Determination of trace elements in porcine brain by inductively coupled plasma-mass spectrometry,electrothermal atomic absorption spectrometry,and instrumental neutron activation analysis

Methods have been developed for the analyses of trace metals in various areas of porcine brains, (temporal, parietal, frontal cortex, both right and left hemispheres). Determinations were carried out using inductively coupled plasma-mass spectrometry (ICP-MS) and electrothermal atomic absorption spectrometry (ETAAS). The elements investigated were Li, Mn, Cu, Zn, Cd, Hg, and Pb by ICP-MS and Cu, Cd, and Mn by ETAAS. For determination by ICP-MS, a method of standard additions calibration coupled with internal standards was used, and for ETAAS, standard additions calibrations were prepared. The accuracy of all methods was determined using NIST and IAEA certified reference material. A small number of pig brains were analyzed by instrumental neutron activation analysis for Cr, Co, Cs, Fe, Rb, Se, Sc, Sb, and Zn using the comparator method of analysis. Four separate NIST standard reference materials have been used to examine the validity of the comparator method.     

高原鼢鼠和甘肃鼢鼠胆汁无机元素含量分析

<正>无机元素在动物发育、免疫调节、代谢和繁殖等方面发挥着重要作用(刘季科等,1991;蒲俊华等,2010;Talebnejadetal.,2021;Gashkinaet al., 2022)。现代医学已证明,无机元素的种类和含量影响药材的药性和药效(谭文敏,2015;陈虹等,2017),其已逐渐成为动物药鉴别、炮制加工、质量评价和寻找替代品的重要依据(罗兴洪等,2004)。熊胆属于传统珍稀濒危动物药,     

Studies on some trace and minor elements in blood

Blood is one of the widely used specimens for biological trace element research because of its biological significance and ease of sampling. We have conducted a study of the blood of the Kalpakkam township population for trace and minor elements. For this purpose, analytical methods have been developed and standardized in our laboratory for the elemental analysis of blood plasma and red cells. Inductively coupled plasma-mass spectrometry (ICP-MS), a relatively new technique, has been applied for the analysis of trace elements. Details regarding spectral interference and matrix interference encountered in the analysis of blood and the methods of correcting them have been discussed. Flame atomic absorption spectrometry (AAS)/atomic emission spectrometry (AES) has been applied for the determination of minor elements. Precision and accuracy of these methods have also been discussed.     

RNAA as compared to ICP-MS for the analysis of normal human serum

The merits of radiochemical neutron activation analysis (RNAA) and inductively coupled plasma mass spectrometry (ICP-MS) are critically discussed for the determination of trace and ultratrace elements in normal human serum. For RNAA, two semiautomated procedures, allowing the determination of up to 18 elements, are briefly described. ICP-MS has a series of interesting features for the determination of trace elements. Matrix and spectral interferences can mostly be avoided or corrected for. After a simple 5- or 10-fold dilution and addition of an internal standard, more than 20 elements can be measured precisely and accurately.     

Enriched stable isotopes of elements used as tracers: methods of presenting high-performance liquid chromatographic-inductively coupled argon plasma mass spectrometric data

High-performance liquid chromatography (HPLC) of biological fluids and tissue cytosolic preparations was employed in conjunction with argon-induced inductively coupled plasma mass spectrometry (ICP-MS) to investigate the distribution of stable isotopes as tracers. The common way of presenting the data from the ICP-MS is by plotting the count rates versus the retention time of HPLC fractions. Additional information can be derived, e.g., the composite peaks can be further resolved, and the level of enrichment in various biological components can be expressed by alternative ways of presenting these data. The two additional approaches described here involve presenting the ratios of enriched tracer with a suitable naturally abundant mass number of the same element, and by expressing the extent of enrichment by the tracer isotope in a given fraction to the same mass number in the fraction derived from an untreated source. Each method of presentation has different merits and drawbacks. The data therefore may be best presented in more than one way to emphasize the conclusions from a given experiment. Observations are presented after simultaneously injecting stable isotopes of three essential elements, copper, selenium and zinc, into mice. Plasma and liver cytosolic fractions were analysed and data represented in different ways as indicated above.     

Measurement of trace elements in proteins extracted from liver by size exclusion chromatography-inductively coupled plasma-mass spectrometry with a magnetic sector mass spectrometer

Proteins are extracted from liver into aqueous buffer at pH 7 and separated by size exclusion chromatography (SEC). Inductively coupled plasma mass spectrometry (ICP-MS) with a magnetic sector mass spectrometer is used to identify those protein fractions that contain Cu, Zn, Mn, Fe, Cd, S, P, Mo, Co, Ca, or Mg. The experimental setup provides very high sensitivity. Measurements at medium spectral resolution remove polyatomic interferences for some difficult elements like Fe, S, and P. Some elements are found in different molecular weight proteins; for example, cadmium binds to four different protein fractions (>400 kDa, 70 kDa, and metallothionein). Other elements like Mo, Ca, and Mg are present only in low-molecular-weight proteins or other small molecules.     

