基于Sr稳定同位素和矿物元素的鲍鱼产地溯源技术研究

为探究Sr稳定同位素和矿物元素结合鉴别鲍鱼地理起源的可行性，本试验以辽宁大连、山东长岛、山东荣成及福建连江4个产地皱纹盘鲍(Haliotis discus hannai)为研究对象，利用电感耦合等离子体质谱仪(ICP-MS)测定鲍鱼不同组织(壳肌、裙边、消化腺性腺、外套膜)中⁸⁷Sr/⁸⁶Sr、⁸⁸Sr/⁸⁶Sr和20种矿物元素特征及差异，通过3种化学计量学方法构建鲍鱼产地溯源模型并筛选优质指标。结果表明，4种组织的22种指标(除消化腺性腺Li元素)在4个产地间有显著性差异(P<0.05)；通过主成分分析(PCA)降维处理，22种指标可在一定程度上区分不同产地鲍鱼，但依然有重叠现象；采用两种判别分析方法建立鲍鱼壳肌、裙边、消化腺性腺、外套膜产地判别模型，利用偏最小二乘法判别分析(OPLS-DA)得出4个组织的正确判别率分别为99.0%、97.0%、99.0%和95.5%，利用线性判别分析(LDA)得出4个组织交叉验证的正确判别率分别为97%、97.5%、99.0%和96.0%，两种模型均展现了...     

杨梅中稳定同位素和多元素特征在其产地溯源中的应用

为探讨杨梅稳定同位素与多元素的特征及其产地溯源应用的可能性,采用稳定同位素质谱(EAIRMS)和等离子发射光谱质谱法(ICP-MS)测定杨梅中稳定同位素比率(如δ~(15)N、δ~(13)C、δD和δ~(18)O等)和多元素(如Li、Be、Na、K和Fe等)含量,并结合化学计量学主成分分析(PCA)和线性判别分析(LDA)建立判别模型,对浙江、福建、云南、贵州和江苏等省份的杨梅进行产地溯源技术研究。单因素方差分析(One-way ANOVA)表明,各产地杨梅中稳定同位素比率和其他矿物元素的含量具有一定的地域特征,但并不具有显著性差异,利用单指标无法区分各省份杨梅。PCA分析中,前3个主成分(累计方差贡献率仅为42.77%)的得分分布散点图均有部分重叠,不能有效区分杨梅产地。PCA-LDA方法将所有样本分为浙江类、福建类、其他省类(包括云南、贵州、江苏省样品)3类,利用蒙特卡洛随机法随机产生训练集和测试集分别用于建模和模型准确度验证,经过2 000次的循环计算,该模型对浙江省杨梅判别结果的准确率高达99.6%,福建省杨梅判别结果的准确率为90.3%,其他省份判别结果的准确率为98.4%。综上,利用稳定同位素和多元素检测并结合PCA-LDA法能够初步对杨梅进行产地溯源和判别,具有一定的可行性和应用价值。     

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。     

甜瓜中矿物元素分布特征及其相关调控机制研究

为明确甜瓜不同部位24种矿物元素的分布特征及其相关性,本研究以新疆甜瓜为试材,采用电感耦合等离子体质谱(ICP-MS)测定Cu、Ni、Cr、As、Pb、Cd、Fe、Al、Zn、B、Mn、Sr等24种矿物质元素含量,并分析甜瓜中重金属与其他矿物质元素分布特征及其内在相关性。结果表明,甜瓜中矿物元素含量在瓜皮上的富集大于瓜肉中的富集,重金属与微量元素在甜瓜瓜皮与瓜肉的分布表现为两端含量高,越靠近中间含量越低。常量元素在瓜皮的分布表现为两端含量高,越靠近中间含量越低,而在瓜肉中表现为两端含量低,越靠近中间含量越高。多元相关性分析热感图结果表明,Ni与Mo、Cr与Na、As与Na呈中度负相关,其他V、K、P等元素均与重金属元素呈正相关。研究表明,甜瓜不同部位矿物元素富集水平不同,部分元素与重金属的富集具有协同或拮抗作用,后续可通过调控相关元素降低甜瓜重金属富集水平提高甜瓜安全性。     

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。     

茶叶中同位素与多元素特征及其原产地PCA-LDA判别研究

本研究采用稳定同位素质谱和等离子发射光谱质谱法测定茶叶中同位素比率和多元素含量,并结合主成分分析(PCA)和线性判别分析(LDA)法建立模型,对福建、山东和浙江出产的茶叶,以及浙江余姚、金华和西湖出产的茶叶进行产地溯源判定.结果表明,不同产地的茶叶中稳定同位素δ15N、δ13C、δD、δ180数值范围不同,而且Li、Be和Na等27个矿物元素的含量变化也较大,具有一定的地域特征.PCA法能够区分不同产地的茶叶,但不同产地样本存在部分重合;而采用PCA-LDA法能够有效区分不同产地的茶叶,其中福建、山东和浙江产地的判定准确率为99％,浙江余姚、金华和西湖产地的判定准确率为86％.因此,利用稳定同位素和矿物多元素检测结合PCA-LDA法能够较好进行茶叶产地溯源,具有一定的可行性和应用价值.     

