Determination of Ultratrace Amounts of Copper(Ⅱ) in Water Samples by Electrothermal Atomic Absorption Spectrometry After Cloud Point Extraction

A novel approach was developed for the determination of ultratrace amounts of copper in water samples by using electrothermal atomic absorption spectrometry （ETAAS） after cloud point extraction （ CPE ）. 1-（ 2-Pyridylazo ） -2- naphthol was used as the chelating reagent and Triton X-114 as the mieellar-forming surfactant. CPE was conducted in a pH 8. 0 medium at 40 ℃ for 10 rain. After the separation of the phases by contrifugafion, the surfactant-rieh phase was diluted with 1 mL of a methanol solution of 0. 1 mol/L HNO3. Then 20μL of the diluted surfactant-rieh phase was injected into the graphite furnace for atomization in the absence of any matrix modifier. Various experimental conditions that affect the extraction and atomization processes were optimized. A detection limit of 5 ng/L was obtained after preconeentration. The linear dynamic range of the copper mass concentration was found to be 0-2.0 ng/mL, and the relative standard deviation was found to be less than 3. 1% for a sample containing 1.0 ng/mL Cu （ Ⅱ ）. This developed method was successfully applied to the determination of uhratraee amounts of Cu in drinking water, tap water, and seawater samples.

Uncertainty in Detecting Copper and Zinc Contents in Maize Flour by Flame Atomic Absorption Spectrometry with Wet Digestion Method

[ Objective] This study aimed to evaluate the uncertainty in detecting copper and zinc contents in maize flour by flame atomic absorption spectrometry. [ Method] Combined with the actual inspection experience, the uncertainty in detecting copper and zinc contents in maize flour by tame atomic absorption spec- trometry was evaluated to establish the mathematical model. The uncertainty sources in the experimental process were investigated to analyze several components af- fecting the uncertainty in sample detection, including sample weighing, standard material transfer, solution dilution and volume setting, curve fitting, and repeat- ability of measurement instruments. [ Result] Standard curve fitting and repeatability test were two major factors that significantly affected the combined standard uncertainty. However, in the actual detection process, standard curve calibration and repeated detection procedures should be controlled strictly. Finally, the ex- panded uncertainty of copper and zinc contents in maize flour was （ 1.38 ± 0.08） mg/kg and （ 10.20 ± 1.20） mg/kg, respectively. [ Conclusion] This study provided reference for improving the accuracy and reliability of the detection method.

Determination of Copper and Lead Contents in Soil of the Yellow River Wetland in Shaanxi Province by Flame Atomic Absorption Spectrometry

[Objectives] The contents of copper and lead in the soil of the Yellow River Wetland were determined by flame atomic absorption spectrometry, which provides a theoretical basis for the treatment of soil pollution. [Methods] The soil was digested with a concentrated nitric acid-hydrofluoric acid-perchloric acid system, and the contents of heavy metals such as copper and lead in the Yellow River Wetland of Shaanxi Province were determined by flame atomic absorption spectrometry. [Results] The correlation coefficients reached 0.999 5 in the range of 0.00-1.00 mg/L, indicating good linearity. [Conclusions] The method is simple in operation, good in reproducibility, high in sensitivity to most elements, and can be widely used.

Flow Injection Semi-online Preconcentration Graphite Furnace Atomic Absorption Spectrometry for Determination of Cadmium,Copper and Manganese

A micro-flow injection sorbent extraction preconcentration system was combined with a graphite furnace atomic absorption spectrometry that formed an integrated system for the determination of trace amounts of elements. The analytical performances of the prospsed method for determining Cd, Cu and Mn were studied. The analytes were preconcentrated with a thiol resin(Type 190, produced by Nankai University, China) whose active group is -SH. The elements to be determined were preconcentrated onto the column for 60 s and then rinsed with deionized water and eluted with 30 μL of 1 mol/L HCl. The graphite furnace atomic absorption spectrometry(GFAAS) determination of the concentrated analyte was carried out in parallel with the next preconcentration cycle. Enrichment factors 41, 22 and 20 and detection limits(3 σ , n =10) 0.36, 3.8 and 7.0 ng/L for Cd, Cu and Mn, respectively, along with a sampling frequency of 20 h -1 , were obtained with a 60 s loading time at a sample flow rate of 3.5 mL/min. The analytical results for a number of water samples show that the flow-injection semi-online column preconcentration can not only eliminate the effect of some concomitant elements, such as Li, Na, K, Ca and Mg, on the determination of the analyte, but also enhance the sensitivity.