Assessment of the contamination from devices used for sampling and storage of whole blood and serum for element analysis

An assessment of potential contamination risk associated with devices routinely used in hospitals and clinical laboratories for sampling and storage of whole blood and serum was made by analysis of leachates from the devices. The devices checked were disposable stainless steel needles, different types of blood collection tubes; serum separation tubes, disposable plastic pipettes and plastic vials used for serum storage. Concentrations of about 70 elements in solution after leaching with 0.05 mol l(-1) HNO3 were determined by double focusing sector field inductively coupled plasma mass spectrometry (sector field ICP-MS). For the elements present in blood/serum at concentrations higher than 10 ng ml(-1) (Na, Ca, Mg, P, Fe, Br, Si, Zn, Cu, Rb, Se and I) contribution from devices was as a rule negligible (less than 1% of expected concentrations in the body fluids), but for the majority of trace and ultra-trace elements it may significantly affect or even prevent accurate determination. The highest trace element contribution was found to derive from commercially available blood collection and serum separation tubes. Apparent concentrations of Al, Ba, Th, rare earth, and some other elements resulting from contamination were higher than normal serum concentrations all types of tubes tested for.     

Trace element analysis of proteins directly from 2d-page: an efficient strategy for metalloproteomics

Inductively coupled plasma-mass spectrometry (ICP-MS) is a sensitive analytical method to detect the total concentrations of elements in biological samples, but it is unable to identify molecules that can bind to metals, and for this reason it is vital to combine this method's use with other biochemical techniques. Therefore, in order to identify elements complexed to specific proteins, a very relevant combination of bidimensional electrophoresis followed by ICP-MS was used. Protein spots from gels were excised and submitted directly to element detection, a method not reported before. This report focused on the use of plasma from people with laryngeal carcinoma. Most elements were below detection level, with only Cr and Pb being observed in all samples. Although the relationship between metals and laryngeal cancer was not conclusive, it is possible to affirm that the methodology utilized here is successful and has the advantage of determining to which proteins the elements bind.     

The potential of inductively coupled plasma mass spectrometry (ICP-MS) for the simultaneous determination of trace elements in whole blood, plasma and serum.

The advantages accruing to biochemical and clinical investigations from a method that allows the simultaneous quantification (RSD < or = 10%) of many elements in blood, plasma, and serum at concentrations equal to one-hundredth of the lower limits of the normal ranges are undeniable. The suitability of inductively coupled argon plasma low-resolution quadrupole mass spectrometry (ICP-MS), a simultaneous method with low detection limits, is evaluated for the quantification of inorganic constituents in whole blood, plasma, and serum with consideration of the dilution associated with the mineralization of the samples, of isobaric and polyatomic interferences and of normal ranges. Of the 3 bulk elements, the 3 major electrolytes, the 15 essential elements, the 8 toxic elements, the 4 therapeutic elements, and the 14 elements of potential interest (total of 47 elements) only 7 elements (Ca, Cu, K, Mg, Rb, Sr, Zn) can be simultaneously quantified under these rigorous conditions in serum and only 8 elements (additional element Pb) in whole blood. Quantification of elements in the Seronorm Standards "Whole Blood" and "Serum" showed, that this list of simultaneously determinable elements in these matrices is reasonable. Although this list is disappointingly short, the number of elements determinable simultaneously by ICP-MS is still larger than that by ICP-AES or GFAAS. Improved detectors, more efficient nebulizers, avoidance of interferences, better instrument design, and high-resolution mass spectrometers promise to increase the number of elements that can be determined simultaneously.     

