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.     

Mineral Composition of Fresh and Cured Jellyfish

The inorganic constituents of fresh and cured jellyfish (Rhopilema esculentum), including Zn, Co, Ni, Ba, Mn, Fe, Mg, Ca, Cu, Al, Sr, Mo, Cr, Cd, Pb, Si, V, Ti, Na, K, Li, and Rb, were determined by using inductively coupled plasma optical emission spectrometry. The fresh and cured jellyfish were treated by lyophilization and microwave digestion in turn. Zn, Co, Fe, Mg, Ca, Al, Sr, Cr, Li, and K were used as the added standards to evaluate accuracy. The results show that different parts of jellyfish, such as the umbrella, oral arms, and gonads, contain different amounts of inorganic elements. The relative standard deviation values (RSD) of all elements range from 0.8% to 8.6%. For most of determined elements, RSD values are under 5%. All inorganic elements of the jellyfish can be determined simultaneously after once dissolution. The method is accurate, rapid, and convenient to determine inorganic constituents of the biological sample containing high water content.     

Survey of bottled drinking waters sold in Canada for chlorate, bromide, bromate, lead, cadmium and other trace elements

Mineral, spring and other bottled drinking waters sold in Canada in the winter of 1995-96 were surveyed for chlorate, bromide, bromate, Cr(VI), Li, B, Al, Mn, Cu, Zn, Sr, Ba, Be, V, Cr, Co, Ni, As, Se, Mo, Ag, Cd, Sb, Tl, Pb, Na, K, Ca and Mg. Chlorate and bromide were determined by ion chromatography (IC) with conductivity detection, Cr(VI) by IC with colorimetric detection, bromate by solvent extraction and gas chromatography (GC), trace elements by inductively coupled plasma mass spectrometry (ICPMS), and Na, K, Ca and Mg by flame atomic absorption spectrometry (FAA). Most chemicals in the 199 samples analysed were well within national and international drinking water guidelines. World Health Organization and/or Canadian drinking water guidelines were exceeded for B (22 samples), Al (9), Cr (1), Mn (5), Ni (1), As (10), Se (24) and Pb (1). Bromate levels are reported for information purposes and are considered as the maximum concentrations in the samples. In three distilled water products, unexpectedly high concentrations of Cu (88-147 µg l^-1) and Ni (16-35 µg l^-1) were found, and a comparison of distilled and non-distilled waters from two of the brands suggested the likely cause to be contamination during the distillation process. Li concentration in one sample was at a therapeutic dose and could pose an overdose risk to individuals on Li medication.     

电感耦合等离子体原子发射光谱法同时测定江西脐橙中多种微量元素

采用硝酸-高氯酸对江西赣南8个县所产的脐橙样品进行消解,电感耦合等离子体原子发射光谱法(ICP-AES)同时测定试样中Al、As、Ba、B、Ca、Co、Cr、Cu、Fe、K、Li、Mg、Mn、Ni、P、Pb、Zn、Be、Cd、Se、Sr、La、Ce、Y、Sm、Lu等元素的含量。该法的相对标准偏差为0.42%～4.51%,加标回收率为87.7%～114.1%。实验结果表明:脐橙中含有丰富的K、Ca、P和Mg,不同县所产的脐橙各种微量元素含量存在一定差异。     

Monitoring the Authenticity of Organic Grape Juice via Chemometric Analysis of Elemental Data

Elemental determination was carried out on 36 grape juice samples (19 organic and 17 ordinary), with the goal of identifying significant differences between the two types of juice for classification purposes. Inductively coupled plasma-mass spectrometry was used for the determination of 24 elements, Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cu, Fe, La, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, Se, Sn, Ti, V, and Zn. Ba, Ce, La, Mg, P, Pb, Rb, Sn, and Ti concentrations were found to be higher in organic versus ordinary samples, while Na and Va concentrations were higher in ordinary versus organic samples. The remaining investigated elements exhibited statistically equivalent concentration levels in both types of samples. Principal component analysis (PCA) and soft independent modeling of class analogy (SIMCA) statistical techniques of the elemental fingerprints were readily able to discriminate organic from ordinary samples and can be used as alternative methods for adulteration evaluation.     