水稻种植模式对水稻籽粒离子组的影响

亚细胞、细胞、器官乃至有机体内所有矿质元素的组合称为离子组。离子组是植物化学元素指纹,能够定量、精准地反映环境因子驱动下植物体产生的无机化学响应。为探求不同种植模式对水稻籽粒离子组的影响,采用大田试验,研究比较了长期常规种植、绿色蛙稻和有机蛙稻3种水稻种植模式水稻籽粒中矿质元素含量的差异和元素间的相关关系,并探讨了土壤中可利用态元素向水稻籽粒中的转移效率。21种元素含量通过高通量元素分析电感耦合等离子体质谱仪(ICP-MS)测定,并利用主成分分析和方差分析等统计方法分别对数据进行综合分析和各元素处理间差异分析。结果表明,各元素在水稻籽粒中的浓度顺序为:KPMgCaMnZnFeCuRbNaBaMoBNiSrAsCrCdSeCoCs。主成分分析结果表明,不同水稻种植模式对水稻籽粒离子组有显著影响,第1主成分占总变量的32.7%,区分了有机和绿色种植模式;第2主成分占总变量的27.1%,将常规种植模式和另外两种模式区分开。不同水稻种植模式对水稻籽粒离子组有显著影响。与常规种植相比,绿色蛙稻模式下籽粒第1主族元素K、Na、Cs、Rb含量显著增加21%、31%、59%、72%,Mn、Cd的含量显著增加23%、441%,B和Cr的含量显著降低63%和51%;有机模式下水稻籽粒中Co、Ni和Cd含量分别增加60%、286%和488%,而Ca、B、Mo、Sr和Cr的含量显著降低38%、60%、20%、27%和96%,而同主族元素间的竞争并未发现。因此,从水稻必需元素吸收角度出发,绿色蛙稻种植模式优于有机和常规种植模式;但绿色和有机蛙稻种植模式对一些非必需元素的吸收也为水稻食品安全带来隐患。因此,科学的养分管理和合理种植结构的调整对保证水稻食品的安全有非常重要的意义和价值。     

基于矿质元素指纹的粉葛产地溯源研究

为明确矿质元素指纹对粉葛产地鉴别的可行性,筛选出鉴别粉葛产地的有效指标,本研究采用电感耦合等离子体质谱仪(ICP-MS)测定陕西、湖北、广西3个地域粉葛和土壤样品中B、Na、Mg、P、K、Ca、Mn、Co、Cu、Zn、Rb、Sr、Mo、Cd、Cs、Ba、La、Ce、Pr、Nd、Sm和Ti 22种矿质元素含量,并结合主成分分析、逐步判别分析和聚类分析对不同地域样品进行分类。结果表明,除B、Cu元素外,其余元素含量在不同地域粉葛间均存在显著差异(P<0.05);不同地域间粉葛矿质元素含量表现出独有的地理指纹特征,经逐步判别分析筛选出Mg、P、Co、Rb和Sr 5种元素,经回代检验和交叉检验的整体判别率分别为97.7%和93.0%;相关性分析结果表明,粉葛中Rb、Sr和Ti元素含量与对应土壤中的元素呈极显著正相关(P<0.01)。因此,矿质元素指纹结合多元统计分析能够在一定程度上实现不同产地粉葛的鉴别,这为粉葛产地溯源的可行性提供了技术支持。     

浦江葡萄同位素与矿物元素特征及地理标志保护模型构建

为探讨稳定同位素与矿物元素在葡萄产地鉴别上的可行性,本研究分别从浦江、浙江其他产地(慈溪、温岭)、上海和安徽4个不同产地采集代表性葡萄样品;通过稳定同位素比率质谱(EA-IRMS)元素分析仪和电感耦合等离子体质谱(ICP-MS)测定其同位素比率与矿物质元素含量,结合化学计量学统计工具对浦江葡萄开展原产地判别研究.结果表...     

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.     

