Direct chromium speciation using X‐ray spectrometry and chemometrics

Chromium is a chemical element that occurs in two principal distinct forms: trivalent (Cr(III)) and hexavalent (Cr(VI)). As chromium toxicity depends on its oxidation state, the concentrations of both the species should necessarily be determined, and not only that of total chromium. Using X‐ray spectrometry allied to chemometrics, this work presents a new method for chromium speciation, with no prior separation and/or preconcentration of Cr(III) and Cr(VI) species. Spectra of several solutions containing different concentrations of Cr(III) and Cr(VI) were obtained. The data were treated through principal component analysis and partial least squares regression. The results obtained show that direct speciation using a conventional X‐ray spectrometer is possible, with calculated limits of detection and quantification for Cr(III) and Cr(VI) being lower than 17 and 50 µg g^?1, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

流动注射在线分离富集-火焰原子吸收光谱法测定环境水样中Cr(Ⅲ)和Cr(Ⅵ)的形态

采用单阀阴离子和阳离子交换树脂微柱并联 ,两柱交替采样逆向洗脱流动注射在线分离富集环境水样中Cr(Ⅲ )和Cr(Ⅵ ) ,分别用 15 %HNO3和 8%NH4 NO3洗脱 ,火焰原子吸收光谱法直接检测。富集 1min时Cr(Ⅲ )和Cr(Ⅵ )的特征浓度分别为 :1 5 0 μg·L- 1 和 1 39μg·L- 1 ,Cr(Ⅲ )和Cr(Ⅵ )检出限 (3σ)分别为 1 0 3μg·L- 1 和 0 5 4 μg·L- 1 ;相对标准偏差 (10 μg·L- 1 )分别为 :3 4 1%和 1 80 % ,分析样品加标回收率在 93 5 %～ 10 7 5 %之间。     

悬浮进样探针原子化石墨炉原子吸收法测定地质样品中的铬

本文应用探针恒温原子化技术 ,系统研究了铬的分析性能 ,应用固体悬浮进样 ,直接测定了地质样品中的痕量铬 ,方法的 RSD为 3.0 %～ 6 .5 % ,检测限为 5 .1× 10 - 1 2 g铬 ,标准物质的测定结果满意     

离子印迹聚合物在线分离富集-流动注射-化学发光法测定铜

研究了以铜(Ⅱ)离子作为模板离子,合成了铜(Ⅱ)离子印迹聚合物并将其做成固相萃取柱,直接安装在流动注射系统上,对样品中的铜(Ⅱ)离子进行在线分离富集;经H2SO4+乙醇混合溶液洗脱液在线洗脱后.在H2SO4介质中,铜(Ⅱ)离子催化高锰酸钾氧化桑色素发生化学发光反应.据此建立了灵敏简单流动注射化学发光法测定铜的新方法.在...     

不等流速络合法流动注射预富集火焰原子吸收测定自来水中的铅

建立了一种环保、高效、简便的不等流速络合法流动注射与火焰原子吸收联用测定自来水中痕量铅的新方法。通过调节样品溶液和络合剂的流速,即增大样品溶液流速,减小络合剂(吡咯啶二硫代氨基甲酸铵：APDC)流速,从而增大了浓集系数,提高了富集效率,和传统等量络合法相比,富集倍数大大提高。样品进样流速10.4 mL·min-1 ,进样时间60 s,Pb的浓集系数由传统方法的30达到59,检测限为5.6 μg·L-1,样品输出为40·h-1。0.5 mg·L-1Pb2+的相对标准偏差(n=11)为2.1%。Pb2+在自来水中的回收率范围为98.5%到102%。此法用于自来水中痕量Pb的测定,获得了满意的结果。     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

氮化铝铬的制备及其光学性质

利用直接氮化法得到了氮化铝和氮化铬,并用两种途径得到Cr³⁺掺杂的氮化铝样品。用X射线衍射仪分析了样品晶相并测试了两种样品的激发和发射光谱,计算了晶体场劈裂参数D_q和Racah参数B及D_q/B分别为1 800,693.69和2.59。光谱数据表明,Cr³⁺在氮化铝中属于强场环境,光发射来自于最低激发态²E能级,与在氧化铝中的环境相似。根据光谱数据给出了Cr³⁺在氮化铝晶体场中的能级。     

