Minimizing photooxidation in pasteurized milk by optimizing light transmission properties of green polyethylene films.

The effect of different amounts of transmitted green light on photooxidation in pasteurized milk was studied. Five different green films produced with combinations of pigments and additives to minimize exposure to harmful wavelengths with regard to photosensitizers (400-450 and 600-650 nm) were evaluated. In addition, a non-colored transparent film and an orange film were compared with 1 selected green film. Pasteurized milk (3.9% fat) was packed in an air atmosphere and exposed to light for 14, 20, 26, and 32 h at 4 °C under the different films. Samples stored in the dark were control samples. The results showed that the most-effective green film had low overall light transmission, and also almost completely blocked light wavelengths shorter than 450 nm and wavelengths longer than 600 nm, which prevented photooxidation of riboflavin and chlorophyllic compounds. Chlorophyll degradation was highly correlated with sensory properties (coefficient of determination = 0.80-0.94). To preserve milk quality, total blocking of all visible light would be preferable. If total blocking is not feasible, then light transmission for wavelength below 450 nm and above 650 nm should be minimized (e.g., less than 5%). The newly developed green film can be used as a prototype for protection of dairy products to reduce the degradation of photosensitizers.

Effect of different colored filters on photooxidation in pasteurized milk.

The effect of different colored filters and atmospheres on photooxidation and quality in milk was studied. Pasteurized bovine milk (3.9% fat) was packed in 2 different atmospheres (air and N(2)) and exposed to light for 20 h at 4 degrees C under 8 transparent filters with different light transmission properties. The following transparent, noncolored, and colored filters based on polyethylene terephthalate (PET) were used: noncolored (PET), noncolored with 2 different UV-block regions, yellow, green, amber, orange, and red. Control samples were stored in darkness and in a carton. Sensory evaluation showed off flavors significantly increased in milk stored under all filters compared with the control samples. Variation in atmosphere resulted in significant differences in formation of rancid flavor in milk stored under different filters. Milk samples stored in N(2) underwent the most sensory deterioration under orange and red filters, whereas milk samples stored in air were most deteriorated under noncolored filters. According to the oxidation compounds measured by gas chromatography, milk samples stored under noncolored and orange filters were highly oxidized, whereas red, green, and amber filters offered better protection against photooxidation. Fluorescence spectroscopy was used to examine the degradation of photosensitizers (riboflavin, protoporphyrin, and chlorophyllic compounds) in the milk samples. Degradation of protoporphyrin and chlorophyllic compounds in N(2) correlated well with sensory properties related to photooxidation (R(2)=0.75-0.95). The study indicates that protoporphyrin and chlorophyllic compounds were effective photosensitizers in milk. To avoid photooxidation in milk, it is therefore important to protect it against light from the UV spectrum as well as light from the entire visible region.

Front-face fluorescence measurement of photosensitizers and lipid oxidation products during the photooxidation of butter.

This paper shows that fluorescence spectroscopy can measure both degradation of photosensitizers and formation of lipid oxidation products in light-exposed butter. The photosensitizers were already notably degraded after 4 h of light exposure, whereas fluorescent lipid oxidation products were detected after 5 d. The fluorescence measurements were highly correlated with sensory assessments of acidic and rancid flavor. Photosensitizer degradation is therefore a promising indirect indicator of the onset of lipid oxidation in butter. Sensory analysis and measurement of peroxide value showed that the level of lipid oxidation was significantly higher for butter stored in air compared with butter stored in nitrogen (N2). This might be explained by the formation of singlet oxygen from direct photooxidation and type II photosensitized oxidation. Addition of the singlet oxygen quencher beta-carotene reduced the rancid flavor intensity in the air and N2 packages from 9.0 to 4.9 and from 6.5 to 4.7, respectively. Results indicate that lipid oxidation in the butter stored in N2 was mainly caused by type I photosensitized reactions, because addition of beta-carotene had little effect on the rancid flavor intensity.

Active photosensitizers in butter detected by fluorescence spectroscopy and multivariate curve resolution.

