电镀废水中Cr（Ⅵ）的次甲基蓝分光光度法研究

在H2SO4溶液中,以次甲基蓝（MB）为显色剂,利用铬（Ⅵ）与次甲基蓝（MB）在水浴加热条件的显色反应,建立了一种测定电镀废水中微量铬（Ⅵ）的新光度法。反应产物的最大吸收波长为573nm,摩尔吸光系数为1.40×10^4L·mol^-1·cm^-1,检出限为2.4×10^-7g·mL^-1,铬（Ⅵ）含量在10—50μg/25mL范围内有良好的线性关系,相关系数为0.9991,用于测定电镀废水中的微量铬（Ⅵ）,加标回收率为97.5%—104.5%,相对标准偏差≤0.46%。     

维生素C对大鼠急性肺损伤时铁元素水平的干预作用

将ALI实验动物随机分为13组,其中6组为维生素C治疗组,ALI后均立即给予维生素C治疗,依照采集肺组织标本不同时间点分为：6h组、8h组、12h组、16h组和24h组（均12h追加一次维生素C）、36h组;用生理盐水替换维生素C为6组阳性对照组;阴性对照1组。用原子分光光度计检测肺组织铁含量。阴性对照组铁含量为25.1828μg·g-1;损伤期大鼠体内铁元素均比正常值低,治疗组和对照组组内均有明显差异（P〈0.05）;各时间点治疗组与阳性照相比均呈有意义改变（P〈0.01）;各时间点的治疗组、阳性对照组与阴性对照组相比均呈有意义改变（P〈0.05或P〈0.01）。ALI时铁含量降低;用VC后铁有一定程度升高,说明VC对ALI时铁的水平有一定调节作用。     

铬诱导植物根细胞壁化学成分变化的FTIR表征

随着制革、电镀等行业的发展,铬污染已成为严重的环境问题而受到人们的关注。铬在植物体内主要积累于根部,植物根细胞壁化学变化与金属元素在植物体内的蓄积行为有密切关系。与其他方法比较,应用OMNI采样器-FTIR直接测定法表征细胞化学成分变化具有简便、快速和准确的优点。文章用FTIR对凤眼莲(Eichhornia crassipes)和空心莲子草(Alternanthera philoxeroides)根细胞壁进行了测定、分析和指认,并利用半定量分析方法研究了铬处理和对照处理下根细胞壁红外光谱的差异。结果表明,铬处理的凤眼莲和空心莲子草根细胞壁上的—OH向低频分别发生了20和6 cm-1的位移,同时凤眼莲的根细胞壁上—OH和自由羧基COO-等吸附位点数目较对照均有所增加,而空心莲子草则相反。说明这些基团与铬的结合密切相关,进一步解释了凤眼莲耐铬及其在根部积累铬的机理,说明FTIR在监测逆境诱导植物化学成分变化和环境绿色修复方面具有广泛的应用前景。     

中老年糖尿病轻重度患者血清中的铁铬钴镍

对１２８例中老年糖尿病患者进行了血清中微量元素铁,铬,钴,镍的含量测定,并与正常对照进行了比较。结果表明,血糖正常组和高血糖组的糖尿病患者血清铁铬水平均低于正常对照组,且两病例组与对照组比较铬水平有非常显著差异（Ｐ〈０．０１）。血清镍水平患病初期降低,后升至正常,高血糖组与对照组比较差异显著（Ｐ〈０．０５）,两病例组间差异非常显著（Ｐ〈０．００１）,血清钴水平随情加重而逐渐升高,但无统计学上的显著     

浊点萃取-石墨炉原子吸收光谱法测定药物胶囊中的痕量铬（Ⅵ）

采用硝基苯胲铵盐（铜铁试剂）、吡咯烷基二硫代甲酸铵（APDC）为络合剂,Triton X-114为表面活性剂的浊点萃取体系分别富集药物胶囊中的痕量Cr（Ⅲ）和总铬,富集后的Cr（Ⅲ）和总铬用石墨炉原子吸收光谱法进行测定.讨论了溶液pH值、表面活性剂浓度、络合剂浓度、平衡温度、平衡时间等对浊点萃取效率的影响.在优化的实验条件下,铬（Ⅵ）的检出限为0.031μg/L,相对标准偏差为1.2％（C=2.0μg/L,n=6）,加标回收率为98.4％-102.1％.应用该法测定药物胶囊中的痕量Cr（Ⅵ）,结果令人满意.     

