贵州名优茶与产地土壤矿质元素相关性及其溯源影响的研究

为探究贵州省名优茶产地不同深层土壤对茶叶矿质元素溯源效果的影响,以土壤-茶叶的多矿质元素法结合主成分分析(PCA)、反向传播(BP)神经网络法、逐步线性判别分析(SLDA)对茶叶产地进行溯源。结果显示,不同产地的茶叶和土壤具有独特的矿质元素指纹,茶叶中Fe、Mn、K、Ca、Mg、Cu的含量与土壤中对应元素含量显著相关(P<0.05),以这6种矿质元素含量结合PCA可有效区分茶叶的地理起源;不同深层土壤对茶叶产地的溯源有不同影响,通过SLDA法、BP神经网络法明确了以60~80 cm的土层进行产地溯源的效果最优,产地溯源验证判别率分别为98.5%(SLDA法)和100%(BP神经网络法),并基于SLDA法确定了Zn、Cu、P、Mn、Fe、Mg和K 7种元素构建的贵州名优茶产地溯源模型。此外,研究发现茶叶产地溯源几乎不受茶树品种的影响。本研究结果为贵州省名优茶矿质元素指纹图谱的建设及土壤-茶叶产地溯源的关系研究提供了理论依据。     

不同/相同水系中华绒螯蟹元素“指纹”的产地差异性

为了开发有效的中华绒螯蟹产地判别技术,本试验以辽河水系和长江水系4个不同产地(盘锦、洪泽湖、兴化和梁子湖)的中华绒螯蟹(Eriocheir sinensis)为研究对象,统一使用第三步足为试样,研究了Na、Mg、Al、K、Ca、Mn、Fe、Cu、Zn、Sr、Ba、Tl等12种元素"指纹"的产地差异性。结果显示,4个产地中华绒螯蟹间Na、Mg、Al、K、Mn、Fe、Cu、Sr、Ba、Tl含量差异达到极显著水平(P0.01)。主成分分析显示出与各产地关联较大的元素分别为:盘锦,Fe、Mn、Al、Na、Cu、Ba、Zn和K;洪泽湖,Mg、Sr和Tl;兴化,Ca、Mg、Sr、Tl、K和Zn;梁子湖,Fe、Mn、Al、Na、Cu、Ba。判别分析所得到的4产地正确判别率达100%。本研究进一步证实了"元素"指纹对不同/相同水系中华绒螯蟹产地判别均具有实用潜力,为今后的大范围应用提供新的理论依据。     

基于矿物元素指纹图谱的黑龙江黄豆产地溯源

该研究探讨了矿物元素指纹分析技术对黑龙江黄豆产地溯源的可行性,筛选出判别黑龙江黄豆产地溯源的有效指标。利用电感耦合等离子体质谱仪(inductively coupled plasma mass spectrometry,ICP-MS)测定来自齐齐哈尔和北安2个地域50份黄豆样品中52种矿物元素的含量,并对数据进行了方差分析、主成分分析和判别分析。研究表明,46种矿物元素含量在地域间存在显著差异,通过逐步判别分析筛选出8项元素指标建立黄豆产地判别模型,所建立的模型对黄豆产地整体交叉检验判别率为95.7%。As、Ru、Gd含量在黄豆与土壤间呈显著正相关(P0.05),Tb含量在黄豆与土壤间呈极显著正相关(P0.01),由4种元素建立的判别模型对产地判别准确。因此,上述元素是黄豆矿物元素产地鉴别较可靠的指纹信息指标。     

基于矿物元素指纹的羊肉产地溯源技术

为探讨矿物元素指纹对羊肉产地溯源的有效性,找寻表征地域特性的元素指标,利用电感耦合等离子体质谱仪分析中国内蒙古自治区阿拉善盟、锡林郭勒盟和呼伦贝尔市3个牧区,及重庆市和山东省菏泽市2个农区脱脂羊肉和土壤样品中4种常量元素(K、Ca、Na、Mg)和13种微量元素(V、Mn、Fe、Cr、Ni、Cu、As、Be、Sb、Zn、Se、Ba、Tl)的含量,对其进行方差分析、相关分析和判别分析。结果表明,羊肉中矿物元素含量组成在地域间有明显差异,农区元素含量普遍高于牧区。脱脂羊肉中Ca、Zn、Be、Ni、Fe、Ba、Sb、Mn和Se9种元素含量的地域差异与土壤相关,它们对农牧区的正确判别率达90%以上,对5个地域的正确判别率在70%～100%之间。利用羊肉中矿物元素指纹分析技术可鉴别和追溯羊肉的产地来源,为羊肉及其他食品的产地溯源研究提供方法参考。     

