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1.
Carbon isotope analyses (δ13C) of some New Zealand Manuka honeys show that they often fail the internationally recognised Association of Official Analytical Chemists sugar test (AOAC method 998.12) which detects added C4 sugar, although these honeys are from unadulterated sources. Failure of these high value products is detrimental to the New Zealand honey industry, not only in lost export revenue, but also in brand and market reputation damage. The standard AOAC test compares the carbon isotope value of the whole honey and corresponding protein isolated from the same honey. Differences between whole honey and protein δ13C values should not be greater than +1.0‰, as it indicates the possibility of adulteration with syrups or sugars from C4 plants such as high fructose corn syrup or cane sugar. We have determined that during the standard AOAC method, pollen and other insoluble components are isolated with the flocculated protein. These non‐protein components have isotope values which are considerably different from those of the pure protein, and can shift the apparent δ13C value of protein further away from the δ13C value of the whole honey, giving a false positive result for added C4 sugar. To eliminate a false positive C4 sugar test for Manuka honey, prior removal of pollen and other insoluble material from the honey is necessary to ensure that only the pure protein is isolated. This will enable a true comparison between whole honey and protein δ13C isotopes. Furthermore, we strongly suggest this modification to the AOAC method be universally adopted for all honey C4 sugar tests. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

2.
In this study, the method for determining the stable carbon isotope ratio value was validated. Measurement uncertainty of stable carbon isotope ratio value of whole honey and its extracted protein derived from repeatability, reference gas, reference standards and calibration curve was calculated by applying the “bottom-up” approach according to Eurachem/CITAC guide. The expanded uncertainties for all results ranged from 0.14 to 0.19 ‰, with most of them between 0.15 and 0.16 ‰ (the coverage factor k = 2, the level of confidence p is approximately 95 %). The percentage contribution of each source to the relative combined uncertainty was calculated. The data indicated that calibration curves have more contribution to the relative combined uncertainty than repeatability and reference standards. On the other hand, the measurement uncertainty of C-4 sugar content in honey was estimated. Based on these results, 58 honey samples, such as acacia, chaste, Northeast China black bee, flowers and jujube honey, have been gathered to determine the C-4 plant sugar content adulteration in honey by elemental analyzer with an isotope ratio mass spectrometer. It can be found that all honey samples were not adulterated by C-4 plant sugar.  相似文献   

3.
The carbon and nitrogen stable ratios of royal jelly (RJ) samples from various origins are determined using an elemental analyser linked online to an isotope ratio mass spectrometer to evaluate authenticity and adulteration. The (13)C/(12)C and (15)N/(14)N stable isotope ratios are measured in more than 500 RJs (domestic, imported and derived from feeding experiments) in order to obtain isotopic measurements that take into account seasonal, botanical and geographical effects. Authenticity intervals are established for traditional beekeeping practices, without feeding, in the range -22.48 to -27.90‰ for δ(13)C. For these samples, the δ(15)N values range from -1.58 to 7.98‰, depending on the plant sources of pollen and nectar. The δ(13)C values of the commercial samples vary from -18.54 to -26.58‰. High δ(13)C values are typical of sugar cane or corn syrups which have distinctive isotopic (13)C signatures because both plants use the C4 photosynthetic cycle, in contrast to most RJs which are derived from C3 plants. These differences in the (13)C-isotopic composition allow the detection of the addition of such sugars. RJs from traditional sources and from industrial production by sugar feeding are thus successfully distinguished.  相似文献   

4.
液相色谱/元素分析-同位素比值质谱联用法鉴定蜂蜜掺假   总被引:8,自引:0,他引:8  
费晓庆  吴斌  沈崇钰  丁涛  李丽花  路颖 《色谱》2011,29(1):15-19
采用液相色谱/元素分析-同位素比值质谱联用法(LC/EA-IRMS)对国内蜂蜜掺假情况进行了研究。基于测定得到的38个纯正蜂蜜样品的碳同位素δ13C值数据,提出了纯正蜂蜜样品的δ13C值要求: 蛋白质和蜂蜜的δ13C差值(Δδ13CP-H)≥~0.95‰,果糖和葡萄糖的δ13C差值(Δδ13CF-G)在~0.64‰至0.53‰范围内,各个组分间的δ13C最大差值(Δδ13Cmax)<2.09‰。对150个日常检测样品、蜂农和蜂蜜供应商的蜂蜜样品分别采用本文建立的LC/EA-IRMS和国家标准方法(EA-IRMS)进行鉴定,LC/EA-IRMS方法检出58个掺有C3或C4植物糖浆的阳性样品,而EA-IRMS方法仅检出7个掺有C4植物糖浆的阳性样品,可见新方法大大提高了对蜂蜜掺假的鉴别能力。  相似文献   

