Simultaneous Determination of Cadmium,Copper, Lead and Zinc in Amino Acid Parenteral Nutrition Solutions by Anodic Stripping Voltammetry and Sample Digestion by UV Irradiation

Abstract

Irradiation with ultraviolet (UV) energy was investigated to assay cadmium, copper, lead, and zinc by anodic stripping voltammetry (ASV) in amino acid parenteral nutrition (PN) solutions. Sample digestion by UV irradiation showed the best performances to liberate the metals from the samples (metal recoveries between 90% and 102%) in comparison with classical oxidative wet digestion methods. The best UV digestion condition was obtained with 1:10 diluted PN samples irradiated during 10 h at 90±3°C with the addition of one aliquot of 50 µL concentrated H₂SO₄ and repeated additions of 50 µL 30% (v/v) H₂O₂ at each 60 min irradiation interval. By using the UV digestion procedure cadmium, copper, lead, and zinc were simultaneously assayed in commercial amino acid PN solutions by ASV. The metal concentrations ranged between 1.3 to 4.4 for cadmium, 2.9 to 40.8 for copper, 4.4 to 16.8 for lead, and 1.4 to 208.5 for zinc. The ASV method correlated well with atomic absorption spectrometry measurements to assay the investigated analytes in amino acid PN samples after the UV digestion.     

Irradiation techniques for the release of bound heavy metals in natural waters and blood

Irradiation techniques are compared with conventional acid digestion procedures for the release of bound heavy metals in natural waters and in blood, before their determination by anodic stripping voltammetry. Ultra-violet irradiation of acidified water with a 550-W mercury vapour lamp releases bound zinc, cadmium, lead and copper after 4 h. The same results can be achieved with a 30-Mrad dose of high-energy γ-irradiation. These techniques are also effective for the release of metals in whole blood and blood plasma, where sample volumes as small as 200 μl are adequate in analyses for zinc, copper and lead. By comparison with acid digestion and solvent extraction methods, irradiation treatments offer the advantages of minimum sample manipulation and negligible reagent blanks.     

Investigations of oxidative UV photolysis

Summary Oxidative UV photolysis according to DIN standard 38406 E 16 [1] has been investigated as a sample preparation method for voltammetry. UV photolysis has decisive advantages compared with mineral acid digestion owing to the simple procedure and the very low blank values, which in turn are due to the minimal reagent addition required. For UV photolysis with a high pressure mercury lamp, an apparatus has been used that employs a new type of sample cooling and that allows the simultaneous irradiation of 12 samples. The sample preparation for the voltammetric determination of zinc, cadmium, lead, copper, nickel and cobalt has been optimized using a model water solution and subsequently tested with real matrices. The type of organic matrix and the irradiation temperature determine the irradiation time required. To digest aromatic compounds, it is advantageous to work at reaction temperatures of ca. 90°C. The application of UV photolysis centers on water samples slightly polluted with organic compounds; however, it can also be used with more heavily polluted wastewaters. As the digestion times are at most 60 min, the method is of interest for routine analysis.     

锌(Ⅱ)-茜素紫络合物的极谱行为及应用

用线性扫描示波极谱法研究了锌 ( ) -茜素紫络合物的伏安行为 ,发现在含有 0 .1 mol/L KCl,p H=9.96的 Britton- Robinson缓冲溶液中锌 ( ) -茜素紫络合物产生一灵敏的极谱吸附波 ,其峰电位为 - 1 .2 7V( vs.SCE) ,峰电流与锌 ( )的浓度在 8× 1 0 - 8～ 2× 1 0 - 6 mol/L的范围内呈线性关系 ,检出限为 5× 1 0 - 8mol/L。研究了电极反应机理 ,并用建立的方法成功地测定了发样中的锌     

Organic complexation and total dissolved trace metal analysis in estuarine waters: comparison of solvent-extraction graphite furnace atomic absorption spectrometric and chelating resin flow injection inductively coupled plasma-mass spectrometric analysis