Cs^＋-K^＋ Exchange in Z-Cut KTiOPO4 Crystal Covered with Chromium Masking Layer

Cs^＋-K^＋ ion exchanges are performed on z-cut KTiOPO4 crystals with chromium coating covered. The temperature of ion exchange is 430℃, and the time range from 15min to 30min. The dark mode spectra of the samples are measured by the prism coupling method. The channel structures on the samples are observed by a microscope and the near field pattern of the channel waveguides are measured by the end-fire coupling method. The refractive index of the samples increases and the increments at surface are modulated due to the existence of Cr film. In the region covered by Cr film, the refractive index of the samples at the surface increases dramatically in a shallow layer. The results of energy dispersive x-ray spectra indicate that in the region covered with Cr film, Cr ions participate in the ion exchange process, and enhance the refractive index. The results may provide a possibility that achieves index enhancement and Cr doping synchronically.     

空气隔离法流动注射在线预富集火焰原子吸收测定水样中的痕量铜和镉

研究了高效的在线流动注射编结反应器预富集火焰原子吸收系统直接测定水样中的痕量铜和镉。实验中将样品溶液和作为沉淀剂的氨水溶液输入编结反应器中,产生的铜和镉的氢氧化物沉淀被吸附在反应器壁内,然后通入一段空气流,再用硝酸洗脱并直接输送至火焰原子化器。在pH 5条件下,样品流速为4.4 mL·min-1,经90 s预富集,测定铜和镉的灵敏度分别提高34倍和36倍,检测限达1.9和0.3 μg·L-1。对铜和镉含量分别为30, 20 μg·L-1的溶液连续测定11次的相对标准偏差分别为2.3％和2.6％。此法用于饮用水和环境水样中痕量铜和镉的测定,获得了满意的结果。     

铬蓝黑R负载活性炭对Cr（Ⅲ）和Pb（Ⅱ）的吸附性能

研究了新型吸附材料铬蓝黑R（钙试剂）负载改性的活性炭对样品中Cr（Ⅲ）和Pb（Ⅱ）的固相萃取（SPE）并用电感耦合等离子体-原子发射光谱法（ICP-AES）进行检测.优化了pH值、吸附剂用量、流速等条件以达到定量吸附（≥95％）,同时研究了洗脱剂的最佳洗脱条件以及共存离子干扰等问题.本法测定Cr（Ⅲ）和Pb（Ⅱ）的检出限分别为0.91ng·mL-1和0.65ng·mL-1,将其应用于土壤沉积物、猪肝、黄河水中的Cr（Ⅲ）和Pb（Ⅱ）含量的测定,加标回收率在98％-101％之间;用于测定标准物质中Cr（Ⅲ）和Pb（Ⅱ）的含量,结果与标准物参照值一致.     

Flow injection thermal lens spectrometric detection of hexavalent chromium

A new highly sensitive flow-injection analysis (FIA) method with thermal lens spectrometric detection (TLS) was developed for determination of hexavalent chromium (Cr(VI)) in water. TLS measurements of Cr(VI) with diphenylcarbazide (DPC) method in a batch mode are subject to lower sensitivity and are less reproducible due to photodegradation of Cr-DPC complex during the measurement. In a FIA mode the decomposition of Cr-DPC induced by an intensive excitation laser source (140 mW at 514.5 nm) can be avoided or significantly reduced. For this purpose a FIA-TLS system was assembled and Cr(VI) determined by on-line generation of Cr(VI)-DPC. Under optimal conditions, a linear calibration graph was obtained for the range of Cr(VI) concentrations 1–20 μg/L. A LOD (limits of detection) value of 0.07 μg/L was achieved for Cr(VI) in water.     

