In vivo and in vitro inductively coupled plasma mass spectrometry quantification of minerals and heavy metals in Qishiwei Zhenzhu pill and their effect on intestinal flora

OBJECTIVE Cerebral ischemia or ischemic stroke is due to insufficient blood supply to the brain,which causes hypoxia or ischemia in some areas.This work aimed to quantify the minerals and heavy metals in Qishiwei Zhenzhu pill in vivo and in vitro,analyze its effect on the types and abundance of intestinal flora,and study its mechanism on inflammation and apoptosis pathways as a treatment for cerebral ischemia.METHODS Microwave digestion and inductively coupled plasma mass spectrometry(ICP-MS)were used to determine the minerals and heavy metals in 10 batches of Qishiwei Zhenzhu pill in vitro.With the use of the middle cerebral artery obstruction(MCAO)model,ICP-MS was applied to determine the content of minerals and heavy metals in hepatic portal vein blood,abdominal aortic blood,brain,liver,kidney,hair,urine and feces at different time periods.On this model,the ileum,cecum,and colon tissues were tested for intestinal pathology,and 16S rRNA was used for sequencing.Species taxonomy,αdiversity,and species microbial composition and structure analysis were also performed.Polymerase chain reaction and Western blotting were employed to determine the mRNA and protein expression of p38 MAPK,caspase-3,IL^(-1)βand TNF-αin the ischemic brain tissues of rats.RESULTS The average content of heavy metals in the 10 batches of Qishiwei Zhenzhu pill samples is in the descending order Hg>Cu>Pb.Significant differences in the metal elements are found among Qishiwei Zhenzhu pill from different manufacturers but not among the different batches of the same manufacturer.An extremely low content of heavy metals are absorbed into the blood or accumulated in the brain,liver,kidney,and other tissues.Stool is the main excretion route of minerals and heavy metals from Qishiwei Zhenzhu pill.This medicine helps repair the intestinal mucosa in MCAO rats.At the phylum level,it can regulate the abundance of Firmicutes and Proteobacteria in the intestinal flora of rats with cerebral ischemia.At the genus level,it can adjust the abundance of Escherichia Shigella.At the species level,it can adjust the abundance of Lactobacillus yoelii and Lactobacillus reuteri.Cluster classification results show that Qishiwei Zhenzhu pill can improve the intestinal flora of rats with cerebral ischemia,reduce the mRNA and protein expression of caspase-3 and IL^(-1)βin rat brain tissues,and have a tendency to decrease the mRNA expression of p38 MAPK and TNF-α.CONCLUSION Quantifying the minerals and heavy metals in Qishiwei Zhenzhu pill in vivo and in vitro will help improve their quality standards.Minerals and heavy metals are mainly excreted in feces,accumulate in extremely low levels in various tissues,and do not damage the intestinal mucosa.The effective material basis of Qishiwei Zhenzhu pill in treating cerebral ischemia may be related to their Li,Cr,and Cd elements.These pills can improve the environment of intestinal flora,and their mechanism of treatment for cerebral ischemia may be related to the down-regulation of IL^(-1)βinflammatory factor and inhibition of cell apoptosis.

Direct Determination of Trace Impurities in High Purity Zinc Oxide by High Resolution Inductively Coupled Plasma Mass Spectrometry

The determination of trace impurities in high purity zinc oxide by high resolution inductively coupled plasma mass spectrometry （ HR-ICP-MS ） was investigated. To overcome some poteutially problematic spectral iuterference, measurements were acquired in both middle and high resolution modes. The matrix effects due to the presence of excess HCl and zinc were evaluated. The optimum conditions for the determination were tested and discussed. The standard addition method was employed for quantitative analysis. The detection limits ranged from 0.02μg/ g to 6 μg/ g depending on the elements. The experimental resalts for the determination of Na, Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Mo, Cd, Sb and Pb in several high purity zinc oxide powders were presented.

