化学—X—射线荧光光谱法测定地质样品中的痕量稀土元素

本文采用对氯偶氮氯膦（ＣＰＡ－ＰＣＬ）为螯合剂。ＶＳ－Ⅱ型强碱性阴离子交换纤维为载体，以先吸着后螯合方式对稀土元素与基体元素进行分离与富集，并经酸溶制备成溶液，采用溶液进样法直接由Ｘ射线荧光光谱法（ＸＲＦＳ）测定１５个稀土元素。该法具有简便、螯合剂用量少、基体效应小的特点，精密度、准确度及检测限均能满足地质样品分析要求，取得满意结果。     

硬质合金中微量稀土元素总量的测定

本文采用偶氮氯膦Ⅲ比色法,测定硬质合金中微量稀土元素,並对其主体元素钨、钼、钛、钴、钽和铌等在测定条件下的行为进行了研究。试验结果表明,以硝酸、氢氟酸分步分解试样,用氟化铵代替氢氟酸沉淀稀土元素而与共存元素分离,可避免钴的共沉淀。方法易于掌握,有较高的准确度和精密度。对三个试样(其稀土含量在0.09～5%范围内),由不同分析人员以该法进行了80余次单次测定,相对偏差为11～5%。主要试剂盐酸-柠檬酸钠缓冲溶液(pH=2);偶氮氯膦Ⅲ溶液—0.02%,乙醇(8+92)溶液;混合稀土标准溶液(10微克/毫升)—按Y∶La∶Ce=50:     

十氯酮-二氯甲烷溶液标准物质的定值与不确定度评定

制备了十氯酮-二氯甲烷溶液标准物质,采用气相色谱-质谱联用法(GC-MS)和红外光谱法(IR)对十氯酮原料定性鉴定,并采用气相色谱法(GC/FID)及多家实验室联合定值法对十氯酮的纯度进行定值,测得十氯酮原料纯度为99.9%。在(20±4)℃下,以重量-容量法配制十氯酮-二氯甲烷溶液标准物质,对溶液进行均匀性与稳定性分析、量值核验,并对其量值结果进行了不确定度评定。     

新显色剂对(间)氟偶氮氯膦与稀土元素的显色反应

目前,已研究过氯、溴和碘取代基对偶氮氯膦类试剂显色性能的影响,而对于氟取代基的影响尚未见报道。我们新合成了对(间)氟偶氮氯膦显色剂,并研究了该试剂与稀土元素的显色反应及测定钢中稀土元素的方法。 试验采用的仪器为UV-3000型分光光度计,721型分光光度计。主要试剂为0.05％的     

茶叶中稀土元素的萃取分离-ICP-AES法测定

采用1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮(PMBP)苯溶液萃取分离-ICP-AES法同时测定茶叶中15种稀土元素,消除了基体的干扰,并对样品前处理方法、萃取分离条件进行了考查.方法回收率为: 92.3%～112%,相对标准偏差＜2.5%.在最佳工作条件下,测定了茶叶标准物质(GBW07605)中稀土元素,结果与标准值吻合.     

微波消解-电感耦合等离子体质谱(ICP-MS)法同时测定紫菜中16种稀土元素

以农贸市场和超市的紫菜为样品,经过微波消解,利用电感耦合等离子体质谱(ICP-MS)法对紫菜中16种稀土元素进行同时测定。通过在线引入内标溶液,在0~2.00μg/L范围内检测信号(CPS)与稀土元素含量之间呈现良好的线性关系,相关系数R2均大于0.999 9,相对标准偏差(RSD)小于3.3%。用来测定国家标准物质GBW10052(GSB-30)和GBW10045中的稀土元素,所得结果与标准值基本一致,从而建立了一种快速、准确测定紫菜中痕量稀土元素的方法。     

2-乙基己基膦酸单(2-乙基己基)酯树脂色层分离电感耦合等离子体原子发射光谱法测定钢中微量稀土元素

本文采用2-乙基己基膦酸单(2-乙基己基)酯(P-507)树脂,使微量稀土元素与钢中的基体元素,铁、钛、钒和钼分离,以 3.0 mol/L盐酸溶液洗脱P-507色层柱上的稀土元素,采用电感耦合等离子体原子光谱法(ICP-AES)同时测定了钢中La、Ce、Pr、Nd、Sm、Y和 Gd 7种微量稀土元素.试样的标准加入回收率99.3％～108％;相对标准偏差小于5％.     

