7种单花蜂蜜中矿物元素的测定及蜜种特征研究

目的 采用电感耦合等离子体质谱仪(ICP-MS)测定蜂蜜中K、Ca、Na、Mg、Fe、Sr、Mn和Cu共8种元素矿物元素含量, 并建立将其用于蜜种特征评价的方法。方法 7种中国不同地理位置的单花蜂蜜经微波消解后, 由电感耦合等离子体质谱仪测定, 以Sc、Ge、In和Bi 为内标元素在线校正, 采用外标法定量。结果 本方法中各元素线性关系良好, 相关系数在0.9990~1.0000之间, 检出限在 0.01~0.2 mg/kg之间, 不同添加水平下的回收率在88.0%~120.0%范围内, 相对标准偏差小于5%。椴树蜜和枣花蜜含有较丰富的K, 荞麦蜜中的Mn和Cu含量最高, 枣花蜜中的Ca、Na、Mg和Sr含量最高, 葵花蜜中的Ca和Mg含量仅次于枣花蜜中的值, 荆条蜜中的Fe含量最高, 洋槐蜜和油菜蜜中的矿物元素水平相对较低。通过计算各元素与Mg含量的比值可以建立蜂蜜元素指纹图谱, 从而实现不同蜂蜜的依次鉴别。结论 该方法能够快速准确地测定不同蜂蜜中的矿物质元素含量, 有助于评价不同蜂蜜的特征及营养价值, 并对蜜源植物和产地的真实性进行判定。     

Contribution to the study of avocado honeys by their mineral contents using inductively coupled plasma optical emission spectrometry

Avocado honey samples were analyzed by inductively coupled plasma optical emission spectrometric. First, the botanical origin of the honeys was confirmed by melissopalynological analysis. Twenty-four minerals were quantified for each honey sample. The elements Al, Ba, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, S, Se, Si and Zn were detected in all samples; seven elements were very abundant (Ca, K, Mg, Na, P, S and Si), six were not abundant (Al, Cu, Fe, Li and Zn) and 11 were trace elements (As, Ba, Cd, Co, Cr, Mo, Ni, Mo, Pb, Se, Sr and V).     

Minor and trace elements in different honey types produced in Siena County (Italy)

The concentrations of 23 chemical elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Sb, Se, Sr, Th, Tl, U, Zn) were determined in 51 honey samples of different botanical origin produced in Siena County (Italy). K, Ca, Na and Mg were the most abundant elements, with mean contents of 1195, 257, 96.6 and 56.7 mg/kg, respectively. The Fe, Zn and Sr contents generally ranged from 1 to 5 mg/kg. Except for Ba, Cu, Mn and Ni, the trace element contents were below 100 μg/kg. The analytical data indicated a good level of quality of the honeys, especially with regard to the concentrations of toxic trace elements, such as As, Cd, Pb and Sb, and suggested a significant influence of the botanical origin on the element composition. Some local geological and geochemical features also seemed to affect the chemistry of the honey.     

Comparison of mineral and trace element contents in onion cultivars (Allium cepa L.)

BACKGROUND: P, Na, K, Ca, Mg, Fe, Cu, Zn, Mn and Se were determined in five traditional onion cultivars (Allium cepa L.) from Tenerife (Guayonje, San Juan de la Rambla, Carrizal Alto, Carrizal Bajo and Masca) and a commercial cultivar (Texas Early Grano 502) grown under the same agronomic, soil and climatic conditions in order to find out differences between these cultivars. RESULTS: Carrizal Alto presented the highest K content and lowest P, Na, Fe, Zn, Mn and Se. Texas cultivar had the highest P, Mg and Se contents, and the lowest contents of Ca, Cu and Mn. There were clear differences in the mineral and trace elements contents between the two seed origins of San Juan de la Rambla cultivar. Many correlations were found between the parameters analyzed, emphasizing the Fe? Zn and Ca? Mn correlations. CONCLUSION: There were differences in the mineral and trace element composition between the onion cultivars. The environment and agronomic practices could affect the genetic information of the seeds, determining changes in the mineral and trace element composition. Linear discriminant analysis is a useful tool for differentiating onion samples according to cultivar and seed origin. Copyright © 2008 Society of Chemical Industry     