5.
The present study was aimed to investigate the variation of stable isotopic ratios of carbon, nitrogen, hydrogen, and oxygen in wheat kernel along with different processed fractions from three geographical origins across 5 years using isotope ratio mass spectrometry (IRMS). Multiway ANOVA revealed significant differences among region, harvest year, processing, and their interactions for all isotopes. The region contributed the major variability in the δ13C ‰, δ2H ‰, δ15N ‰, and δ18O‰ values of wheat. Variation of δ13C ‰, δ15N ‰, and δ18O ‰ between wheat whole kernel and its products (break, reduction, noodles, and cooked noodles) were ?0.7‰, and no significant difference was observed, suggesting the reliability of these isotope fingerprints in geographical traceability of wheat‐processed fractions and foods. A significant influence of wheat processing was observed for δ2H values. By applying linear discriminant analysis (LDA) to the whole dataset, the generated model correctly classified over 91% of the samples according to the geographical origin. The application of these parameters will assist in the development of an analytical control procedure that can be utilized to control the mislabeling regarding geographical origin of wheat kernel and its products.  相似文献   

6.
The effects of feeding bees artificial sugars and/or proteins on the sugar compositions and 13C isotopic measurements of royal jellies (RJs) were evaluated. The sugars fed to the bees were two C4 sugars (cane sugar and maize hydrolysate), two C3 sugars (sugar beet, cereal starch hydrolysate), and honey. The proteins fed to them were pollen, soybean, and yeast powder proteins. To evaluate the influence of the sugar and/or protein feeding over time, samples were collected during six consecutive harvests. 13C isotopic ratio measurements of natural RJs gave values of around −25 ‰, which were also seen for RJs obtained when the bees were fed honey or C3 sugars. However, the RJs obtained when the bees were fed cane sugar or corn hydrolysate (regardless of whether they were also fed proteins) gave values of up to −17 ‰. Sugar content analysis revealed that the composition of maltose, maltotriose, sucrose, and erlose varied significantly over time in accordance with the composition of the syrup fed to the bees. When corn and cereal starch hydrolysates were fed to the bees, the maltose and maltotriose contents of the RJs increased up to 5.0 and 1.3 %, respectively, compared to the levels seen in authentic samples (i.e., samples obtained when the bees were fed natural food: honey and pollen) that were inferior to 0.2% and not detected, respectively. The sucrose and erlose contents of natural RJs were around 0.2 %, whereas those in RJs obtained when the bees were fed cane or beet sugar were as much as 4.0 and 1.3 %, respectively. The combination of sugar analysis and 13C isotopic ratio measurements represents a very efficient analytical methodology for detecting (from early harvests onward) the use of C4 and C3 artificial sugars in the production of RJ.  相似文献   

7.
Honey is frequently subject to adulteration with relatively cheap high fructose corn syrup. Not only is this a serious consumer fraud but it is a major threat to the apicultural industry. Stable isotope ratio analysis using mass spectrometry may be used to detect honey that has been adulterated with high fructose corn syrup due to the fact that honey, usually from C3 plants, has a different 13C:12C ratio than high fructose corn syrup which is a C4 plant product  相似文献   

8.
《Analytical letters》2012,45(16):2620-2634
The aim of this study was to quantify the effects of preservation methods and preservation times on the stable carbon and nitrogen isotope values in the tissues of six mollusk species (Mytilus edulis, Crassostrea gigas, Ruditapes philippinarum, Acanthochiton seulschnochilon, Littorina brevicula, and Rapana venosa). To identify potential preservation effects on δ13C and δ15N values and to examine temporal changes in the effects of preservation, repeated analyses were carried out after 1 day, 5 days, 15 days, 1 month, 3 months, 6 months, and 12 months of preservation. The results showed that drying preservation was the most suitable method for preserving samples, while freezing and chemical preservation significantly affected the stable isotope values compared with those of the controls. The effects of preservatives on the tissues of different mollusk species were statistically significant for both δ13C and δ15N values. Shifts in the δ13C and δ15N values, due to freezing and chemical preservation, were higher in Acanthochiton seulschnochilon, Littorina brevicula, and Rapana venosa than in the other three species. The effects of preservatives on carbon isotope values were variable. In most cases, the shift of the δ13C values from the control samples were less than 1% for those of the treated samples. The δ13C and δ15N data from the preserved samples could thus be used in food web reconstruction studies. Further studies will be necessary, however, in order to elucidate the effects of preservation type and time on other species.  相似文献   