Design of a new technique based on combination of ultrasound waves via magnetite solid phase and cloud point microextraction for determination of Cr(III) ions

In this work, we focused on development of a new techniques by coupling of ultrasound irradiation, cloud point method and magnetite solid phase microextraction for the extraction and preconcentration of Cr(III) ions from aqueous solutions. In order to reduce cost and improve practicability of proposed process a new efficient and regenerable magnetite sorbent (functionalized chitosan grafted-amino graphene oxide (GO) decorated by zinc ferrite nanoparticles (CS-GO-Zn: Fe₂O₄)) was synthesized through hydrothermal method and then characterized by FT-IR, FE-SEM, EDS and XRD analysis. Effect of initial sample volume and type, volume and concentration of eluent on the ER%_Cr(III) were investigated and optimized using one at a time method. Correlation between the main and interaction effects of other operational parameters such as Cr(III) ion concentration, CS-GO-Zn: Fe₂O₄ mass, sonication time, pH and solution temperature on the ER%_Cr(III) were investigated and optimized by central composite design coupled with desirability function approach. The results revealed that there were significant effects for most investigated terms on the ER%_Cr(III) and maximum ER% of 88.09% was obtained in desirability value of 1.0. This maximum efficiency was obtained at 0.035 µg/mL Cr(III) ion concentration, 40.16 °C temperature, 0.016 g of CS-GO-Zn: Fe₂O₄, pH 6.36 and 9.20 min sonication time. In addition, under the optimal conditions the linear range, limit of detection, enrichment factor and relative standard deviation were found to be 0.02–4.4 µg/mL, 0.002 µg/mL, 23.23 and 1.68% respectively. Finally, the method was successfully applied to the separation and preconcentration of Cr(III) ion from tap, river and mineral waters.     

Sub‐ppm determination of Hg and Cr in water: Cr speciation

A sensitive and alternative analytical procedure for the determination of chromium and mercury content in natural waters by coprecipitation with APDC and determination using an absolute thin layer EDXRF method is described. The use of ¹⁰⁹Cd and ²³⁸Pu annular radioisotope sources, the influence of the chromium oxidation states and the elemental concentration were studied. At pH 4, 100% recovery was found for mercury. The coprecipitation of Cr(VI) was not quantitative (75%) but constant for the selected concentration range (5–100 µg/l). On the other hand, Cr(III) did not precipitate at the same pH. The relative standard deviations (RSD) were lower than 9.0% for mercury (10 µg/l) and 5.0% for chromium (50 µg/l). The detection limits (DLs) for mercury and chromium were 0.4 and 0.6 µg/l when the ²³⁸Pu source was employed. Nevertheless, higher DL values were achieved using ¹⁰⁹Cd (0.6 and 3.3 µg/l). The proposed method was applied to the analysis of surface water samples. An alternative and simple chromium speciation procedure without chemical separation of Cr species is recommended. Copyright © 2007 John Wiley & Sons, Ltd.     

Target-ion source unit ionization efficiency measurement by a method of stable ion beam implantation

At the IRIS facility a rather precise method of the target-ion source unit ionization efficiency measurement has been developed. The method exploits an off-line mass-separator for the implantation of the ion beams of selected stable isotopes into a tantalum foil placed inside a Faraday cup in the focal plane of the mass-separator. After the implantation of the required amount of the investigated species, tantalum foil has been inserted into the volume of the target-ion source unit prepared for the on-line utilization at the IRIS on-line separator. The first tests have ensured the ionization efficiency values (90±10)% for Rb and (85±10)% for Cs in the empty combined target-ion source unit, which was used as a reference one. For the target-ion source unit with UC target material inside the measured value of the ionization efficiency of Rb was (52±20)%.     

