Intra-muscular and inter-muscular variation in carbon turnover of ovine muscles as recorded by stable isotope ratios

In the case of muscle-based foods, the incorporation of dietary isotopic signals into muscle tissue is a dynamic process and it is not known whether all muscles, or locations within a muscle, have the same isotopic composition. Therefore, an experiment was conducted in which 28 lambs were switched from a control diet to an isotopically distinct experimental diet offered at two different energy allowances (EA). Small, albeit significant, differences were detected in tissue carbon (C) turnover within the muscle Longissimus dorsi. Inter-muscular comparison showed similar C half-lives for four of the five analysed muscles. The results also clearly demonstrated that the EA had a significant impact on intra- and inter-muscular C turnover. The findings of similar tissue C turnover of several muscles sold as meats and the comparable tissue-diet fractionation of the analysed muscles (both within the same EA) will enable scientists to analyse different meat samples according to availability without introducing large biases. However, EA must be considered a factor of uncertainty.     

进样量和信号强度对气相色谱-燃烧-同位素比值质谱测定δ13C和δ15N的影响

采用气相色谱-燃烧-同位素比值质谱（GC-C-IRMS）法对咖啡因化合物和混合体系中特定氨基酸的δ13C和δ15N进行测定,在保证高测定精度和准确度的前提下,探讨GC C IRMS对进样量和信号强度变化的响应特征。分析结果表明,当C质量≥ 1 ng或m/z 44信号≥ 100 mV时,以及N质量≥5 ng或m/z 28信号≥ 100 mV时,咖啡因δ13C和δ15N测定结果的精度（<03‰）和准确度（<02‰）均能够满足实验室测试要求。针对混合体系中氨基酸δ13C和δ15N的测定,GC C IRMS可以在极少的进样量下实现对特定氨基酸色谱峰的有效分离。12种氨基酸δ13C测定结果未表现出对m/z 44信号强度的依赖性（斜率接近0）,其δ13C平均测定精度为056‰;而δ15N测定结果表现出良好的时间稳定性（4天）,与元素分析 稳定同位素比值质谱（EA IRMS）单独测定结果的平均偏差为077‰。     

牛肉中孕酮的气相色谱/燃烧炉/同位素比质谱检测

建立了牛肉中孕酮的气相色谱/燃烧炉/同位素比质谱(GC/C/IRMS)检测方法。牛肉样品用乙腈振荡和超声辅助提取,经Na Cl脱水,有机相离心和旋转蒸发后以Zn Cl2脱脂,然后用LC-C18、LC-Si、LC-NH2固相萃取柱净化,过滤液经半制备液相色谱(Pre-HPLC)的C18柱纯化,最后分析物以GC/C/IRMS系统分析。牛肉中加标外源性孕酮δ13C值为-30.64±0.24‰(n=6),牛肉内源性孕酮δ13C值为-25.70±0.13‰(n=6),单因素方差分析(ANOVA,p值=2.23×10-140.05)显示,内源性孕酮和外源性孕酮的δ13C值存在显著差异性,且牛肉中加标外源性孕酮δ13C值与孕酮标准溶液的δ13C值无差异性。同时,经模拟实验可知,实际样品中内外源性孕酮混合物的δ13C值与外源性孕酮的δ13C值具有同源性。结果表明,本方法特异性和准确性好,GC/C/IRMS是鉴别激素来源的有效工具,该方法填补了国内鉴别激素来源技术空白。     

Characterization of Swiss vineyards using isotopic data in combination with trace elements and classical parameters

The objective of this work was to study methods to check the geographical origin of Swiss wines. Authentic grape samples from the vintages 2000 and 2001 were collected in representative locations, and the wines produced from these samples were subjected to isotopic (²H/¹H_ethanol; ¹⁸O/¹⁶O_{wine water}), elemental (Mn, Al, B, Ba, Ca, Fe, Mg, Na, Rb, Sr, Zn) and FT-IR (ethanol, pH, total acidity, volatile acidity, malic acid, fructose, tartaric acid, lactic acid, succinate, citric acid, glycerol, 2,3-butandiol, dry matter and relative density (d₂₀)) analyses. The results showed that the variables ¹⁸O/¹⁶O_{wine water}, strontium, rubidium, and ethanol%, when considered in a monovariate approach, allowed the best discrimination of the geographical origins of Swiss wines. By using a combination of all variables (multivariate approach), Switzerland was divided in four main production zones with a separation power that has never before been achieved. These zones were defined as Tessin, Valais, Romandie and Alemanique. A fifth zone (Graubünden) could be evidenced in vintage 2001.     

