Determination of arsenic in urine by hydride generation atomic fluorescence spectrometry with ammonium persulfate digestion / 中华地方病学杂志

Objective:To establish a hydride generation atomic fluorescence method using ammonium persulfate as the digestion reagent for determination of arsenic in urine (hereinafter referred to as this method).Methods:The collected urine samples with ammonium persulfate were heated and digested on the tubular electric heating automatic control constant temperature digester (60 holes), with 5% hydrochloric acid solution as reaction medium and current carrier and 1.5% potassium borohydride solution as reducing agent. Arsenic content was determined with a four-channel atomic fluorescence spectrometer. The arsenic standard solution of 0 - 10 μg/L was prepared to determine the standard curve of this method, and the method was evaluated from the detection limit, linear range, correlation coefficient, precision, standard addition recovery experiment, and urine arsenic quality control sample detection. The standard method "Determination of Arsenic in Urine by Hydride Generation Atomic Fluorescence Spectrometry" (WS/T 474-2015, referred to as the standard method) was used for comparison experiments.Results:When the sampling volume was 1 ml, the detection limit of this method (digest with 1 ml 1.5 mol/L ammonium persulfate) was 0.03 μg/L. In the range of arsenic content from 0 - 10 μg/L, the linear relationship between arsenic content and fluorescence intensity was good, and the correlation coefficients ( r) were all 0.999 9. The relative standard deviations( RSD) of the three replicates of urine samples with different concentrations were 1.00%, 0.89% and 0.49%, respectively. Urine arsenic quality control samples were tested, and the test results were all within the range of public values; the overall average recovery was 102.29%, and the recovery range was 92.10% - 108.15%. Compared with the standard method in the determination results of 20 urine samples, the difference was not statistically significant ( t = - 0.40, P > 0.05). Conclusions:The hydride generation atomic fluorescence spectrometry using ammonium persulfate as digestion reagent for the determination of arsenic in urine has the advantages of low detection limit, good precision, high accuracy, small amount of sampling and digestion reagent, simple operation, and less harmful gas generation in sample pretreatment. It is suitable for rapid determination of arsenic in urine in large quantities.

Quantitative Determination of Arsenic Species in Feed Using Liquid Chromatography-Hydride Generation Atomic Fluorescence Spectrometry / 分析化学

A sensitive and rapid method using liquid chromatography-hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS) was developed for the simultaneous determination of seven arsenic species As3+, As5+,MMA, DMA, p-ASA, 4-OH and ROX in feeds. The isolation of the analytes from feed samples was accomplished using methanol water (1:1, V/V). The target compounds were separated on a PRP-X100 anion exchange column and then analyzed by HG-AFS. The mobile phase was 15 mmol/L (NH4)2HPO4and 10 mmol/L potassium acid phthalate. Good linearity was obtained for all of the seven arsenic species, with linear coefficients higher than 0.9964. The LODs of the seven arsenic species were between 5 and 30 μg/kg. Average recoveries for the seven analytes were in the ranges of 76.3%-108.1%, with intra- and inter-day repeatability lower than 7.7% and 17.4%,respectively. This validated method was successively applied to the determination of arsenic species in feed. This method was sensitive,simple,cheap and low operation cost,and could be used for the determination of the arsenicspecies in feeds.

Determination of Total Arsenic and Arsenic Species in Blood of Acute Promyelocytic Leukemia Patients Treated with Arsenous Acid / 中国药师

Objective:To quantify the plasma concentrations of inorganic arsenic (As(III) and As(V)) and methylated metabo-lites ( MMA and DMA) , and to detect the total amount of arsenic in blood cells and plasma by high performance liquid chromatogra -phy-hydridegeneration-atomic fluorescence spectrometry ( HPLC-HG-AFS) and HG-AFS methods to clarify the arsenic species in acute promyelocytic leukemia (APL) patients.Methods:The blood cells and plasma were digested by the mixture of HNO 3-H2O2 and ana-lyzed by HG-AFS.For the arsenic species , the plasma samples were prepared with perchloric acid to precipitate protein .The superna-tant was separated on an anion-exchange column in 6 min with isocratic elution using 13 mmol · L-1 CH3 COONa, 3 mmol · L-1 NaH2 PO4 , 4 mmol· L-1 KNO3 and 0.2 mmol· L-1 EDTA-2Na.Results:The methods provided linear range of 0.2-20 ng· ml-1 for total arsenic and 2.0-50 ng· ml-1 for four arsenic species (r>0.9950).The spiked recoveries ranged from 81.2％to 108.6％, and the coefficients of variation for intra-and inter-batch precision were less than 9.3％and 12.5％, respectively.The developed methods were applied successfully in the assay of total arsenic and arsenic species in 5 APL patients.Conclusion:The method is simple, fast and accurate , which can be applied in the assay of arsenic compounds in plasma and blood cells in APL patients .