利用协同催化效应萃取催化光度法测定痕量铬

研究了在pH 5.5的HAc-NaAc介质中,利用Fe(Ⅲ),Cr(Ⅵ)对H₂O₂氧化邻氨基酚的协同催化作用,用萃取平衡控制反应时间和水相中邻氨基酚的浓度及协同催化反应进行的程度,通过测量424 nm下有机相的吸光度,建立了协同萃取催化光度法测定铬的新方法。方法的线性范围为：0.001 0～0.90 mg·L-1,检出限为5.0×10-6g·L-1。用于自来水和废水中铬的测定,结果满意。     

双微柱在线富集-火焰原子吸收光谱法测定环境水样中痕量镉

采用单阀双阳离子交换树脂微柱并联,设计了双柱交替采样逆向洗脱在线富集系统,该系统与原子吸收测量技术相结合, 实现了在线富集-火焰原子吸收光谱法测定水中镉, 富集1 min时, 分析速度为60样/h, 测定镉的特征浓度为0.931 μg·L-1, 线性范围分别为0～90 μg·L-1, 相对标准偏差分别为2.69 %、检出限(3σ)为0.808 μg·L-1该法对实际水样加标回收率在95.0%～103.7%之间。     

苦荞茶对水溶液中铅、铜、镉、锌、铬离子吸附作用的研究

生物吸附法以其材料易得、吸附效果好、易解析、环境友好等优点而被广泛的应用于水溶液中低浓度重金属离子的吸附去除。光谱学显示苦荞茶含有多种基团且表面结构疏松，对水溶液中金属离子具有一定吸附潜力。探讨苦荞茶对水溶液中铅、铜、镉、锌、铬离子吸附作用光谱分析。采用扫描电镜(SEM)、能谱分析(EDS)、傅里叶红外光谱(FTIR)对苦荞茶吸附铅、铜、镉、锌、铬前后进行表征，初步解析苦荞茶对水溶液中铅、铜、镉、锌、铬离子吸附作用。使用等温吸附方程(Langmuir，Freundlich，Temkin和Dubinin-Radushkevich) 与动力学方程(准一级、准二级和颗粒内扩散)来评价苦荞茶对水溶液中铅、铜、镉、锌、铬离子吸附方式及行为。响应面法是一种数学建模的优化方法，能回归拟合各因素与实验结果之间的函数关系，从而确定实验因素及其交互作用对目标值的影响程度。采用响应面法考察目标离子初始浓度(A)、吸附剂颗粒大小(B)、吸附剂投加量(C)和吸附时间(D)四个因素对苦荞茶吸附水溶液中铅、铜、镉、锌、铬离子能力的影响作用及程度。等温吸附方程显示，苦荞茶对水溶液中铅、铜、镉、锌、铬离子吸附方式以多层吸附方式为主，伴有其他吸附类型，苦荞茶对目标重金属吸附量排序为：铅＞镉＞铜＞锌＞铬，即为：30.67＞16.18＞13.85＞10.81＞8.43 mg·g-1。动力学方程与苦荞茶扫描电镜(SEM)提示，苦荞茶对水溶液中铅、铜、镉、锌、铬离子吸附过程符合准二级动力学，其吸附速率由液膜扩散和颗粒内扩散作用共同控制，而且苦荞茶表面疏松的结构出现表面趋于平滑，孔洞出现融合的现象。能谱分析(EDS)与傅里叶红外光谱(FTIR)证实了水溶液中铅、铜、镉、锌、铬离子被苦荞茶所吸附，苦荞茶中-OH，-CH₂，-CH₃，CO， -NH，-C-O，CH基团参与水溶液中铅、铜、镉、锌、镉离子结合吸附作用并存在同一类型的基团吸附结合不同目标离子的现象。响应面法构建考察因素影响苦荞茶对水溶液中铅、铜、镉、锌、铬离子去除能力模型，其调整回归决定系数分别为Adj R2_Pb=97.10，Adj R2_Cu=98.44，Adj R2_Cd=94.55，Adj R2_Zn=92.71，Adj R2_Cr=97.02，说明非线性模型可用来评价考察因素对苦荞茶吸附水溶液中铅、铜、镉、锌、铬离子影响作用。响应面法分析表明，考察因素[离子初始浓度(A)、吸附剂颗粒大小(B)、吸附剂投加量(C)和吸附时间(D)]对铅、铜、镉、锌、铬离子去除率影响作用大小排序为：铅离子(A＞D＞B＞C)、铜离子(A＞C＞D＞B)、镉离子(A＞B＞C＞D)、锌离子(B＞C＞A＞D)、铬离子(C＞B＞D＞A)。研究结果说明，苦荞茶对水溶液中铅、铜、镉、锌、铬离子具有良好的吸附作用，为苦荞茶拓展新的应用途径提供了参考依据。     