基于稳定同位素和矿质元素的决明子产地特征与溯源判别研究

为了更加精确高效地对中药决明子产区进行判别,本研究采用稳定同位素比质谱(IR-MS)和电感耦合等离子体质谱(ICP-MS)技术分别检测不同产地决明子稳定同位素比值和多种矿质元素含量特征,并结合化学计量学模型主成分分析(PCA)和人工神经网络(ANN)对决明子产地进行判别。方差统计结果表明,在优质产区(浙江新昌)决明子区别于普通产区决明子方面,19种矿质元素含量存在显著差异(P<0.05);PCA分析(同位素+矿物元素)显示,前2个主成分累计方差贡献率为45.23%,且该模型可显著区分道地产区决明子;ANN模型分析对浙江新昌产区的决明子判别正确率高达100%,且产地判别总体正确率高于90%。以上结果表明,稳定同位素比值和矿质元素含量结合化学计量学模型分析可有效判别决明子不同产区。本研究结果为决明子产地溯源提供了一种新的方法。     

关中东部全新世黄土——古土壤序列微量元素分布特征及意义

X-荧光光谱仪、磁化率仪和激光粒度仪对尧禾村(YHC)全新世黄土-古土壤序列的微量元素、磁化率、粘粒(<5μm)含量进行了测量。将磁化率曲线、粘粒曲线、Rb/Sr变化曲线和Ba/Sr变化曲线进行了对比分析发现:YHC剖面的磁化率曲线、粘粒曲线、Rb/Sr曲线和Ba/Sr曲线具有高度的同步同向变化趋势,可很好的指示研究区域内全新世的气候变化。而元素的含量变化是该区域气候变化的结果,其中Pb元素在黄土中的含量明显高于古土壤层,属于淋失性元素。Mn、Cr、Cu、Zn、Co、Ti元素在古土壤含量高于黄土层,属于富集性元素。     

加工方式对木姜叶柯甜茶速溶粉稳定同位素指纹的影响

为了研究加工方式对甜茶速溶粉稳定同位素指纹的影响,进而验证δ¹³ C、δ¹⁵ N用于甜茶及其速溶粉产地溯源的可行性,本试验分别以烘箱烘干和微波杀青2种烘干方式制备甜茶老叶和嫩叶4种原料,采用热水浸提、离心并干燥(喷雾干燥和冷冻干燥)的方法制备甜茶速溶粉,得到喷雾干燥速溶粉(ITSD)、冷冻干燥速溶粉(ITFD)和速溶粉副产物(ITBP)三类加工样品,并采用元素分析-同位素比率质谱仪(EA-IRMS)测定样品中的δ¹³C、δ¹⁵N值。结果表明,不同产地(湖南、四川、江西)甜茶杀青嫩叶δ¹³C、δ¹⁵N值存在显著差异(P<0.05),烘箱烘干法与微波杀青法制得的原料茶δ¹⁵N值存在差异,且 δ¹³C、 δ¹⁵N值在速溶粉加工产品(原料、速溶粉及副产物)间存在显著差异(P<0.05),但不同烘干原料制备的所有样品δ¹³ C、δ¹⁵N值之间存在极显著相关(P<0.01)。本研究结果为基于δ¹³C、δ¹⁵N溯源指纹进行甜茶原料或速溶茶粉的产地溯源提供了理论依据。     