Trace element contamination in feather and tissue samples from Anna’s hummingbirds

Trace element contamination (17 elements; Be, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Ba, Hg, Tl, and Pb) of live (feather samples only) and deceased (feather and tissue samples) Anna's hummingbirds (Calypte anna) was evaluated. Samples were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS; 17 elements) and atomic absorption spectrophotometry (Hg only). Mean plus one standard deviation (SD) was considered the benchmark, and concentrations above the mean + 1 SD were considered elevated above normal. Contour feathers were sampled from live birds of varying age, sex, and California locations. In order to reduce thermal impacts, minimal feathers were taken from live birds, therefore a novel method was developed for preparation of low mass feather samples for ICP-MS analysis. The study found that the novel feather preparation method enabled small mass feather samples to be analyzed for trace elements using ICP-MS. For feather samples from live birds, all trace elements, with the exception of beryllium, had concentrations above the mean + 1 SD. Important risk factors for elevated trace element concentrations in feathers of live birds were age for iron, zinc, and arsenic, and location for iron, manganese, zinc, and selenium. For samples from deceased birds, ICP-MS results from body and tail feathers were correlated for Fe, Zn, and Pb, and feather concentrations were correlated with renal (Fe, Zn, Pb) or hepatic (Hg) tissue concentrations. Results for AA spectrophotometry analyzed samples from deceased birds further supported the ICP-MS findings where a strong correlation between mercury concentrations in feather and tissue (pectoral muscle) samples was found. These study results support that sampling feathers from live free-ranging hummingbirds might be a useful, non-lethal sampling method for evaluating trace element exposure and provides a sampling alternative since their small body size limits traditional sampling of blood and tissues. The results from this study provide a benchmark for the distribution of trace element concentrations in feather and tissue samples from hummingbirds and suggests a reference mark for exceeding normal. Lastly, pollinating avian species are minimally represented in the literature as bioindicators for environmental trace element contamination. Given that trace elements can move through food chains by a variety of routes, our study indicates that hummingbirds are possible bioindicators of environmental trace element contamination.     

TRACE ELEMENT ANALYSIS OF PROTEINS DIRECTLY FROM 2D-PAGE: AN EFFICIENT STRATEGY FOR METALLOPROTEOMICS

Inductively coupled plasma–mass spectrometry (ICP-MS) is a sensitive analytical method to detect the total concentrations of elements in biological samples, but it is unable to identify molecules that can bind to metals, and for this reason it is vital to combine this method's use with other biochemical techniques. Therefore, in order to identify elements complexed to specific proteins, a very relevant combination of bidimensional electrophoresis followed by ICP-MS was used. Protein spots from gels were excised and submitted directly to element detection, a method not reported before. This report focused on the use of plasma from people with laryngeal carcinoma. Most elements were below detection level, with only Cr and Pb being observed in all samples. Although the relationship between metals and laryngeal cancer was not conclusive, it is possible to affirm that the methodology utilized here is successful and has the advantage of determining to which proteins the elements bind.     

Distribution of rare earth elements in seaweed: implication of two different sources of rare earth elements and silicon in seaweed

Rare earth elements (REEs) and Si in five species of seaweed, ambient surface seawaters, and suspended solid particles in the seawaters were determined separately. Inductively coupled plasma mass spectrometry (ICP-MS) was used for REEs and inductively coupled plasma emission spectrometry (ICP-ES) was used for Si in order to evaluate REEs as a tracer in seaweeds and to understand the source of inorganic elements, especially Si, in seaweeds. Two different REE patterns, one similar to that of the seawater solution and another resembling that of suspended particles, were observed in seaweeds, and the variation of REE patterns seems to show a clear dependence on the abundance of Si. The REE pattern and Si concentration seem to vary depending on the division: green and red algae showed REE patterns similar to that of suspended particles, but brown algae showed patterns closer to that of seawater solutions and relatively lower Si concentration. The possibility of contamination from silicate particles on the surface of seaweeds was ruled out for several reasons. Silicate particles, not dissolved silicate, have been identified as the direct source of REEs and Si in plants ( Fu et al. 1998 ), and seaweeds are no exception. We have to consider that seaweeds can take up Si from suspended particles through their blade or branches. From the appearance of tetrad-effect-like variation of REEs, Si is assumed to enter a dissolved state just before the particles are taken up. From the results of a sonication experiment, REEs, once taken up as silicate particles, seem to be separated from Si in the thallus.     

Multielement analysis of biological samples by inductively coupled plasma-mass spectrometry

Interest in the biological behavior of a growing number of elements, along with increasing recognition of the importance of interactions among them, demands a versatile and reliable technique for multielement analysis of biological samples. Significant improvements over the sensitivity achieved with conventional inductively coupled plasma (ICP) optical emission spectrometries have been realized with the introduction of quadrupole mass spectrometry (MS) for detection of ions in the plasma. The hybrid technique of ICP-MS promises to be a method of rapid multielement analysis, at detection limits that approach or surpass those of other technologies. However, the application of ICP-MS to analyses of biological interest is truly in its infancy. Here we report the use of ICP-MS for the determination of more than 30 elements of biological interest in a tissue and a biological fluid (rat liver and serum, respectively). Experimental values of the elements serve as a basis for discussion of analytical protocols, performance criteria, and certain problems peculiar to ICP-MS.     