Photoluminescence of chromium doped and chromium diffused GaAs

Photoluminescence (PL) measurements on the 0.84 eV Cr-related PL line have been made on both Cr diffused and Cr doped GaAs. In the former case, no luminescence is observed below a diffusion temperature of 800°C. The form of the PL spectrum is found to be the same, independent of whether the majority donor species is group IV(Si) or group VI(Te). PL profiling experiments are used to show that the PL intensity is proportional to the concentration of chromium. Although it is possible that a group VI donor is involved, the insensitivity of the spectrum to different donor species and its linear dependence on chromium concentration suggest that the luminescent centre is a [Cr_Ga-V_As] complex.Measurements on growth doped material are typified by the low intensity near the seed and the scatter in PL intensity in samples where the measured [Cr] is nearly constant. By comparison with the results on the diffused material, the anomalously low PL intensity near the seed end is deduced to be indicative of the high crystal stoichiometry in this region.     

纳米TiO2预分离/富集FAAS法同时测定Cr(Ⅲ)和Cr(Ⅵ)的研究

纳米材料是近年来受到广泛重视的一种新兴功能材料,具有一系列新异的物理化学特性和一些优于传统材料的特殊性能.其中一点是随着粒径的减小,表面原子数迅速增大,表面原子周围缺少相邻的原子,具有不饱和性,易与其他原子相结合而稳定下来,因而具有很大的化学活性.纳米材料对许多金属离子具有很强的吸附能力,是痕量元素分析较为理想的分离富集材料.文章利用火焰原子吸收法(FAAS)研究了纳米TiO2(金红石型)对Cr(Ⅵ)/Cr(Ⅲ)的吸附性能,并应用于水样中铬的形态分析.吸附体系中pH对Cr(Ⅵ)和Cr(Ⅲ)的吸附有很大影响,当pH＞6时,纳米TiO2对Cr(Ⅲ)的吸附率大于90%,而对Cr(Ⅵ)基本不吸附,从而达到二者的分离.pH 6.5微酸性条件下,纳米TiO2吸附Cr(Ⅲ),然后以2mol.L-1HCl洗脱,得到Cr(Ⅲ)的含量,剩余水溶液中测定Cr(Ⅵ)含量.该法测定Cr(Ⅵ)和Cr(Ⅲ)的检出限分别为57和41 ng·mL-1,RSD分别为2.6%和3.4%(2.0μg·mL-1Cr,n=6),Cr(Ⅵ)和Cr(Ⅲ)的线性范围分别为0～9.0和0.1～10μg·mL-1.该法选择性好,大多数共存离子不干扰测定.该法简便快速,用于工业废水、地表水中铬的形态分析,结果较满意.     

微珠析相微萃取-石墨炉原子吸收法测定岩石样品中痕量铬

采用二苯碳酰二肼为络合剂,正戊醇为萃取剂,乙醇为助溶剂,建立了微珠析相微萃取-石墨炉原子吸收法测定地质样品中痕量Cr的分析方法。实验详细探讨了微珠析相微萃取的析相条件、石墨炉原子吸收工作参数及共存离子的干扰,优化了体系萃取条件。实验结果表明：微珠析相微萃取既起到了分离富集的作用,在石墨炉升温程序中又起到了基体改进剂的作用;当萃取剂用量为0.2～1.5 mL时,使之与水完全互溶所需助溶剂体积约为水相体积的0.2～0.5倍;方法线性范围为0～10 μg·L-1,检出限为0.057 μg·L-1,相对标准偏差（RSD）为3.3%（c= 2.5 μg·L-1,n=11）;当萃取剂用量为1.5 mL、水相体积15 mL时,与直接溶液进样相比其灵敏度可提高10倍。所建立的方法用于地质标准参考物质AGV-2和G-2中Cr的测定,测定值与参考值具有较好的一致性。