In this study, fluorescence excitation and emission matrices and multivariate curve resolution (PARAFAC) were used to detect and characterize active photosensitizers spectrally in butter. Butter samples were packed under high (air) and low oxygen (<0.05%) atmospheres and exposed to violet, green, or red light. Six photosensitizers were found: riboflavin, protoporphyrin, hematoporphyrin, a chlorophyll a-like molecule, and two unidentified tetrapyrrols. By estimation of relative concentrations, we could follow how each sensitizer was photodegraded as function of wavelength, oxygen level, and time. The degradation rate of protoporphyrin, hematoporphyrin, chlorophyll a, and one of the tetrapyrrols correlated well (0.83-0.91) with the formation of sensory measured oxidation. The results suggest that mainly type I photoreactions were responsible for the degradation of photosensitizers in both high and low oxygen atmosphere. Type II photoreactions (generation of singlet oxygen) were involved in the oxidation of butter stored in air. The study shows that PARAFAC modeling of fluorescence landscapes is an excellent tool for studying photooxidation in complex systems.

Measurement of lipid oxidation and porphyrins in high oxygen modified atmosphere and vacuum-packed minced turkey and pork meat by fluorescence spectra and images.

This paper illustrates that fluorescence spectroscopy and imaging can be used to measure the extent and distribution of lipid oxidation in meat. Minced turkey thighs and pork semimembranosus muscles were stored for 7 and 12 days at 4°C in high oxygen (O(2)) modified atmosphere packages and vacuum. Turkey meat packed in high O(2) atmosphere was oxidised already after 7 days of storage. The sensory rancid odour score was 4.7 (on a scale from 1 to 9) and the TBARS value was 1.86mg MDA/kg. There was also an increase in fluorescence emission intensity in the 410-550nm region, which arises from lipid oxidation products. The combination of unsaturated fatty acids and access to O(2) resulted in lipid oxidation gradients in the turkey meat samples, and these gradients were clearly visualised by fluorescence images. In comparison, pork meat was more stable against lipid oxidation, with TBARS values <0.2mg MDA/kg and no development of fluorescent lipid oxidation products was detected. The fluorescence spectra measured in the present experiment suggest that turkey thighs and pork semimembranosus muscle in addition to protoporphyrin also have a natural content of Zn protoporphyrin. The porphyrin content was higher in pork meat than in turkey meat. It increased during storage time when the meat was packed in vacuum, and it decreased with O(2) availability. The distribution of porphyrins in the meat was visualised by fluorescence imaging.

Raman and near-infrared spectroscopy for quantification of fat composition in a complex food model system.

Raman and near-infrared (NIR) spectroscopy have been evaluated for determining fatty acid composition and contents of main constituents in a complex food model system. A model system consisting of 70 different mixtures of protein, water, and oil blends was developed in order to create a rough chemical imitation of typical fish and meat samples, showing variation both in fatty acid composition and in contents of main constituents. The model samples as well as the pure oil mixtures were measured using Raman and NIR techniques. Partial least squares regression was utilized for prediction, and fatty acid features were expressed in terms of the iodine value and as contents of saturated, monounsaturated, and polyunsaturated fatty acids. Raman spectroscopy provided the best results for predicting iodine values of the model samples, giving validated estimation errors accounting for 2.8% of the total iodine value range. Both techniques provided good results for predicting the content of saturated, monounsaturated, and polyunsaturated fatty acids in the model samples, yielding validated estimation errors in the range of 2.4-6.1% of the total range of fatty acid content. Prediction results for determining fatty acid features of the pure oil mixtures were similar for the two techniques. NIR was clearly the best technique for modeling content of main constituents in the model samples.

Feasibility of NIR interactance hyperspectral imaging for on-line measurement of crude composition in vacuum packed dry-cured ham slices.

There is a growing market for packaged slices of dry-cured ham. The heterogeneity of the composition of slices between packages is an important drawback when aiming to offer consumers a product with a known and constant composition which fits individual consumer expectations. The aim of this work was to test the feasibility of NIR interactance imaging for on-line analysis of water, fat and salt and their spatial distribution in dry-cured ham slices. PLSR models for predicting water, fat and salt contents with NIR spectra were developed with a calibration set of samples (n=82). The models were validated with an external validation set (n=42). The predictive models were accurate enough for screening purposes. The errors of prediction were 1.34%, 1.36% and 0.71% for water, fat and salt, respectively. The spatial distribution of these components within the slice was also obtained.