A method for detection of selenium in grain by hydride generation-atomic fluorescence spectrometry and its application / 中华地方病学杂志

Objective To establish a rapid, simple and accurate method for detection of selenium in grain that is suitable in Chinese situation. Methods Nitric acid and perchloric acid(7: 3, v/v) were used to digest the grain samples by heating on a hot plate. Selenium was determined with hydride generation atomic fluorescence spectrometry. Sample detection limit, precision, accuracy(recovery, method characteristics and method control) were studied. And the grain samples of Shandong Province were determined by this method. Results The lowest detection limit was 4 μg/kg. The coefficient of correlation of working curve was 0.999 9. Intra-day precision was 1.32%, day precision was 4.17%. The total average rate of recovery was 100.5% with a range of 96.7% - 105.5%, and the average rates of recovery were 104.0%, 99.0% and 98.4% (n = 6). The determination results of corn reference material [(0.022 ± 0.006) mg/kg] were in the standard value range [(0.021 ± 0.008) mg/kg]. The determination results of the samples [(0.424 ± 0.096) mg/kg] were consistent with the results of national standard fluorescence method [(0.406 ± 0.108) mg/kg]. The contents of selenium in wheat, maize and sweet potato samples from five regions of Shandong Province were:Shanting:(0.030 3 ± 0.025 2),(0.016 8 ± 0.013 5),(0.015 4 ± 0.002 9) mg/kg; Anqiu:(0.020 3 ± 0.000 1), (0.020 4 ± 0.009 9), (0.017 1 ± 0.007 5) mg/kg; Ju'nan:(0.021 3 ± 0.013 9), (0.018 5 ± 0.007 8),(0.019 9 ± 0.003 6)mg/kg;Yishui:(0.025 7 ± 0.006 2),(0.020 6 ± 0.003 2), (0.018 2 ± 0.003 2) mg/kg; Wulian:(0.020 3 ± 0.004 7), (0.020 1 ± 0.008 9), (0.018 4 ± 0.007 3) mg/kg. Conclusions The method has the advantages of higher precision and accuracy, less time, less pollution, less aciduse, easier operation and repeatability.It is very suitable for measuring selenium content in large amount of food samples.

A method for determination of arsenic in urine by hydride generation atomic fluorescence spectrometry using hydrogen peroxide as the main digestion reagent to digest urine / 中华地方病学杂志

Objective To establish a method for determination of arsenic in urine,using hydrogen peroxide as the main digestion reagent to digest urine,and using hydride generation atomic fluorescence spectrometry (HG-AFS) to determine arsenic (this method was referred to below),the feasibility of the application in the monitoring of endemic arsenic poisoning was discussed.Methods Temperature control instrument (60 holes) and supporting special calibration tube were used to digest urine.Digestion reagents was mainly hydrogen peroxide plus a small amount of nitric acid and sulfuric acid,HG-AFS was used to determinate.Based on standard curve to calculate linear relationship.Using this method to determinate detection limit,precision,accuracy and stability of samples,this method was compared with the national hygienic standard method (DDCAg method,WS/T 28-1996).Results The detection limit was 0.8 μg/L (1 ml of urine was tested),the correlation coefficient was larger than 0.999 5.Precision:3 samples were determined,the arsenic contents were (11.0 ± 0.6),(39.2 ± 1.0),(174.4 ± 3.8) μg/L and the relative standard deviations were 5.03％,2.59％ and 2.17％,respectively.Recovery rate:3 samples were determined for standard addition recovery test,the average recovery rate was 99.4％ and the recovery rate ranged between 94.0％-104.3％.Methods contrast:this method [(125.9 ± 61.6) μg/L] and DDCAg method [(121.3 ± 52.5) μg/L] were used to determinate 20 samples from endemic arsenic poisoning areas,respectively,the determination results of the two methods were not significantly different (t =1.22,P ＞ 0.05).Conclusions This method is built successfully,it has good precision and accuracy,it needs small amount of sample and reagent,the amount of harmful gases generated is greatly reduced,and it is easy to operate and beneficial to operator's health.Therefore,it is a good method to determine arsenic in urine,and it can be applied in prevention of endemic arsenism.