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。     

多壁碳纳米管对稀土元素的吸附性能

研究了改性多壁碳纳米管(MWCNTs)对稀土元素的吸附。 采用硝酸、次氯酸钠、过氧化氢、高锰酸钾4种方法对MWCNTs进行改性,考察了改性MWCNTs对稀土元素的吸附能力。 采用紫外-可见分光光度法测定稀土元素的浓度,比较了未处理和不同方法处理的MWCNTs对稀土元素的吸附能力。实验结果表明,NaClO改性的MWCNTs对稀土元素的吸附能力最强。以稀土元素钐(Sm)、钆(Gd)、镱(Yb)为代表,研究了NaClO改性MWCNTs对稀土元素的吸附性能。 考察了溶液pH值、离子强度、吸附剂用量、温度等因素对吸附性能的影响。当溶液pH值在2~7范围内,NaClO改性的MWCNTs对Sm、Gd、Yb的吸附随pH值增大而增强。 当离子强度和MWCNTs的用量增大时,对稀土元素的吸附能力降低。3种元素在NaClO改性的MWCNTs上的吸附均为放热过程,其反应焓变ΔH分别为：-6.44、-5.63和8.31 kJ/mol。吸附等温线符合Langmuir和Freundlich等温吸附方程。     

电感耦合等离子体质谱(ICP-MS)法测定高钨基体样品中稀土元素的含量

准确测定钨矿和钨酸盐晶体等高钨基体样品中稀土元素的含量有助于开展矿床地球化学特征研究及钨酸盐激光晶体材料的制备和性质研究。在高钨基体样品电感耦合等离子体质谱法（ICP-MS）分析时,为了考察高钨及高含量阳离子等基体组成对分析结果的影响,实验针对Na2WO4、CaWO4、NaY(WO4)2、MnWO4和(Fe,Mn)WO4等高钨基体样品,采用硝酸和氢氟酸高压密闭消解,加入稀土元素并用2% HNO3溶液稀释定容配制成稀土元素浓度为1 ng·g-1的基体匹配标准溶液;同时,直接用2% HNO3溶液配制稀土元素浓度相同的非基体匹配标准溶液以对比系统考察两种基体溶液中稀土元素的相对灵敏度系数（RSC）差异。结果显示,基体匹配溶液与2% HNO3溶液中稀土元素的RSC相对偏差基本小于15%,表明基体效应的影响可以忽略不计。进而,为了准确测定常见高钨基体样品中稀土元素的含量,实验建立了基于ICP-MS的高钨基体样品中稀土元素准确定量分析方法,该方法线性关系好（R2 ? 0.9997）,检出限低（0.5 ~ 27.9 pg·g-1）,准确度理想（相对误差-6.25 ~ 10.74%）。采用该方法测定了钨酸钙单晶实际样品中稀土元素的含量并将其与基体匹配法的测定结果进行比对,结果显示两者相对偏差为0.80 ~ 12.75%,说明本文所建立的分析方法可靠,能用于定量测定高钨基体样品中稀土元素的含量。     

泡沫塑料动态快速分离富集金方法的研究

本文系统研究了泡沫塑料动态快速分离富集金的方法。对泡沫塑料柱的处理方法,再生及主要共存离子干扰的消除等均做了较详细的研究。提出了一种简便,不控速的金分离富集的方法。该法用于分析0.051～3.59g/t四种不同含量的金标样,结果与推荐值吻合,5次分析结果,相对标准偏差<5％,同时,可用泡沫塑料柱当天连续使用分析拿标样,回收率为93％—109％。     

Synthesis of Polyacrylaminothiourea Chelating Fiber and Properties of Concentration and Separation of Trace Noble Metal Ions from Samples

A novel polyacrylaminothiourea chelating fiber was synthesized simply and rapidly from nitrilon (an acrylonitrile-based synthetic fiber), which was applied to preconcentrate and separate of trace amount of Au(Ⅲ）,Pt(Ⅳ）,Pd(Ⅳ） and Ir (Ⅳ） ions from solution of samples.The analyzed ions can be quantitatively concentrated by the fiber up to a flow rate of 20.0mL/min at pH2, and can also be desorbed with 15 mL of 4mol/L HCl 3% thiourea from the fiber column with recoveries of 96.5%-100%.The chelating fiber can be reused for ten times,the recoveries of these ions are still over 92%,and hundred to thousand times of excess of Fe(Ⅲ）,Al（Ⅲ）,Ca(Ⅱ），Mg（Ⅱ）,Ni(Ⅱ）,Mn（Ⅱ),Cu(Ⅱ），Zn(Ⅱ），and Cd(Ⅱ） cause no interference on the determination of the analyzed ions by inductively-coupled plasma atomic emission spectrometry (ICP-AES).The static saturation adsorption capacities of the fiber for the analytes are in the range of 1.15-2.80mmol/g.The relative standard deviations for the determination of 20.0ng/mL each of Au(Ⅲ）,Pt(Ⅳ）,Pd(Ⅳ）and Ir(Ⅳ） are in the range of 0.7%-3.0%.The recoveries for test from standard additions to real solution samples are between 96% and 100%.The concentration of each ion in powder sample detected by the method is in good agreement with the certified value.     