青海高原油菜蜜稳定同位素产地特征与环境响应机制研究

为探究青海油菜蜜稳定同位素特征及影响因素,本研究利用元素分析-稳定同位素比率质谱(EA-IRMS)建立了油菜蜜总δ¹³C值及其内源蛋白质δ¹³C、δ¹⁵N、δ²H、δ¹⁸O值的检测方法,分析了青海不同产地、不同年份油菜蜜及其内源蛋白质同位素特征差异,探讨了油菜蜜内源蛋白质稳定同位素与产地环境之间的关系。结果表明,青海省区域内油菜蜜内源蛋白质的δ¹³C值和δ¹⁵N值较稳定,不同产地、不同年份间无显著差异;不同年份油菜蜜内源蛋白质的δ¹⁸O值差异极显著(P<0.01),不同产地油菜蜜内源蛋白质的δ¹⁸O值及δ²H值均存在极显著差异(P<0.01)。在环境影响因素中,油菜蜜内源蛋白质δ¹⁸O值与生产季节降水量呈显著负相关(r=-0.822,P<0.05)。本研究结果为青海高原油菜蜜真实性鉴别与产地溯源研究提供了理论依据与技术支撑。     

用微量元素对东北大米产地识别的技术

为探讨元素指纹分析技术对东北三省大米产地识别的可行性,筛选出可以区分不同产地大米的标志元素,该研究采用电感耦合等离子体质谱（Inductively Coupled Plasma Mass Spectrometry,ICP-MS）测定东北三省主要水稻产区土壤-作物籽实中Li、B、Be等23种微量元素含量,利用相关分析、方差分析、偏最小二乘回归分析等多种分析方法对不同产地大米及土壤中微量元素含量进行分析,建立识别东北三省大米产地的判别模型。结果表明：大米中Mo、Zn含量与土壤中Mo、Zn含量呈显著正相关（P<0.01）;3个省份大米中Ga、Pb、Sr、Zr、Ba元素分布表现出一致性,而另外18种元素表现出显著差异性（P<0.05）。对18种显著差异元素建立产地识别模型,发现正交偏最小二乘回归分析和多层感知器神经网络分析建立的判别模型能较好地对东北三省大米进行有效区分和识别,多层感知器神经网络分析中整体检验组的综合正确判别率为96.3%;在Fisher判别分析中利用逐步判别法筛选出的7种元素建立的判别模型能有效识别东北三省大米产地,判别正确率为93.8%。研究表明基于微量元素含量特征能够对东北三省大米产地进行有效识别,可为保护地区特色产品提供技术参考。     

青海黑青稞营养及活性成分分析与评价

为明确青海不同品种黑青稞的营养及化学成分含量,筛选优异种质资源,本研究开展了12种黑青稞营养及化学成分分析与评价。结果表明,参试黑青稞蛋白、总淀粉、直链淀粉、粗脂肪、粗纤维、灰分、β-葡聚糖含量在部分品种间存在显著差异(P<0.05),黑青稞具有较高含量的蛋白质(12.19%~14.07%)、纤维(2.13%~3.64%)、直链淀粉(18.96%~25.94%)和β-葡聚糖(3.91%~7.50%);参试黑青稞中Ca、K、Zn含量存在品种间显著差异(P<0.05),其余测定的矿物质含量存在部分品种间显著差异(P<0.05),其中K(581.42 mg·100g^-1)、Mg(171.90 mg·100g^-1)、Ca(90.28 mg·100g^-1)、Na(17.33 mg·100g^-1)含量较高;参试黑青稞蛋白中总必需氨基酸含量平均值为319.90 mg·g^-1(接近WHO/FAO推荐值360 mg·g^-1),第一限制性氨基酸为赖氨酸,第二限制性氨基酸为甲硫氨酸和胱氨酸,第三限制性氨基酸为苏氨酸;参试部分黑青稞品种的总酚、游离酚、结合酚、总黄酮、游离黄酮、结合黄酮及花色苷含量存在显著差异(P<0.05);主成分筛选出950、Z536、Z533黑青稞综合品质较优,聚类分析将12个黑青稞品种分为4类,第1类蛋白质、多酚、黄酮、β-葡聚糖含量较高;第2类花色苷、氨基酸含量较高;第3类纤维含量较高;第4类淀粉含量较高。本研究结果为黑青稞营养功能品质评价及加工利用奠定了基础,也为特异青稞资源的筛选提供了参考。     

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.     