微波消解-电感耦合等离子体质谱法测定虾皮中28种元素

目的建立电感耦合等离子体质谱法(inductively coupled plasma mass spectrometry,ICP-MS)测定虾皮中K、Na、Ca、Mg、Fe、Mn、Cu、Zn、P、Li、Al、V、Cr、Co、Ni、As、Rb、Sr、Se、Mo、Ag、Cd、Pb、Ba、Ga、Cs、Ti、Bi 28种元素含量的分析方法。方法采用硝酸-过氧化氢消解体系,通过在线加入Ge、Rh、Re内标进行基体效应校正,碰撞反应池模式(kinetic energy discrimination,KED)消除多原子离子干扰,以国家标准物质大虾(GBW 10050)为研究对象,验证方法准确度。结果方法检出限为0.001-0.681 mg/kg,相对标准偏差(relative standard deviations,RSD)为0.6%~8.2%,各元素标准曲线线性关系良好,相关系数r²大于0.999,样品回收率为87.4%~110.0%。虾皮中常量元素K、Na、Ca、Mg等含量较高,Pb、Cd、Cr等重金属元素含量较低,Al、As需根据其存在形态评估可能存在的健康安全风险。结论该方法准确高效,灵敏度高,可应用于虾皮样品分析。     

Geographical traceability of “Arròs de Valencia” rice grain based on mineral element composition

The geographical traceability of rice grain samples involves the use of analytical methodologies that allow their differentiation on the basis of the rice composition, thus confirming their authenticity. In this paper, trace element determination of rice samples by inductively coupled plasma optical emission spectroscopy (ICP-OES) has been addressed to achieve a complete geographical origin classification. Samples (107) from Spain including Valencia, Tarragona, Murcia and Extremadura, Japan, Brazil and India were employed as training set whereas the validation set was formed by 46 samples of the aforementioned geographical origins. Data were processed by linear discriminant analysis (LDA), using as analytical variable the concentration of 32 elements (Al, As, Ba, Bi, Cd, Ca, Cr, Co, Cu, Fe, Pb, Li, Mg, Mn, Mo, Ni, K, Se, Na, Sr, Tl, Ti, Zn, La, Ce, Pr, Nd, Sm, Eu, Ho, Er and Yb), enabling a 91.30% of correct classification for the validation set.     

浓香型白酒蒸馏过程中金属元素的迁移变化规律

利用微波消解结合电感耦合等离子体质谱检测的方法测定泸州老窖浓香型白酒蒸馏过程中,蒸馏前后的酒糟、底锅水及所得的酒样样品中Na、K、As、Pb、Cd、Sn、Ti、Mg、Fe、Cu、Mn、Zn、Ca、Al、Ni、Cr和Ba 17 种金属元素的含量,并借助SPSS统计学软件采用t检验分析酒体中对应元素的来源。结果表明,蒸馏之后超过94%的金属元素仍保留在糟醅中,不到6%的金属元素转移至白酒及底锅水中。Pb、Mn、Cr等重金属元素的转移率显著低于Na、K、Ca和Mg等矿质元素,有效减少了酒中Pb、Mn、Cr等重金属的超标几率。酒样中的Ca、Cu、K、Mg、Na、Zn和Ba等元素主要来源于糟醅,而蒸馏使用的设备则会引入Fe、Ni、Al、Sn元素,Pb和Cr等有害重金属。     

金属元素在汾酒中的作用及应用研究

采用火焰原子吸收法测Na、K、Ca、Mg、Fe、Zn、Cu、Mn、Ni、Li、Pb、Cd 和Cr 含量;石墨炉原子吸收法测Mo、Sr、Ba、Co、Ti、Al 和Sn 含量;原子荧光光度法测Hg、As、Se 和Sb 含量,对汾酒不同生产用水、不同贮存容器所贮新酒中24 种金属元素进行了定量分析,并初步探讨了酒中金属元素的作用机制。结果显示,汾酒中金属元素的种类和含量与生产用水及贮存容器的使用密切相关,因此用不同的水源和容器,酒中金属元素的种类和含量不同,从而影响汾酒的口感和老熟。在此基础上,对汾酒生产中合理使用水源和容器也做出了科学合理的指导。     

Simultaneous application of dissolution/precipitation and surface complexation/surface precipitation modeling to contaminant leaching