9.
Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well‐established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound‐specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography–combustion–isotope ratio mass spectrometry (GC‐C‐IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post‐analysis correction for the accurate measurement of δ13 C values, leading to increased measurement error. Here, we describe a method for δ13 C isotope ratio measurement and quantification of BPCAs from soil‐derived PyOM, based on ion‐exchange chromatography (IEC‐IRMS). The reproducibility of the δ13 C measurement of individual BPCAs by IEC‐IRMS was better than 0.35‰ (1σ). The δ13 C‐BPCA analysis of PyOM in soils, including at natural and artificially enriched 13 C‐abundance, produced accurate and precise δ13 C measurements. Analysis of samples that differed in δ13 C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual δ13 C‐BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of δ13 C‐BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

10.
Stable isotope techniques in food web studies often focus on organic carbon in food sources which are subsequently assimilated in the tissue of consumer organisms through diet. The presence of non‐dietary carbonates in bulk samples can affect their δ13C values, altering how their results are interpreted. Acidification of samples is a common practice to eliminate any inorganic carbon present prior to analysis. We examined the effects of pre‐analysis acidification on two size fractions of sediment organic matter (SOM) from marine and freshwater wetlands and pure muscle tissue of a common freshwater invertebrate (Cherax destructor). The elemental content and isotopic ratios of carbon and nitrogen were compared between paired samples of acidified and control treatments. Our results showed that acidification does not affect the elemental or isotopic values of freshwater SOM. In the marine environment acidification depleted the δ13C and δ15N values of the fine fraction of saltmarsh and δ15N values of mangrove fine SOM. Whilst acidification did not change the elemental content of invertebrate muscle tissue, the δ13C and δ15N values were affected. We recommend to researchers considering using acidification techniques on material prepared for stable isotope analysis that a formal assessment of the effect of acidification on their particular sample type should be undertaken. Further detailed investigation to understand the impact of acidification on elemental and isotopic values of organic matter and muscular tissues is required. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

11.
Stable isotope ratios ((13)C/(12)C and (15)N/(14)N) were measured in royal jelly (RJ) samples by isotope ratio mass spectrometry (IRMS) to evaluate authenticity and adulteration. Carbon and nitrogen isotope contents (given as delta values relative to a standard, delta(13)C, delta(15)N) of RJ samples from various European origins and samples from commercial sources were analyzed. Uniform delta(13)C values from -26.7 to -24.9 per thousand were observed for authentic RJ from European origins. Values of delta(15)N ranged from -1.1 to 5.8 per thousand depending on the plant sources of nectars and pollen. High delta(13)C values of several commercial RJ samples from -20.8 to -13.3 per thousand indicated adulteration with high fructose corn syrup (HFCS) as a sugar source. Use of biotechnologically produced yeast powder as protein source for the adulterated samples was assumed as delta(15)N values were lower, as described for C(4) or CAM plant sources. RJ samples from authentic and from adulterated production were distinguished. The rapid and reliable method is suitable for urgent actual requirements in food monitoring.  相似文献   

12.
A commercial interface coupling liquid chromatography (LC) to a continuous‐flow isotope ratio mass spectrometry (CF‐IRMS) instrument was used to determine the δ13C of dissolved organic carbon (DOC) in natural waters. Stream and soil waters from a farmland plot in a hedgerow landscape were studied. Based on wet chemical oxidation of dissolved organics the LC/IRMS interface allows the on‐line injection of small volumes of water samples, an oxidation reaction to produce CO2 and gas transfer to the isotope ratio mass spectrometer. In flow injection analysis (FIA) mode, bulk DOC δ13C analysis was performed on aqueous samples of up to 100 μL in volume in the range of DOC concentration in fresh waters (1–10 mg C.L–1). Mapping the DOC δ13C spatial distribution at the plot scale was made possible by this fairly quick method (10 min for triplicate analyses) with little sample manipulation. The relative contributions of different plot sectors to the DOC pool in the stream draining the plot were tentatively inferred on the basis of δ13C differences between the hydrophilic and hydrophobic components. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

13.
Honey adulteration is a complex problem which currently has a significant economic impact and undeniable nutritional and organoleptic consequences. This paper describes the development of an effective anionic chromatographic method (HPAEC-PAD) for honey analysis and adulteration detection. The method relies on the use of chemometric methods to process chromatograms in order to achieve a better discrimination between authentic and adulterated honeys by linear discriminant analysis and to quantify adulteration levels by partial least squares analysis. This approach was investigated using honey samples adulterated from 10 to 40% with various industrial bee-feeding sugar syrups. Good results were obtained in the characterization of authentic and adulterated samples (96.5% of good classification) using linear discriminant analysis followed by a canonical analysis. The application of the partial least squares modeling method provided a corresponding linear regression model allowing the percentage of adulteration of new samples to be estimated directly from sample chromatograms.Additionally, a bee-feeding experiment on a small apiary was conducted in order to evaluate the effect of supplying hives with bee-feeding syrups. This practice is specific to the apicultural area. It has been demonstrated that bee-feeding can modify the sugar composition of the produced honey if it is conducted without safeguards.  相似文献   