Uncertainty Estimation for the Determination of Trace Heavy Metals in Human Hair by Flame and Electrothermal Atomic Absorption Spectrometry

Trace element analysis on hair samples has been widely used to assess wildlife and human exposure to different contaminants present in the environment or at the workplace. Pollutants due to the presence of toxic metals in environment not only enter the body by breading, water, and foodstuff accumulates in hair, but they could be adsorbed directly on the hair from environment. In order to remove adsorbed elements and thus determine the internally bound elements correctly, hair sample must be washed. In the present work, we propose uncertainty estimation for the analytical results that are obtained from determination of cadmium, lead, copper, iron, manganese and nickel in human hair by flame and electrothermal atomic absorption spectrometry （FAAS and ETAAS）. To estimate the uncertainty of analytical result obtained, two types of bias are calculated in the assessment of trueness： a proportional bias and a constant bias. Nested design was applied for calculating proportional bias and Youden method to calculate the constant bias. The results we obtained for proportional bias are calculated from spiked samples. In this case, the concentration found is plotted against the concentration added and the slop of standard addition curve is an estimate of the method recovery. Estimated method of average recovery in human hair is： （1.019 ±0.026）, （0.918 ±0.014）, （1.073±0.016）, （1.0597± 0.017）, （1.073± 0.020） and （0.934± 0.117） for Cd, Pb, Mn, Ni, Fe and Cu respectively.

FLAME ATOMIC ABSORPTION DETERMINATION OF COPPER IN CEREALS FOOD SAMPLES WITH THE PRECONCENTRATION OF POTASSIUM TETRATITANATE WHISKER

A simple and reliable method has been developed for separation and preconcentration of trace amounts of copper ions in cereals food for subsequent measurement by flame atomic absorption spectrometry （FAAS）. The Cu^2＋ ions are adsorbed selectively and quantitatively during the passage. The retained copper ions were desorbed from the potassium tetratitanate whisker with 10.0mL of 2mol/L sulphuric acid solutions as eluent and were determined by FAAS. The linear range was 0.05μg/mL-0.20μg/mL in the original solution with a correlation coefficient of 0.9998. The detection limit of the proposed method is 2. lng/mL in the original solution （3σ, n=9）. Determination of copper in standard ions showed that the proposed method has good accuracy （recovery was more than 95%）. The method was successfully applied for recovery and determination of copper in cereals food samples

A novel method for the determination of trace copper in cereals by dispersive liquid-liquid microextraction based on solidification of floating organic drop coupled with flame atomic absorption spectrometry

A novel,simple,rapid,efficient and environment-friendly method for the determination of trace copper in cereal samples was developed by using dispersive liquid-liquid microextraction based on solidification of floating organic drop（DLLME-SFO） followed by flame atomic absorption spectrometry.In the DLLME-SFO,copper was complexed with 8-hydroxy quinoline and extracted into a small volume of 1-dodecanol,which is of low density,low toxicity and proper melting point near room temperature. The experimental parameters affecting the extraction efficiency were investigated and optimized.Under the optimum conditions, the calibration graph exhibited linearity over the range of 0.5—500 ng/mL with the correlation coefficient（r） of 0.9996.The enrichment factor was 122 and the limit of detection was 0.1 ng/mL.The method was applied to the determination of copper in the complex matrix samples such as rice and millet with the recoveries for the spiked samples at 5.0 and 10.0 u,g/g falling in the range of 92.0-98.0%and the relative standard deviation of 3.9-5.7%.

Determination of Copper by Flame Atomic Absorption Spectrometry after Preconcentration with Activated Carbon Impregnated with a New Schiff Base

A simple and reliable method for the extraction and determination of trace amounts of copper（Ⅱ） ions using activated carbon （AC） impregnated by a new Schiff base 5-[（4-heptyloxyphenyl）azo]-N-（4-propyloxyphenyl）-salicylaldimine （HPPS） and atomic absorption spectrometry is presented. Recovery efficiency and the influence of pH value, volume of sample solution, effect of different eluents, and interfering ions were evaluated. The limit of detection （3σ） was 2.62 ng.mL^-1 and the relative standard deviation （n=10） was 1.5%. Under optimum conditions, the copper ions were concentrated 25 fold using 250 mL of sample solution and 10 mL of eluent. This procedure has been successfully applied to the determination of copper in different water samples.

Preconcentration and Determination of Copper（Ⅱ） Using Octadecyl Silica Membrane Disks Modified by 1,5-Diphenylcarhazide and Flame Atomic Absorption Spectrometry

A simple and reproducible method for the rapid extraction and determination of trace amounts of copper（Ⅱ） ions using octadecyl-bonded silica membrane disks modified by 1,5-diphenylcarbazide （DPC） and atomic absorption spectrometry was presented, which was based on complex formation on the surface of the ENVI-18 DISK^TM disks followed by stripping of the retained species by minimum amounts of appropriate organic solvents. The elution was efficient and quantitative. The effect of potential interfering ions, pH, ligand amount, stripping solvent, and sample flow rate were also investigated. Under the optimal experimental conditions, the break-through volume was found to be about 1000 mL providing a preconcentration factor of 400. The maximum capacity of the disks was found to be （255±5） lag for Cu^2＋, and the limit of detection of the proposed method was 5 ng per 1000 mL. The method was applied to the extraction and recovery of copper in different water samples.