Determination of trace multi-elements in coal fly ash by inductively coupled plasma mass spectrometry

The contents of Cr, Cu, Ni, As, Cd and Pb in coal fly ash were determined by a high resolution inductively coupled plasma mass spectrometry method. The sample digestions were performed in closed microwave vessels with HNO3, HClO4 and HF. The optimum conditions for the determination were obtained. The applicability of the proposed method was validated by the analysis of coal fly ash reference material (NIST SRM 1633a). The results show that most of the spectral interferences can be avoided by measuring in the high resolution mode (maximum mass resolution R=9 000). The detection limit is from 0.05 to 0.21 μg/g, and the precision is fine with relative standard deviation less than 4.3%.

Uncertainty Evaluation of Simultaneous Determination of Lead, Cadmium and Arsenic in Cosmetics by Inductively Coupled Plasma Mass Spectrometry

This study aimed to evaluate the uncertainty of simultaneous determination of lead(Pb),cadmium(Cd)and arsenic(As)in cosmetics by microwave digestion-inductively coupled plasma mass spectrometry(ICP-MS)with ^72Ge,^115In and ^209Bi as internal standards.According to the method of Safety and Technical Standards for Cosmetics(2015),a mathematical model was established to evaluate the sources and components of uncertainty for the determination of lead,cadmium and arsenic in cosmetics.The results showed that the uncertainties in the determination of lead,cadmium,and arsenic elements in cosmetics were(10.1±0.6)mg/kg,k=2,(4.84±0.28)mg/kg,k=2,(2.04±0.18)mg/kg,k=2,respectively.The main factors that affect the uncertainty of determination results were standard substance,calibration curve,recovery and measurement repeatability.

Determination of Palladium II in 5% Pd/BaSO₄by ICP-MS with Microwave Digestion, and UV-VIS Spectrophotometer

Determination palladiums have been reported 5% (w/w) Pd/BaSO4 known as Rosenmund Catalyst. The determination of palladium II known as Rosenmund Catalyst is always an expensive procedure usually involving procedures such as flame atomic absorption spectrophotometry, emission spectrometry, and many spectrophotometric methods. In this study, palladium II in 5% Pd/BaSO4, was synthesized and employed to develop an extractive UV-Visible Spectrophotometric, and an inductively coupled plasma mass spectrometry ICP/MS methods for the determination of palladium II. Specification for Pd is 4.85% to 5.10%;the result was 4.97% for the UV-Visible spectrophotometer and 4.90% for the ICP/MS. Both results meet the requirements.

Determination of wholesome elements and heavy metals in safflower(Carthamus tinctorius L.)from Xinjiang and Henan by ICP-MS/ICP-AES

An inductively coupled plasma mass spectrometry （ICP-MS） or inductively coupled plasma atomic emission spectrometry （ICP-AES） was developed to determine 19 elements in safflower, a traditional Chinese medicinal herb from Xinjiang Autonomous Region and Henan Province of China. Totally 19 elements in safflower included heavy metals, i.e. As, Cd, Cu, Hg and Pb, and wholesome elements, i.e. Al, Ca, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Se, Sr, V and Zn. The results showed that the concentrations of heavy metals in safflower samples were both low, all of which met the national hygiene standards except for Pb in Xinjiang sample. Meanwhile, the distribution tendency of elements in the two samples was similar, which indicated that the plant might absorb given elements in a proportional way. The method can be used for the quality control of elements in safflower, and it provides a way for the determination of the contents of safflower from Xinjiang and Henan.

微波消解-电感耦合等离子体质谱法同时测定有机肥料中9种有毒有害元素的含量

提出了微波消解-电感耦合等离子体质谱法(ICP-MS)同时测定有机肥料中As、Cd、Co、Cr、Ni、Pb、Sb、Tl、V等9种有毒有害元素含量的方法。取0.10 g有机肥料样品于聚四氟乙烯微波消解罐中,以2.5 mL盐酸、7.5 mL硝酸和2.0 mL氢氟酸为混合酸进行微波消解。消解结束后,于140℃赶酸,然后加入1.0 mL 50%(体积分数)硝酸溶液,再用水定容至50 mL,摇匀,过滤,取滤液待测,在线加入混合内标溶液。结果表明:9种元素标准曲线的线性范围均为2~100μg·L^(-1),方法检出限(3s)为0.59~66.75μg·kg^(-1);按照标准加入法对典型有机肥料样品进行回收试验,9种元素测定值的相对标准偏差(n=7)为2.0%~3.5%,回收率为81.5%~112%。

