近红外光谱结合化学计量学方法检测蜂蜜产地

为了实现蜂蜜产地的快速判别,应用近红外光谱结合化学计量学方法对蜂蜜产地进行了判别分析。kennard-Stone法划分训练集和预测集。光谱用一阶导数加自归一化预处理后,再用小波变换（WT）进行压缩和滤噪。结合滤波后光谱信息,分别用径向基神经网络（RBFNN）和偏最小二乘-线性判别分析（PLS-LDA）建立了苹果蜜产地和油菜蜜产地的判别模型。对不同小波基和分解尺度进行了讨论。对苹果蜜,WT-RBFNN模型和WT-PLS-LDA模型都是小波基为db1、分解尺度为2时的预测精度较好,都为96.2%。对油菜蜜：WT-RBFNN模型在小波基为db4和分解尺度为1时,预测精度较好,为85.7%;WT-PLS-LDA模型在小波基为db9、分解尺度也为1时,预测精度较好,为90.5%。研究表明：WT结合线性的PLS-LDA建模比WT结合非线性的RBFNN建模更适于蜂蜜产地判别;近红外光谱技术具有快速判别蜂蜜产地的潜力。     

Geographical characterization of polyfloral and acacia honeys by nuclear magnetic resonance and chemometrics

The importance of geographical origin determination is an increasing and pressing requirement for all foods. Honey is one of the largest studied foods due to its nutritional and medicinal properties in a correct diet. In this paper, a total of 41 honey samples (polyfloral and acacia) from different countries have been analyzed in terms of (1)H NMR spectroscopy coupled with multivariate statistical methods. Unsupervised principal component analysis resulted as an efficient tool in distinguishing (1)H NMR spectra of polyfloral and acacia honey samples and for geographical characterization of the latter ones. Hierarchical projection to latent structures discriminant analysis was successfully applied for the discrimination among polyfloral honey samples of different geographical origins. (13)C NMR spectroscopy was applied to honey samples with the aim to investigate possible sugar isoforms differentiation. Our preliminary data indicated a different isoforms ratio between betaFP and betaFF only for polyfloral Argentinean samples, while Hungarian samples showed resonance shifts for some carbons of alphaFF, betaFP, betaFF, and alphaGP isoforms for both varieties. These data confirmed the potentiality of (13)C spectroscopy in food characterization, especially in sugar-based foods.     

Application of stable isotope ratio analysis to the characterization of the geographical origin of olive oils.

To gain information about the geographical origin of oil samples, measurements of delta(13)C and delta(18)O of the whole oil and some of its fractions have been performed on samples coming from fruits of Olea europaea L. produced in Greece, Morocco, Spain, Italy, Tunisia, and Turkey. The results obtained by applying statistical procedures have given pieces of evidence that oil samples have shown the trend to cluster according to the different climatic areas of growing environment of fruits. Some confusion has been observed for samples coming from neighboring countries having similar climates.     

Typicality and geographical origin markers of protected origin cheese from The Netherlands revealed by PTR-MS

Volatile fingerprints of 30 cumin cheese samples of artisanal farmers' cheese of Leiden with EU Protected Designation of Origin (PDO) and 29 cumin cheese samples of varying commercial Dutch brands without PDO protection were used to develop authentication models. The headspace concentrations of the volatiles, as measured with high sensitivity proton-transfer mass spectrometry, were subsequently subjected to partial least-squares discriminant analysis (PLS-DA). Farmers' cheese of Leiden showed a distinct volatile profile with 27 and 9 out of the 60 predominant ions showing respectively significantly higher and lower concentrations in the headspace of the cheese in comparison to the other cumin cheeses. The PLS-DA prediction models developed classified in cross-validation 96% of the samples of PDO protected, artisanal farmers' cheese of Leiden correctly, against 100% of commercial cumin cheese samples. The characteristic volatile compounds were tentatively identified by PTR-time-of-flight-MS. A consumer test indicated differences in appreciation, overall flavor intensity, creaminess, and firmness between the two cheese groups. The consumers' appreciation of the cumin cheese tested was not influenced by the presence of a name label or PDO trademark.     

