteins from Dicentrarchus labrax sea bass white muscle. Activity of cathepsins B, D, H, and L was quantified in protein extract, whereas calpain activity was evaluated after isolation from its endogenous inhibitor. High-pressure processing up to 500 MPa enhanced the activity of cathepsin B, H, and L, whereas the activity of cathepsin D increased up to 300 MPa and decreased above 300 MPa. With regard to calpain activity, high-pressure processing led to a decrease of activity, which was zero above 400 MPa. We suggest a leading explanation based on simultaneous deactivation of enzymes and an increase of liberation from lysosomes for cathepsins and on dissociation of subunits for calpains.     

Application of near-infrared reflectance spectroscopy (NIRS) to the evaluation of carotenoids content in maize

The importance of including antioxidant compounds in the diet is well recognized. These compounds remediate the detrimental activity on animal cells of the so-called reactive oxygen substances (ROS). Many papers have reported on the determination of both hydrophilic and hydrophobic antioxidant compounds present in a large number of vegetables, and all methods involve the extraction from the matrix of the compounds to be determined. Because some problems may arise, such as the completeness of the extraction and the stability of the extracted compound during the extraction steps, the possibility of analyzing these compounds in the native matrix would be useful. Here is reported the application of near-infrared spectroscopy (NIRS) to the determination of the content of carotenoids in maize, comparing the obtained data with those derived from high-performance liquid chromatography (HPLC) determination of the extract obtained from the same samples. Equations for predicting carotenoid content in maize were derived using scores from modified partial least-squares (MPLS) as independent variables. Cross-validation procedures indicated good correlations between HPLC values and NIRS estimates. The results show that NIRS, a well-established and widely applied technique, can be applied to determine the maize carotenoids and that samples are readily analyzed in minutes, the only required step being their grinding.     

Bruise detection in Pacific pink salmon (Oncorhynchus gorbuscha) by visible and short-wavelength near-infrared (SW-NIR) spectroscopy (600-1100 nm)

Visible and short-wavelength near-infrared (SW-NIR) spectroscopy (600-1100 nm) was used to detect bruises in intact, whole Pacific pink salmon (Oncorhynchus gorbuscha). The measurements were performed noninvasively through the skin and scales in the diffuse reflectance mode. Digital images of bruised and nonbruised regions of fish were captured after the fish samples were filleted. Image analysis was conducted using Adobe Photoshop 7.0 with relative gray values used as reference values in a partial least-squares (PLS) model. A PLS cross-validation model using six latent variables yielded a standard error of prediction (SEP = 0.05%, R = 0.83). Approximately 84% of all nonbruised spectra were correctly classified, whereas approximately 81% of all bruised spectra were correctly classified. These results suggest that visible and SW-NIR could be used to control the bruise defect of fish products during processing, thereby improving product consistency and quality.     

Biological Parameters Towards Polycyclic Aromatic Hydrocarbons Pollution: A Study with Dicentrarchus labrax L. Exposed to the Model Compound Benzo(a)pyrene

The objective of the present study was to investigate the short-term effects of benzo(a)pyrene (BaP) on juvenile sea bass (Dicentrarchus labrax L.) using a multiparameter approach. At the end of the 96?h of exposure to a range of BaP concentrations (2?C256???g?l^?1) in laboratorial conditions, a suite of biomarkers involved in biotransformation pathways, oxidative stress and damage, neurotransmission and energetic metabolism were analysed. Levels of BaP metabolites in bile and BaP-type compounds in tissues were also included as biomarkers of exposure, and the post-exposure swimming velocity was used as a toxicity endpoint at a higher level of biological organisation. In addition, a time-series experiment on the levels of bile BaP metabolites was also performed. Increased levels of BaP metabolites in bile and BaP-type compounds in liver and brain of exposed fish were found, indicating BaP uptake, metabolisation and distribution by different tissues. BaP induced oxidative stress and damage, but no significant effects on the post-exposure swimming velocity, neurotransmission and energetic pathways were found. An increase in the levels of BaP metabolites in bile over time was also observed, reaching a threshold similar at all the concentrations tested. Overall, this integrative multiparameter study reflecting different biological responses of D. labrax was suitable to assess the effects caused by the short-term exposure to BaP and may be useful in the marine environmental risk assessment of polycyclic aromatic hydrocarbons pollution. The observed toxic effects also highlight the relevance of short-term exposure to relatively high concentrations of chemicals, as can occur in the case of punctual heavy chemical releases, such as oil spills in the marine environment.     