基于石墨消解法测定海洋沉积物中7种重金属的含量

鉴于目前常用的海洋沉积物中重金属测定的消解方法存在工作效率低、操作复杂、交叉污染、人员危险性高等问题,通过比对和参考现行规范、标准和文献资料中海洋沉积物重金属的不同消解方法,提出了全自动石墨消解海洋沉积物的方法,并以原子荧光光谱法测定汞和砷的含量,以电感耦合等离子体质谱法测定铜、铅、锌、镉、铬的含量。以6 mL盐酸、2 mL硝酸和8 mL水为消解酸,于100℃消解0.2 g样品1.5 h;消解结束后,冷却至室温,用水定容至50 mL,按照原子荧光光度计的工作条件测定汞和砷的含量。以5 mL盐酸、5mL硝酸为消解酸,先于120℃消解0.2 g样品1 h;然后加入2 mL硝酸、5 mL氢氟酸和2 mL高氯酸,于180℃继续消解4 h;消解结束后,冷却至室温,用水定容至50 mL,按照电感耦合等离子体质谱仪的工作条件测定铜、铅、锌、镉、铬的含量。结果表明:汞、砷标准曲线的线性范围分别在1.00μg·L^(-1)以内和10.0μg·L^(-1)以内,铜、铅、锌、镉、铬标准曲线的线性范围在100μg·L^(-1)以内,汞、砷、铜、铅、锌、镉、铬的检出限(3 s)为0.006~0.522 mg·kg^(-1);使用有证海洋沉积物标准物质进行验证,7种重金属测定值均在认定值的不确定度范围内,相对标准偏差(n=6)为1.4%~7.4%;对3种实际样品进行回收试验,回收率为92.5%~111%。

临沧勐库熟茶基体重金属成分分析标准物质的制备研究

[目的]建立临沧勐库熟茶基体重金属成分分析标准物质的制备方法。[方法]将筛选的临沧勐库熟茶通过干燥、粉碎、筛分、研磨、混匀、均匀性初检、分装,制备得到临沧勐库熟茶基体重金属成分分析标准物质,对均匀性和稳定性进行检验;参考食品安全国家标准,10家实验室采用微波消解-电感耦合等离子体质谱法,对标准物质中Cr、Cu、As、Cd、Pb元素含量进行联合定值,评定定值结果的测量不确定度。[结果]制备得到的临沧勐库熟茶基体重金属成分分析标准物质的均匀性良好,稳定性达到12个月,其中Cr、As元素的定值结果分别为(1.534±0.126)、(0.108±0.018) mg/kg。[结论]该临沧勐库熟茶基体重金属成分分析标准物质满足基体标准物质的要求,可用于普洱茶熟茶检测的质量控制。

电感耦合等离子体质谱法测定平阴玫瑰中13种稀土元素

目的建立微波消解电感耦合等离子体质谱法(ICP-MS)测定玫瑰及其制品中13种稀土元素含量的分析方法。方法样品经微波消解后,以铑(^(103)Rh)、铟(^(115)In)、铼(^(185)Re)为内标元素通过在线方式加入,用ICP-MS进行定量测定。以两种国家认证的标准物质进行方法准确度验证。结果各稀土元素质量浓度在0.1~20µg/L范围内线性关系良好(r≥0.9996),检出限在0.072~0.258μg/kg之间,平均回收率在87%~116%之间,相对标准偏差(RSD)为0.8%~4.3%。对实际样品检测发现,玫瑰及其制品中13种稀土元素均有检出,其中铈(^(140)Ce)平均含量最高,镥(^(175)Lu)平均含量最低。结论该检测方法快速、准确、操作简便、灵敏度和回收率高,能够满足玫瑰及玫瑰制品中稀土元素的测定要求。