加工精度对大米矿物元素指纹信息影响研究

矿物元素指纹分析技术已逐渐被应用到农产品的产地溯源中,大米中的矿质元素指纹信息的稳定性不仅与环境(地域和年际)密切相关,还受品种和加工精度的影响。研究农产品矿物元素指纹信息在不同加工等级与不同品种间的稳定性,解析品种、加工精度及其交互作用对各元素含量变异的贡献率,筛选出受品种、加工精度影响较小的元素作为产地溯源的指纹信息。可为农产品产地矿物元素指纹溯源技术的应用提供理论参考。本研究以水稻作为模式生物,于2013年收获期在黑龙江同一地市的3个品种的水稻样品,加工成5个不同等级,利用电感耦合等离子体质谱仪(ICP-MS)测定不同等级大米中49种矿物元素的含量。对数据进行单因素方差分析、多因素方差分析。大米中元素Na、Mg、Al、K、Ca、Cr、Mn、Fe、Co、Cu、Zn、Rb、Sr和Ba含量与加工精度密切相关;元素Na、Mg、Al、K、Ca、Cr、Mn、Cu、Zn、Rb和Mo含量与品种密切相关;在今后产地溯源技术筛选溯源指标时应考虑这些元素。     

Mineral profile of “fino” wines using inductively coupled plasma optical emission spectrometry methods

Fifty wines from the Denomination of origin (DO) of Condado de Huelva were analysed for mineral content by measuring 12 elements (Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, P, Sr and Zn) using Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES). Samples were previously digested by heating with H₂O₂/HNO₃ mixture. The results obtained showed that metal data set were non-normally distributed and accordingly, non-parametric statistics were applied. The average levels (medians) of these elements found in the samples are as follows, in mg/L: 2.54 (Al); 0.06 (Ba); 82.58 (Ca); 0.21 (Cu); 3.53 (Fe); 865.34 (K); 68.87 (Mg); 0.71 (Mn); 32.77 (Na); 71.61 (P); 0.48 (Sr); 0.56 (Zn). The interrelation of metal couples was studied through the Spearman non-parametric sample correlation, being Fe/Al, P/Mg, and Zn/Ba the most important correlations established. As a result of this study, we can suggest that the contribution to the safety intake limits (per week) of the studied elements through the wine consumption is not significant. Actually, they range between 0.1% in Fe and 11.9% in Mg, for normal drinkers.     

Multivariate analysis techniques as tools for categorization of Southern Spanish cheeses: nutritional composition and mineral content

Minerals and trace elements content of 22 samples of cheeses belonging to different Protected Designation of Origin located in Southern Spain were analyzed (Ca, Mg, P, Zn, Fe, Mn, Cu, K and Na). Similarly, protein, fat, moisture, pH and ash content were determined as well. Direct correlation was found between the following elements: Ca–Zn (r = 0.870), Ca–Mg (r = 0.767), Ca–P (r = 0.960), Mg–P (r = 0.792), Mg–Zn (r = 0.579) and P–Zn (r = 0.889). Furthermore, positive correlations were found between Ca-proteins (r = 0.560), Zn-proteins (r = 0.627) and P-proteins (r = 0.715), showing cheeses as a good dietary sources in these micronutrients. The use of vegetal rennet in cheeses reported the highest levels of minerals and trace elements. On the other hand, pattern recognition analysis of multielemental data based on mineral and trace element content was used to determine geographical traceability and to refuse possible imitations with a correct classification in 98.9% of cases.     

柳河大米产地环境及其矿物元素分布特征的典范对应分析

为筛选稳定可靠的柳河大米产地确证元素,通过2 次典范对应分析研究影响吉林省柳河大米采样点分布的环境因子,分析大米产地确证元素在区域尺度内的影响关系及其稳定性。典范对应分析结果表明,2 个环境梯度轴分别解释大米矿物元素含量总方差的17.3%和23.4%,柳河大米矿物元素含量和环境变量之间存在较强的空间相关性,受产地环境变量影响最大的为Se元素,Ca、Zn、Mg含量受其影响最小,Mg、Ca、Na、Mn、Zn具有较好的稳定性和空间代表性,可作为柳河大米产地确证的指标元素。研究结果为建立柳河大米确证模型提供有效的理论依据。     

MINERAL COMPOSITION OF MEDLAR (MESPILUS GERMANICA) FRUIT AT DIFFERENT STAGES OF MATURITY

Abstract The mineral composition of medlar fruit collected (June 15 - October 8) in Turkey at five stages of development was studied. In the fruit, 32 minerals were analyzed and 16 minerals (Al, Ba, Ca, Cu, Co, Fe, K, Li, Mg, Mn, Na, Ni, P, Sr, Ti and Zn) were present at detectable levels. The ripe medlar fruit was richest in potassium (7370 μg/g dry wt), calcium (1780 μg/g dry wt), phosphorus (1080 μg/g dry wt), magnesium (661 μg/g dry wt) and sodium (183 μg/g dry wt). During the fruit development, Al, Ba, Fe, Mn, P, Sr, and Zn were highest in August (unripe fruits) while the concentrations of K, Ca, Mg and Cu gradually decreased throughout development. The ripe medlar fruit is an important source of nutritionally needed minerals and trace elements, in particular Ca, Cu, Fe, K, Mg, Mn, Na and Zn, for human populations in southeastern Europe, Turkey and Iran.     