Synthesis and Applications of Poly(Acrylphenylamidrazone-Phenyl-Hydrazide-Acylphenylhydrazine) Chelating Fiber for Preconcentration and Separation of Trae In(III), Zr(IV), Tl(I), V(V), Ga(III) and Ti(IV) from Solution Samples

 An ICP-OES method using a new poly (acrylphenylamidrazone-phenylhydrazide-acylphenylhydrazine) chelating fiber to preconcentrate and separate trace In(III), Zr(IV), Tl(I), V(V), Ga(III) and Ti(IV) ions from solution samples has been established. The new chelating fiber was synthesized using polyacrylonitrile fiber as a starting material and the structure of the chelating fiber was determined by FT infrared spectrometry. The acidity, adsorption rate, re-use, capacity and interference on the adsorption of ions on the chelating fiber as well as the conditions of desorption of these ions from the chelating fiber were investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES). The results show that the relative standard deviations for the determination of 10 ng/ml In, Tl, Ga and 1 ng/ml Zr, V, Ti were lower than 2.5%. The results obtained for these ions in real solution samples by this method were basically in agreement with the given values with average errors of less than 4%. Received November 29, 2000. Revision May 22, 2001.     

Synthesis of polyacrylaminoimidazole chelating fiber and properties of concentration and separation of trace Au, Hg and Pd from samples

A novel polyacrylaminoimidazole chelating fiber is synthesized simply and rapidly from nitrilon (an acrylonitrile-based synthetic fiber) and used for the preconcentration and separation of trace Au(III), Hg(II) and Pd(IV) ions from solution samples. The analyzed ions can be quantitatively concentrated by the fiber up to a flow rate of 15.0 mlmin(-1) at pH 3 and can also be desorbed with 15 ml of 4 M HCl+3% thiourea from the fiber column, with recoveries of 96.5-100%. The chelating fiber is reused ten times; the recoveries of these ions are still over 92%, and 100-1000 times of excess of Fe(III), Al(III), Ca(II), Mg(II), Ni(II), Mn(II), Cu(II), Zn(II) and Cd(II) causes no interference in the determination of these ions by inductively coupled plasma atomic emission spectrometry. The capacities of the fiber for the analytes are in the range of 1.56-2.92 mmolg(-1). The results show that the relative standard deviations for the determination of 50.0 ngml(-1) each of Au(III), Hg(IV) and Pd(IV) are in the range of 0.7-2.1%. The recoveries of a standard added in real solution samples are between 97 and 99%, and the concentration of each ion in powder sample detected by the method is in good agreement with the certified value.     

ICP-OES内标法测定地质勘查石膏样品中氧化钙和三氧化硫

采用电感耦合等离子体发射光谱法测定地质勘查石膏样品中氧化钙和三氧化硫,样品经2 mol/L盐酸溶解,以钇元素作为内标物在线加入。用国家一级标准物质对精密度及准确度进行验证,6次测定相对标准偏差为0.16%~0.34%;相对误差为-0.50%~0.20%;与化学分析方法结果对照,相对偏差为-0.42%~0.38%,满足DZ/T0130.3-2006对准确度及精密度的要求。     

一体化碰撞反应 (iCRC)-电感耦合等离子体质谱法测定地质样品中痕量稀土元素

钡以及轻稀土元素氧化物对中、重稀土元素的干扰一直是质谱测试中存在的问题。建立了石墨粉垫底碳酸钠-硼酸混合熔剂熔融前处理样品,以_¹⁰³Rh为内标校正,一体化碰撞反应-电感耦合等离子体质谱仪法测定地质样品中稀土元素含量的方法。探讨了碳酸钠-硼酸混合熔剂熔融前处理样品注意事项、碰撞模式下碰撞气流量和离子透镜的参数的优化、干扰校正试验等问题,采用国家标准物质GBW07403、GBW07405、GBW07427、GBW07429验证,实验结果表明,各元素线性关系良好,相关系数均大于0.999,方法检出限在0.01～0.03mg/kg之间,相对误差为0.13%～7.1%,相对标准偏差为0.79%～6.59%,测试结果与标准值相吻合。对实际样品分析,得到平滑的球粒陨石归一化的稀土元素配分曲线,证明测定结果是合理可信的。该方法熔剂用量少,过程空白低,对器皿的侵蚀小,直接加热浸取,简化了操作过程,适用于大批量地质样品中稀土元素的测定。     