饮用水中的铬也会致癌

吸入六价铬（Cr^6＋）能够致癌已不是新闻，然而美国国家毒理学项目（National Toxicology Program，NTP）最近的研究显示，饮用水中的Cr^6＋也能致癌。Cr^6＋化合物广泛用于电镀工艺和纺织行业，在饮用水源中也有发现。美国政府制定了严格的呼吸暴露工作相关规程，美国环保署的饮用水标准将每升的铬含量限制在0．1毫克。     

萃取光度法测定电镀废水中的微量Cr(Ⅵ)

利用二甲基吲哚羰花青(DIC)染料与Cr(Ⅵ)配合物的显色反应,对含Cr(Ⅵ)电镀废水中痕量铬(Ⅵ)进行测定。结果表明,在H_2SO_4介质中,甲苯萃取显色反应物具有高的灵敏度,反应产物的最大吸收波长为560nm;摩尔吸光系数为2.5×10~5L·mol(-1)·cm~(-1)。Cr(Ⅵ)量在0.01～2.1mg·L~(-1)范围内符合比尔定律。该法用于测定电镀废水中的铬(Ⅵ),得到了满意的结果。     

台湾桤木根叶养分内循环对施肥的响应

对比分析了施肥与未施肥退耕地7年生台湾桤木树叶和细根中N、P、K、Ca、Mg 5种元素内循环差异。结果发现：生活叶和落叶,活细根和死细根中各养分含量和5种元素总养分含量均为树叶〉极细根〉细根;树叶和细根都存在养分内循环,但树叶内循环率高于细根。各养分元素在树叶和细根中的内循环率并不一致,三大元素中K内循环率最高,N次之,P最低;Mg的内循环率较低,而Ca则表现为富集。施肥与树叶和细根中养分变化显著相关（P〈0.01）,施肥后树叶和细根中N,K含量和总养分含量增加,而P、Ca、Mg的含量减少;施肥与树叶养分内循环率变化显著相关（P〈0.01）,与细根养分内循环率变化中度相关,而与极细根养分内循环率变化不相关。     

含磺酸基的有机络合剂对铬(Ⅲ)增感作用的研究应用

本文对１３种含磺酸基的有机络合剂在铬的火焰原子吸收光谱分析中的作用进行了实验。发现含磺酸基的有机络合剂普遍能提高铬（Ⅲ）的吸光度。初步探讨了磺酸基的增感、消除干扰作用，选择了含磺酸基的有机络合剂存在时酸度、浓度、干扰离子量和线性范围等条件，并用茜素红、铬天青Ｓ直接测定水系沉积物中的微量铬，结果令人满意。     

含磺酸基的有机络合剂结铬（Ⅲ）增感作用的研究应用

本文对13种含磺酸基的有机络合剂在铬的火焰原子吸收光谱分析中的作用进行了实验，发现含磺酸基的有机络合剂普遍能提高铬（Ⅲ）的吸光度。初步探讨了磺酸黄的增感、消除干扰作用，选择了含磺酸基的有机络合剂存在时酸度、浓度、干扰离子量和线性范围等条件，并用茜素红、铬天青S直接测定水系沉积物中的微量铬，结果令人满意。     

A study of direct- and pulse-current chromium electroplating on rotating cylinder electrode (RCE)

Direct- and pulse-current (DC and PC) chromium electroplating on Cr-Mo steel were performed in a sulfate-catalyzed chromic acid solution at 50 °C using a rotating cylinder electrode (RCE). The electroplating cathodic current densities were at 30, 40, 50 and 60 A dm⁻², respectively. The relationship between electroplating current efficiency and the rotating speed of the RCE was studied. The cross-sectional microstructure of Cr-deposit was examined by transmission electron microscope (TEM). Results showed that DC-plating exhibited higher current efficiency than the PC-plating under the same conditions of electroplating current density and the rotating speed. We found the critical rotating speed of RCE used in the chromium electroplating, above this rotating speed the chromium deposition is prohibited. At the same plating current density, the critical rotating speed for DC-plating was higher than that for PC-plating. The higher plating current density is, the larger difference in critical rotating speeds appears between DC- and PC-electroplating. Equiaxed grains, in a nanoscale size with lower dislocation density, nucleate on the cathodic surface in both DC- and PC-electroplating. Adjacent to the equiaxed grains, textured grains were found in other portion of chromium deposit. Fine columnar grains were observed in the DC-electroplated deposit. On the other hand, very long slender grains with high degree of preferred orientation were detected in PC-electroplated deposit.     

