微波消解-电感耦合等离子体质谱法(ICP-MS)测定板栗中的矿物元素及稀土元素[ ]

采用微波消解前处理方法,结合电感耦合等离子体质谱技术,建立了板栗中钠（Na）、钾（K）、镁（Mg）、锰（Mn）、铁（Fe）、钒（V）、钴（Co）等19种矿物元素及镧（La）、铈（Ce）、镨（Pr）、钕（Nd）、钐（Sm）、铕（Eu）、钆（Gd）、铽（Tb）、镝（Dy）、钬（Ho）、铒（Er）、铥（Tm）、镱（Yb）、镥（Lu）、钇（Y）等15种稀土元素的同时分析测定方法。该方法检出限为0.0027~0.78μg?L-1,相对标准偏差为1.4%~6.3%。通过国家标准物质GBW10019苹果的准确率实验验证,测定结果均在标准证书值范围内。实验结果表明,该方法适用于板栗中矿物元素及稀土元素的同时测定。     

电感耦合等离子体质谱法测定硫化物单矿物中痕量稀土元素

硫化物单矿物基体复杂,在利用电感耦合等离子体质谱仪测定其中稀土元素时,基体效应干扰严重,为准确测定其中的稀土元素,必须对样品进行分离富集。采用硝酸-氢氟酸体系溶解样品,通过Fe(OH)_3共沉淀和阴离子交换树脂(AG1-X8)去除基体元素,利用电感耦合等离子体质谱法测定稀土元素。通过测定两种国家标准物质硫化物单矿物(GBW 07267,GBW07268,GBW07270)中稀土元素来验证该方法,方法检出限为0. 003(Tm)～0. 138(Ce) ng·g~(-1),加标回收率在91%～113%之间。     

微波消解电感耦合等离子体质谱法测定桃中稀土元素及其分布

以市场销售的桃为实验材料,利用微波消解电感耦合等离子体质谱法(ICP-MS)同时测定桃中稀土元素的含量。样品经过硝酸-氢氟酸-双氧水微波消解,实现了桃中16种稀土元素的测定。各元素的检出限在0.004~0.020μg·g-1之间,方法精密度在0.78%~2.96%,回收率在95.0%~106.0%之间。比较了稀土元素在果皮和果肉中的分布。结果表明,稀土元素在果皮中的含量明显高于果肉。本法快速、准确,可用于桃等水果中稀土元素的测定。     

电感耦合等离子体质谱法同时检测红枣中铅、砷、镉、汞、铜、锌和16种稀土元素

为了研究哈密、若羌和和田红枣中铅、砷、镉、汞、铜、锌和16种稀土元素的含量情况,了解红枣重金属及稀土元素摄入的风险,建立同时检测红枣中铅、砷、汞、铜、锌和16种稀土元素的方法。红枣样品用微波消解法进行样品前处理,以电感耦合等离子体质谱法测定红枣中铅、砷、镉、汞、铜、锌和16种稀土元素的含量。各元素校准曲线的相关系数均大于0.999 0,检出限为0.01~0.05μg/L。加标回收率为92.1%~105.2%,测定结果的相对标准偏差为1.2%~3.6%(n=6)。用该方法测定苹果标准物质(GBW 10019),测定值与标准值一致。该方法适用于红枣类样品中多元素污染物快速检测及风险评估,红枣样品分析结果表明铅、砷、镉、汞、铜和稀土元素在3种红枣中的含量较低,风险监测数据表明红枣中存在重金属铅、镉摄入性风险。     

八极杆碰撞/反应池(ORS)-电感耦合等离子体质谱(ICP-MS)法测定复杂矿物中的稀土元素

对未知复杂矿物样品采用扫描电子显微镜-能谱法解析样品,确定基本成分后选择合适的样品前处理方法。实验中采用过氧化钠熔融法熔解样品,用水浸出,硝酸酸化后制备待测样品溶液。以Rh为内标,用八极杆碰撞/反应池(ORS)-电感耦合等离子体质谱(ICP-MS)法测定了复杂样品中的稀土元素。多次测定同一混合标准溶液结果的相对标准偏差(RSD,n=11)小于4%,加标回收率为90%~110%。方法适用于未知复杂矿物中稀土元素的测定。     

ICP-AES法测定方铅矿中多元素的方法研究

采用电感耦合等离子体原子发射光谱法(ICP-AES)进行方铅矿中多元素同时测定.通过对方铅矿样品化学处理试验建立了HCl-NH4Cl-HNO3的溶矿体系.本体系采用基体匹配、背景系数和元素干扰系数校正及元素内标法确定了最佳综合实验测试条件.本实验建立的ICP-AES法同时测定方铅矿中镉、钴、铜、铁、铟、铅、锌7种元素的方法,本方法测量相对误差RE (n=8)为1.50%～7.50%,相对标准偏差RSD (n=8)为1.7%～5.7%.经国家一级标准物质GBW 07269分析验证可以满足方铅矿单矿物样品的分析要求.     