Ultrasound-assisted emulsification solidified floating organic drop microextraction for the determination of trace amounts of copper in water samples

A simple and efficient liquid-phase microextraction(LPME)technique was developed using ultrasound-assisted emulsification solidified floating organic drop microextraction(USAE-SFODME)combined with flame atomic absorption spectrometry,for the extraction and determination of trace copper in water samples.1-(2-Pyridylazo)-2-naphthol(PAN)was used as chelating agent.Microextraction efficiency factors(including extraction solvent type,extraction volume,time,temperature,and pH),the amount of the chelating agent,and salt effect were investigated and optimized.Under the optimum extraction conditions,figures of merit of the proposed method were evaluated.The calibration graph was linear in the range of 20–600 mg·L^(–1)with a detection limit of 0.76 mg·L^(–1).The relative standard deviation(R.S.D)for ten replicate measurements of 20 and 400 mg·L^(–1)of copper was 3.83%and 2.65%,respectively.Finally,the proposed method was applied to tap water,river water,and sea water,and accuracy was assessed through the analysis of certified reference water or recovery experiments.

Solid Phase Extraction of Trace Copper（Ⅱ） Using Octadecyl Silica Membrane Disks Modified with N,N′-Disalicylideneethylenediamine

A simple and reproducible method for the rapid extraction and determination of trace amounts of copper（Ⅱ） ions using octadecyl-bonded silica membrane disks modified by N,N′-disalicylideneethylenediamine （DESDA） and atomic absorption spectrometry was presented. The method is based on complex formation on the surface of the ENVI-18 DISK^TM disks followed by stripping of the retained species by minimum amounts of appropriate organic solvents. The elution is efficient and quantitative. The effects of potential interfering ions, pH, ligand amount, stripping solvent, and sample flow rate were also investigated. Under the optimal experimental conditions, the break-through volume was found to about be 1000 mL providing a preconcentration factor of 500. The maximum capacity of the disks was found to be （389±4） μg for Cu^2＋. The limit of detection of the proposed method is 5 ng per liter. The method was applied to the extraction and recovery of copper in different water samples.

火焰原子吸收光谱法测定配合饲料中铜、铁和锰含量的不确定度评定

研究旨在建立火焰原子吸收光谱法测定配合饲料中铜、铁和锰含量的不确定度评定方法,真实反映测量的置信度和准确性。首先分析测定过程中的不确定度来源,对不确定度分量进行量化,然后通过数学模型计算出饲料中铜、铁和锰含量,合成扩展不确定度。结果显示:饲料中铜、铁和锰的含量分别为(11±2)、(214±10)、(92±4)mg/kg,不确定度为扩展不确定度,包含因子为2,对应的置信水平是95%。本研究发现样品消解、样品溶液浓度测定和含量重复性测量是影响饲料中铜、铁、锰含量测量中不确定度的主要因素,应特别关注样品的前处理过程、标准工作液的配制,并使待测样品的浓度落在曲线的中间位置,以提高检测准确性。

石墨炉原子吸收光谱法测量干香菇镉含量的不确定度来源评定

依据国家计量技术规范《测量不确定评定与表示》(JJF 1059.1—2012),针对干香菇镉含量的原子吸收光谱法(石墨炉法)检测过程,分析测量不确定度的来源,不确定度主要来源于测量重复性、标准物质、样品制备、线性拟合标准曲线、石墨炉原子吸收光谱仪等5个方面,通过建立相应的数学模型,计算评定上述5个方面来源的相对标准不确定度分别为0.00743、0.00268、0.02275、0.00866和0.00005,合成标准不确定度为0.0151 mg∕kg,最终得出测量结果的扩展不确定度为0.03 mg∕kg。结果表明,在该试验中标准曲线线性拟合计算质量浓度是不确定度引入的最主要因素。

火焰原子吸收光谱法测定岩石样品中铜、铅、锌的研究

主要研究火焰原子吸收光谱法测定岩石样品中的铜、铅、锌。采用石墨消解仪和HF-HCl-HNO3-HClO4酸系消解样品的前处理方法效果相对较好,酸性介质可用盐酸或硝酸溶液,浓度宜为2%~5%。通过实验得出:铜、铅、锌的检出限分别为0.012μg/mL、0.057μg/mL、0.009μg/mL,测定下限分别为0.048μg/mL、0.228μg/mL、0.036μg/mL,方法RSD值(精密度)1.0%~3.6%,加标回收率97.29%~101.0%,符合岩石矿物分析规范的要求。火焰原子吸收光谱法测定铜、铅、锌具有操作简便、实验用时短、干扰少及较好的准确度和精密度的特点。