单(6-对氨基苯甲酸-6-脱氧)-β-环糊精的合成及其对Cr(Ⅵ)的荧光识别

合成了新型荧光探针单(6-对氨基苯甲酸-6-脱氧)-β-环糊精(ACD)。探讨了与Cr2O27-的识别反应。在pH4·90的NaAc-HAc缓冲溶液中,Cr2O72-能使ACD的荧光猝灭,据此建立了测定Cr(Ⅵ)的新方法,在最优化实验条件下,线性范围为5·20~1040μg·L-1,检出限1·26μg·L-1。22种常见离子干扰实验结果表明该试剂对Cr2O72-有较高的选择性识别效果。此法用于电镀液、电镀废液中痕量Cr(Ⅵ)的测定,结果令人满意。     

Radioanalytical determination of 239+240Pu and 241Am in bioassay samples by anion exchange and extraction chromatography: Preliminary considerations about the two methods

During the radiation protection surveillance of exposed workers samples of urine and faeces were collected. Anion exchange chromatography was used for the separation of Pu. We investigated a technique to purify and separate Pu and Am isotopes using extraction chromatography with TRU resin. We tested different procedures to dissolve organic matter and eliminate interferences for chromatographic elution. At the end of the proces we have succeeded in electroplating the two radionuclides separately. We have also studied extraction chromatography with UTEVA resin to purify Pu isotopes and separate it from natural uranium radioisotopes, present in some biological samples. We validated a method for the determination of Pu in biological samples and a rather constant chemical yield and resolved peaks were obtained. The preliminary studies on TRU resin have indicated that it is possible to combine extraction and anion-exchange chromatography for analysing separately Pu and Am isotopes from the same sample aliquote.     

微乳液增敏催化光度法测定痕量铬的研究

研究了在微乳液(溴化十六烷基三甲基胺(CTMAB)/正戊醇/正庚烷/水)介质中,痕量铬(Ⅵ)催化过氧化氢氧化茜素红的褪色反应,建立了测定痕量铬的催化动力学新方法。在微乳液体系中,方法的灵敏度比在表面活性剂CTMAB体系中提高了72.5%,催化反应的表观活化能为55.7 kJ·mol-1。水浴温度升高,灵敏度显著提高,校准曲线在不同的反应温度下线性范围不同,在80 ℃反应温度下,线性范围为2.4～75 μg·L-1,检出限达4.27×10-10g·mL-1,相对标准偏差为1.84%(n=11)。该法已应用于电镀废水中铬(Ⅵ)的测定,结果令人满意。     

Elemental analysis of particulate matter in a metal workshop and of biological samples from exposed workers

During metal welding and cutting, large amounts of particulate matter (PM) are produced that might represent a significant health risk for the exposed workers. In the present pilot study, we performed an elemental analysis of fine PM collected in a metal workshop. Also, elemental analysis of the hair and nail samples collected from workers exposed to the workshop dust and control group was done. Concentrations of 15 elements in PM were measured with X‐Ray Fluorescence (XRF) and Particle Induced X‐ray Emission (PIXE), whereas inductively coupled plasma mass spectrometry (ICP‐MS) was used to determine 12 elements in hair and nail samples. Mean 8‐hr concentrations of PM_2.5, Fe, and Mn in the vicinity of welders were up to 1803, 860, and 30 μg/m³, respectively, whereas in the nearby city, daily PM_2.5 concentrations are on average 11 μg/m³. We found that several elements, especially Fe and Mn, had substantially higher concentrations in hair and nail samples of exposed workers than in the control group, which indicates the accumulation of metals in workers' tissues, although limit values were not exceeded.     