The measured concentrations of cadmium, cobalt, copper, nickel, lead, zinc, and manganese in acidified (pH<2) estuarine water samples analyzed for total dissolved trace metal concentrations using on-line chelating resin column partitioning with inductively coupled plasma-mass spectrometry (CRCP-ICP-MS) were compared to those analyzed by graphite furnace atomic absorption spectrometry (GFAAS) after liquid-liquid extraction using a combination of 1-pyrrolidinedithiocarbamate/diethyldithiocarbamate (PDC/DDC). Although there was good agreement between the two sets of analyses for cadmium, lead, manganese, and zinc concentrations, those of cobalt, copper, and nickel determined by CRCP-ICP-MS were found to be 10-20% lower than those determined by solvent-extraction GFAAS. The different yields were positively correlated (R>0.961, simple linear regression) to the dissolved organic carbon (DOC) concentration of the samples. Good agreement between the two methods for cobalt and copper was achieved after ultraviolet (UV) digestion of the acidified samples. Samples collected from the South Bay of the San Francisco Estuary with high DOC showed the greatest difference for cobalt, copper, and nickel which is tentatively attributed to complexation with humic material for copper and cobalt and strong synthetic chelating agents such as ethylenediaminetetraacetic acid (EDTA) for nickel. This is consistent with previous studies on copper, nickel and cobalt complexation in this region. We recommend UV digestion of acidified estuarine samples prior to multi-element analysis by chelating resin flow injection ICP-MS methods.     

Determination of mobile form contents of Zn, Cd, Pb and Cu in soil extracts by combined stripping voltammetry

The amount of mobile forms of Zn, Pb, Cd and Cu in extracts obtained by treating soil samples with ammonium nitrate were determined by an appropriate combination of anodic and cathodic stripping voltammetry with hanging mercury drop electrode. Every analysis required three mercury drops: on the first one, zinc was determined; on the second, cadmium and lead; on the third, copper was determined. Zinc, lead and cadmium were determined by conventional differential-pulse anodic stripping voltammetry. For copper determination, adsorptive differential-pulse cathodic stripping voltammetry with amalgamation using chloride ions as a complexing agent was applied. The standard deviation of the results was from 1 to 10% depending on the metal content in the sample. Voltammetric results were in good agreement with the AAS analysis. No microwave digestion of soil extracts was necessary.     

Oxidative Modification in Human Hair: The Effect of the Levels of Cu (II) Ions,UV Exposure and Hair Pigmentation

Protein oxidative degradation is implicated in a wide range of deleterious effects. For human hair, this oxidative damage can lead to significant observable changes in fiber physical and visual properties. A redox proteomic approach was applied to map molecular modification in human hair proteins and correlate this modification with the abundance of copper (II) ions, the levels of UV exposure and the general level of hair pigmentation. An increase in oxidative modification was observed with increasing copper (II) ion levels, regardless of the pigmentation level. Significantly, increased protein oxidative modification was also observed to occur in both lightly and darkly pigmented hair tresses even in the absence of irradiation, albeit at lower relative levels. Modification levels increased with increased copper (II) ion concentration. This new finding indicates that the level of copper (II) ions in human hair plays a key role in mediating protein oxidation, with or without exposure to UV light. Overall, these results strongly suggest that minimization of the level of copper (II) ions in human hair will mitigate and/or slow protein oxidative modification and therefore lower overall hair damage.     

头发中微量铜和锌的 5-Br-PADAP 分光光度法测定

研究了测定铜和锌时多种掩蔽剂联合掩蔽头发中的干扰离子。测定铜时用六偏磷酸钠和焦磷酸钾联合掩蔽;测锌时用柠檬酸钠、六偏磷酸黄和铜试剂联合掩蔽。在表面活性剂OP存在下,5－Br-PADAP显色,不经分离,直接在水事测定斑秃患者头发中的铜和锌。铜络合物的最高吸收峰在558nm,锌络合物的最高吸收峰在560nm,在25mL溶液中,铜在0－37．5mg/L,锌在0－238mg/L范围内符合beer定律。斑秃患者头发中锌和铜低于正常人。     

Stripping voltammetric determination of traces of catechol compounds preceded by adsorptive accumulation of metal complexes

Catechol compounds are quantified by controlled adsorptive accumulation of their metal complexes onto a hanging mercury drop electrode followed by stripping voltammetry. By using tin(IV) as a redox marker for quantifying the surface-bound species, selectivity can be improved relative to conventional oxidative methods; dopamine can be quantified in the presence of ascorbic acid. The method allows measurements of micromolar levels of catechol, dopamine, l-dopa, 3,4-dihydroxyphenylacetic acid and caffeic acid. The adsorptive stripping response is evaluated with respect to preconcentration time and potential, tin(IV) and analyte concentrations, stripping mode, reproducibility and possible interferences. Analogously, solochrome violet RS and dimethylglyoxime can be quantified after accumulation of their iron(III) and nickel(II) complexes, respectively. Detection limits are 7×10^?9 M for solochrome violet RS and 5×10^?8 M for caffeic acid (1- and 5-min preconcentration, respectively).     