Determination of industrial pollution effects on citrus honeys with chemometric approach

The aim of this study was to determine the levels of essential, trace and toxic elements, such as K, Ca, Fe, Cu, Al, Ni, Sn, Pb and Cd in citrus honeys from different regions (industrialized and nonindustrialized) of Hatay, Turkey. K, Ca, Na and Mg were the most abundant elements, with mean contents of 363.5, 256.6, 88.1 and 37.7 mg/kg, respectively. The trace element mean contents ranged between 0.032 and 15.58 mg/kg. Significant differences in Fe, Cu, Al, Ni, Sn, Pb, Cd, Co and Sr levels were observed between two different regions. The findings that Fe, Cu, Al, Ni, Sn, Pb, Cd, Co and Sr contents in citrus honeys from industrialized regions were higher than citrus honeys from non-industrialized regions indicate that the honeys were affected by industrial pollution. Chemometric methods were applied to classify honey according to mineral content. Cluster analysis showed three clusters corresponding to the three different regions.     

基于产地、品种和年份影响矿物元素含量的大米判别

通过分析品种、年份与产地及其交互作用对大米矿物元素含量造成的差异,筛选有效特征指标,结合统计分析进行产地判别。以连续3?a（2016—2018年）在查哈阳、五常和建三江地区种植9?个品种的90?份田间试验样本为研究目标,采用电感耦合等离子体质谱仪测定样品的52?种元素。结果表明：Mg、Ca、Cr、Mn、Zn、As、Rb、Sr、Ag、Cd、Ba、La、Sm、Dy、Ho、Er、Pb、U受产地影响较大;Na、Mg、Al、Ca、Pb、U、V受年份影响较大;Na、Cr、Co、Ni、Tl、U、Mg、Al、La、Ho受品种影响较大。实验对筛选到与产地直接相关的18?种元素进行主成分分析和判别分析。6?个主成分累计贡献率80.333%。建立的判别模型对3?个产地的判别正确率均为100%,交叉验证率为100%。说明由这些元素组成的模型可以对样本实现正确判别。     

Mineral composition in four varieties of avocado (Persea gratissima, L.) from the island of Tenerife

The contents of macroelements (Na, K, Ca, Mg, and P) and microelements (Fe, Cu, Zn, Mn, and B) of four varieties of avocado obtained and consumed in the island of Tenerife, Canary Islands, have been determined. The samples mineral contents of the different avocado varieties showed significant differences. Thus, the concentration levels of Ca, Mg, and Mn are higher in the Hass variety; those of K, Fe, and Zn, in the Orotava variety; those of Na and B in the Hass and Fuerte varieties; that of P in the Arona and Hass varieties; and that of Cu in the Arona and Fuerte varieties. The area of origin of Hass avocado also influences the mineral content of the samples: those from the north of Tenerife show higher contents of K, Ca, P, Fe, Cu, Zn, and B, and those from the south, of Na, Mg, and Mn.     

Characterization of Spanish honeys with protected designation of origin "Miel de Granada" according to their mineral content

Honey attributes such as geographical origin or specified botanical sources often command a premium price due to their organoleptic or pharmacoactive properties. "Miel de Granada" is a highly quality product with protected designation of origin (PDO) which includes six monofloral honeys and two multifloral honeys. Our objective was the characterization of "Miel de Granada" according to their metal content. Metal content was specific enough and allowed discrimination from honeys of different botanical and geographical origins and confirmed the authenticity of PDO labelling as Granada product with the determination of only five elements (K, Na, Ca, Mg and Zn). Chemometric techniques as cluster analysis and ANOVA were used to classify honeys according to their botanical and geographical origin in the metal data. Metal content marks the differences in honey samples and can be used as a tool to assess the quality of honeys. ANOVA showed significant differences among rosemary honeys from different geographical areas despite the botanical factor weight. Our research contributes to the groundwork studies to determine the geographical origin of Spanish honeys.     