This paper discusses the modeling of anion and cation leaching from complex matrixes such as weathered steel slag. The novelty of the method is its simultaneous application of the theoretical models for solubility, competitive sorption, and surface precipitation phenomena to a complex system. Selective chemical extractions, pH dependent leaching experiments, and geochemical modeling were used to investigate the thermodynamic equilibrium of 12 ions (As, Ca, Cr, Ba, SO4, Mg, Cd, Cu, Mo, Pb, V, and Zn) with aqueous complexes, soluble solids, and sorptive surfaces in the presence of 12 background analytes (Al, Cl, Co, Fe, K, Mn, Na, Ni, Hg, NO3, CO3, and Ba). Modeling results show that surface complexation and surface precipitation reactions limit the aqueous concentrations of Cd, Zn, and Pb in an environment where Ca, Mg, Si, and CO3 dissolve from soluble solids and compete for sorption sites. The leaching of SO4, Cr, As, Si, Ca, and Mg appears to be controlled by corresponding soluble solids.     

电感耦合等离子体质谱法测定蜂蜜中的微量元素

建立了用带八极杆碰撞/反应池的电感耦合等离子体质谱仪(ORS-ICP-MS)测定蜂蜜中Na、Mg、Al、K、Ca、Cr、Mn、Fe、Ni、Cu、Zn、As、Se、Mo、Cd、Ba、Hg、Pb等18种微量元素的方法。样品用HNO3+H2O2分解后,试液直接用ORS-ICP-MS法同时上述微量元素。采用八极杆碰撞/反应池技术,在池内引入惰性气体氦气或氢气,有效地消除了多原子离子对待测元素的干扰,确定了实验的最佳测定条件。结果表明,各元素的检出限在1.05～73.45ng/L之间,加标回收率在92.2%～106.8%之间,相对标准偏差(RSD)小于2.73%。     

百香果中矿物元素分析

采用高压密封硝化罐消解样品,应用ICP-AES 法测定百香果果汁、果皮、种仁中20 种矿物元素 (Na、K 、C a 、Mg、Z n 、F e 、S r 、Cu 、Co 、Mn、Ge 、S e 、S n 、B a 、A l 、P b 、Hg、As 、C r 、Cd) 的含量,设计正交试验方案,通过方差分析选择最佳的试验操作条件,其回收率在95.0%～104.0% 之间,相对标准偏差小于2.15%。实验结果表明：百香果果汁、果皮、种仁中均含有丰富的Na、K、Ca、Mg、Zn、Fe、Ge等对人体有益的矿物元素,而对人体有害的元素均未检出,营养价值高,极具开发价值。     

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.     

Concentrations and bioconcentration factors of minerals in yellow-cracking bolete (xerocomus subtomentosus) mushroom collected in noteć forest, poland

Abstract: Yellow‐cracking Bolete (Xerocomus subtomentosus) mushrooms and soil were collected from Note? Forest–a large forested enclave in western part of Poland. Mercury was determined by cold vapour atomic absorption spectroscopy and the other elements by inductively coupled plasma atomic emission spectroscopy. K, P, and Mg were particularly abundant, with mean values of 46000, 8400, and 1100 mg/kg dry weight (dw) in caps followed by Na, Rb, Zn, and Ca with mean concentrations of 580, 350, 200, and 170 mg/kg dw, respectively. In descending order, the mean concentrations of Fe, Al, Cu, and Mn were 52, 49, 46, and 14 mg/kg dw, while the mean for the remaining elements was around 1.0 mg/kg dw or less. The elements such as Ca, Cu, Hg, K, Mg, Na, P, Rb, Zn, Ag, Cd, and Ni were accumulated (with bioconcentration factor (BCF) > 1), while Al, Ba, Fe, Mn, Sr, Co, Cr, and Pb were excluded (BCF < 1) in the fruiting bodies. The Pb and Cd content did not exceed the maximum levels set by the EU for cultivated mushrooms. Mercury in a conventional meal (300 g) portion of Yellow‐cracking Bolete was far below the provisionally tolerable weekly intake of 0.004 mg/kg body weight (bw) as reevaluated recently by WHO. Practical Application: The method presented in this study allows one to determine the content of 20 elements (Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr, and Zn) in caps and stipes of Yellow‐cracking Bolete (Xerocomus subtomentosus) mushrooms and soil samples collected from Poland. This study has revealed that the total Cd, Hg, and Pb dose provided to human body due to consumption of Yellow‐cracking Bolete does not pose threat to a consumer's health.     