鲜食玉米果穗含水率近红外光谱无损检测影响因素

为了获取鲜食玉米果穗高质量近红外光谱,该研究基于近红外漫反射光谱技术开展试验参数对鲜食玉米果穗光谱特征影响及建模验证探究。根据果穗棒状特征,搭建多维度综合试验装置,采集光源类型、光强大小、探测距离和光源角度共4类不同参数下的900～1700 nm光谱数据,进行卤素灯杯与光纤光源、卤素灯杯功率20与40 W、探测距离10 ～50 mm和30°、45°及60°卤素灯杯夹角的对比试验,分析光谱差异及曲线分布规律,采用标准差和光谱面积极差指标进行光谱质量评价。进一步开展建模验证试验,针对30°和45°卤素灯杯夹角下的光谱,经多元散射校正（multiplicative scatter correction,MSC）、标准正态变量校正（standard normal variate,SNV）、一阶导数（first derivative ,FD）和趋势校正（detrending ,DT）预处理后,应用偏最小二乘回归（partial least squares,PLS）和支持向量机（support vector machines SVM）方法建立了含水率预测模型,并对建模性能进行了对比。试验结果表明,卤素灯杯、功率20 W、探测距离40 mm对应所选果穗的光谱响应充分、干扰少,与果穗特征相匹配,曲线采用标准差和光谱面积极差分别为0.83和187.2,综合光谱曲线质量评价和建模性能对比,卤素灯杯夹角45°优于30°。通过SNV预处理后的SVM预测模型具有更好的性能,校正集和预测集决定系数分别为0.943、0.880,均方根误差分别为0.708、0.932,剩余预测偏差为2.956。该研究结果可为基于近红外漫反射光谱技术的鲜食玉米果穗内在品质无损检测提供技术支撑。     

Use of near-infrared spectroscopy and feature selection techniques for predicting the caffeine content and roasting color in roasted coffees

Near-infrared spectroscopy (NIRS), combined with diverse feature selection techniques and multivariate calibration methods, has been used to develop robust and reliable reduced-spectrum regression models based on a few NIR filter sensors for determining two key parameters for the characterization of roasted coffees, which are extremely relevant from a quality assurance standpoint: roasting color and caffeine content. The application of the stepwise orthogonalization of predictors (an "old" technique recently revisited, known by the acronym SELECT) provided notably improved regression models for the two response variables modeled, with root-mean-square errors of the residuals in external prediction (RMSEP) equal to 3.68 and 1.46% for roasting color and caffeine content of roasted coffee samples, respectively. The improvement achieved by the application of the SELECT-OLS method was particularly remarkable when the very low complexities associated with the final models obtained for predicting both roasting color (only 9 selected wavelengths) and caffeine content (17 significant wavelengths) were taken into account. The simple and reliable calibration models proposed in the present study encourage the possibility of implementing them in online and routine applications to predict quality parameters of unknown coffee samples via their NIR spectra, thanks to the use of a NIR instrument equipped with a proper filter system, which would imply a considerable simplification with regard to the recording and interpretation of the spectra, as well as an important economic saving.     

Detection of SNPs in fish DNA: application of the fluorogenic ribonuclease protection (FRIP) assay for the authentication of food contents

The fluorogenic ribonuclease protection (FRIP) assay was used to detect single nucleotide polymorphisms (SNPs) in commercially produced fish products. By using fluorescence resonance energy transfer (FRET) between fluorophore and quencher labeled probes, the species-specific cleavage of sample RNA was detected by measuring the fluorescence intensity during the FRIP assay. We were able to discriminate raw and thermally processed eel and tuna species using the FRIP-based SNP detection method. Furthermore, the intensity of fluorescence was correlated with the mutant/wild-type ratio. These results suggest that the FRIP assay is a useful method for the in situ confirmation of labels of fishery foods during food production.     

The application of proximal visible and near-infrared spectroscopy to estimate soil organic matter on the Triffa Plain of Morocco

Soil organic matter (SOM) is a fundamental soil constituent. The estimation of this parameter in the laboratory using the classical method is complex time-consuming and requires the use of chemical reagents. The objectives of this study were to assess the accuracy of two laboratory measurement setups of the VIS-NIR spectroscopy in estimating SOM content and determine the important spectral bands in the SOM estimation model. A total of 115 soil samples were collected from the non-root zone (0–20 cm) of soil in the study area of the Triffa Plain and then analysed for SOM in the laboratory by the Walkley–Black method. The reflectance spectra of soil samples were measured by two protocols, Contact Probe (CP) and Pistol Grip (PG)) of the ASD spectroradiometer (350–2500 nm) in the laboratory. Partial least squares regression (PLSR) was used to develop the prediction models. The results of coefficient of determination (R²) and the root mean square error (RMSE) showed that the pistol grip offers reasonable accuracy with an R² = 0.93 and RMSE = 0.13 compared to the contact probe protocol with an R² = 0.85 and RMSE = 0.19. The near-Infrared range were more accurate than those in the visible range for predicting SOM using the both setups (CP and PG). The significant wavelengths contributing to the prediction of SOM for (PG) setup were at: 424, 597, 1432, 1484, 1830,1920, 2200, 2357 and 2430 nm, while were at 433, 587, 1380, 1431, 1929, 2200 and 2345 nm for (CP) setup.     