极谱配合吸附波法同时测定人发锌、铅、铜与评价

本文介绍用极谱配合吸附波方法同时快速测定人发中的锌、铅、铜,并着重研究了人发样品的预处理方法。对青岛市区各不同年龄组健康者与厌食症儿童发样测定的统计分析结果进行了评价。     

电感耦合等离子体光谱法测定铜冶炼烟尘中锌

本实验介绍了电感耦合等离子体光谱法测定铜冶炼烟尘中锌含量的分析方法。针对样品碳,硅含量高的特点,有针对性的研究了样品的消解方法,确定采用盐酸、硝酸、氢氟酸、高氯酸对铜冶炼烟尘样品进行消解。同时进行了干扰试验,确定样品中高含量的铜,铅,砷等对样品测定结果没有影响。并对仪器的工作参数进行了优化。方法检出限为为0.011 mg/L,测定下限为0.019 mg/L,3个样品的相对标准偏差在0.54%~0.92%之间,加标回收率在96%~101.14%之间。该方法样品消解完全,流程短,操作简单,快速,测定准确度高,可以满足铜冶炼烟尘中锌含量的测定。     

Determination of zinc and copper in human hair by slurry sampling employing sequential multi-element flame atomic absorption spectrometry

The present work proposes a direct method based on slurry sampling for the determination of zinc and copper in human hair samples by multi-element sequential flame atomic absorption spectrometry. The slurries were prepared by cryogenic grinding and sonication of the samples. The optimization step was performed using univariate methodology and the factors studied were: nature and concentration of the acid solution, amount sample/slurry volume, sonication time, and particle size. The established experimental conditions are the use of a sample mass of 50 mg, 2 mol L^− 1 nitric acid solution, sonication time of 20 min and slurry volume of 10 mL. Adopting the optimized conditions, this method allows the determination of zinc and copper with detection limits of 88.3 and 53.3 ng g^− 1, respectively, and precision expressed as relative standard deviation (RSD) of 1.7% and 1.6% (both, n = 10) for contents of zinc and copper of 100.0 and 33.3 μg g^− 1, respectively. The accuracy was checked and confirmed by analysis of two certified reference materials of human hair. The procedure was applied for the determination of zinc and copper in two human hair samples. The zinc and copper contents varied from 100.0 to 175.6 and from 3.2 to 32.8 μg g^− 1, respectively. These samples were also analyzed after complete digestion in a closed system and determination by FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.     

微波消解-电感耦合等离子体原子发射光谱(ICP-AES)法测定含铜污泥中多种重金属

为了填补现有方法的技术空白,本方法采用微波消解和电感耦合等离子体原子发射光谱法（ ICP-AES）相结合,实现对含铜污泥中铅、锌、铬、镉、砷、镁、铝、锑量的同时测定。首先采用盐酸-硝酸-氢氟酸微波消解进行样品的前处理,消解后加入高氯酸置于电热板进行除碳并赶酸,溶样效果理想,且有效避免了高温溶样对易挥发元素砷、锑的损失,整个过程安全、高效、无损。溶样后以电感耦合等离子体发射光谱法（ ICP-AES）进行测定。对含铜污泥的分解方法进行了合理选择,并对测定时的元素分析谱线及各测定元素间干扰情况等进行了讨论。该方法的加标回收率在95.31%~107.28%%,相对标准偏差（RSD）在0.31%~2.05%之间（n=7),结果表明,该方法准确度高,操作简单快捷,可同时测定多种元素,能满足批量的测定含铜污泥中铅、锌、镍、铁、镉、铬、砷、锑含量的测定要求。     

Effect of coordination sphere of the copper center and Cu―Cu distance on catechol oxidase and nuclease activities of the copper complexes

To explore the effect of Cu―Cu distance in the structure of copper complexes on their catechol oxidase and nuclease activity, six copper complexes with a similar coordination sphere but different Cu―Cu distances were synthesized and characterized with elemental analysis, single‐crystal X‐ray diffraction, molar conductivity measurements, IR and UV–visible spectroscopy. Complex 1 is a binuclear copper complex and complex 4 is a polynuclear complex with a Z‐chain structure, as evidenced by their crystal structures. Complementary characterizations showed that complexes 2 and 3 have a similar binuclear structure to the complex 1 ; and complexes 5 and 6 are analogous to complex 4 . The catechol oxidase activity of complexes 1 , 2 , 3 is quite akin to that of 4 , 5 , 6 , suggesting that the catechol oxidase activity of the complexes was determined by the coordination environment of the copper center, when Cu―Cu distance is large. In contrast, DNA cleavage activity of the complexes 1 , 2 and 3 are much higher than that of 4 , 5 and 6 , indicating that the planar ligand structure in the complexes 4 , 5 and 6 is more critical than the copper coordination sphere and the Cu―Cu distance for their nuclease activity. Copyright © 2014 John Wiley & Sons, Ltd.     