金矿石中铅含量的测量不确定度评定

本研究依据GB/T 20899.5—2021方法1火焰原子吸收光谱法测定金矿石中的铅含量,建立数学模型,分析整个测定过程中不确定度的来源。样品的称量、定容体积、稀释及标准曲线的拟合等都会引入一定的不确定度分量。本文分别通过A类或B类评定方式对这些不确定度分量进行计算,并合成标准不确定度u,在置信概率为95%的情况下,取包含因子k=2,计算得扩展不确定度U=0.05%。计算发现,B类不确定度的贡献大于A类不确定度,而B类不确定度分量贡献最大的部分为标准曲线带来的不确定度,可以通过增加标准溶液数量以及试液的测量次数来降低标准曲线带来的不确定度影响。实验表明,在条件一致的情况下,试液测量次数由3次增加到5次,扩展不确定度可由0.05%降至0.04%。

石墨炉原子吸收分光光度法测定水中铟不确定度分析

铟作为一种环境污染物,其化合物具有致癌作用和生物毒性,是水质监测的一项重要的指标。为了确定检测过程中不确定度的主要来源,如实反映测量数据的置信度和准确度,提高检测质量,对石墨炉原子吸收分光光度法测定水中铟不确定度进行分析和评估。参照不确定度的评定规范和石墨炉原子吸收分光光度法对水中铟的测定原理建立数学模型,分析了包括重复性、标准储备液、标准曲线配制、标准曲线拟合、测量仪器以及样品前处理等不确定度来源,分别计算了各不确定度分量、合成标准不确定度和扩展不确定度。结果表明水中铟的平均值为19μg/L,扩展不确定度为5.6%,水中铟含量结果表示为19±2μg/L,k=2。经过评估分析,测定水中铟的不确定度的主要影响因素为样品的重复性处理和标准溶液的配制。

使用控制图法对原子荧光法测定土壤中砷进行不确定度评定

根据《检测实验室中常用不确定度评定方法与表示》(GB/T 27411-2012)中控制图法,在期间精密度测量条件下按照《土壤和沉积物汞、砷、硒、铋、锑的测定微波消解/原子荧光法》(HJ 680-2013)对土壤中砷进行重复测量,得到34组测量数据。首先计算其正态统计量(A^(2*)),并判断数据的正态性、独立性和分辨力适宜性;其次再绘制控制图,使用失控准则判断测量系统处于受控状态;最后使用t检验判断数据统计上的偏倚受控。三者均满足的情况下,可视期间精密度标准偏差为实验室土壤中砷的测量不确定度。

FAAS测定铅矿石中铜含量的不确定度评定

本研究采用FASS检测技术,根据GB/T14353.1-2010的实验标准方法对铅矿石中铜元素的含量进行测定。然而实验测量过程中会产生不可避免的不确定度,因此对实验过程中产生的不确定度进行评定,结果表明测量铅矿石样品中铜的含量为284±27.49μg/g,确定了实验过程中产生不确定度的主要来源,包括样品重复性测量、样品称量、样品体积定容、标准曲线拟合及标准溶液的配制,对比发现标准曲线拟合的不确定度对测量结果的影响最大。

干制木耳中铅含量的测量不确定度评定

本文参考国家标准采用火焰原子吸收光谱法测定干制木耳中的铅含量,并通过测定不确定度,评估铅含量测定的准确性。结果表明,当干制木耳中铅含量为0.829 mg·kg^(-1)时,扩展不确定度为0.102 mg·kg^(-1)(k=2,p=95%)。不确定度评定结果表明,该方法的扩展不确定度主要来源于标准工作曲线的拟合,其次是试样重复性测定、原子吸收光谱仪、制备系列浓度的铅标准工作溶液、铅标准溶液、试样消化液定容体积;试样称量的影响最小,基本可忽略不计。

石墨炉原子吸收法测定地表水中铅的不确定度评定

对石墨炉原子吸收法测定地表水中铅从重复测定样品、工作曲线拟合、铅标准溶液及配制、样品前处理过程四方面进行不确定度分析,发现不确定度最大的部分来源于工作曲线拟合,之后是样品重复测定和样品前处理过程。在工作曲线拟合方面应适当缩小标准曲线范围,使工作曲线覆盖范围尽量与实际样品浓度相匹配,同时严格规范曲线配制的操作过程。在样品的重复测定方面,确保仪器运行的稳定是减小不确定度的关键。