Use of chemical profiling to differentiate geographic growing origin of raw pistachios

The objective of this study was to demonstrate the feasibility of chemical profiling methods combined with multivariate methods to differentiate the geographical growing regions of pistachios (Pistachia vera). Elemental analysis (Ba, Be, Ca, Cu, Cr, K, Mg, Mn, Na, V, Fe, Co, Ni, Cu, Zn, Sr, Ti, Cd, and P) of pistachios samples was performed using inductively coupled plasma atomic emission spectrometry. Analysis of inorganic anions and organic acids (selenite, bromate, fumarate, malate, selenate, pyruvate, acetate, phosphate, and ascorbate) of pistachio samples was performed using capillary electrophoresis. Bulk carbon and nitrogen isotope ratios were performed using stable isotope MS. There were nearly 400 pistachio samples analyzed from the three major pistachio growing regions: Turkey, Iran, and California (United States). A computational evaluation of the trace element data sets was carried out using statistical pattern recognition methods including principal component analysis, canonical discriminant analysis, discriminant analysis, and neural network modeling. Several linear discriminant function models classified the data sets with 95% or higher accuracy. We report the development of a method combining elemental analysis and classification techniques that may be widely applied to the determination of the geographical origin of foods.     

Multi-element analysis of South African wines by ICP-MS and their classification according to geographical origin

Wines from three important wine-producing regions, Stellenbosch, Robertson, and Swartland, in the Western Cape Province of South Africa, were analyzed by ICP-MS and the elemental composition used in multivariate statistical analysis to classify the wines according to geographical origin. The method is based on the assumption that the provenance soil is an important contributor to the trace element composition of a wine. A total of 40 elements were determined in 40 wines. Of these, 20 elements: Li, B, Mg, Al, Si, Cl, Sc, Mn, Ni, Ga, Se, Rb, Sr, Nb, Cs, Ba, La, W, Tl, and U showed differences in their means across the three areas. In a stepwise discriminant analysis procedure, functions based on linear combinations of the log-transformed element concentrations of Al, Mn, Rb, Ba, W, and Tl were generated to correctly classify wines from each region. In an alternative approach, a pairwise discriminant analysis procedure, not previously used in wine provenance studies, was tested. In this procedure, the classification was done in three steps, with each step classifying a wine as coming from a certain region or not. The combination of elements characterizing wines from a particular region was different in each region. The discriminant functions were based on the following elements: Al, Mn, Rb, Ba, and W for Stellenbosch; Se, Rb, Cs, and Tl for Robertson; and Al, Mn, Rb, Sr, Ba, and Tl for Swartland. After this procedure, the classification of the wines into one of the groups was 100% successful.     

Multielement analysis of Canadian wines by inductively coupled plasma mass spectrometry (ICP-MS) and multivariate statistics

Trace element fingerprints were deciphered for wines from Canada's two major wine-producing regions, the Okanagan Valley and the Niagara Peninsula, for the purpose of examining differences in wine element composition with region of origin and identifying elements important to determining provenance. Analysis by ICP-MS allowed simultaneous determination of 34 trace elements in wine (Li, Be, Mg, Al, P, Cl, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Mo, Ag, Cd, Sb, I, Cs, Ba, La, Ce, Tl, Pb, Bi, Th, and U) at low levels of detection, and patterns in trace element concentrations were deciphered by multivariate statistical analysis. The two regions were discriminated with 100% accuracy using 10 of these elements. Differences in soil chemistry between the Niagara and Okanagan vineyards were evident, without a good correlation between soil and wine composition. The element Sr was found to be a good indicator of provenance and has been reported in fingerprinting studies of other regions.     

Determining the geographic origin of potatoes using mineral and trace element content

To characterize potatoes according to their geographic origin and variety, 10 mineral and trace elements (Mg, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Cd, and Ba) were determined in Italian potato samples. The data collected were successively elaborated using statistical techniques, namely, linear discriminant analysis (LDA). LDA was able to classify and discriminate the potatoes from Fucino both from those of other areas of Italy and from those of the four provinces of Abruzzo. A net separation between the Fucino potatoes and those of the other areas of Abruzzo was observed. LDA discriminated also the three potato varieties cultivated in the Fucino basin. The presence of these 10 mineral and trace elements was a good means for establishing the geographical place of origin of Fucino potatoes.     