Usefulness of near-infrared reflectance (NIR) spectroscopy and chemometrics to discriminate fishmeal batches made with different fish species

Near-infrared reflectance (NIR) spectroscopy combined with chemometrics was used to identify and authenticate fishmeal batches made with different fish species. Samples from a commercial fishmeal factory (n = 60) were scanned in the NIR region (1100-2500 nm) in a monochromator instrument in reflectance. Principal component analysis (PCA), dummy partial least-squares regression (DPLS), and linear discriminant analysis (LDA) based on PCA scores were used to identify the origin of fishmeal produced using different fish species. Cross-validation was used as validation method when classification models were developed. DPLS correctly classified 80 and 82% of the fishmeal samples. LDA calibration models correctly classified >80% of fishmeal samples according to fish species The results demonstrated the usefulness of NIR spectra combined with chemometrics as an objective and rapid method for the authentication and identification of fish species used to manufacture the fishmeal.     

Use of near-infrared spectroscopy for screening the individual and total glucosinolate contents in Indian mustard seed (Brassica juncea L. Czern. & Coss.)

The potential of near-infrared spectroscopy (NIRS) for screening the sinigrin, gluconapin, 4-hydroxyglucobrassicin, and total glucosinolate contents of Indian mustard (Brassica juncea L. Czern. & Coss.) seed was assessed. Intact seed samples of this species were analyzed by NIRS and their reference values regressed against different spectral transformations by modified partial least-squares (MPLS) regression. The coefficients of determination (r (2)) for sinigrin, gluconapin, 4-hydroxyglucobrassicin, and total glucosinolate contents were, respectively, 0.86, 0.95, 0.33, and 0.82. The standard deviation to standard error of prediction (SEP) ratio, and SEP to standard error of laboratory ratio were for these constituents as follows: sinigrin, 2.59 and 2.70; gluconapin, 4.16 and 2.08; 4-hydroxyglucobrassicin, 1.18 and 1.40; and total glucosinolates, 2.18 and 1.60. By comparison of commercial sinigrin spectrum with the first MPLS loadings of the sinigrin equation, it can be concluded that the molecule of sinigrin has a specific signal in the seed spectrum of Brassica.     

Use of fourier transform near-infrared reflectance spectroscopy for rapid quantification of castor bean meal in a selection of flour-based products

Methodology was developed and evaluated for the rapid detection of castor bean meal (CBM) containing the toxic protein ricin by using Fourier transform near-infrared (FT-NIR) spectroscopy and multivariate techniques. The method is intended to be a prototype to develop a more general approach to detect food tampering. Measurements were made on an FT-NIR system using a diffuse reflection-integrating sphere. Flours spiked with caffeine, crystalline sugar, and corn meal, 1-20% w/w, were used as test articles to evaluate the methodologies. Food matrices (bleached flour, wheat flour, and blueberry pancake mix) spiked with CBM (0.5-8% w/w) were analyzed. Multiplicative scatter correction transformed partial least-squares regression models, using a specific NIR spectral region, predicted CBM contamination in foods with a standard error of cross-validation of <0.6% and a coefficient of determination (R(2)) of >94%. Models discriminated between flour samples contaminated with CBM and other protein sources (egg white, soybean meal, tofu, and infant formula). CBM had loading spectra with bands characteristic of amide groups (4880 and 4555 cm(-1)) and lipids (5800, 5685, 4340, and 4261 cm(-1)).     