微波消解结合ICP-OES和ICP-MS测定奇亚籽中多种矿物质元素的含量

建立奇亚籽中K (钾)、Na (钠)、Ca (钙)、Mg (镁)、Fe (铁)、Mn (锰)、Zn (锌)、Cu (铜)、P (磷)、B (硼)、Pb (铅)、Cd (镉)、As (砷)、Cr (铬)、Al (铝)、Ni (镍)16种矿物质元素的方法。样品经微波消解,以电感耦合等离子发射光谱(ICP-OES)测定K、Na、Ca、Mg、Fe、Mn、Zn、Cu、P、B含量,电感耦合等离子质谱(ICP-MS)测定Pb、Cd、As、Cr、Al、Ni含量。结果表明,此方法的ICP-OES检出限范围在0.00850~0.10200 mg/L,定量限范围在0.0283~0.3400 mg/L;ICP-MS检出限范围在0.00471~0.11330 mg/L,定量限范围在0.0157~0.3777 mg/L。线性相关系数均为r＞0.999,加标回收率为90.4%~99.8%,相对标准偏差为0~4.1%。同时用国家标准物质大米(GBW10045(GSB-1))和小麦(GBW10011(GSB-2))评价了方法的准确性,测定结果在标准值范围内。奇亚籽中含有丰富的P、K、Ca、Mg,其中P含量最高,为6860 μg/g,Ca含量为4085 μg/g,K含量为2798 μg/g,Mg含量为2515 μg/g;Fe、Zn、Al、Mn、Cu、Na、B含量(由高到低)在5~100 μg/g。同时检测出重金属危害元素Pb、Cd、Cr、Ni,其中Pb含量符合食品安全国家标准GB 2762-2017的限量要求,未能检测出As。该方法污染小、简便、高效、准确度高,适用于奇亚籽等植物类样品中多种化学元素的测定。     

Elemental Composition of Various Sour Cherry and Table Grape Cultivars Using Inductively Coupled Plasma Atomic Emission Spectrometry Method (ICP-OES)

Three sour cherry and three table grape cultivars were analyzed using inductively coupled plasma optical emission spectrometry. The elements: Na, K, Ca, Mg, Fe, Cu, Zn, Mn, Cr, Cd, Co, Pb, and Ni were detected in all samples; four elements are very abundant (K, Na, Ca, and Mg), and four are not abundant (Cu, Fe, Mn, and Zn). Five of them are trace elements (Cr, Cd, Co, Pb, and Ni) at <0.1 mg/kg. Among the 13 elements analyzed, potassium was the most abundant element distributed throughout all categories of fruits. Iron was the predominant minor element constituents. Manganese concentration was the highest in table grape cultivars. The accuracy of the results was evaluated by spike recovery tests. Analysis of variance was used to establish the metals with significant difference in mean content between the cultivars from sour cherries and between table grapes. Principal component analysis was used to evaluate the distribution of metals.     

Metal contents in “oloroso” sherry wines and their classification according to provenance

“Oloroso” sherry wines, belonging to the denominations of origin Jerez-Xérès-Sherry (JX), Montilla-Moriles (MM) and Condado de Huelva (CH) (Andalusia, Spain), were analysed for their contents of Ca, Mg, Fe, Cu, Mn and Zn by flame atomic absorption spectrophotometry, and Na, K, Al and Sr by flame atomic emission spectrophotometry. Among the three denominations of origin, differences in the mean contents were found for Na, Mg, Fe, Al and Sr. Cluster analysis showed that these differences were significant. Linear discrimination analysis, using Na, Mg, Fe, Al and Sr, gave 100% recognition ability and 93% prediction ability.     

Genotypic variation of mineral elements contents in rice (<Emphasis Type="Italic">Oryza sativa</Emphasis> L.)

Mineral nutrition of potassium (K), calcium (Ca), sodium (Na), magnesium (Mg), iron (Fe), zinc (Zn), copper (Cu) and manganese (Mn) are important for human health. The method of inductively coupled plasma mass spectrometry (ICP-MS) was employed to determinate the contents of K, Ca, Na, Mg, Fe, Zn, Cu and Mn in milled rice (Oryza sativa L.) of 274 rice genotypes. The results showed that the visible difference could be found for the contents of eight elements in milled rice among rice genotypes studied. It existed the possibility to select the genotype(s) with abundant of mineral nutrient from the genetic resource. Meanwhile, the contents of mineral elements in brown rice were significantly higher than those in milled rice. The averages of K, Mn and Cu contents of indica rice were significantly lower than those of japonica rice, while no significant difference was found for other five element contents between indica and japonica rice genotypes. The average contents of Na and Cu in non-glutinous rice genotypes were higher than those in glutinous ones, whereas the averages of K and Mn contents in non-glutinous rice genotypes were lower in present experiment. Additionally, the K, Ca and Mg contents of milled rice from white brown rice were significantly higher than those from red brown rice, and Ca content of milled rice from white brown rice was also visibly higher than that from black brown rice. For microelements, significant difference was observed for Zn content between milled rice from red and white brown rice, or between milled rice from red and black brown rice. Some genotypes with abundant mineral nutrient in milled rice had been selected and could be used in rice nutrient breeding.     