Minerals content in Basilicata region (southern Italy) honeys from areas with different anthropic impact

The aim of this study was to examine the minerals content (toxic elements, macro-elements and trace elements) of Basilicata region (southern Italy) honeys and compare the mineral profile of honeys classified as rural, industrial and urban according to anthropic characteristics of geographical origin. Overall, Ca, Na, Mg, Fe, Al, Zn and Mn were the most abundant elements detected in honeys, with average contents exceeding 1 ppm, whereas heavy metals content was lower than the maximum limit established for honey. Statistical analysis revealed significant differences (P < 0.05) among honeys as function of anthropic characteristics of geographical origin, with the exception for Se, Co and Ag content. Industrial honeys were characterised by the highest Zn, Cr, Sn, Cd and Pb content, urban honeys showed the highest As, Fe, Ni, Mn, Na, Mg and Ca content, whereas rural honeys showed the highest Cu, Al and Ba content (P < 0.05). The findings of this study highlighted that honeys mineral profile is closely related to different content of elements in environment, which is affected by anthropogenic activities.     

Toxic and nutrient elements in yerba mate (Ilex paraguariensis)

Toxic and nutrient elements were investigated in yerba mate (Ilex paraguariensis) from South America. Fifty-four brands of commercialised yerba mate from Argentina, Brazil, Paraguay and Uruguay were analysed for Al, Ba, Ca, Cu, Fe, K, Mg, Mn, P, Sr, and Zn, using inductively coupled plasma optical emission spectrometry (ICP-OES), and Li, Be, Ti, V, Cr, Ni, Co, As, Se, Rb, Mo, Ag, Cd, Sb, La, Ce, Pb, Bi and U using inductively coupled plasma mass spectrometry (ICP-MS). Antimony, Se, Ag and Bi were not detected in any sample whereas the limits of detection (LODs) of these elements were 0.19, 0.40, 0.003 and 0.001 μg g^?1, respectively. Analysis of variance (ANOVA) revealed that the concentrations of Cd, Ti, Ni, As, Mo, U, Li and Be in yerba mate were not statistically different with regard to the country of origin, while those of the other investigated elements differed.     

基于无机多元素分析鉴别我国主要进口大米产地

目的利用大米中无机多元素分析数据建立判别模型,实现对4个我国进口大米主要产地的鉴别。方法采用ICP-MS和ICP-OES分析技术,测定了泰国、巴基斯坦、柬埔寨、缅甸4个产地的76份大米样本中磷、钾、镁、钙、锌、钠、锰、铁、铷、铜、硼、铝、钼、镍、钡、锶、砷、钛、硒、铬、钴、铯、铅、镉、锂、钒、银、锑、铍、铊、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钪、钇等46种无机元素含量。通过对检测数据进行单因素方差分析、Fisher判别分析,建立了产地判别模型。结果4个产地大米的部分元素存在显著性差异,产地判别模型的原始校验准确率100%,交叉验证准确率96.1%。结论所建方法和判别模型对泰国、巴基斯坦、柬埔寨、缅甸所产大米具有很好产地鉴别能力。     

Simultaneous Determination of 20 Inorganic Elements in Preserved Egg Prepared with Different Metal Ions by ICP-AES

In the present study, 20 inorganic elements in three parts of preserved eggs prepared with different metal ions, including Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Li, K, Mg, Mn, Mo, Na, P, Pb, Zn, Se, and Sr, were determined simultaneously by using inductively coupled plasma–atomic emission spectrometry (ICP-AES). The recoveries obtained by the standard addition method ranged between 84.4 and 112.2 %, and RSDs were lower than 8.76 %, The detection limits of the method for the 20 elements were in the range of 0.4–10 μg?L^?1. The determination results showed that three parts of preserved eggs prepared with different metal ions are all rich in essential inorganic elements, such as Na, K, P, Ca, Mg, Fe, Cu, and Zn, and the contents of most of the inorganic elements in egg yolk are higher than in egg white. In comparison with fresh duck eggs, the contents of Na, Cu, Fe, Al, and Mn are significantly increased in three parts of preserved eggs prepared with different metal ions. Metal ions added in pickling solution would significantly affect the content of element added in preserved eggs. High contents of Pb (20.15 μg/g in egg shell, 18.99 μg/g in egg white, and 0.96 μg/g in egg yolk) were found in preserved eggs with PbO. Meanwhile, the experimental results indicated that the ICP-AES technique is easy to operate, rapid, accurate, and highly sensitive to determine many inorganic elements simultaneously in preserved egg.     