δ18O of Ethanol in Wine and Spirits for Authentication Purposes

Since 1986 the European Union has established official isotopic analysis methods for detecting the illegal addition of sugar and water to wine and to enable geographical traceability. In this paper we investigate the possibility of using analysis of the ¹⁸O/¹⁶O stable isotope ratio (expressed as δ¹⁸O) of ethanol to improve detection of the watering of wine and to determine the origin of ethanol. Sixty‐nine authentic wine samples from all over Italy, 59 spirits from fruit and cereals, 5 chemically synthesized ethanols, one concentrated and rectified must, one beet and one cane sugar, one fresh must, and 6 waters with increasing δ¹⁸O values were considered. Ethanol was recovered by distillation, using a Cadiot spinning band column, following the official OIV methods. The residual water was trapped by storing the distillate for at least 24 h on a molecular sieve. The ¹⁸O/¹⁶O ratio was measured using a pyrolyser interfaced with an isotope ratio mass spectrometer. The δ^‐18O of ethanol is significantly related to the δ¹⁸O of the fermentation water and can be considered as a reliable internal reference. The values ranged from +24‰ to +36‰ in wine (years 2008 to 2012), +10‰ to +26‰ in fruit and cereal distillates, and from –2‰ to +12‰ in synthetic ethanol. The method was shown to be effective in improving detection of the watering of wine and determining the origin of ethanol (from grapes, other fruit, or synthesis), but not in detecting the addition of cane or beet sugar to wine.     

Flash HT和GasBench II-IRMS分析水中氢氧同位素的方法比较

为了建立一种更准确、更快速的水中氢氧同位素比值检测分析方法,采用在线的连续流元素分析仪 稳定同位素质谱仪联用（Flash HT-IRMS）,碳还原高温热转化法和多用途气体制备仪-稳定同位素质谱仪联用（GasBench II-IRMS）水平衡法分析了不同来源水样中的氢氧同位素组成。结果显示,Flash HT和GasBench II-IRMS两种分析系统均能获得较好的氢氧同位素分析测试精密度,分别小于0.5‰（δD）和0.1‰（δ¹⁸O)。对比两种分析系统,Flash HT-IRMS分析系统的重现性和精度均优于GasBench II-IRMS。另外,Flash HT-IRMS分析系统可以实现在线单次分析过程中同时测定水中氢氧同位素组成,而且分析时间短、样品消耗量少,仅需0.1 μL。因此,对于微量水样中氢氧同位素组成的分析,Flash HT-IRMS测定系统更具优势。     

水平衡法与高温转化法在矿泉水氢氧稳定同位素测定中的应用

为了鉴别不同品牌矿泉水标注水源地信息真伪,对11种不同品牌饮用水的氢氧稳定同位素(δD和δ18 O)进行测定。结果表明,水平衡法(GasBench-IRMS)和高温转化法(TC/EA-IRMS)的测定结果一致性较好,两种方法测定6种不同饮用水的δD和δ18 O的平均差异分别为(0.6±1.59)‰和(0.02±0.13)‰。水平衡法需要较长的制备和测定时间,但δD和δ18 O的测定精度明显优于高温转化法。11种饮用水δD和δ18 O变化范围较大,其δD和δ18 O受不同品牌饮用水的水源地降水影响形成明显的地域性。虽然无法区分矿泉水是否由其他类别饮用水伪造,但δD和δ18 O可以为特定区域(如高海拔与沿海地区)以及产地相近的矿泉水水源地鉴别提供依据。