电感耦合等离子体质谱法测定鲜河蚌肉水提物中5种元素含量

目的建立测定鲜河蚌肉水提物中铜(Cu)、砷(As)、镉(Cd)、汞(Hg)、铅(Pb)含量的电感耦合等离子体质谱(ICP-MS)法。方法采用微波消解法对样品进行前处理。采用ICP-MS法测定,等离子体射频功率为1550 W,等离子体气体流速为15.0 L/min,辅助气体(氩气)流速为0.90L/min,雾化气流速为1.05L/min,蠕动泵速为0.1r/s,采样深度为8 mm,调谐模式为No Gas模式,重复3次。结果Cu、As、Cd、Hg、Pb质量浓度分别在0~500 ng/mL、0~200 ng/mL、0~10 ng/mL、0~5 ng/mL、0~20 ng/mL范围内与仪器响应值线性关系良好(r≥0.9996,n=5),检测限分别为0.0205,0.0045,0.0008,0.0042,0.0051 mg/kg,定量限分别为0.0682,0.0149,0.0027,0.0141,0.0170 mg/kg;精密度、重复性试验结果的RSD均小于5%;平均加样回收率分别为99.60%,106.16%,108.93%,115.30%,103.40%,RSD分别为0.84%,6.03%,1.15%,3.56%,0.55%(n=6)。参考《药用植物及制剂外经贸绿色行业标准》,9批样品中的Cu、Hg、Pb均符合限量标准,As、Cd超标的样品分别有8批、2批。结论该方法操作简单,结果准确,可用于测定鲜河蚌肉水提物中Cu、As、Cd、Hg、Pb的含量。

破壁灵芝孢子粉中多种重金属元素及硒含量检测方法探讨

采用微波消解进行前处理,三重四极杆-电感耦合等离子体质谱法测定破壁灵芝孢子粉中镉、铬、镍、砷、铅、汞及硒元素含量,对方法条件进行优化和讨论,并对20批次破壁灵芝孢子粉进行测定。结果表明,镉、铬、镍、砷、铅和汞元素在氦气碰撞模式,硒元素在氧气反应模式下,采用内标校正定量,可达到良好的测定效果。在优化的条件下,各元素线性关系良好,检出限均可达μg·kg^(-1)级别;镉、铬、镍、砷、铅及硒元素的加标回收率在90.3%~105.0%,汞的加标回收率在82.1%~92.5%;方法精密度在5%以内。此方法前处理操作简便,检测灵敏度高,稳定性好,给灵芝孢子粉多元素测定提供了良好的技术支撑。

常压密闭微波消解-电感耦合等离子体质谱法测定磷矿石中的稀土元素

磷矿石中的稀土元素测定方法主要使用电感耦合等离子体质谱法(ICP-MS),样品处理方式主要采用敞口混合酸溶和碱熔。传统的酸溶和碱熔处理矿石样品时间较长,试剂加入量大,操作过程较为繁琐,且易造成环境污染。微波消解直接向样品释放能量,工作效率高,且易挥发元素被保留在消化溶液中,防止挥发造成结果偏差及环境污染。本文采用微波消解对磷矿石进行处理,并在二次消解过程中加入饱和硼酸络合溶矿过程中产生的不溶物氟化钙,在线加入铑和铼双内标的方式,建立了ICP-MS测定磷矿石中15种稀土元素的方法。结果表明:二次消解过程中加入饱和硼酸能有效地络合沉淀,彻底溶解样品,经上机测定后15种稀土元素的相对标准偏差(RSD)在0.68%~4.52%之间,回收率在93.1%~106.6%之间,方法检出限为0.003~0.029μg/g。选取两个磷矿石样品,用本方法与混合酸(盐酸-硝酸-氢氟酸-硫酸)酸溶方法进行对比试验,相对标准偏差在-5.82%~5.99%之间,表明本方法测定稀土元素是有效可行的。对于样品的前处理方法,酸溶、碱熔和微波消解都有各自的特点,微波密封消解能避免一些能形成易挥发组分的损失并且外源性污染少。本方法拓展了测定磷矿石中稀土元素的样品前处理方法,操作性强,是对现行方法的有益补充。