14.
A mounting body of evidence suggests that changes in energetic conditions like prolonged starvation can be monitored using stable isotope ratios of tissues such as bone, muscle, hair, and blood. However, it is unclear if urinary stable isotope ratios reflect a variation in energetic condition, especially if these changes in energetic condition are accompanied by shifts in dietary composition. In a feeding experiment conducted on captive bonobos (Pan paniscus), we monitored urinary δ(13)C, δ(15)N, total C (carbon), total N (nitrogen), and C/N ratios and compared these results with glucocorticoid levels under gradually changing energy availability and dietary composition. Measurements of daily collected urine samples over a period of 31 days showed that while shifts in urinary isotope signatures of δ(13)C and δ(15)N as well as total C were best explained by changes in energy consumption, urinary total N excretion as well as the C/N ratios matched the variation in dietary composition. Furthermore, when correcting for fluctuations in dietary composition, the isotope signatures of δ(13)C and δ(15)N as well as total C correlated with urinary glucocorticoid levels; however, the urinary total N and the C/N ratio did not. These results indicate for the first time that it is possible to non-invasively explore specific longitudinal records on animal energetic conditions and dietary compositions with urinary stable isotope ratios and elemental compositions, and this research provides a strong foundation for investigating how ecological factors and social dynamics affect feeding habits in wild animal populations such as primates.  相似文献   

15.
由于蜂蜜蜜种多,成分复杂,加之蜂蜜掺假方式繁多,采用传统的方式很难对蜂蜜进行快速准确的鉴别。通过对国内多个地区的蜂蜜进行调研,采集来自全国20个省份多个蜜种的蜂蜜,利用中红外光谱仪对样品进行光谱扫描,采用主成分分析和聚类分析的方法,利用化学计量软件进行模型的建立。该识别模型不仅能较准确地判别蜂蜜是否掺假(准确率为95.36%),还能对添加量在10%以上的掺假方式进行预判,判别准确率为97.78%,符合判别模型的建立要求。利用中红外光谱技术对蜂蜜掺假进行鉴别的方法有效、可行。  相似文献   

16.
A system was developed for the automatic measurements of 13CO2 efflux to determine biodegradation of extra carbon amendments to soils. The system combines wavelength‐scanned cavity ring down laser spectroscopy (WS‐CRDS) with the open‐dynamic chamber (ODC) method. The WS‐CRDS instrument and a batch of 24 ODC are coupled via microprocessor‐controlled valves. Determination of the biodegradation requires a known δ13C value and the applied mass of the carbon compounds, and the biodegradation is calculated based on the 13CO2 mixing ratio (ppm) sampled from the headspace of the chambers. The WS‐CRDS system provided accurate detection based on parallel samples of three standard gases (13CO2 of 2, 11 and 22 ppm) that were measured simultaneously by isotope ratio mass spectrometry (linear regression R2 = 0.99). Repeated checking with the same standards showed that the WS‐CRDS system showed no drift over seven months. The applicability of the ODC was checked against the closed static chamber (CSC) method using the rapid biodegradation of cane sugar – δ13C‐labeled through C4 photosynthesis. There was no significant difference between the results from 7‐min ODC and 120‐min CSC measurements. Further, a test using samples of either cane sugar (C4) or beetroot sugar (C3) mixed into standard soil proved the target functionality of the system, which is to identify the biodegradation of carbon sources with significantly different isotopic signatures. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