Differentiation of carbohydrate gums and mixtures using fourier transform infrared spectroscopy and chemometrics

Guar gum, a nonionic galactomannan, is used as an economical thickener and stabilizer in the food industry and is often combined with xanthan, locust bean gum (LBG), or carboxymethylcellulose (CMC) to promote synergistic changes in viscosity or gelling behavior via intermolecular interactions; however, the adulteration of LBG with guar gum is a well-known industrial problem. The ability to identify the purity of gums and concentrations of individual gums in mixtures would be advantageous for quality control in the food industry. Fourier transform infrared spectroscopy (FTIR) methods are rapid and require minimum sample preparation. The objectives of this study were to evaluate the ability of FTIR techniques to (1) differentiate LBG with a variety of mannose/galactose (M/G) ratios, (2) differentiate guar, LBG, tara, and fenugreek gums, (3) differentiate pure guar gum from guar gum mixed with LBG, xanthan gum, or CMC, (4) quantify LBG, xanthan gum, and CMC in guar gum, and (5) quantify guar gum in LBG. Two FTIR methods were used: diffuse reflectance (DRIFT) on powdered gum samples added to KBr at 5%, w/w, and attenuated total reflectance (ATR) on 1%, w/w, gum solutions. Spectra were collected and then analyzed by multivariate statistical procedures (chemometrics). The DRIFT method provided better discrimination and quantitative results than the ATR method. Canonical variate analysis (CVA) of DRIFT spectra (1200-700 cm(-1)) was able to classify LBG with various M/G ratios, pure galactomannans, and pure versus mixtures of gums with 100% accuracy. Quantification of an individual gum in gum mixtures (0.5-15%, w/w) was possible using partial least-squares (PLS) analysis of DRIFT spectra with R2 > 0.93 and using this approach for quantifying guar gum added to LBG resulted in an R2 > 0.99, RMSEC = 0.29, and RMSEP = 3.31. Therefore, the DRIFT FTIR method could be a useful analytical tool for quality control of select gums and gum mixtures used in the food industry.     

Evaluation of the botanical origin of estonian uni- and polyfloral honeys by amino acid content

The free amino acid content of 61 honey samples from Estonia has been determined by HPLC-UV with precolumn derivatization with diethyl ethoxymethylenemalonate. Analyzed samples were seven types of unifloral honeys and polyfloral honeys. The main amino acids found in Estonian honeys were proline and phenylalanine. The resulting data have been analyzed by t test and principal component analysis (PCA). t Test revealed that some amino acids (alpha-alanine, beta-alanine, asparagine, gamma-aminobutyric acid, glutamine, glycine, histidine, ornithine, phenylalanine, proline, serine, and tryptophan) are more potent for assigning honey botanical origin than others. PCA enabled differentiation of some honey types by their botanical origin. In the space of the two first principal components, heather honeys form a cluster that is clearly separable from, for example, polyfloral honeys. It is concluded that analysis of the free amino acid profile may serve as a useful tool to assess the botanical origin of Estonian honeys.     

Inductively coupled plasma optical emission spectrometric determination of minerals in thyme honeys and their contribution to geographical discrimination

Twenty-four Spanish thyme honey samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Twenty-four minerals were quantified for each honey. The elements Al, As, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, P, Pb, S, Se, Si, Sr, and Zn were detected in all samples; seven elements are very abundant (Ca, K, Mg, Na, P, S, and Si), and six are not abundant (Al, Cu, Fe, Li, Mn, and Zn). Eleven of them are trace elements (As, Ba, Cd, Co, Cr, Ni, Mo, Pb, Se, Sr, and V) at <1 mg kg(-)(1). Classification of thyme honeys according to their origin (coast, mountains) was achieved by pattern recognition techniques on the mineral data. By means of principal component analysis, a good separation by geographical origin is obtained when scores for the two first principal components are plotted. Classification functions of 11 metals (Al, As, Cr, Cu, K, Li, Mg, Na, P, S, and V) were obtained using stepwise discriminant analysis and applied to classify correctly approximately 100% of the honey samples.     

NMR characterization of saccharides in Italian honeys of different floral sources

The saccharide profiles of 5 different botanical species in 86 Italian honey samples were investigated by 1H and 1H-13C NMR spectroscopy. Nineteen saccharides were identified in the aqueous extracts, namely, fructose, glucose, gentiobiose, isomaltose, kojibiose, maltose, maltulose, melibiose, nigerose, palatinose, sucrose, turanose, erlose, isomaltotriose, kestose, maltotriose, melezitose, raffinose, and maltotetraose. PCA performed on NMR spectral regions, in particular between 4.400 and 5.700 ppm and the fructose signal at 4.050 ppm, revealed a partial sample grouping. The score contribution plots derived from PCA performed using the mean values for the buckets of the anomeric region for each floral source allowed the identification of saccharides characterizing different honeys. OPLS-DA models were further evaluated to confirm the previous findings. OPLS-DA models were also built to highlight differences between polyfloral and high mountain polyfloral honeys and between high mountain polyfloral and rhododendron honeys, both collected at high altitude; S-plots highlighted the characteristic saccharides.     