电感耦合等离子体质谱分析大气颗粒中重金属离子含量的不确定度评定

评定了电感耦合等离子体质谱法测定大气颗粒物中重金属离子镉和铅含量的不确定度。建立了微波消解-电感耦合等离子体质谱对PM_(10)中重金属离子含量测试的数学模型,对影响测试过程的各个要素进行了分析,讨论了各不确定度分量,包括测量重复性、溶液定容、标准工作曲线拟合、标准物质、称量和仪器稳定性等,并开展了不确定度合成计算和扩展不确定度计算。结果表明,当大气颗粒物样品中镉和铅的质量浓度测量值分别为0.026、0.251μg/m^(3)时,扩展不确定度分别为0.000462、0.0036μg/m^(3)(k=2)。该方法可为建立大气颗粒物中重金属离子的分析和评价方法提供参考依据。

不同蛋白原料中矿物质元素含量分析

本试验旨在研究不同蛋白原料中常量元素、微量元素、重金属元素等26种元素的含量及分布规律,分析其含量差异可能成因,为不同蛋白原料科学利用提供数据依据。本实验利用电感耦合等离子体质谱(ICP-MS)技术,系统分析了鸡肉粉、鱼粉、花生浓缩蛋白、大豆浓缩蛋白、棉籽蛋白、菌体蛋白、藻粉和昆虫粉等8种15批次的蛋白原料中元素组成及分布规律。结果表明,所有蛋白原料均含有供试矿物质元素,不同种类的蛋白原料矿物质元素含量差异较大(P<0.05);某些元素在同种不同来源的原料中含量水平差异显著(P<0.05);存在蛋白原料中单一元素含量明显高于其他原料的现象(P<0.05)。通过对数据结果的分析有利于推广应用新型蛋白质饲料原料,促进我国养殖业的可持续发展。

地质样品铊同位素分析预处理方法优化

铊同位素体系可以示踪天体演化、古环境变化、矿床成因及污染物迁移等地质过程。然而,目前用于铊同位素分析的样品消解和离子交换方法耗时较长,往往需要两周甚至更久;为了提高化学前处理效率,本文采用微波消解法分解样品,以AG1-X8阴离子交换树脂纯化铊,采用多接收器电感耦合等离子体质谱(MC-ICP-MS)测试,仪器的质量歧视用铅同位素标准溶液(NIST SRM981)校正。通过考察消解条件、淋洗曲线和基质效应,结果表明:采用微波消解法,在2mL硝酸-2mL氢氟酸-0.5mL高氯酸的混合酸体系中选用适当的消解程序可以将0.2g土壤标准物质GBW07406消解完全,总耗时不超过2h;利用AG1-X8树脂,上样后,依次以2mL 2mol/L硝酸-1%溴水淋洗6次、2mL超纯水淋洗1次和2mL 0.1mol/L盐酸-6%二氧化硫淋洗5次(收集铊),可有效地纯化铊;常见共存元素的干扰实验结果显示,树脂填充量为2mL时,该淋洗流程所允许上样溶液中含有三价铁和三价铝离子的量分别不应超过2.56mmol和4.90mmol,否则会使铊的回收率降低。将此方法应用于4个地质标准物质中铊同位素比值的测定,ε^(205)TlGSB Tl的精密度(2SD,n=6)均优于0.3;与文献的结果对比显示,标准物质NOD-P-1、GBW07406和GSP-2的ε^(205)Tl差值(ε^(205)Tl_(NIST 997)-ε^(205)Tl_(GSB Tl))均为0.8,NOD-A-1的ε^(205)Tl差值为0.7,说明方法具有较好的准确性;此外,可以估算标准物质GSB 04-1758-2004相对于NIST 997的ε^(205)Tl值应约等于0.8。