微波消解-电感耦合等离子体发射光谱(ICP-OES)法测定茄子中矿物元素含量

采用微波消解HNO_3+H_2O_2湿法制取样品溶液,全谱直读电感耦合等离子体发射光谱(ICPOES)法同时测定茄子中K、Na、Mg、Al、Ca、B、Ba、Cr、Cu、Fe、Sn、Mn、P、Sr、Zn 15种矿物元素,实际样品测定结果显示,Al元素含量超过国家规定标准(≤100mg/kg),微量元素Ca含量相对较高。各元素的检出限为1.0~440μg/L,标准样品的加标回收率93.5%~109%,相对标准偏差在2.1%~6.5%(n=6)。实验方法简单、重现性好,可用于测定茄子样品中各矿物元素含量。测定结果为茄子的深入研究提供基础数据。     

高压密闭消解-电感耦合等离子体质谱法测定煤中稀土元素

煤作为有机物与无机物的复杂混合物,含有多种微量元素,不同的微量元素信息代表不同的地质意义,稀土元素可以提供丰富的沉积环境与物源信息。采用高压消解罐,选用硝酸和氢氟酸混合酸消解样品,建立了电感耦合等离子体质谱法测定16种稀土元素的方法。讨论了样品量、消解试剂、质谱干扰等影响因素,各元素的方法检出限在0.001～0.016μg/g,NIST SRD 1632d煤标准样品实测值和标准值一致,标准样品测定结果与实测样品结果相对标准偏差(RSD,n=11)小于5%,可满足煤中稀土元素的准确测定,为煤类样品中稀土元素测定提供了新的参考方法。     

电感耦合等离子体原子发射光谱(ICP-AES)法测定镧玻璃废粉中稀土元素总量及配分量

建立了电感耦合等离子体原子发射光谱(ICP-AES)法测定镧玻璃废粉中稀土元素总量和配分量的分析方法。样品经碱熔融后分离硅、铝等元素及钠盐,用硝酸和高氯酸破坏滤纸和溶解沉淀,用ICP-AES法测定稀土元素总量和配分量。讨论了溶解样品条件、共存元素干扰等影响测定的各种因素。实际样品的稀土总量与草酸盐重量法测定结果一致,配分量与X-射线荧光光谱(XRF)法、电感耦合等离子体质谱(ICP-MS)法测定结果一致。RSD(n=11)在0.15%~1.1%,加标回收率为97%~105%。测定范围为:La_2O_3/REO(80%~98%);CeO_2/REO(2%~20%);REO(16%~70%)。方法能快速准确地测定镧玻璃废粉中稀土元素总量及配分量。     

动能歧视(KED)-电感耦合等离子体质谱(ICP-MS)法测定贵州沉积型稀土矿中16种稀土元素

贵州沉积型稀土矿主要含有高岭土-锐钛矿石等矿物,存在高含量Si、Al、Fe、Ti、Zr等难溶基体元素,采用高压密闭微波消解法处理难以将其完全溶解,易使测定结果偏低,需再次消解或进一步电热板敞开酸溶处理,方法耗时长,不利于大批量样品检测需求。同时电感耦合等离子体质谱法(ICP-MS)在测定稀土元素时存在基体效应和质谱干扰,影响了检测数据的准确性。本文采用过氧化钠熔融分解样品,熔融物冷却后引入三乙醇胺溶液,在碱性溶液中,大量基体元素与三乙醇胺形成稳定配合物,并与大量溶剂钠盐存于溶液中,稀土元素与Ca、Mg、Sr、Ba等留存于沉淀,经过滤,实现稀土元素与大量基体元素分离,随后沉淀用(1+1)硝酸复溶,并以103Rh和185Re为在线注入内标协同降低基体干扰;启用动能歧视(KED)模式以降低测定过程中潜在的质谱干扰。实验结果表明:高压密闭微波消解法消解液浑浊有残渣,溶矿耗时长,测试结果偏低,碱溶法酸化后溶液清亮透明,稀土元素测定值准确性高;经条件试验,采用10%三乙醇胺溶液提取能较大降低基体干扰;启用KED模式可降低测定过程中的质谱干扰,且准确度优于STD模式;碱溶法方法检出限为0.008μg/g~0.049μg/g,测定下限为0.034μg/g~0.195μg/g,相对标准偏差RSD在0.78%～10.2%之间,相对误差RE在0.0225%~13.5%之间。经实际样品验证,碱熔法较适用于贵州沉积性稀土矿中16种稀土元素的测定。     

