Use of near-infrared spectroscopy for fast fraud detection in seafood: application to the authentication of wild European sea bass (Dicentrarchus labrax)

The possibility of using near-infrared spectroscopy (NIRS) for the authentication of wild European sea bass ( Dicentrarchus labrax ) was investigated in this study. Three different chemometric techniques to process the NIR spectra were developed, and their ability to discriminate between wild and farmed sea bass samples was evaluated. One approach used spectral information to directly build the discrimination model in a latent variable space; the second approach first used wavelets to transform the spectral information and subsequently derived the discrimination model using the transformed spectra; in the third approach a cascaded arrangement was proposed whereby very limited chemical information was first estimated from spectra using a regression model, and this estimated information was then used to build the discrimination model in a latent variable space. All techniques showed that NIRS can be used to reliably discriminate between wild and farmed sea bass, achieving the same classification performance as classification methods that use chemical properties and morphometric traits. However, compared to methods based on chemical analysis, NIRS-based classification methods do not require reagents and are simpler, faster, more economical, and environmentally safer. All proposed techniques indicated that the most predictive spectral regions were those related to the absorbance of groups CH, CH(2), CH(3), and H(2)O, which are related to fat, fatty acids, and water content.     

Quantification of the Robusta fraction in a coffee blend via Raman spectroscopy: proof of principle

Among the 100 different known Coffea species, Coffea arabica L. (Arabica) and Coffea canephora Pierre (Robusta) are the only two of commercial interest. They differ in a range of agronomic, genetic, and chemical properties. Due to the significant price difference between Arabica and Robusta, there is an economic incentive to illicitly replace Arabica with Robusta. Therefore, it is crucial to have accurate methods to determine the Robusta-to-Arabica-ratio in blends. This paper presents the proof of principle of a new and fast approach to determine the Robusta fraction in a blend based on Raman spectroscopy. The oils of two references (a pure Robusta and pure Arabica coffee) and six blends thereof consisting of different Robusta and Arabica fractions were extracted using a Soxhlet system. The solutes were analyzed by means of Raman spectroscopy without further workup. Using the intensity ratio between two Raman peaks, one characteristic for kahweol and one characteristic for fatty acids, allowed determinination of the Robusta content in a given mixture. The intensity ratio is linearly dependent on the Robusta content of the compound. Above a Robusta content of 75 wt %, kahweol was not detectable. The Raman data are in agreement with results obtained from the very time-consuming multistep DIN 10777 procedures based on HPLC.     

Free hydroxycinnamic acids, lycopene, and color parameters in tomato cultivars

Concentrations of antioxidant compounds (total phenolic compounds, free hydroxycinnamic acids, and lycopene) and color parameters ( a*, b*, and L*) were determined in 167 tomato samples belonging to five cultivars (Dorothy, Boludo, Dunkan, Dominique, and Thomas) produced on the island of Tenerife. Chlorogenic, caffeic, p-coumaric, and ferulic acids were identified and quantified in the tomato samples. Chlorogenic acid had the highest mean concentration, whereas the p-coumaric was not detected in almost half of the tomato samples. The cultivar, cultivation method, and production region had little influence on the concentration of analyzed parameters. Considerable seasonal variations in the levels of these parameters were observed. Many correlations were observed between the antioxidant compounds and color parameters. The tomato samples tended to be differentiated according to the sampling period when discriminant analysis was applied.     

Authentication of the botanical origin of honey by near-infrared spectroscopy

Fourier transform near-infrared spectroscopy (FT-NIR) was evaluated for the authentication of eight unifloral and polyfloral honey types (n = 364 samples) previously classified using traditional methods such as chemical, pollen, and sensory analysis. Chemometric evaluation of the spectra was carried out by applying principal component analysis and linear discriminant analysis. The corresponding error rates were calculated according to Bayes' theorem. NIR spectroscopy enabled a reliable discrimination of acacia, chestnut, and fir honeydew honey from the other unifloral and polyfloral honey types studied. The error rates ranged from <0.1 to 6.3% depending on the honey type. NIR proved also to be useful for the classification of blossom and honeydew honeys. The results demonstrate that near-infrared spectrometry is a valuable, rapid, and nondestructive tool for the authentication of the above-mentioned honeys, but not for all varieties studied.     