Multivariate correlation between color and mineral composition of honeys and by their botanical origin

The mineral content and color characteristics of 77 honey samples were analyzed. Eighteen minerals were quantified for each honey. Multiple linear regression (MLR) was used to establish equations relating the colorimetric CIELAB coordinates to the mineral data. The results obtained shown that lightness (L) was significantly correlated with S, Ca, Fe, As, Pb, and Cd for the dark honey types (avocado, heather, chestnut, and honeydew). For the light and brown honey types (citrus, rosemary, lavender, eucalyptus, and thyme), C(ab) and b showed the lower correlation with the mineral content of the honeys; their regression functions involve a few independent variables (Mg and Al for b and only Al for C(ab)). Furthermore, by means of application of linear discriminant analysis to the mineral content, it was possible to obtain a model that classifies the honeys by their lightness. The prediction ability of the built model, determined with the test set method, was 85%.     

Classification and characterization of manuka honeys based on phenolic compounds and methylglyoxal

Manuka honey from New Zealand is often considered to be a medicinal product of special value due to its high level of antimicrobial activity. Therefore, the distinct authentication of its botanical origin is of great importance. Aside from the common pollen analysis, it is in this respect particularly the analysis of the phenolic acids, flavonoids, and norisoprenoids that is described as useful. In the present study, numerous manuka honeys were analyzed by UPLC-PDA-MS/MS after solid-phase extraction and compared to other kinds of honey to define marker substances characteristic for manuka honeys. The PDA profiles obtained differed markedly from each other so that the individual honey samples could be assigned to three groups. For the honeys of group 1 the comparably high concentrations of 4-hydroxybenzoic acid, dehydrovomifoliol, and benzoic acid proved to be typical, whereas the profiles of group 2 showed high kojic acid and 2-methoxybenzoic acid intensities. The manuka honeys of group 3, on the other hand, yielded high amounts of syringic acid, 4-methoxyphenyllactic acid, and methyl syringate. Furthermore, the comprehensive comparison of manuka honeys to other unifloral honeys revealed that especially kojic acid, 5-methyl-3-furancarboxylic acid, leptosin, unedone, 2-methoxybenzoic acid, 4-methoxyphenyllactic acid, 3-hydroxy-1-(2-methoxyphenyl)penta-1,4-dione, and methyl syringate were useful for distinguishing manuka honeys from the other kinds of investigated honeys. Moreover, kojic acid, unedone, 5-methyl-3-furancarboxylic acid, 3-hydroxy-1-(2-methoxyphenyl)penta-1,4-dione, and lumichrome were identified in manuka honey for the first time.     

Authentication of the botanical and geographical origin of honey by mid-infrared spectroscopy

The potential of Fourier transform mid-infrared spectroscopy (FT-MIR) using an attenuated total reflectance (ATR) cell was evaluated for the authentication of 11 unifloral (acacia, alpine rose, chestnut, dandelion, heather, lime, rape, fir honeydew, metcalfa honeydew, oak honeydew) and polyfloral honey types (n = 411 samples) previously classified with 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 error rates of the discriminant models being calculated by using Bayes' theorem. The error rates ranged from <0.1% (polyfloral and heather honeys as well as honeydew honeys from metcalfa, oak, and fir) to 8.3% (alpine rose honey) in both jackknife classification and validation, depending on the honey type considered. This study indicates that ATR-MIR spectroscopy is a valuable tool for the authentication of the botanical origin and quality control and may also be useful for the determination of the geographical origin of honey.     

Authentication of the botanical and geographical origin of honey by front-face fluorescence spectroscopy

Front-face fluorescence spectroscopy, directly applied on honey samples, was used for the authentication of 11 unifloral and polyfloral honey types (n = 371 samples) previously classified using traditional methods such as chemical, pollen, and sensory analysis. Excitation spectra (220-400 nm) were recorded with the emission measured at 420 nm. In addition, emission spectra were recorded between 290 and 500 nm (excitation at 270 nm) as well as between 330 and 550 nm (excitation at 310 nm). A total of four different spectral data sets were considered for data analysis. Chemometric evaluation of the spectra included principal component analysis and linear discriminant analysis; the error rates of the discriminant models were calculated by using Bayes' theorem. They ranged from <0.1% (polyfloral and chestnut honeys) to 9.9% (fir honeydew honey) by using single spectral data sets and from <0.1% (metcalfa honeydew, polyfloral, and chestnut honeys) to 7.5% (lime honey) by combining two data sets. This study indicates that front-face fluorescence spectroscopy is a promising technique for the authentication of the botanical origin of honey and may also be useful for the determination of the geographical origin within the same unifloral honey type.     