利用电感耦合等离子体质谱法测定肥料重金属砷、镉、铅、铬含量

选取7个不同的肥料样品,采用硝酸-盐酸(王水)消解,消解液中砷(As)、镉(Cd)、铅(Pb)、铬(Cr)重金属元素含量采用电感耦合等离子体质谱(ICP-MS)法氦碰撞模式测定。结果显示,根据固体称重量为0.2 g,定容体积50 mL,Cr、As、Cd、Pb方法检出限分别为0.018、0.008、0.005、0.021 mg/kg,定量限分别为0.061、0.025、0.016、0.069 mg/kg,根据液体称重量1.0 g,定容体积50 mL,Cr、As、Cd、Pb方法检出限分别为0.004、0.002、0.001、0.004 mg/kg,定量限分别为0.012、0.005、0.003、0.014 mg/kg,待测样品分别进行6组重复测定,结果显示Cr相对标准偏差(RSD)在3.8%~16.8%之间,As的RSD为3.9%~56.5%,Cd的RSD为0.0%~25.7%,Pb的RSD为4.2%~24.5%,样品加标回收率为67.4%~122.0%。4家实验室对不同肥料种类抽取样品进行实验室比对测定,分析显示所有参与实验室测试值之间存在一致性,经柯克伦检验剔除离群值,保留歧离值后,将格拉布斯检验应用于通过柯克伦检验后的单元平均值,各元素均未发现有单个或成对歧离值或离群值存在。方法精密度和准确度满足要求,结论认为ICP-MS可用于肥料中As、Cd、Pb、Gr含量的测定分析。

2022—2023年阜阳市食品重金属污染情况调查分析

目的:调查分析2022—2023年阜阳市食品风险监测6种食品中Pb、Cd、总Hg、总As、Cr5种重金属污染情况,为食品安全风险监测提供数据支持。方法:采用随机采样的方法,采集阜阳市三区五县农贸市场及各类商超小麦粉、玉米粉、大米、茶叶、黄豆和蔬菜等样品,电感耦合等离子体质谱法检测,对同一重金属元素在不同样品中检出情况及不同重金属元素在相同样品中检出情况进行分析。结果:80份样品中有2份大米样品Pb超标,超标率为2.5%;5种重金属检出率依次为Cr(83.8%)>总As(78.8%)>Cd(61.3%)>Pb(45%)>总Hg(0%);茶叶样品中Cr、Pb最高检出值较高,分别为0.645 mg·kg^(-1)和0.559 mg·kg^(-1),大米样品Pb、Cd、总As最高值分别为0.816 mg·kg^(-1)、0.166 0 mg·kg^(-1)、0.251 0 mg·kg^(-1),存在一定的污染风险;总Hg均未检出,5种重金属检出情况具有统计学差异,χ^(2)=146.323,P<0.001;超标情况无统计学差异,χ^(2)=4.401,P=0.198;结论:2022—2023年监测的80份样品中有2份大米样品Pb超标,且均来自农贸市场样品,应加强农贸市场食品安全监管力度;大米、小麦粉、玉米粉样品Pb(2份超标样品除外)、Cd、总As检出率及最大检出值偏高,虽低于标准限值,但存在一定的污染风险,茶叶中Pb、Cd、总As、Cr检出率均为100%,明显高于黄豆和蔬菜样品,未出现超标样品,总体污染状况良好,食品卫生质量相对安全,但存在污染风险,特别应加强谷物和茶叶重金属的连续监测。

电容器薄膜用聚丙烯原料微量元素分析方法

为了精确分析电容器薄膜用聚丙烯原料中微量元素,介绍了电容器薄膜用聚丙烯原料进行元素测定时的干法灰化法以及微波消解法两种预处理方法,比较了不同方法对分析结果的影响。对比了几种分析手段的特点,选择电感耦合等离子体质谱法作为分析手段。相比于干法灰化法,微波消解法的准确度和精密度都较高,微波消解法结合ICP-MS法适用于测定电容器薄膜用聚丙烯原料中的微量金属元素,建立了基于ICP-MS法测定电容器薄膜用聚丙烯原料中微量金属元素含量的方法。

微波消解-电感耦合等离子体质谱法测定肥料中9种污染元素

采用电感耦合等离子体质谱法(ICP-MS)测定,超级微波消解并优化不同类型肥料的消解条件,建立了超级微波-ICP-MS测定多种类型肥料中V、Cr、Co、Ni、As、Cd、Hg、Tl、Pb 9种污染元素含量的方法。本方法的线性相关系数均大于0.9999,方法检出限范围为0.000500~0.0293 mg/kg,各元素加标回收率为85.0%~110%,该方法灵敏度高、准确度较好,可实现不同类型肥料样品中多元素的准确测定。