Distribution of 32 Elements in Organic Surface Soils: Contributions from Atmospheric Transport of Pollutants and Natural Sources

Data are presented for 32 elements (Li, Be, B, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ge, As, Rb, Sr, Y, Zr, Mo, Ag, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Hf, Tl, Pb, Bi) in organic-rich surface soils in Norway, based on samples from 464 sites. By considering geographical distributions based on isopleths, results from factor analysis, and ANOVA of median values from 12 different geographical regions, the contributions from natural and anthropogenic sources are estimated for each element. Long-range atmospheric transport of pollutants from areas out of Norway is a dominant source for Cd, Sb, Pb, and Bi and also a strongly contributing factor for Zn, As, Mo, and Tl. Also V, Ni, Cu, and Ge are somewhat affected, but other factors dominate for these elements. Local point sources of pollution provide significant contributions to soil concentrations of Ni, Cu, Zn, As, Mo, and Cd. The local bedrock is the overriding source of Li, Be, Ti, V, Cr, Mn, Rb, Zr, Cs, Ba, REE, Hf, and probably of Ge and Ag. Surface enrichment by root uptake in plants and return to the soil surface by decaying plant material is particularly evident for Mn, Zn, Rb, Cs, and Ba. These elements show no clear difference between south and north in the country, indicating that their plant uptake does not depend on latitude. In the case of B and Sr, atmospheric deposition of marine aerosols is an important source. Rb and Ag, and to a less extent Mn, Ga, and Ba, appear to be depleted in soils near the coast presumably due to cation exchange with airborne marine cations.     

Trace elements in surface soils from the mineralized area of Madison County, Missouri, U.S.A.

Duplicate, bulked surface soil samples, from sites 10m apart, were collected at 97 locations 1000 m apart on a regular grid measuring 8x11 km. Data were obtained for Ag, Ba, Be, Cd, Co, Cr, Cu, Li, Mn, Ni, Pb, V and Zn. One field sample was a good predictor of its nearby duplicate for Co, Cu, Ni and Pb, satisfactory for Ba, Be, Cr, Mn and Zn, but poorer for Cr, Li and V. Maps of the variation in precision of the field samples did not reveal any association between abandoned mine sites and high variability. The median coefficient of variation for trace elements in the field duplicates was between 8 and 19.5%. The duplicated field data were averaged to yield a mean soil metal concentration at each sample location. Concentrations of Ba, Be, Cr, Li, Sr and V were comparable with other published values for similar soils in Missouri. Concentrations of Co, Cu, Mn, Ni, Pb and Zn were higher which was explained by pollution from mining activities. A graphical technique was used to calculate background levels for metals in the second group. Samples of forest litter were collected at 12 locations: Ag, Ba, Cd, Mn, Sr and Zn concentrations were higher in the litter whereas Li and V concentrations were higher in the subjacent mineral soil. Computer isoline maps of the distribution of elements revealed an association between areas of high soil Cu, Co, Ni, Pb and Zn and abandoned mines or mineralized rocks.     

Effects of fertilization, crop year, variety, and provenance factors on mineral concentrations in onions

Mineral concentrations of onions (Allium cepa L.) grown under various conditions, including factors (fertilization, crop year, variety, and provenance), were investigated to clarify how much each factor contributes to the variation of their concentrations. This was because the mineral concentrations might be affected by various factors. The ultimate goal of this study was to develop a technique to determine the geographic origins of onions by mineral composition. Samples were onions grown under various conditions at 52 fields in 18 farms in Hokkaido, Japan. Twenty-six elements (Li, Na, Mg, Al, P, K, Ca, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Mo, Cd, Cs, Ba, La, Ce, Nd, Gd, W, and Tl) in these samples were determined by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. Fertilization conditions and crop years of onions caused variations of P, Ni, Cu, Rb, Sr, Mo, Cs, and Tl concentrations in onions; different onion varieties also showed variations in numerous element concentrations. However, the variations of mineral compositions of onions by these factors were smaller than the differences between production places with a few exceptions. Furthermore, Na, Rb, and Cs in group IA of the periodic table, Ca, Sr, and Ba in group IIA, and Zn and Cd in group IIB showed similar concentration patterns by group; this result demonstrated that elements in the same periodic groups behaved similarly in terms of their absorption in onions.     

Accumulation and distribution pattern of macro- and microelements and trace elements in Vitis vinifera L. cv. Chardonnay berries

This paper describes the accumulation pattern of 42 mineral elements in Vitis vinifera L. berries during development and ripening and their distribution in berry skin, seeds, and flesh around harvest time. Grape berries were sampled in two different vineyards with alkaline soil and analyzed using a ICP-MS. Although elemental amounts were significantly different in the grapes from the two vineyards, the accumulation pattern and percentage distribution in different parts of the berries were generally quite similar. Ba, Eu, Sr, Ca, Mg, Mn, and Zn accumulate prior to veraison. Al, Ce, Dy, Er, Ga, Gd, Ho, La, Nd, Pr, Sm, Sn, Zr, Th, Tm, U, Y, and Yb accumulate mainly prior to veraison but also during ripening. Ag, As, B, Cd, Cs, Cu, Fe, Ge, Hg, K, Li, Na, P, Rb, Sb, Se, and Tl accumulate progressively during growth and ripening. With regard to distribution, Ba, Ca, Eu, Fe, Mn, P, Sr, and Zn accumulate mainly in the seeds, Al, B, Ga, Sn, and the rare earths analyzed, except for Eu, accumulate mainly in the skin, and Ag, As, Cd, Cs, Cu, Ge, Hg, K, Li, Mg, Na, Rb, Sb, Se, Th, Tl, U, and Zr accumulate mainly in the flesh. A joint representation of the accumulation and distribution patterns for the elements in the berry is also given.     