Establishment and evaluation of a method for determination of total arsenic in urine by test-tube rapid digestion hydride generation atomic fluorescence spectrometry / 中华地方病学杂志

Objective To establish and evaluate a method for determination of total arsenic in urine by test-tube rapid digestion hydride generation atomic fluorescence spectrometry.Methods After digestion of urine samples using graduated test-tube and graphite digestion apparatus,arsenic content in urine was determined with atomic fluorescence spectrometer.Then the test results were evaluated by using quality control measures,such as precision and accuracy experiments,and the results between different laboratories were reviewed and compared.Results The urinary arsenic was in a linear range of 0-0.300 mg/L,correlation coefficient (r) ＞ 0.999 3,detection limit was 0.000 21 mg/L,relative standard deviation (RSD) ≤4.62％ and the recoveries of standard addition were 93.9％-104.3％.The value of standard reference material measured was within the allowable range.The blind sample of the national urinary arsenic was qualified.Conclusions This method is suitable for large scale determination of urinary arsenic for its micro sample amount needed,less interference and strong practicability.The error results are in a controlled range.

The hydride generation atomic fluorescence spectrophotometry method for determination of urinary arsenic / 中华地方病学杂志

Objective To apply hydride generation atomic fluorescence spectrophotometry (HG-AFS method) in urinary arsenic detection,and to provide a better,newer and more convenient detection method for quantitative analysis of urinary arsenic.Methods According to the Guide to Develop Biological Sample Inspection Method(WS/T 68-1996) and Guide for Establishing Occupational Health Standards-part 5:Determination Methods in Biological Materials (GB/T 210.5-2008),HG-AFS method was established to detect arsenic content in urine after modification of the method for sample pretreatment,and to verify the linear range of standard curve and linearity,detection limit,precision,accuracy,stability of the sample,and to compare the experimental results of HG-AFS method with those of standard methods of WS/T 28-1996 and Determination of Arsenic in Urine by Cyanide Generation Atomic Fluorescence Method (WS/T 474-2015).Results The HG-AFS method linear range was from 0-100 μg/L,the correlation coefficient r =0.999 9,the detection limit was 0.07 μg/L,the precision was 1.96％-3.97％,and the recovery rate was 95.1％-105.0％.There was no statistical significance between HG-AFS method,the standard of WS/T 28-1996 or WS/T 474-2015 methods (t =1.539,0.353,all P ＞ 0.05).Conclusion The new method is superior to the current detection method owing to its low detection limit,high precision,good accuracy,and wide linear range.

Quantitative Determination of Selenium Species in Se-enriched Yeast Using Liquid Chromatography-Hydride Generation Atomic Fluorescence Spectrometry / 分析化学

A rapid and sensitive method has been developed for the simultaneous determination of four selenium species Se(Ⅵ), Se(Ⅵ), selenomethionine, and Se-methylselenocysteine in Se-enriched yeast by liquid chromatography-hydride generation atomic fluorescence spectrometry (HPLC-HG-AFS). The isolation of the analytes from yeast samples was accomplished by proteaseⅩⅣ and trypsin enzymatic digestion. The target compounds were separated on a PRP-X100 anion exchange column and analyzed by HG-AFS. The mobile phase was 20 mmol/L (NH4)2HPO4. Good linearity was obtained for all the selenium species, with linear correlation coefficients higher than 0. 9996. The LODs of the four species were between 0. 5 and 5. 0 μg/kg. Average recoveries for the four analytes were in the ranges of 82 . 5%-101 . 2%, with intra-and inter-day RSD lower than 8. 6% and 14. 5, respectively. The proposed analytical method is simple, sensitive, with low operation cost, making it applicable for the determination of the selenium species in Se-enriched feeds.

Mercury Speciation Determination in Fish and Soil Samples Based on Low Pressure LC-AFS Combined with Rapid Sample Pretreatment / 分析化学

The build-in low-pressure monolithic column combined with hydride generation atomic fluorescence spectrometry ( HG-AFS ) was employed for speciation analysis of fish meat. The sample pretreatment and separation approach could be accomplished within 30 min. The proper amount of fish sample was weighed and smashed into puree. The extraction solution composed of 10% HCl, 1% thiourea, and 0. 15% KCl was added before loaded into the automatic temperature controlled vertex system with 2000 r/min. The sample solution was separated through Merck monolithic column, with 3% ( V/V) acetonitrile, 30 mmol/L amonium acetate and 0. 03%(V/V) 2-mercaptoethanol (2-ME) as the eluent. The after-column eluent was digested by novel UV digestion device with pipeline sintered into the lamp, and then detected by hydrid-generation AFS. The rapid LC separation enabled fast mercury speciation of fish sample within 10 min. The different UV lamp digestion effects, eluent components, carrier gas, shield gas, lamp current, as well as PMT working power was optimized. Under the optimal conditions, the robust system achieved detection limits (DL) of 0. 15 μg/L and 0. 14 μg/L for methylmercury and HgⅡ, respectively. The RSD (n=7) was less than 5%, the linear correlation coefficient was 0 . 999 , and the matrix spiked recovery was in the range of 85%-110% for Hg speciation. This method was used for the determination of Hg speciation in fish and soil samples, and was proofed to be a reliable, easy approach for daily inspection.