电极表面特性对甘油介质击穿特性的影响

基于几种常见的电极表面处理工艺,制作了外形一致、表面不同的砂纸打磨、羊毛抛光、金属电镀和非金属电镀四种同轴电极,对比了电极在微观下的形貌特点,通过实验研究了不同电极表面特性与甘油介质耐压的关系。搭建了基于晶闸管控制的空心脉冲变压器升压实验平台,最大输出电压500 kV,上升时间26 s。实验结果表明:四种电极的微观形貌存在较大差异,并引起了甘油击穿特性的不同,在相同充电电压条件下,甘油的平均击穿场强为210~260 kV/cm;与使用常规的砂纸打磨电极相比,使用羊毛抛光、金属电镀、非金属电镀电极可分别使击穿场强提高14.51%,11.60%,19.67%,其中非金属电镀电极表面均匀程度远高于其他电极,最高击穿场强可达288 kV/cm,比对照组平均击穿场强提高33.09%。     

Influence of the Elemental Composition and Concentration of Surfactants on the Atomic Absorption of Chromium

Systematic investigations of the influence of the elemental composition and concentration of surfactants on the atomic absorption of chromium have been carried out. It is shown that sodium dodecyl sulfate maximally increases the analytical signal and selectivity in chromium determination. The atomic-absorption technique of determining the quantitative content of chromium in sewage of industrial enterprises with application of sodium dodecyl sulfate as a chemical modifier has been developed. The detection limit for chromium is 1.2 μg/dm³. Reported at the 5th All-Russia Conference on Analysis of Environmental Objects “Ekoanalitika-2003” with participation of foreign scientists, October 6–10, 2003, St. Petersburg, Russia. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 546–550, July–August, 2005.     

Initial oxidation of duplex stainless steel

Three different techniques were used to produce thin oxide layers on polished and sputter-cleaned duplex stainless-steel samples. These samples were exposed to 10⁻⁵ mbar of pure oxygen inside the vacuum chamber, exposed to ambient conditions for 24 h, and plasma oxidized. The oxide layers thus produced were analysed using XPS depth profiling in order to determine the oxide layers’ compositions with depth. We found that all the techniques produce oxide layers with different traces of metallic components and with the maximum concentration of chromium oxide shifted towards the oxide-layer-bulk-metal interface. A common characteristic of all the oxide layers investigated is a double-oxide stratification, with regions closer to the surface exhibiting higher concentrations of iron oxide and those more in-depth exhibiting higher concentrations of chromium oxide. A simple non-destructive Thickogram procedure was used to corroborate the thickness estimates for the thinnest oxide layers.     

A reliable method by ultra-performance liquid chromatography coupled with tandem mass spectrometry to quantify and confirm simultaneously the presence of solvent metabolites in workers' urine

Ultra-performance liquid chromatography coupled with tandem mass spectrometry was used for the biological monitoring of workers occupationally exposed to solvents. The method was developed using a triple quadrupole to investigate the relevant urinary metabolites of styrene, namely mandelic acid and phenylglyoxylic acid. The method provides quantitative and qualitative data to give additional assurance about the nature of the contaminant analyzed in workers' urine. A full scan and a product ion scan were acquired within the chromatographic peak acquired in MRM. For the two metabolites, the repeatability was 96%, the precision ≥97%, and the accuracy ≥93?±?3%. The quantitative performances were not influenced by the inclusion of simultaneous full scan acquisition as compared to a usual quantitative approach. Footprints of each substance of interest were obtained at each injection, and full scan data can be interrogated for the presence of interferences and other contaminants. The method developed has been submitted to random real samples from both non-occupationally and occupationally exposed workers. The urines of non-occupationally exposed workers were all free of mandelic acid, phenylglyoxylic acid and putative interferences showing the high selectivity of the method. However, the urines of occupationally exposed workers were robustly quantified. The levels of mandelic acid and phenylglyoxylic acid ranged between 0.2 and 9?mM, and the footprints of each metabolite and structural information were acquired in parallel with the quantitative results, thus providing unquestionable data about the nature of the contaminant and the levels reported. The combination of qualitative information acquired simultaneously with quantitative results provides the structural information needed in case of questions, without any harmful effect on the robustness and throughput of the quantitative analysis.