3,5—二羟基甲苯比色法测定棉纤维表面糖的方法研究

本文研究了在非离子表面活性剂存在下,糖在强酸介质中转化成糠醛类衍生物同3.5-二羟基甲苯发生显色反应的条件。在硫酸介质中,糠醛与3,5-二羟基甲苯形成化合物的最大吸收波长为λ_(max)=425nm,线性范围0.04～0.20mg/ml,用于测定棉纤维表面的糖,方法的相对标准偏差为1.3％,回收率92％～105％。     

重铬酸钾容量法测定地质样品中的有机碳

目前,地质样品中有机碳的测定方法有干烧法（高温电炉灼烧）和湿烧法（重铬酸钾氧化）两大类。另外还有ICP-AES法、微波消解法、过硫酸钾法、电导法、石墨电热消解法、比色法等,然而这些有机碳测定方法仍然存在许多不尽如人意的地方。干烧法要求实验条件苛刻,操作繁琐,不易掌握,受碳酸盐的干扰。湿烧法虽然操作比较简单,但方法受样品中还原性物质的干扰,如氯根、亚铁等,上述方法都有待完善和优化改进。如：探索因不同样品基体差异而产生的干扰元素消除方法;寻找更合适的指示剂;本文采 用重铬酸钾-容量法测定地质样品中的有机碳,在220±10℃恒温电热板上,用0.4 mol/mL重铬酸钾溶解样品。通过优化熔矿温度、熔矿时间、熔剂浓度的优化选择,进行了氯离子的干扰试验。样品中含氯化物低的样品通过加入0.1 g硫酸银消除,样品中含氯化物高的样品通过高温灼烧减量消除。氧化指示剂选用邻菲啰啉或苯二氨基苯甲酸。本方法适用于土壤、水系沉积物、岩石等地质调查样品中有机碳的测定,方法相对标准偏差（RSD）在0.80%～4.41%之间,准确度（RE）在-3.15%～+1.15%之间。通过标准物质验证,方法技术指标满足地质行业规范DZ/T0130.4-2006中有机碳的分析要求,建立了一种简单、快捷、经济、准确的测定地质样品中有机碳的测定方法,满足地球化学调查批量样品生产的需要。     

Validation of a solid phase extraction-high performance liquid chromatographic method for the determination of eprosartan in human plasma

In this work, a solid phase extraction-reversed phase high performance liquid chromatographic (SPE-RP-HPLC) method with photometric detection for monitoring the antihypertensive drug eprosartan has been validated in order to assure good quantitation of eprosartan in plasma samples obtained from patients under cardiovascular treatment. This analytical method was developed by using experimental design and quantitation was accomplished with the internal standard method. No interferences were observed from endogenous compounds of plasma and other drugs which are commonly co-administered in elderly patients. The recoveries of eprosartan from plasma samples, measured at three levels of the linear concentration range (150-4000 ng/mL) were found to be between 93.4 and 102.8%. The intraday and interday precision and accuracy (measured by relative standard deviation, RSD, and relative error, RE, respectively) were always lower than 13% (RSD) and 4% (RE). Stability studies showed that eprosartan stock solutions are stable for at least 3 months when stored at 8 degrees C and plasma samples containing the drug were stable at least during the whole analytical method.     

分散液-液微萃取-高效液相色谱法测定环境水样中的多环芳烃

建立了简便、快速、有效的分散液-液微萃取-高效液相色谱-荧光检测(DLLME-HPLC-FLD)测定环境水样中15种多环芳烃(PAHs)的方法。重点探讨了萃取剂的种类和用量、分散剂的种类和用量以及萃取时间等对PAHs萃取效率的影响。在优化的条件下,评价了方法的可靠性。15种PAHs在0.01～10 μg/L范围内呈良好的线性关系,相关系数r均不小于0.9913,峰面积的相对标准偏差(RSD)在2.3%～4.7%之间(n=6)。在优化条件下,富集因子和萃取回收率良好,分别为674～1032和67.4%～103.2%,15种PAHs的检出限(S/N=3)在0.0003～0.002 μg/L之间。建立的方法应用于敖江水样中PAHs的检测,平均加标回收率在79.5%～92.3%之间,RSD在4.3%～6.7%范围内(n=5)。该方法适用于环境水样中痕量PAHs的分析。