Determining quality of caviar from Caspian Sea based on Raman spectroscopy and using artificial neural networks.

The purpose of this study was to evaluate the feasibility of Raman spectroscopy for predicting purity of caviars. The 93 wild caviar samples of three different types, namely; Beluga, Asetra and Sevruga were analysed by Raman spectroscopy in the range 1995 cm(-1) to 545 cm(-1). Also, 60 samples from combinations of every two types were examined. The chemical origin of the samples was identified by reference measurements on pure samples. Linear chemometric methods like Principal Component Analysis (PCA) and Linear Discriminant Analysis (LDA) were used for data visualisation and classification which permitted clear distinction between different caviars. Non-linear methods like Artificial Neural Networks (ANN) were used to classify caviar samples. Two different networks were tested in the classification: Probabilistic Neural Network with Radial-Basis Function (PNN) and Multilayer Feed Forward Networks with Back Propagation (BP-NN). In both cases, scores of principal components (PCs) were chosen as input nodes for the input layer in PC-ANN models in order to reduce the redundancy of data and time of training. Leave One Out (LOO) cross validation was applied in order to check the performance of the networks. Results of PCA indicated that, features like type and purity can be used to discriminate different caviar samples. These findings were also supported by LDA with efficiency between 83.77% and 100%. These results were confirmed with the results obtained by developed PC-ANN models, able to classify pure caviar samples with 93.55% and 71.00% accuracy in BP network and PNN, respectively. In comparison, LDA, PNN and BP-NN models for predicting caviar types have 90.3%, 73.1% and 91.4% accuracy. Partial least squares regression (PLSR) models were built under cross validation and tested with different independent data sets, yielding determination coefficients (R(2)) of 0.86, 0.83, 0.92 and 0.91 with root mean square error (RMSE) of validation of 0.32, 0.11, 0.03 and 0.09 for fatty acids of 16.0, 20.5, 22.6 and fat, respectively.

On-line determination and control of fat content in batches of beef trimmings by NIR imaging spectroscopy.

An NIR imaging scanner was calibrated for on-line determination of the fat content of beef trimmings. A good calibration model was obtained for fat in intact beef (R=0.98, RMSECV=3.0%). The developed model could be used on single pixels to get an image of the fat distribution, or on the average spectrum from each trimming/portion of trimmings passing under the scanner. The fat model gave a rather high prediction error (RMSEP=8.7%) and a correlation of 0.84 when applied to 45 single trimmings with average fat content ranging from 1.6 to 49.3% fat. Test measurements on streams of trimmings making up batches varying from 10 to 24 kg gave a much lower prediction error (RMSEP=1.33%). Simulations based on true measurements indicate that the RMSEP decreases with increasing batch size and, for the present case, reached about 0.6% for 100 kg batches. The NIR scanner was tested on six batches of intact trimmings varying from 145 to 210 kg and gave similar fat estimates as an established microwave system obtained on the ground batches. The proven concept should be applicable to on-line estimation of fat in trimmings in order to determine the batch fat content and also to control the production of batches to different target fat levels. A possible requirement for the concept to work properly is that the trimming or layer of trimmings on the belt is not too thick. In this study maximum thickness was about 8 cm. Thicker trimmings might be measured, but careful hardware adjustments are then required.

Comparison of 2 high-throughput spectral techniques to predict differences in diet composition of grazing sheep and cattle.