17.
We report the first high‐precision characterization of molecular and intramolecular δ15N of nucleosides derived from mammalian DNA. The influence of dietary protein level on brain amino acids and deoxyribonucleosides was determined to investigate whether high protein turnover would alter amino acid 15 N or 13 C values. Pregnant guinea pig dams were fed control diets, or high or low levels of dietary protein throughout gestation, and all pups were fed control diets. The cerebellar DNA of offspring was extracted at 2 and 120 days of life, nucleosides isolated and δ15N and δ13C values characterized. Mean diet δ15N was 0.45 ± 0.33‰, compared with cerebellar whole tissue and DNA δ15N = +4.1 ± 0.7‰ and ?4.5 ± 0.4‰, respectively. Cerebellar deoxythymidine (dT), deoxycytidine (dC), deoxyadenosine (dA), and deoxyguanosine (dG) δ15N were +1.4 ± 0.4, –2.1 ± 0.9, –7.2 ± 0.3, and ?10.4 ± 0.5‰, respectively. There were no changes in amino acid or deoxyribonucleoside δ15N values due to dietary protein level. Using known metabolic relationships, we developed equations to calculate the intramolecular δ15N values originating from aspartate (asp) in purines (pur) or pyrimidines (pyr), glutamine (glu), and glycine (gly) to be δ15NASP‐PUR, δ15NASP‐PYR, δ15NGLN, and δ15NGLY +11.9 ± 2.3‰, +7.0 ± 2.0‰, –9.1 ± 2.4‰, and ?31.8 ± 8.9‰, respectively. A subset of twelve amino acids from food and brain had mean δ15N values of 4.3 ± 3.2‰ and 13.8 ± 3.1‰, respectively, and δ15N values for gly and asp were 12.6 ± 2.2‰ and 15.2 ± 0.8‰, respectively. A separate isotope tracer study detected no significant turnover of cerebellar DNA in the first six months of life. The large negative δ15N difference between gly and cerebellar purine N at the gly (7) position implies either that there is a major isotope effect during DNA synthesis, or that in utero gly has a different isotope ratio during rapid growth and metabolism from that in adult life. Our data show that cerebellar nucleoside intramolecular δ15N values vary over more than 40‰ and are not influenced by dietary protein level or age. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

18.
A total of 117 honeysuckle (Lonicera japonica Thunb.) samples from four major regions of production in China, including Fengqiu in Henan, Pingyi in Shandong, Julu in Hebei, and Xiushan in Chongqing, were analyzed to determine their geographical origin. δ13C, δ15N, and δ18O values were determined by isotope ratio mass spectrometry (IRMS), and the contents of 18 elements (Fe, Mn, Cu, Zn, K, Ca, Mg, Pb, Cd, Cr, As, Hg, Se, Sr, Ni, Co, B, and Mo) were measured by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). Multivariate statistical analysis by analysis of variance (ANOVA), principal component analysis (PCA), and linear discriminant analysis (LDA) were performed. The results showed that there were very significant differences in the stable isotope ratios and elemental concentrations in honeysuckle based on geographical origin, with plants from each region having a unique fingerprint. Discriminant functions were established to distinguish the origin of honeysuckle using suitable indicators including Cd, Cr, As, Hg, Se, Co, Ni, Sr, Fe, δ13C, δ15N, and δ18O. Cross-validated cases of 95.7% were correctly classified.  相似文献   

19.
The study presents a comparison of two phloem sugar extraction methods. The amount of phloem sugar extracted and the carbon isotope composition (δ13C) of the total extracts and of the main phloem compounds separated by high‐performance liquid chromatography (sucrose, glucose, fructose and pinitol) are compared. These two phloem sap extraction methods are exudation in distilled water and a new method using centrifugation, which avoids the addition of any solvent. We applied both extraction methods on phloem discs sampled from 38‐year‐old Pinus pinaster trees in south‐western France throughout the period from June 2007 to December 2008 on different time‐scales: hourly, daily and monthly. We found that the centrifugation method systematically extracted ca. 50% less compounds from the phloem discs than the exudation method. In addition, the two extraction methods provided similar δ13C values of the total extracts, but the values obtained by the exudation method were 0.6‰ more negative than those calculated from the mass balance using the individual constituents. Over the growing season, both extraction methods exhibited lower total sugar content and more 13C‐enriched phloem sap in summer compared with winter values. These findings suggest that both extraction methods can be applied to study the carbon isotope composition of phloem sap, and the centrifugation method has the advantage that no solvent has to be added. The exudation method, however, is more appropriate for the quantification of the amounts of phloem sugars. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

20.
《Analytical letters》2012,45(3):498-507
Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Isotopic Ratio Mass Spectrometry (IRMS) were used in this study to trace heavy metal and isotopic content of soil into the fruit juices. This work presents a preliminary study on the carbon isotope signature and trace metal content investigated on the soil-plant-fruit pulp chain. The samples were collected from Transylvanian areas. Our results for fruit juices are compared with allowable limits for drinking water in the United Kingdom (NS30). The results for soil samples were compared with the maximum value reported for normal range values of natural soils cited by the EEA (European Environment Agency) report. The results obtained for δ13C values on the soil - leaf - fruit pulp chain for grape, pear, and apple samples show depletion in 13C isotope, as the trend of the values reported in literature for the soil–leaf–fruit chain.  相似文献   

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