化学元素用于识别褐飞虱不同地理种群的可行性研究

研究褐飞虱Nilaparvata lugens (Stal)不同地理种群成虫体内化学元素组成特点, 筛选出可用于褐飞虱不同地理种群识别的化学元素种类。应用电感耦合等离子体质谱（ICP-MS）半定量分析检测存在于褐飞虱体内的化学元素, 对各元素进行巢式设计方差分析, 初步筛选出地理种群间具有显著差异的元素; 然后对这些元素采用ICP-MS全定量分析, 进一步筛选、 验证地区间差异显著而年份间差异不显著的元素。结果表明, 褐飞虱体内存在57种化学元素, 巢式设计方差分析筛选出了地区间具有显著性差异的27种元素。随后的ICP-MS全定量分析及统计检验, 筛选出各地理种群都存在而含量不同的Ce, Nd, Pr, Sm, Gd, Th, V, Tl, Mo, Cs, Fe和Mn 12种元素。不同地理种群褐飞虱成虫体内的一些化学元素含量存在着显著差异, 有助于褐飞虱远距离迁入虫源地的识别研究, 可为追溯褐飞虱地理来源提供新的方法。     

压力罐消解ICP-MS法同时测定全血中5种微量元素

为了建立同时测定全血中微量元素铬、锰、砷、镉、铅的电感耦合等离子体质谱(ICP-MS)分析法,采用压力罐消解技术对全血样品进行消化,使用ICP-MS法对全血中的五种微量元素铬、锰、砷、镉、铅含量进行测定。结果显示,全血样品中所测定的5种微量元素浓度为0~0.20μg·mL-1时,线性关系良好,相关系数r>0.999,各元素相对标准偏差(RSD)均小于5.0%(n=6),加标回收率为88.4%~107.6%,本法对铬、锰、砷、镉、铅的最低检出浓度分别为0.60、1.4、0.70、0.048、0.18μg·L-1。表明运用ICP-MS同时检测全血中微量元素具有良好的准确度和精密度、灵敏度高、检出限低、元素之间的干扰少,方法高效可行。     

Content of trace elements and chromium speciation in Neem powder and tea infusions

Total concentrations of selected trace elements in Neem powder and in Neem tea were determined by inductively coupled plasma mass spectrometry (ICP-MS). The data revealed that despite high total concentrations of the potentially toxic elements Al and Ni in Neem powder, their amounts dissolved in Neem tea were low. Total concentrations of the other toxic elements Pb, As and Cd were also very low and do not represent a health hazard. In contrast, total concentrations of the essential elements Fe, Cu, Zn, Se Mo and Cr in Neem powder were high and also considerable in Neem tea. Consuming one cup of Neem tea (2 g per 200 mL of water) covers the recommended daily intakes for Cr and Se and represents an important source of Mo and Cu.Speciation analysis of Cr by high performance liquid chromatography (HPLC) coupled to ICP-MS with the use of enriched Cr isotopic tracers to follow species interconversions during the analytical procedure demonstrated that toxic Cr(VI) was not present either in Neem powder or in Neem tea. Its concentrations were below the limits of detection of the HPLC–ICP-MS procedure applied. The speciation analysis data confirmed that even Cr(VI) was added, it was rapidly reduced by the presence of antioxidants in Neem leaves. By the use of enriched Cr isotopic spike solutions it was also demonstrated that for obtaining reliable analytical data it is essential to apply the extraction procedures which prevent Cr species interconversions, or to correct for species transformation.     

A non-radioactive method for measuring Cu uptake in HepG2 cells

At present, all data on Cu uptake and metabolism have been derived from radioactive uptake experiments. These experiments are limited by the availability of the radioactive isotopes 64Cu or 67Cu, and their short half-life (12.5 and 62 h, respectively). In this paper, we investigate an alternative method to study the uptake of Cu with natural isotopes in HepG2 cells, a liver cell line used extensively to study Cu metabolism. In nature, Cu occurs as two stable isotopes, 63Cu and 65Cu (63Cu/65Cu = 2.23). This ratio can be measured accurately using inductively coupled plasma mass spectrometry (ICP-MS). In initial experiments, we attempted to measure the time course of Cu uptake using 65Cu. The change in the 63Cu/65Cu ratio, however, was too small to allow measurement of Cu uptake by the cells. To overcome this difficulty, the natural 63Cu/65Cu ratio in HepG2 cells was altered using long-term incubation with 63Cu. This had a significant effect on Cu concentration in HepG2 cells, changing it from 81.9 +/- 9.46 pmol microg DNA(-1) (week 1) to 155 +/- 8.63 pmol microg DNA(-1) (week 2) and stabilising at 171 +/- 4.82 pmol microg DNA(-1) (week 3). After three weeks of culture with 2 microM 63Cu the 63Cu/65Cu changed from 2.18 +/- 0.05 to 15.3 +/- 1.01. Cu uptake was then investigated as before using 65Cu. Uptake was linear over 60 min, temperature dependent and consistent with previous kinetics data. These observations suggest that stable isotope ICP-MS provides an alternative technique for the study of Cu uptake by HepG2 cells.     