High-resolution MAS NMR and chemometrics: characterization of the ripening of Parmigiano Reggiano cheese

We performed a preliminary NMR investigation on grated Parmigiano Reggiano cheese of different ripening ages. Principal component analysis (PCA) and discriminant analysis (DA) were able to successfully group the analyzed samples according to their respective ages.     

Determination of the geographic origin of rice by chemometrics with strontium and lead isotope ratios and multielement concentrations

The objective of this study was to develop a technique for determining the country of origin of rice in the Japanese market. The rice samples included a total of 350 products grown in Japan (n = 200), the United States (n = 50), China (n = 50), and Thailand (n = 50). In this study, (87)Sr/(86)Sr and Pb isotope ((204)Pb, (206)Pb, (207)Pb, and (208)Pb) ratios and multielement concentrations (Al, Fe, Co, Ni, Cu, Rb, Sr, and Ba) were determined by high-resolution inductively coupled plasma mass spectrometry. By combining three chemometric techniques based on different principles and determination criteria, the countries of origin of rice were determined. The predictions made by 10-fold cross-validation were around 97% accurate. The presented method demonstrated the effectiveness of determining the geographic origin of an agricultural product by combining several chemometric techniques using heavy element isotope ratios and multielement concentrations.     

Application of inorganic element ratios to chemometrics for determination of the geographic origin of welsh onions

The composition of concentration ratios of 19 inorganic elements to Mg (hereinafter referred to as 19-element/Mg composition) was applied to chemometric techniques to determine the geographic origin (Japan or China) of Welsh onions (Allium fistulosum L.). Using a composition of element ratios has the advantage of simplified sample preparation, and it was possible to determine the geographic origin of a Welsh onion within 2 days. The classical technique based on 20 element concentrations was also used along with the new simpler one based on 19 elements/Mg in order to validate the new technique. Twenty elements, Na, P, K, Ca, Mg, Mn, Fe, Cu, Zn, Sr, Ba, Co, Ni, Rb, Mo, Cd, Cs, La, Ce, and Tl, in 244 Welsh onion samples were analyzed by flame atomic absorption spectroscopy, inductively coupled plasma atomic emission spectrometry, and inductively coupled plasma mass spectrometry. Linear discriminant analysis (LDA) on 20-element concentrations and 19-element/Mg composition was applied to these analytical data, and soft independent modeling of class analogy (SIMCA) on 19-element/Mg composition was applied to these analytical data. The results showed that techniques based on 19-element/Mg composition were effective. LDA, based on 19-element/Mg composition for classification of samples from Japan and from Shandong, Shanghai, and Fujian in China, classified 101 samples used for modeling 97% correctly and predicted another 119 samples excluding 24 nonauthentic samples 93% correctly. In discriminations by 10 times of SIMCA based on 19-element/Mg composition modeled using 101 samples, 220 samples from known production areas including samples used for modeling and excluding 24 nonauthentic samples were predicted 92% correctly.     

Self-incompatibility reactions in wild species of the genusBeta and their relation to taxonomical classification and geographical origin

Summary The expression of self-incompatibility (SI) rejection patterns in 29 accessions of wildBeta species was studied at the anatomical level. Three different SI-related pollen tube rejection patterns were observed: (1) The pollen germinate from many pores and the pollen tubes are very short, often with swollen tips. (2) The pollen germinate and grow along the stigmatic papillae, where the self-incompatibility response takes place at the basis of the stigmatic papillae. (3) The pollen germinate and the pollen tubes grow with a distinct direction towards the style; the self-incompatibility response is observed at the border between the stigma and the style. In general the patterns observed inB. vulgaris L. subsp.vulgaris sensu lato seem to be in accordance with an ongoing microevolutionary process that has given rise to the largemaritima complex (viz.B. trojana Pamuk?uoğlu,B. atriplicifolia Rouy, andB. maritima (L.) Arcangeli), in which it seems that the variation is related to geographical origin. The data support the idea that the endemicB. vulgaris subsp.adanensis (Pamuk?uoğlu) Ford-Lloyd & Williams forms a distinct, self-compatible group separated from themaritima complex and also thatB. macrocarpa Gussone should be retained as a separate self-compatible species. For the sectionCorollinae Ulbrich the rejection patterns are in accordance with a division into two subsections (viz.,Lomatogonae andTrigynae) previously suggested on the basis of phenotypical and molecular data. The results fromProcumbentes Ulbrich are interpreted as evidence forB. procumbens Smith andB. webbiana Moquin being more related to each other than toB. patellaris Moquin, reflecting also a similar taxonomic relationship.     