Diet composition can be estimated in free-ranging animals by the use of n-alkane and long-chain fatty alcohol concentrations in feces. However, this technique involves relatively laborious and costly analytical techniques. Two spectroscopy techniques were investigated as a way of determining whether dietary differences are likely, thus indicating whether the more expensive and labor-intensive techniques for more detailed analysis are justified. Fourier-transform infrared spectroscopy (FTIR) and front-face fluorescence emission spectroscopy (lambda(excitation) = 380 nm, lambda(emission) = 600 to 760 nm) were used to analyze fecal samples collected from 2 different breeds of cattle and sheep (4 groups in total, n = 6 per group) grazing moorland plants in 2 grazing sessions. These fecal samples were also analyzed for alkane and alcohol concentrations. Fourier-transform infrared spectra, particularly in the alkane regions, demonstrated clear separation between animal species. Fluorescence emission spectra showed similar separation; fluorophores were most likely chlorophylls and their derivatives. Multivariate analysis of all 3 data sets showed similar variation within and between groups of cattle and sheep, indicating differences in diet selection particularly between species, but also between breed and grazing session. Both spectroscopy methods showed utility in suggesting differences in diet composition that would be worth investigating using more detailed chemical analyses. Of the 2 techniques, the FTIR spectroscopy gave the better comparative results, being able to detect differences in sampling months that were detected with alkanes and alcohols that the fluorescence emission spectroscopy did not detect.

Natural faecal fluorophores and the potential of chlorophyll based markers to optimise fluorescence as a real-time solution for the detection of faecal contamination on carcasses.

More accurate and sensitive visualisation of faecal contamination in the abattoir would significantly reduce the risk posed by harbouring pathogenic micro-organisms. We carried out a preliminary investigation of the range of fluorophores found naturally in faeces from typical ruminant diets. Sixteen ewes were offered either: i) fresh forage (FF), ii) grass silage (GS), iii) grass hay (GH) or iv) concentrate and barley straw (CB). Animals offered FF diets had a greater concentration (P<0.001) of chlorophyll based compounds in their faeces and subsequent fluorescent emission spectra. In a second experiment we investigated a range of fluorescent markers against a basal concentrate and barley straw diet. Ten Cheviot sheep were split into five treatment groups during a duplicate 5 × 5 Latin square design. Four of the groups received a chlorophyll based marker at a rate of 2g/d: i) Mg-Chlorophyllin (MgC), ii) Fe-Chlorophyllin (FeC), iii) Zn-Chlorophyllin (ZnC) or iv) Spirulina (Chlorophyll a extract from blue green algae, Sp). The last group received no supplement as the control (Con). The appearance of chlorophyllin markers and their derivatives in faeces was similar with mean concentrations of 3.1 and 7.2 µg/g DM, respectively. The most intense fluorescent signal was shown with MgC followed by ZnC, FeC, Sp and Con at 685 nm. The use of markers in pre-slaughter diets would improve the accuracy of faecal detection as a result of greater fluorescence and specific emission wavelengths which do not overlap with natural meat components to help with visualisation.

Nondestructive measurement of light-induced oxidation in dairy products by fluorescence spectroscopy and imaging.

The purpose of this paper is to demonstrate the potential of solid-sample fluorescence spectroscopy in nondestructive assessment of light-induced oxidation in different dairy products such as Swiss cheese, cream cheese, and sour cream. Analytical and quantitative spectral properties of fluorescence were elucidated by use of principal component analysis with designed experiments involving different levels of air and light exposure. A significant reduction in fluorescence intensity at approximately 525 nm, and a corresponding increase in the region 415 to 490 nm as a result of illumination was observed on all the products. The effect was ascribed to photodegradation of riboflavin. Variation in two smaller peaks at approximately 620 nm and 630 nm was an interaction effect between exposure to light and air. A pronounced interaction effect between light and air produced intense blue fluorescence and off-flavors on Swiss-like Jarlsberg cheese. High correlations (0.83 to 0.93) between fluorescence spectra and sensory measured off-flavors were obtained for cream cheese. Results indicate that solid-sample fluorescence can be used as a nondestructive and rapid tool to measure the degree of light-induced degradation of riboflavin as well as sensory properties connected to storage of dairy products. Images of fluorescence can be used to visualize the intensity and propagation of this process. The simplicity and rapidity of the method offer rich opportunities for efficient evaluation of factors affecting light-induced oxidation in dairy products, such as packaging materials, light sources, exposure time, and temperature.