Changes in organic acids and sugars during early stages of development of acidic and acidless citrus fruit

Most of the studies on organic acids and sugars in citrus were performed during fruit maturation, and less is known before this stage of development. The aim of our study was to investigate acids and sugars in lemon, lime, and orange from fruit-set toward development. We chose to compare organic acid and sugar accumulation among acidic and acidless varieties within three species. We estimated the acidity by titrimetry and quantified the concentrations of seven organic acids and three sugars by reverse HPLC. During the first 50 days of development, quinic acid was the major organic acid whatever the variety. Afterward, citric acid predominated in acidic varieties, while in acidless, malic acid exceeded it. Fructose substituted citric acid in acidless and could be synthesized either from citric acid or directly from glucose. Our results provided the first complete report on sugar and organic acid accumulation during the early stages of fruit development in several citrus varieties.     

Geographical characterization of greek virgin olive oils (cv. Koroneiki) using 1H and 31P NMR fingerprinting with canonical discriminant analysis and classification binary trees

This work deals with the prediction of the geographical origin of monovarietal virgin olive oil (cv. Koroneiki) samples from three regions of southern Greece, namely, Peloponnesus, Crete, and Zakynthos, and collected in five harvesting years (2001-2006). All samples were chemically analyzed by means of 1H and 31P NMR spectroscopy and characterized according to their content in fatty acids, phenolics, diacylglycerols, total free sterols, free acidity, and iodine number. Biostatistical analysis showed that the fruiting pattern of the olive tree complicates the geographical separation of oil samples and the selection of significant chemical compounds. In this way the inclusion of the harvesting year improved the classification of samples, but increased the dimensionality of the data. Discriminant analysis showed that the geographical prediction at the level of three regions is very high (87%) and becomes (74%) when we pass to the thinner level of six sites (Chania, Sitia, and Heraklion in Crete; Lakonia and Messinia in Peloponnesus; Zakynthos). The use of classification and binary trees made possible the construction of a geographical prediction algorithm for unknown samples in a self-improvement fashion, which can be readily extended to other varieties and areas.     

稻米脂肪酸与食味的关系及土壤水分的调控效应

为探明不同品种稻米脂肪酸与食味的关系及土壤水分的调控效应,进行了不同水稻品种及土壤水势为-30～-35 kPa和-60～-65 kPa的控水处理对糙米优势、中位、劣势粒成分及食味的影响研究.结果表明,"垦鉴稻5号"、"富士光"、"东农V10"的籽粒脂肪酸含量极显著高于"垦稻8号"和"空育131";"空育131"食味值极显著高于"东农V10"、"垦鉴稻5号"、"垦稻8号","富士光"、"东农V10"、"垦鉴稻5号"极显著高于"垦稻8号","富士光"显著高于"东农V10"和"垦鉴稻5号".食味值与脂肪酸、蛋白质含量呈极显著负相关(2002年r为-0.577**、-0.910**,2003年r为-0.845**、-0.980**)、蛋白质与脂肪酸含量呈极显著正相关(2002年,r为0.582**,2003年,r为0.866**):各品种籽粒成分的变异系数均表现脂肪酸>蛋白质>直链淀粉.抽穗前控水除"绥梗3号"分蘖期控水处理外,两品种("上育397"和"绥粳3号")各粒位籽粒的脂肪酸含量均极显著高于CK;同一生育时期两品种的脂肪酸含量多以控水强度大的处理高,但差异多不显著;长穗期控水对两品种各粒位籽粒的食味影响最大,均极显著低于CK;两品种各粒位籽粒成分的变异均以脂肪酸最大,但对食味的通径系数均以蛋白质最大.建议今后在稻米的食味及营养评价中列入脂肪酸指标.     

Characterization of espresso coffee aroma by static headspace GC-MS and sensory flavor profile.