Comparative quality assessment of cultured and wild sea bream (Sparus aurata) stored in ice

Comparative quality assessment of cultured and wild sea bream stored in ice for up to 23 days was achieved by the monitoring of sensory quality, levels of nucleotide, nucleotide breakdown products, and texture by a texturometer. The changes in sensory quality of both raw and cooked fish were assessed using the modified Tasmanian and Torry schemes, respectively. K and related values (freshness indicators), namely, K, K(i), G, P, H, and F(r), were calculated. Linear increases (r(2) > or = 0.99) in K, K(i), G, and P (and a decrease in F(r)) values for cultured sea bream and in the H value for wild sea bream with increasing storage periods were observed. The limit for acceptability of cultured and wild sea bream stored in ice was approximately 16-18 days (average K, K(i), G, and P values: approximately 35-40%; H values: approximately 5% for cultured and 10% for wild; and F(r ) values: approximately 65-70%). The texture of cultured and wild sea bream decreased throughout the storage period, and they were not significantly (p > 0.05) different until after day 16 when the wild sea bream was significantly softer than the cultured. The sensory score of both cultured and wild raw fish showed a good relationship with some freshness and texture indicators over the entire storage period (r(2) values > or = 0.99). These indicators were K, K(i), G, P, and F(r) values for cultured and H value for wild fish.     

Quantification of kavalactones and determination of kava (Piper methysticum) chemotypes using near-infrared reflectance spectroscopy for quality control in vanuatu

Kava ( Piper methysticum Forst f., Piperaceae) has anxiolytic properties and the ability to promote a state of relaxation without the loss of mental alertness. The rapid growth of the nutraceutical market between 1998 and 2000 has been stopped by a ban in Europe and Australia because of some suspicion of liver toxicity. It is now important to develop a fast, cheap, and reliable quality test to control kava exports. The aim of this study is to develop a calibration of the near-infrared reflectance spectroscopy (NIRS) using partial least-squares (PLS) regression. Two hundred thirty-six samples of kava roots, stumps, and basal stems were collected from the Vanuatu Agricultural Research and Technical Centre germplasm collection and from four villages. These samples, representing 45 different varieties, were analyzed using NIRS to record their absorption spectra between 400 and 2500 nm. A set of 101 selected samples was analyzed for their kavalactone content using HPLC. The results were used for PLS calibration of the NIRS. The NIRS prediction of the kavalactone content and the dry matter were in agreement with the HPLC results. There were good correlations between these two series of results, and coefficients ( R (2)) were all close to 1. The measurements were reproducible and had repeatability on par with the HPLC method. The NIRS system has been calibrated for the six major kavalactone content measurements, and it is suggested that this method could be used for quality control in Vanuatu.     

Comparison of diffuse reflectance fourier transform mid-infrared and near-infrared spectroscopy with grating-based near-infrared for the determination of fatty acids in forages

Diffuse reflectance Fourier transform mid infrared (FTMIR) and near-infrared spectroscopy (FTNIR) were compared to scanning monochromator-grating-based near-infrared spectroscopy (SMNIR), for their ability to quantify fatty acids (FA) in forages. A total of 182 samples from thirteen different forage cultivars and three different harvest times were analyzed. Three calibration analyses were conducted for lauric (C12:0), myristic (C14:0), palmitic (C16:0), stearic (C18:0), palmitoleic (C16:1), oleic (C18:1), linoleic (C18:2), and alpha-linolenic (C18:3) acids. When all samples were used in a one-out partial least squares (PLS) calibration, the average R (2) were FTNIR (0.95) > SMNIR (0.94) > FTMIR (0.91). Constituents C18:2 and C16:0 had among the highest R (2) regardless of the spectroscopic method used. The FTNIR did better for C12:0, C14:0, and C18:3. The SMNIR did better for C16:0, C16:1, C18:0, C18:1, and C18:2. A second set of calibrations developed with half of the samples as the calibration set and the rest as the validation set showed that all the methods produce acceptable calibrations, with calibration R (2) above 0.9 for most constituents. However, the SMNIR had a better average calibration relative error than the FTNIR, which was slightly better than the FTMIR. A third set of calibration equations developed using 100 random PLS runs with the 182 samples split randomly also shows that the three spectral methods are satisfactory for predicting FA. It is not clear whether any of the spectral methods is distinctly better than another. Calibration R (2) and validation R (2) were higher for most FA with the SMNIR than the FTMIR and FTNIR.     

Determination of kavalactones in dried kava (Piper methysticum) powder using near-infrared reflectance spectroscopy and partial least-squares regression

Kava (Piper methysticum Forst F.), or àwa in the Hawaiian language, has been used for thousands of years by the people of the South Pacific Islands, in particular Fiji, Vanuatu, Tonga, and Samoa, for social and ceremonial occasions. Kava has the unique ability to promote a state of relaxation without the loss of mental alertness. Kava recently became part of the herbal pharmacopoeia throughout the United States and Europe because of its anxiolytic properties. The active compounds are collectively called kavalactones (or kava pyrones). The need for a less time-consuming and costly method to determine the concentration of kavalactones in dried kava is urgent. The combination of near-infrared reflectance spectroscopy (NIRS) and partial least-squares (PLS) methods has been found to be a convenient, versatile, and rapid analytical tool for determination of kavalactones in dried kava powder. Calibration equations were developed based on the analyses of 110 samples with variable physical and chemical properties collected over time from Hawaii kava growers and validated by analyses of a set of 12 samples with unknown kavalactones concentration. All six major kavalactones and the total kavalactones were measured using NIRS with accuracy acceptable for commercial use. The NIRS measurements are reproducible and have a repeatability on a par with HPLC methods.     