The determination of fluorine in rare earth fluorides by high temperature hydrolysis

The technique of pyrohydrolysis has been applied to the determination of fluorine in the fluorides of scandium, yttrium, and the lanthanons. These fluorides have been divided into two classes according to their rate of hydrolysis. Lutetium, ytterbium, cerium(III), scandium, gadolinium, terbium, dysprosium, holmium, erbium, and thulium florides can be hydrolyzed in 30 min or less. Yttrium, lanthanum, praseodymium, neodymium, samarium, and europium fluorides require from 45 to 150 min for complete hydrolysis. Accelerators, such as uranium oxide (U₃O₈), chromium(III) oxide, and a mixture of these oxides have been used successfully to reduce the tune required for quantitative hydrolysis of the fluorides in the latter group. The use of the correct accelerator reduces the hydrolysis time to 30 min or less for all these fluorides except lanthanum, praseodymium and neodymium.     

Determination of ten rare-earth elements and yttrium in silicate rocks by ICP-AES without separation and preconcentration

Lanthanum, cerium, neodymium, samarium, europium, gadolinium, dysprosium, erbium, ytterbium, lutetium and yttrium have been determined in 8 international rock standards by inductively coupled plasma atomic emission spectrometry (ICP-AES) without prior ion-exchange separation and preconcentration. The results for La, Ce, Nd, Eu, Dy, Yb and Y were in good agreement with the reported values, whereas those for Sm, Gd, Er and Lu were less accurate. However, the results for Sm, Gd, Er and Lu can also be used for studies of petrogenesis.     

Studies on monoxide emission spectrometry of rare-earth elements. IV. Simultaneous determination of Sm, Eu, Gd in Sm---Eu---Gd concentrates by the dual wavelength method

This paper reports the determination of samarium, europium and gadolinium by Sm and Gd monoxide emission and Eu atomic emission. The enhancement effect of other rare earth elements on Sm, Eu and Gd emission was studied. Large amounts of lanthanum (La) were used as enhancing reagents and chemical interference inhibitors and the dual wavelength method was introduced to eliminate spectral interference, in which the analytical wavelengths used were Sm 651.0 nm, Eu 459.4 nm and Gd 461.6 nm and the reference wavelengths were Sm 651.4 nm, Eu 459.8 nm and Gd 461.2 nm. The method has been applied to the assay of Sm, Eu and Gd in synthetic Sm---Eu---Gd concentrates with satisfactory results.     

电感耦合等离子体质谱法测定农产品土壤中痕量稀土元素

建立了电感耦合等离子体质谱法（ICP-MS）测定农产品土壤中15个稀土元素的分析方法．研究了溶样体系用量、标准溶液配制、质谱干扰、内标元素的选择．采用HNO3-HF—H2O2体系电热板溶解样品,稀土元素的溶出率较高．用ICP—MS同时测定土壤中的钇、镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥．以Rh、Re双内标在线校正,有效地降低了信号漂移对分析结果的影响．方法检出限为0．0012—0．0071ng／mL．对实际样品进行连续7次测定,方法精密度为0．2％～4．7％,回收率为97％-114％．经国家标准物质验证,结果与标准值相符．方法弥补了微波消解法的不足,且快速、准确,适合于大批量土壤样品分析．     

Thermogravimetric investigation of scandium,yttrium and the rare earth metal diliturates

Thermolysis curves for scandium, yttrium, lanthanum, cerium(III), neodymium, samarium, gadolinium, dysprosium and erbium diliturates are described, Scandium diliturate forms a 15-hydrate which dehydrates in 3 steps. The other diliturates all form 12-hydrates which dehydrate smoothly. All of the anhydrous diliturates are thermally stable to about 240°.Solubilities in water for scandium, yttrium, lanthanum, cerium(lll), neodymium, samarium. gadolinium, dysprosium and erbium diliturates are given. Scandium diliturate is the most soluble and neodymium diliturate the least soluble. Solubilities of rare earth diliturates not investigated can be predicted approximately.Methods for thermogravimetric determination of yttrium, lanthanum, neodymium, samarium, gadolinium, dyprosium, and erbium as the diliturates have been developed. The precipitates are quite dense, easily handled and filterable. Weighing as the diliturate salts gives these determinations a very favorable gravimetric factor.     