Antioxidant Potential and In Situ Analysis of Major and Trace Element Determination of Ood-saleeb,a Known Unani Herbal Medicine by ICP-MS

The intention of the present research work was to investigate the antioxidant activity and trace element analysis of Ood-saleeb, a known herbal medicine. Preliminary screening of phytochemicals showed that the extract of Ood-saleeb had flavonoids and phenolics. The significant activities in all antioxidant assays were observed in the extract of Ood-saleeb in comparison with the standard antioxidant with respect to dose of Ood-saleeb. Incredible activities to scavenge reactive oxygen species were also observed by the extract of Ood-saleeb. The IC₅₀ values of all factors were determined using ascorbic acid as a standard. The inductive coupled plasma-mass spectroscopy (ICP-MS) was employed for the estimation of trace elements in Ood-saleeb extract. The concentrations of up to 18 elements were detected successfully. Silicon was found in high concentration (85.3 μg/g) while lithium was in low concentration (3 ng/g). The trace elements in the sample were found at different percentage levels which play a key role in the treatment of diseases.     

Determination of major and trace elements in the liver of Wistar rats by inductively coupled plasma-atomic emission spectrometry and mass spectrometry

Inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) were used to determine age-related changes in the concentrations of constituent elements in the livers of Wistar rats of 1 week to 12 months old. At first, sample preparation and analytical conditions were investigated in order to set up a simple routine procedure for measuring multiple elements simultaneously. Seventeen elements in the standard reference samples of bovine and pork livers as well as rat liver samples could be determined with a reasonable precision and reproducibility. They were P, K, Na, Fe, Mg, Ca, Zn, Rb, Cu, Mn, Mo, Al, Co, Sr, Cs, Pb, and Cd in order of the levels of concentration in the adult rat livers. Of these elements, the five major elements (P, K, Na, Fe, Mg, Ca) were determined with ICP-AES and the others with ICP-MS. Although the number of animals was too small to draw a statistically definite conclusion, it seems that age-related changes in the concentrations of these elements could be categorized into three general patterns: (1) remaining essentially constant throughout the animal ages, as observed for P, K, Na, Mg, Ca, Rb, Sr, Cs, and Pb, (2) increasing with age, as observed for Fe, Mn, Mo, Co, and Cd, and (3) decreasing with age, especially in the early stages of growth, as observed for Cu and Zn.     

Metalloprotein separation and analysis by directly coupled size exclusion high-performance liquid chromatography inductively coupled plasma mass spectroscopy

The feasibility of using directly coupled size exclusion high-performance liquid chromatography inductively coupled plasma mass spectroscopy (HPLC/ICP-MS) for the separation and subsequent elemental analysis of metalloproteins in biological samples has been studied. Data, on up to eight elements, was acquired simultaneously and the reconstructed elemental profiles from the chromatographed samples were quantified by flow injection analysis. Absolute and relative detection limits, reproducibility, operational dynamic range, and linearity of response were initially evaluated by analyzing standards of metallothionein protein of known elemental composition for Cd, Zn, and Cu. There was evidence of displacement of Zn from the protein during chromatography and the substitution of Cu sequestered from the mobile phase. Cd associated with the protein was fully recovered during chromatography. Memory effects, due to protein adsorption to the glassware in the torch box, were minimal and there was no degradation of the resolution of the chromatographed peak during extended transport through the HPLC/ICP-MS interface. The versatility of the technique has been demonstrated by the quantitative multi-element analysis of cytosolic metal-binding proteins separated from the polychaete worm Neanthes arenaceodentata. Fidelity of analysis has been demonstrated by two independent procedures: first, by comparing the elemental profiles obtained by directly aspirating the HPLC eluant into the ICP-MS to those obtained by collecting fractions and quantifying the metal content of the proteins in the conventional analytical mode; second, by comparing the stable isotopic profiles for 114Cd obtained by simultaneous ICP-MS analysis with radiometric profiles of 109Cd obtained by counting radioactivity associated with collected fractions.(ABSTRACT TRUNCATED AT 250 WORDS)