The aromas of three espresso coffee (EC) samples from different botanical varieties and types of roast (Arabica coffee, Robusta natural blend, and Robusta Torrefacto blend (special roast by adding sugar)) were studied by static headspace GC-MS and sensory flavor profile analysis. Seventy-seven compounds were identified in all of the EC samples. Among them, 13 key odorants have been quantified and correlated with their flavor notes by applying multivariate statistical methods. Some correlations have been found in the EC samples: some aldehydes with fruity flavors, diones with buttery flavors, and pyrazines with earthy/musty, roasty/burnt, and woody/papery flavors. By applying principal component analysis (PCA), Arabica and Robusta samples were separated successfully by principal component 1 (60.7% of variance), and Torrefacto and Natural Robusta EC samples were separated by principal component 2 (28.1% of total variance). With PCA, the aroma characterization of each EC sample could be observed. A very simple discriminant function using some key odorants was obtained by discriminant analysis, allowing the classification of each EC sample into its respective group with a success rate of 100%.     

Effect of different extraction methods on fatty acids,volatile compounds,and physical and chemical properties of avocado (Persea americana Mill.) oil

Because Mexico is the number one producer of avocados in the world, this fruit has potential as a source for oil extraction. It is appropriate to further investigate the detailed changes that the oil undergoes when different extraction methods are applied. This research paper presents the study of the physical and chemical changes, the fatty acids profile, the trans fatty acid content, and the identification of volatile compounds of the oils from avocado pulp (Persea americana Mill.), obtained by four different extraction methods. The method with the greatest extraction yield was the combined microwave-hexane method. The amount of trans fatty acids produced in the microwave-squeezing treatment was <0.5 g/100 g. On the other hand, the amounts of trans fatty acids produced with the hexane and acetone treatments were 0.52 and 0.87 g/100 g, respectively. The method that caused the slightest modification to the oil quality was a novel combined extraction method of microwave-squeezing proposed by the authors.     

Fatty acid, triacylglycerol, and phytosterol composition in six Tunisian olive varieties

The physicochemical and stability properties as well as the fatty acid, triacylglycerol, sterol, and triterpenic dialcohol compositions of Tunisian olive oil varieties were analyzed. On the basis of our results, we classified all of the monovarietal oils into the extra virgin category. Oleic and linoleic acids were the most useful fatty acids to discriminate three cultivars, Neb Jmel, Chétoui, and Ain Jarboua, from the others. Of the six monovarietal virgin olive oils analyzed, the main triacylglycerols were OOO, POO, PLO plus SLL, and OLO, which was expected given the high oleic acid and low linoleic and linolenic acids content observed in total fatty acids. In total, these accounted for more than 80% of the total HPLC chromatogram peak area. The main sterols found were beta-sitosterol, Delta5-avenasterol, and campesterol. The statistical analysis showed significant differences between oil samples, and the obtained results showed a great variability in the oil composition between cultivars, which is influenced exclusively by genetic factors.     

Modified method for the analysis of free fatty acids in fish

The objective of this study was the development of a method for the quantification of free fatty acids (FFA) using less aggressive reactants against the handler and the environment than those used in the classic method of Lowry and Tinsley. The modified procedure is a variation of the Lowry and Tinsley method employing cyclohexane in place of benzene. The use of benzene is prohibited in certain work processes and laboratories, and the competent authority in each country is actively promoting research into harmless or less harmful products that could replace benzene. A comparison with the traditional AOCS titration method for oil analysis was performed. FFA content in mackerel frozen at -10 degrees C was measured according to the three methods over a 12 month period. The results showed similar values, and good correlations were obtained.     

Multielemental fingerprinting as a tool for authentication of organic wheat, barley, faba bean, and potato

The multielemental composition of organic and conventional winter wheat, spring barley, faba bean, and potato was analyzed with inductively coupled plasma-optical emission spectrometry (ICP-OES) and -mass spectrometry (ICP-MS). The crops were cultivated in two years at three geographically different field locations, each accommodating one conventional and two organic cropping systems. The conventional system produced the highest harvest yields for all crops except the nitrogen-fixing faba bean, whereas the dry matter content of each crop was similar across systems. No systematic differences between organic and conventional crops were found in the content of essential plant nutrients when statistically analyzed individually. However, chemometric analysis of multielemental fingerprints comprising up to 14 elements allowed discrimination. The discrimination power was further enhanced by analysis of up to 25 elements derived from semiquantitative ICP-MS. It is concluded that multielemental fingerprinting with semiquantitative ICP-MS and chemometrics has the potential to enable authentication of organic crops.     