Extraction-spectrophotometric determination of traces of antimony in copper and lead metals and in lead-base alloy with pyrocatechol violet and tri-n-octylamine

A sensitive spectrophotometric method is described for the determination of antimony in copper and lead metals and in lead-base alloy. Optimal conditions have been established for the extraction and determination of antimony. Antimony (III) is extracted from a potassium iodide—sulfuric acid or a hydrobromic—sulfuric acid medium with toluene and converted to an antimony-pyrocatechol violet (PV) complex. The complex is then extracted with tri-n-octylamine (TOA) and the absorbance of the resulting ternary Sb(III)—PV-TOA complex is measured at 555 nm. As little as 0.5 p.p.m. of antimony in copper metal and 0.2 p.p.m. of antimony in lead metal and lead-base alloy can be determined.     

Determination of zinc and copper in human hair by slurry sampling employing sequential multi-element flame atomic absorption spectrometry

The present work proposes a direct method based on slurry sampling for the determination of zinc and copper in human hair samples by multi-element sequential flame atomic absorption spectrometry. The slurries were prepared by cryogenic grinding and sonication of the samples. The optimization step was performed using univariate methodology and the factors studied were: nature and concentration of the acid solution, amount sample/slurry volume, sonication time, and particle size. The established experimental conditions are the use of a sample mass of 50 mg, 2 mol L^− 1 nitric acid solution, sonication time of 20 min and slurry volume of 10 mL. Adopting the optimized conditions, this method allows the determination of zinc and copper with detection limits of 88.3 and 53.3 ng g^− 1, respectively, and precision expressed as relative standard deviation (RSD) of 1.7% and 1.6% (both, n = 10) for contents of zinc and copper of 100.0 and 33.3 μg g^− 1, respectively. The accuracy was checked and confirmed by analysis of two certified reference materials of human hair. The procedure was applied for the determination of zinc and copper in two human hair samples. The zinc and copper contents varied from 100.0 to 175.6 and from 3.2 to 32.8 μg g^− 1, respectively. These samples were also analyzed after complete digestion in a closed system and determination by FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.     

Diagnosis of Metal Poisoning and Evaluation of Chelation Therapy by Differential Pulse Anodic Stripping Voltammetry Coupled to a Novel Digestion Procedure

Abstract

Differential pulse anodic stripping voltammetry, coupled to a closed acid digestion system, has been proven to be an efficient tool for rapid diagnosis of metal poisoning and for evaluating the progress of chelation therapy. This technique and system has been used to determine total zinc, cadmium, lead, bismuth, copper, and thallium in urine, blood, hair, teeth, feces, bone and other tissue for medical management and post-mortem studies. The technique lends itself to determining minute changes in metal concentrations, while its low detection limits provide for the analysis of liquid samples as small as 10 μl. A procedure for rapidly removing metal contaminants from reagents and electrolyte systems was tested and found to be effective for this highly sensitive technique.     

紫外光照射对掺铝氧化锌薄膜导电和透光性质的影响

本文采用光助溶胶—凝胶法制备了掺铝氧化锌(AZO)透明导电薄膜.研究了紫外光照射对薄膜导电性和透光性质的影响.结果表明:光照使薄膜的导电性显著提高,且光照后薄膜方阻的降低幅度随薄膜晶粒尺寸的减小而逐渐增加;而随着紫外光照射时间延长,薄膜的紫外吸收边蓝移,近红外区透光率降低.以上实验现象可能与表面吸附氧解吸引起的载流子浓度增加、迁移率升高以及分层退火处理形成的薄膜结构有关.     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

Analysis of rain water by differential-pulse stripping voltammetry in nitric acid medium

Differential-pulse anodic stripping voltammetry is applied to determine cadmium, lead and copper in rain water acidified with nitric acid to pH 1.5, and zinc after partial neutralization to pH 4.5. Subsequently, cobalt and nickel are measured in the adsorptive mode after formation of their dimethylglyoximates. The effects of pH on the stripping peaks for Zn, Cd, Pb and Cu and of chloride on the stripping peak of copper are reported. Good agreement is found with d.p.s.v. determinations in hydrochloric acid medium and with a.a.s. measurements in most cases. Excellent accuracy is demonstrated; the average relative standard deviation per measurement appears to be between 12 and 22% for the overall analytical procedure for concentrations of 0.15–50 μgl^?1 of the various metals in the samples.