Use of a fractal-like gold nanostructure in surface-enhanced raman spectroscopy for detection of selected food contaminants

The safety of imported seafood products because of the contamination of prohibited substances, including crystal violet (CV) and malachite green (MG), raised a great deal of concern in the United States. In this study, a fractal-like gold nanostructure was developed through a self-assembly process and the feasibility of using surface-enhanced Raman spectroscopy (SERS) coupled with this nanostructure for detection of CV, MG, and their mixture (1:1) was explored. SERS was capable of characterizing and differentiating CV, MG, and their mixture on fractal-like gold nanostructures quickly and accurately. The enhancement factor of the gold nanostructures could reach an impressive level of approximately 4 x 10(7), and the lowest detectable concentration for the dye molecules was at approximately 0.2 ppb level. These results indicate that SERS coupled with fractal-like gold nanostructures holds a great potential as a rapid and ultra-sensitive method for detecting trace amounts of prohibited substances in contaminated food samples.     

Determination of poly(ethylene glycol)-binding to browse foliage, as an assay of tannin, by near-infrared reflectance spectroscopy

Nutritionists are interested in functional assays of tannins that do not require time-consuming and expensive extraction, such as the (14)C-labeled poly(ethylene glycol) (PEG)-binding (PEG-b) assay. This paper reports the application of near-infrared (NIR) spectroscopy to determine the percentage of PEG binding, in place of the (14)C-labeled PEG-b assay of tannin, in Mediterranean woodland vegetation. Calibration was done with 53 samples from 14 species and was validated on 25 samples from 10 species. PEG-b ranged between 1.4 and 20.7% in the samples. The calibration obtained by using the modified partial least-squares (MPLS) method, with all wavelengths in the 1100-2500 nm range combined, and the validation were reasonably linear (R (2) = 0.96 and 0.91, respectively). The accuracies, estimated from the standard errors of cross-validation and prediction, were +/-1.6 and +/-1.7% PEG-b, respectively. The NIRS-aided procedure proposed here can serve as an accurate, inexpensive, time-saving, and environment-friendly functional assay of tannin in Mediterranean browse.     

Application of near-infrared reflectance spectroscopy to the evaluation of rutin and D-chiro-Inositol contents in tartary buckwheat

Tartary buckwheat [Fagopyrum tataricum (L.) Gaench] is rich in rutin and D- chiro-inositol (DCI), which have beneficial effects in the treatment of hemorrhagic diseases and insulin-resistant diseases, respectively. The current methods of extraction and detection of rutin and DCI are complex and time-consuming; a simple way of analyzing these compounds in the native matrix would be desirable. In this work, near-infrared reflectance spectroscopy (NIRS) was applied to determine the contents of rutin and DCI in tartary buckwheat. The spectral data were compared with those determined from high-performance liquid chromatography (HPLC) methods. Models for predicting rutin and DCI contents in buckwheat were developed using a partial least-squares algorithm. Cross-validation procedures indicated good correlations between HPLC data and NIRS predictions (R2 = 0.76 for rutin and R2 = 0.86 for DCI). The rutin content ranged from 0.998 to 1.75%, while the DCI content covered 0.179-0.200%. The results showed that NIRS, a well-established and widely applied technique, could be applied to determine rutin and DCI in tartary buckwheat rapidly and nondestructively.     

Development of a microsatellite-based method for the differentiation of European wild boar (Sus scrofa scrofa) from domestic pig breeds (Sus scrofa domestica) in food

Twenty microsatellites (simple sequence repeats, SSR) were used to discriminate wild boar from domestic pig and to identify mixtures of the two. Reference groups of wild boar and pig samples were collected from the UK and Europe for genetic assignment tests. Bayesian Analysis of Populations software (BAPs) gave 100% correct assignment for blind wild boar and pig samples and correctly identified mixed samples. DNA was extracted from 12 commercial food samples (11 labeled as containing wild boar) including patés, salamis, and sausage, and good SSR profiles were obtained. Eleven samples were correctly assigned as pig, and two as mixed meats. One sample sold as wild boar meat was clearly assigned as pig. A further 10 blind samples of meat cuts were analyzed, eight wild boar and two pig, and all were correctly assigned.