Isolation and identification of mosquito (Aedes aegypti ) biting deterrent fatty acids from male inflorescences of breadfruit (Artocarpus altilis (Parkinson) Fosberg)

Dried male inflorescences of breadfruit ( Artocarpus altilis , Moraceae) are burned in communities throughout Oceania to repel flying insects, including mosquitoes. This study was conducted to identify chemicals responsible for mosquito deterrence. Various crude extracts were evaluated, and the most active, the hydrodistillate, was used for bioassay-guided fractionation. The hydrodistillate and all fractions displayed significant deterrent activity. Exploratory GC-MS analysis revealed more than 100 distinctive peaks, and more than 30 compounds were putatively identified, including a mixture of terpenes, aldehydes, fatty acids, and aromatics. A systematic bioassay-directed study using adult Aedes aegypti females identified capric, undecanoic, and lauric acid as primary deterrent constituents. A synthetic mixture of fatty acids present in the most active fraction and individual fatty acids were all significantly more active than N,N-diethyl-m-toluamide (DEET). These results provide support for this traditional practice and indicate the potential of male breadfruit flowers and fatty acids as mosquito repellents.     

Characterization and quantitation of phenolic compounds in new apricot (Prunus armeniaca L.) varieties

Thirty-seven apricot varieties, including four new releases (Rojo Pasión, Murciana, Selene, and Dorada) obtained from different crosses between apricot varieties and three traditional Spanish cultivars (Currot, Mauricio, and Búlida), were separated according to flesh color into four groups: white, yellow, light orange, and orange (mean hue angles in flesh were 88.1, 85.0, 77.6, and 72.4, respectively). Four phenolic compound groups, procyanidins, hydroxycinnamic acid derivatives, flavonols, and anthocyanins, were identified by HPLC-MS/MS and individually quantified using HPLC-DAD. Chlorogenic and neochlorogenic acids, procyanidins B1, B2, and B4, and some procyanidin trimers, quercetin 3-rutinoside, kaempferol 3-rhamnosyl-hexoside and quercetin 3-acetyl-hexoside, cyanidin 3-rutinoside, and 3-glucoside, were detected and quantified in the skin and flesh of the different cultivars. The total phenolics content, quantified as the addition of the individual compounds quantified by HPLC, ranged between 32.6 and 160.0 mg 100 g(-1) of edible tissue. No correlation between the flesh color and the phenolic content of the different cultivars was observed.     

A quantitative method for the determination of cyclopropenoid fatty acids in cottonseed, cottonseed meal, and cottonseed oil (Gossypium hirsutum) by high-performance liquid chromatography

Cyclopropenoid fatty acids (CPFAs), found in cottonseed, have been shown to have detrimental health effects to susceptible livestock. Previous quantitative analytical methods for the determination of CPFAs expressed these acids in terms of their relative abundance with respect to other fatty acids in the oil, necessitating the concurrent analysis of other fatty acids. The proposed analytical method describes the quantitation of three relevant CPFAs for cotton (malvalic acid, sterculic acid, and dihydrosterculic acid) in cottonseed in micrograms per gram fresh weight of sample. The method involves extraction of the oil, saponification, and derivatization of the free fatty acids with 2-bromoacetophenone to give the phenacyl esters. These esters are then separated by dual-column reverse-phase high-performance liquid chromatography and quantitated via external standards. This is the first method to include external calibration standards for CPFAs and, as such, is capable of direct quantification with no further data conversion required. CPFA data generated from the analysis of cottonseed, cottonseed meal, and cottonseed oil produced in the United States in 2002 are presented.     

Assessment of strawberry aroma through solid-phase microextraction-gas chromatography and artificial neuron network methods. Variety classification versus growing years

In a previous work, the SPME-GC-MS method (chemical analysis) coupled with KSOM-ANN treatment of the results (statistical algorithm) has proved to be efficient to classify 70 strawberry samples harvested in the same year, through the 17 varieties to which they belonged, in a two-dimensional map. As an extension, the present study confirms that these results were not dependent on the year of strawberry production and discusses what effects were observed between results obtained in different years. Samples of different strawberry varieties were harvested during the three campaigns of 2000, 2001, and 2002 and analyzed independently. The chemical data matrix obtained in each case allowed the verification of the proposal that the same discriminative effect could be obtained independently of the year of production by using maps of different sizes. Therefore, 30 measures obtained from samples of 9 varieties in 2000, 54 measures from 13 varieties in 2001, and 80 measures from 20 varieties in 2002 were correctly classified by using 20, 35, and 56 hexagon maps, respectively. In a second analysis based on the 2002 production, the chemical differences between variety aromatic features were noted through the increasing size of the map used. Finally, results relative to 7 varieties cultivated in 2001 and 2002 and stored under exactly the same conditions were computed together for elaborating a single map. An interesting effect of double classification according to the year and the varieties was observed.     