稀土离子对钐-铕-噻酚甲酰三氟丙酮-三正辛基膦化氧己烷萃取体系纸上荧光的增敏作用及其应用

在Sm3 + 、Eu3 + 噻酚甲酰三氟丙酮 三正辛基膦化氧己烷萃取体系中Y3 + 、La3 + 、Gd3 + 、Tb3 + 、Dy3 + 、Lu3 + 等离子可增强Sm3 + 、Eu3 + 的纸上荧光 ,其中以Tb3 + 的增敏效应最强 ,灵敏度提高了 6倍。将滤纸适当处理后可使Sm3 + 、Eu3 + 的检出限分别达到 0 .15和 0 .0 0 7ng。本法用于混合稀土氧化物中 0 .xng级的Sm3 + 和0 0 0xng级Eu3 + 的同时测定 ,结果满意     

Total Reflection X-Ray Fluorescence Determination of Rare Earth Elements in Mineral Water Using a Combined Preconcentration Technique

A combined approach for the simultaneous determination of lanthanum, cerium, praseodymium, neodymium, and samarium in mineral water in the range from?·?10^?2 to 10¹?µg/L by total reflection X-ray fluorescence analysis is reported. The combined technique of preconcentration of the rare earth elements ions includes the codeposition of their hydroxides on a collector and dispersive liquid–liquid microextraction by chloroform to form complexes with 1-(2-pyridylazo)-2-naphthol. The results for the determination of lanthanum and light lanthanides in natural water samples with the combined approach are in good agreement with measurements obtained by inductively coupled plasma–mass spectrometry.     

Synthesis,structure, and luminescent properties of lanthanide coordination compounds with 3-methyl-4-formyl-1-phenylpyrazol-5-one

An exchange reaction of the sodium salt of 3-methyl-1-phenyl-4-formylpyrazol-5-one (HL) with chlorides or nitrates of lanthanides (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Yb) was used to synthesize coordination compounds of composition LnL₃·nSolv (Solv = H₂O or EtOH). According to powder X-ray diffraction data, these compounds constitute two series: one comprises lanthanum and neodymium complexes, and the other, samarium, europium, gadolinium, terbium, dysprosium, and ytterbium complexes. For the complexes of the first series, the structure was solved in a single-crystal diffraction experiment carried out on [La₂(μ-L)₃(L)₃(H₂O)₃]·2MeOH. The lanthanum atoms in the complex are at a distance of 4.222(2) — from each other, and they are structurally nonequivalent and linked by three 5-hydroxy-4-formylpyrazole anions. Solid-phase samples of the coordination compounds under study feature weak luminescence in the spectral regions intrinsic to lanthanide cations.     

Mg(OH)_2共沉淀和直接稀释联用ICP-MS法准确测定海水中的多种常量-微量元素

对海水中多种常量/微量元素分别用Mg(OH)_2共沉淀和直接稀释ICP-MS法进行方法比较研究,分别确定了这些元素适宜的准确分析方法,为海水中常量/微量元素的ICP-MS测定提供了实用的检测手段。结果表明,Mg(OH)_2共沉淀法能够实现对V,Cr,Mn,Co,Cd及稀土元素(La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)等19种微量元素的分离富集和准确测定;10倍直接稀释法能够同时准确测定海水中B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn 13种微量元素,但不适合Zn,Ni,Co和Pb,以及稀土元素等在海水中浓度过低元素的测定;两种方法对适宜测定的元素均操作简便快速,具有较高的准确度和精密度。这两种方法联用,就可用约50 mL的海水实现大洋和近海海水中Co,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu(这15个元素采用Mg(OH)_2共沉淀法)及B,Sr,Li,Rb,I,V,Cr,As,Cd,U,Mo,Cu,Mn(这13个元素采用10倍直接稀释法)等28种元素的准确测定。