Mineral composition of frozen green asparagus

The contents of macroelements (Ca, Mg, Na, K y P) and trace elements (Cu, Fe, Zn and Mn) of frozen green asparagus were determined by atomic absorption spectrometry to investigate the possible changes during 45 and 90 days frozen storage at –18 °C. A significant decrease of mineral concentrations was observed at 45 days of frozen storage. After 90 days, modifications were not observed, except for Cu and P concentrations. The asparagus thickness factor resulted in significant differences in the Cu, Fe, Zn, Ca and K contents. Frozen storage time involved smaller percentages of mineral retention in the <11 mm spear for Ni, Ca, Mg, K and P, and, for the rest of mineral elements, the frozen storage effect was similar for both thicknesses (<11 mm and >14 mm). The highest mineral concentration was found in the apical portion or tip of green asparagus, except for Mn, Cr and K. Mineral retention percentages after frozen storage time were similar in both portions (apical and basal) of the spear.     

NUTRITIONAL ESTIMATION OF CHANGES IN MINERAL CONTENT DURING FROZEN STORAGE OF WHITE ASPARAGUS

Nine essential elements (copper, iron, zinc, manganese, calcium, magnesium, sodium potassium and phosphorous) were determined in white asparagus (Asparagus officinalis, L.) by flame atomic absorption spectrophotometry in order to examine the possible variations in mineral content caused by frozen storage at ?18C for 45 and 90 days. Statistically significant differences were determined during frozen storage for all the mineral elements investigated, except for Ca, Mg, Na and P which did not exhibit any significant differences (p>0.05) and, together with Zn, showed no significant modifications under frozen storage. A diminution in Cu, Fe, Mn and K concentrations was observed during the frozen storage time. Statistically significant differences were established between thicknesses of the asparagus spear in the content of Cu, Fe, Zn, Ca, Na and K and it was seen that the thickness of the asparagus did not fit any specific model. Between portions, all the elements studied displayed statistically significant differences in their concentrations, except for Ca and K (p>0.05) and, for all the minerals elements analyzed, the highest levels were found in the apical portion of the asparagus spear, except for Na with a higher content in the basal portion. White asparagus is an adequate food source of mineral elements, except for Na, and frozen storage does not cause any great variations in the percentages of mineral RDAs (Recommended Dietary Allowances) supplied.     

西藏不同地区畜产品中矿质元素的含量测定及比较分析

摘 要：目的 分析西藏不同地区畜产品中矿质元素的富集规律。本研究以西藏4个地市（拉萨、林芝、日喀则、山南）162份畜产品为研究对象。方法 采用微波消解-电感耦合等离子体质谱法 (Inductively-coupled plasma-mass spectrometry,ICP－MS) 法测定西藏4地市畜产品样品中的Na、Mg、K、Ca、Mn、Fe、Sr、Cu、Zn、Se、Cd、Pb、Cr、As、Hg等15种矿质元素含量。对其所含重金属元素进行测定分析,同时分析不同地区畜产品中矿质元素含量的差异性。结果 各元素均呈良好的线性关系, 相关系数在0.9968~0.9999,畜产品中15种矿质元素检测方法的检出限为0.0000067~0.0638 mg/kg。不同地区畜产品中矿质元素的含量为 K、Na、Mg较高,Ca、Zn、Fe、Cu次之,具有潜在生理毒性的重金属Cd、Pb、Cr、As、Hg含量较低。由4地市畜产品重金属元素检测结果得出,林芝和山南的畜产品中均未检出Cd;日喀则的畜产品中均未检出总As;拉萨和日喀则畜产品中Cd、总Hg均超标。矿物质中由矿质元素含量检测可知,含量最高的常量元素是K,含量均明显高于其它矿质元素,含量最高的微量元素是Fe,。此外,日喀则的畜产品中Mn元素含量均远高于其他它地市。并对不同地区畜产品中矿质元素含量进行分析,明确西藏不同地区畜产品中矿质元素含量的差异。结论 西藏不同地区畜产品中矿质元素含量存在一定差异性。