Multielemental analysis and classification of amaranth seeds according to their botanical origin

The characterization of amaranth seeds (Amaranthus spp.) was developed for Amaranthus hypochondriacus, Amaranthus cruentus, and Amaranthus dubius. The elemental concentrations were determined by inductively coupled plasma optic atomic spectroscopy. Pattern recognition methods were used for the characterization of seed samples: nonsupervised methods included principal components analysis and cluster analysis; supervised methods were linear discriminant analysis and partial least squares discriminant analysis (PLS-DA). Informed are the concentrations of the following elements: Ag, Al, Ba, Ca, Co, Cr, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Ni, P, S, Sr, V, Zn, and Zr. The lowest mineral content was found in A. hypochondriacus, and the highest one was found in A. dubius. For the classification, selected variables for all multivariate methods were Ba, Cr, Li, Mn, Ni, S, and Sr. Nonsupervised methods allowed us to distinguish between the three species of amaranth; however, PLS-DA supervised methods showed the best prediction ability.     

环洞庭湖区两种典型红土理化特性比较研究

通过环洞庭湖区两种典型成因红土的野外勘察与取样、室内磁化率、粒度、微量元素(Li、Rb、Sr、Ba)分析,进行两种不同成因的红土理化性质的比较。研究结果表明,风成成因的红土粒度比基岩风化成因红土明显较细,风成成因红土以粉砂为主,基岩风化型红土为砂和粉砂为主;两种成因红土受到长江中游地区高温高湿的气候条件影响,磁化率均显示为低值,明显低于黄土高原黄土和长江下游下蜀黄土;微量元素Li/Ba、Rb/Sr比值显示为高值,显著高于黄土高原黄土和长江中下游地区下蜀黄土,表明两种红土均经历了强烈的风化淋溶过程,但基岩风化型红土的风化成壤强于风成成因红土,可能基岩风化型红土经历了更长的风化成壤过程。     

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.     

Presence of war related elements in dandelion (Taraxacum officinale) as a possible consequence of military activities in east Croatia

This is the first study on concentrations of war related elements in dandelion from war effected areas of Croatia. Previous research done on human subjects, soil and water has shown abnormalities in distribution of war associated metals and metalloids in war affected areas compared with peacetime locations. Dandelion, as wide spread perennial herb, is considered as very useful plant in determination of trace elements pollution in various ecosystems. Aim of the research was to try to determine whether concentrations of war related elements (Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Ni, P, Pb, Sb, Si, Sr, U, V and Zn) concentrations in dandelion (Taraxacum officinalle) samples in areas of high intensity of combat activities differ from areas of low intensity of combat activities, and to clarify possible contamination in dandelion as an indicator (and edible) plant with it's role in food chain. Leaves of the dandelion were taken at locations (28 locations at 11 settlements) were divided into two major subgroups: high and low intensity of combat activities, at the locations of major explosions, former minefields, army trenches?…?Analysis was done using ICP-MS and data was interpreted using Mann Whitney test and PCA. Results have shown that there is difference in concentration of war related elements among different locations, with generally, higher concentrations of war elements in war areas compared with control group. Maximum concentrations of As, B, Ba, Cd, Co, Cr, Cu, Li, Mg, Ni, P, Pb, Sb, Si, Sr, U, V and Zn were higher in areas of high intensity of combat activities. When results are compared with similar researches, overall presence of metals and metalloids is legally acceptable, however, there are differences in concentrations between war and peacetime locations.     

Barium and Other Trace Metals as Indicators of Vehicle Emissions

In the Siena urban environment, unwashed Q. ilex leaves had a significantly higher Al, Ba, Cr, Fe, Mn, Na, Ni, Pb, Ti, and V content than samples from a neighbouring Mediterranean maquis. Significant relationships between element pairs indicated both the presence of metals emitted by motor vehicles and lithophilic elements, presumably from soil particles, resuspended by wind or turbulence generated by traffic. In order to minimize the effects of soil dust contamination and to seek clues to the metal sources, the estimated substrate contribution was subtracted from the raw concentrations of elements in Q. ilex leaves. Normalization for local soil composition confirmed that automotive emissions are the principal source of pollution in Siena. On the basis of a very significant relationship between normalized concentrations of Pb and Ba and the presence of the latter element in diesel and unleaded gasoline, Ba was recognized as a valuable tracer for vehicle emissions, in the place of Pb.