西瓜稳定同位素与多元素特征分析及其产地溯源技术研究

本研究旨在利用稳定同位素与多元素分析技术结合化学计量学统计方法,开发不同省份西瓜产地溯源新策略。通过元素分析仪-同位素比质谱和电感耦合等离子质谱测定新疆、山东、广西、海南等产地的73份西瓜样本的碳、氮、氢、氧稳定同位素比值(δ¹³C、δ¹⁵N、δ²H、δ¹⁸O)与16种矿物元素含量(Na、K、Ca、Sr、Ba、Pb等)。单因素方差统计分析表明,δ¹³C、δ¹⁵N、δ²H、δ¹⁸O值与Na、K、Ca、Cr、Mn等元素含量特征在各省份西瓜样本间具有显著差异(P<0.05),但单一变量不足以将4个产地的西瓜完全进行区分。通过典则判别分析进行多变量统计分析,提取特征变量,构建线性判别函数,可以实现4个省份西瓜样本的原产地区分。该方法对新疆、山东、海南样本判别准确度高达100%,而广西样本判别率为71.4%,误判为海南产地概率为28.6%。由此可知,该策略能够实现大尺度地理空间的西瓜产地溯源,为其产地标识确证和优质品牌保护提供了有效的技术手段。     

新疆红枣营养品质与稳定同位素及矿物元素特征产地溯源比较

为开发基于营养品质、稳定同位素及矿物元素分析的不同产地新疆红枣地理标志产品溯源新方法,本研究采集了2016年新疆不同产区(若羌、和田、阿克苏、麦盖提等15个县市)97个红枣种植地块的50份灰枣和47份骏枣样本,测定其果肉中13类营养品质指标(蛋白质、还原糖、自由氨基酸、总黄酮等),稳定碳、氮、氢、氧同位素比率(δ¹³C、δ¹⁵N、δ²H和δ¹⁸O)及21种微量矿物元素含量(Na、Mg、K、Fe和Zn等)用于其产地溯源分析与建模。采用单因素方差(one-way ANOVA)法比较不同产区间营养品质、稳定同位素比率及矿物元素特征的差异,利用偏最小二乘判别分析(PLS-DA)分别对两类红枣内在品质特征建立产地判别模型,对比其溯源准确度。结果表明,红枣稳定同位素及矿物元素产地特征差异比营养品质特征更明显,溯源判别准确度得到明显提升。灰枣和骏枣营养品质参数建模总体判别准确度分别为86.00%和85.11%,稳定同位素及矿物元素参数判别准确度分别为94.12%和95.74%,且两种地理标志保护的红枣品牌(若羌灰枣和和田玉枣)产地判别准确度高达100%,而其他产地误判为这两个产地红枣的概率为0%。因此,该策略有望作为新疆红枣产地溯源与地理标志农产品保护的可靠技术。     

Granitic weathering: a Brazilian study

Chemical and mineral studies were carried out on weathered materials from six profiles developed on granites located in different areas of Brazil. Quartz and K-feldspar are the most abundant minerals overall. Kaolinite is the most common secondary mineral and is principally a feldspar weathering product. Mica breakdown is associated with smectite formation in semi-arid regions. In more humid regions mica weathering products include interlayered mica-vermiculite, vermiculite and kaolinite. Changes in the concentrations of Si, Al and K reflect the weathering behaviour of quartz, kaolinite, K-feldspar respectively, although K mobilities sometimes appear to be governed by processes related to the formation of secondary minerals. Ca and Mg are the first elements to exhibit depletion and their removal rates are very fast relative to K. P is also among the most mobile elements. Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba and Pb concentrations were measured. The first row transition metals are the most depleted. Rb and Sr are retained relative to Na, Mg, and Ca, and Ba accumulates as weathering proceeds. Y, Zr, Nb and Pb concentrations show little variation. The conclusion is that the factors controlling deep leaching are complex and the common notion that weathering rates are higher at lower latitudes should be reassessed.