电感耦合等离子体质谱法(ICP-MS)测定砂糖中31种微量元素

利用微波消化－电感耦合等离子体质谱法（ＩＣＰ－ＭＳ）同时测定了白砂糖和赤砂糖中３１种微量元素。白砂糖中检测出２３种,赤砂糖中检出２７种。结果表明,Ｃａ,Ｍｇ,Ｋ,Ｆｅ,Ｍｎ,Ｃｕ等６种元素在赤砂糖中含量比在白砂糖中含量高出４￣４００倍。Ｌｉ,Ｂａ,Ｎａ,Ｐ,Ａｌ,Ｖ,Ｃｒ,Ｎｉ,Ｚｎ,Ｇａ,Ｓｒ,Ａｇ,Ｓｎ,Ｓｈ,Ｂａ,Ｈｇ,Ｐｂ等１７种元素在白砂糖和赤砂糖中的含量无显著差别。本方法具有前处理简单     

Bestimmung der Mineralstoffe und Spurenelemente in Selen-Tee aus dem Enschi-Gebiet, VR China, und in dessen Aufgu? mittels ICP-AES, GFAAS und INAA

Zusammenfassung Das Enschi-Gebiet in der Provinz Hubei ist geochemisch eine der beiden selenreichen Regionen Chinas. Hier werden die grünen und schwarzen Selen-Tees produziert. Drei Proben eines grünen Tees mit verschieden hohen Se-Gehalten sowie eine selenarme Probe wurden in dieser Arbeit untersucht. Die Mineralstoffe und Spurenelemente K, Ca, Mg, Na, P, S, Al, Mn, Fe, Ba, Sr, Co, Ni, Cu, Zn, Mo und Cr wurden mittels Atomemissionsspektrometrie mit induktiv gekoppelter Plasmaanregung (ICP-AES) bestimmt. Außer Mo, Co und Cr wurden alle oben genannten Elemente in den Aufgüssen der untersuchten Selen-Tees ebenfalls mit der ICP-AES gemessen. Die Se-Gehalte in den Teeproben sowie in den Aufgüssen wurden mit Graphitrohr-Atomabsorptionsspektrometrie (GFAAS) bestimmt. Zur Kontrolle der Richtigkeit der Se-Messung wurden die Se-Gehalte in unaufgeschlossenen Teeproben zusätzlich mit instrumenteller Neutronenaktivierungsanalyse (INAA) bestimmt. Es wurden Se-Gehalte im Bereich von 1 bis 8,5 g/g Trockengewicht gemessen. Außer Se wurden insgesamt 17 Elemente im Tee und 14 in dessen Aufguß quantitativ bestimmt. Daraus wurde der Auslaugungsgrad für die einzelnen Elemente berechnet. Bis zu 10% des Se konnten in einem ersten Aufguß ausgelaugt werden.

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Determination of minerals and trace elements in selenium tea from the Enschi District, Peoples' Republic of China, and in its infusions by ICP-AES, GFAAS and INAA

The Enschi district in Hubei province, Peoples Republic of China is geochemically one of the two seleniferous regions, producing both selenium (Se) black tea and the Se green tea. Three samples of green tea with different Se contents and one non-Se tea were analysed. The following mineral and trace elements were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES): K, Ca, Mg, Na, P, S, Al, Mn, Fe, Ba, Sr, Co, Ni, Cu, Zn, Mo, and Cr. Except for Mo, Co, and Cr, all other elements in infusions of the samples analysed were also measured, since their concentrations are lying over their detection limits. The Se content in the tea samples and in the infusions were measured with graphite furnace atomic absorption spectrometry (GFAAS). The accuracy of Se determination was tested by measuring untreated tea samples with instrumental neutron activation analysis (INAA). The Se content in the measured samples was 1 to 8.5 g/g. In addition to Se, 17 other elements were measured in the tea samples and 14 others in the infusions. With this data the extractible part of this elements in the infusion were calculated. Up to 10% of the Se was found in a first infusion.

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1990–1992 Gast-Professor am Hahn-Meitner-Institut, Berlin und am Institut für Lebensmittelwissenschaft und Lebensmittelchemie der Universität Bonn