Near-infrared spectroscopy in saffron quality control: determination of chemical composition and geographical origin

Near-infrared reflectance spectroscopy has been applied for the first time to saffron spice to determine the chemical composition and geographical origin of 111 samples from the there main producers' countries: Iran, Greece, and Spain. The validation procedures with the results obtained by UV-vis and HPLC-DAD measurements demonstrated that this technique is appropriate to determine the following parameters: moisture and volatile content, coloring strength, (250 nm), and (330 nm), established on the ISO 3632 Technical Specification Normative and used to certify saffron quality in the international market. Also, it can be used to estimate the content of the five main crocetin glycosides, the compounds responsible for saffron color, the best correlations being for trans-crocetin di-(beta-D-gentibiosyl) ester (R2= 0.93), trans-crocetin (beta-D-glucosyl)-(beta-D-gentibiosyl) (R2= 0.94), and picrocrocin (R2= 0.92), the compound accepted as responsible for saffron bitterness. Finally, a discriminant analysis among the three geographical origins reveals that Iranian samples are the most different, whereas Greek and Spanish samples are more similar. All of these results reveal that NIRS spectroscopy has an enormous potential for its application to saffron quality control as the results are obtained in 2 min and without any sample manipulation.     

The use of soil data in natural heritage planning and management

Abstract. Native woodland restoration is a conservation priority within the UK and there is an increasing awareness that a long-term strategy is required to guide this process. A GIS-based modelling approach has been developed, which links site conditions as expressed in an integrated soil and land cover dataset with the site requirements for different woodland types. There are three important aspects to the model – the parameter weightings, the added value of the integrated dataset, and the woodland categories which are described and predicted. The initial quantitative and qualitative validation has been encouraging although more is required and planned. The results indicate that for broad strategic planning purposes, predictions of woodland potential are not improved significantly when climatic factors are incorporated. The concept that soil acts as an integrator of other environmental variables is discussed alongside the practical application of the model by a range of users.     

Selenium accumulation in beef: effect of dietary selenium and geographical area of animal origin

Selenium (Se) is an essential nutrient with multiple human health benefits; the single most important dietary source of Se is beef. The Se content of beef varies, and cattle fed a high selenium diet may have Se concentrations in beef that are well above average. Such beef is potentially a unique supplemental source of dietary Se. To examine factors affecting Se accumulation in beef, 16 steers (initial wt 374.4 +/- 33.7 kg) were taken from seleniferous or nonseleniferous areas and fed in a 2 x 2 factorial design with diets high or moderate in Se (11.9 or 0.62 mg Se/kg diet). Diets contained 50% alfalfa, 25% wheat, and 25% corn on a dry matter basis. All dietary Se was from agricultural products, and Se in the high Se diet was primarily from high Se wheat and alfalfa hay. A loin muscle biopsy was taken at the start of the trial to determine initial Se content of beef. Steers were slaughtered after 14 weeks of the trial, and edible carcass (round, sirloin, shoulder clod, and ribeye) and organ samples were collected. Diets did not affect growth or feed intake (P > 0.05), and Se toxicity signs were not observed. Different cuts of meat had similar Se concentrations, and the Se content of all cuts was increased by both high dietary Se and high Se background. Except for liver and kidney, Se in tissues was increased by seleniferous background (P < 0.02) and high dietary Se (P < 0.001). Kidney Se concentrations of animals fed the high Se diet were lowest in animals from seleniferous areas (P = 0.04), suggesting a possible adaptation to the high Se diet. These results demonstrate that cattle fed diets high in Se from agricultural products will accumulate substantial amounts of Se in the beef without developing signs of Se toxicity and that prior Se status regulates Se accumulation in some organs. They further demonstrate that management practices may be altered so as to make beef a significant source of dietary Se.