Fatty acid, triacylglycerol, phytosterol, and tocopherol variations in kernel oil of Malatya apricots from Turkey

The fatty acid, sn-2 fatty acid, triacyglycerol (TAG), tocopherol, and phytosterol compositions of kernel oils obtained from nine apricot varieties grown in the Malatya region of Turkey were determined ( P<0.05). The names of the apricot varieties were Alyanak (ALY), Cataloglu (CAT), C?loglu (COL), Hacihaliloglu (HAC), Hacikiz (HKI), Hasanbey (HSB), Kabaasi (KAB), Soganci (SOG), and Tokaloglu (TOK). The total oil contents of apricot kernels ranged from 40.23 to 53.19%. Oleic acid contributed 70.83% to the total fatty acids, followed by linoleic (21.96%), palmitic (4.92%), and stearic (1.21%) acids. The s n-2 position is mainly occupied with oleic acid (63.54%), linoleic acid (35.0%), and palmitic acid (0.96%). Eight TAG species were identified: LLL, OLL, PLL, OOL+POL, OOO+POO, and SOO (where P, palmitoyl; S, stearoyl; O, oleoyl; and L, linoleoyl), among which mainly OOO+POO contributed to 48.64% of the total, followed by OOL+POL at 32.63% and OLL at 14.33%. Four tocopherol and six phytosterol isomers were identified and quantified; among these, gamma-tocopherol (475.11 mg/kg of oil) and beta-sitosterol (273.67 mg/100 g of oil) were predominant. Principal component analysis (PCA) was applied to the data from lipid components of apricot kernel oil in order to explore the distribution of the apricot variety according to their kernel's lipid components. PCA separated some varieties including ALY, COL, KAB, CAT, SOG, and HSB in one group and varieties TOK, HAC, and HKI in another group based on their lipid components of apricot kernel oil. So, in the present study, PCA was found to be a powerful tool for classification of the samples.     

不同生长阶段墨瑞鳕脂肪酸组成及主成分分析

为比较不同生长阶段墨瑞鳕肌肉中脂肪酸组成的变化,本研究通过气相色谱技术测定墨瑞鳕幼鱼、成鱼、亲鱼肌肉中脂肪酸含量,并对脂肪酸组成进行主成分分析。结果表明,3个不同生长阶段墨瑞鳕的不饱和脂肪酸(UFA)总量分别为52.2%、58.2%、60.1%;在高度不饱和脂肪酸(HUFA)中DHA含量均最高。随着鱼体生长,墨瑞鳕棕榈油酸、油酸、亚油酸、亚麻酸含量均呈上升趋势,从高到低依次为亲鱼>成鱼>幼鱼;肉豆蔻酸、花生一烯酸、花生四烯酸、EPA、DHA 含量呈下降趋势,从高到低依次为幼鱼>成鱼>亲鱼;UFA总量和单不饱和脂肪酸(MUFA)含量呈上升趋势,从高到低依次为亲鱼>成鱼>幼鱼;多不饱和脂肪酸(PUFA)总量和必需脂肪酸(EFA)总量含量呈先升后降趋势,从高到低依次为成鱼>亲鱼>幼鱼。墨瑞鳕不同生长阶段脂肪酸含量大部分存在显著差异,特别是幼鱼与成鱼的脂肪酸含量(除二十碳三烯酸外)均存在显著差异;肉豆蔻酸、花生一烯酸、花生四烯酸、EPA和DHA等5种脂肪酸是墨瑞鳕的主要特征脂肪酸,这5种主要特征脂肪酸之间均互呈强正相关。随着墨瑞鳕的生长发育应及时提高相应阶段功能性脂肪酸的比例,降低相应阶段呈强负相关的主要特征脂肪酸的比例。本研究结果为墨瑞鳕的开发利用以及饲料营养需求等提供了理论参考。