An Ultrasensitive Simultaneous Immunoassay Based on Arsenic and Mercury Ions Labeled SiO2@Au Nanoparticle Probes / 分析化学

An ultrasensitive immunoassay was developed based on As3+ and Hg2+ labeled SiO2 @ Au nanoparticles signal tags and hydride generation-atomic fluorescence spectrometry (HG-AFS) for the detection of carcinoembryonic antigen(CEA) and carbohydrate antigen 19-9 (CA 19-9) respectively. Firstly, amino SiO2@ Au NPs were synthesized for selective absorption of As3+ and Hg2+ ions respectively. Subsequently,the secondary antibody (Ab2) of CEA and CA 19-9 was respectively labeled on As3+ or Hg2+-SiO2 @ Au NPs to prepare the corresponding signal tags for CEA and CA 19-9. Based on the sandwich immunoassay scheme, the tags, two antigen and corresponding first antibodies were bio-conjugated on the bottom of 96-well plate at room temperature to form the immunocomplex. After it was dissolved in alkali solution, As3+ and Hg2+ ions were released in solution and detected by HG-AFS, which concentration was proportional with logarithms of CEA and CA 19-9. The reaction conditions were optimized and the tags were characterized. This assay was based on determination of the concentration of As3+ and Hg2+ for quantization of the corresponding CEA and CA 19-9 antigen. The assay showed a wide linear range from 0. 001 to 100. 0 μg / L for CEA and 0. 01-80 U/ mL for CA 19-9, and a lower detection limit of 0. 5 ng / L and 0. 005 U/ mL respectively. This proposed method was used in real serums samples, the results were consistence with that by ELISA. The immunoassay showed three orders of magnitude of sensitivity lower than that of ELISA, which provides a promising simultaneous immunoassay for the early diagnosis of cancer .

Mechanism of Water Grind Processing of Realgar / 中国药房

OBJECTIVE:To optimize the water grind processing of Realgar.METHODS:The content of As2O3 in the processed product was determined by Hydride generation atomic fluorescence spectrometry.A systematic study was performed on realgar's water grind processing based on dynamic observation under a microscope,product yield,the content of As2O3 etc.RESULTS:The optimized water grind processing of Realgar was as follows:grinding Realgar into paste while adding water with the amount of water and the grinding time investigated;investigating the amount of water added for the grinding of the paste and its Resting time;investigating the standing time of suspension water in the water grind processing,and investigating the drying temperature in the water grind processing.Meanwhile,the grain size of the processed product was processed into round and uniform in shape with their particle size at less than 5 ?m.CONCLUSION:The study has validated and optimized the water grind processing of Realgar and contributed to the reduction of the contents of poisonous components in the processed product.

Determination of Total Selenium in Salt by Hydride Generation-Atomic Fluorescence Spectrometry / 环境与健康杂志

Objective To establish a sensitive, reliable and simple method for determination of selenium(Se) in salt. Methods The salt samples were dissolved in water and added hydrochloric acid, thiourea, placed for 30 minutes under the room temperature, then used HG-AFS to determine Se. Results The linear range was 0.5-20 ?g/L, the detection limit was 0.06 ?g/L, RSD

Determination of Arsenic and Stibium in Fmoes officinalis Ames by Hydride Generation-Atomic Fluorescence Spectrometry / 中国药房

OBJECTIVE:To determine the contents of arsenum (As) and stibium (Sb) in Fmoes officinalis Ames by hydride generation-atomic fluorescence spectrometry.METHODS:The determination conditions were as follows:60 mA electric current and 300 V negative high voltage for As hollow cathode lamp;80 mA electric current and 300 V negative high voltage for Sb hollow cathode lamp,the height of atomizer was 8 mm,the flow rate of carrier gas was 400 mL?min-1;the flow rate of the shield gas was 1 000 mL?min-1,the atomizer temperature was 200 ℃.RESULTS:The linear ranges for both As and Sb were 0～100 ?g?L-1 (r=0.999 9),with detection limits at 0.03 ?g?L-1 and 0.08 ?g?L-1,respectively;The recovery rates were 97.4%～102.2% (RSD=1.86%) and 98.2%～102.6% (RSD=1.66%),respectively.CONCLUSION:The method is rapid,accurate and achieved ideal results in the determination of As and Sb in Fmoes officinalis Ame.

Simultaneous Determination of Trace Arsenic and Mercury in Drinking Water by Hydride Generation Atomic Fluorescence Spectrometry / 环境与健康杂志

Objective To establish the simultaneous determination of arsenic and mercury in the drinking water by hydride generation atomic fluorescence spectrometry (HGAFS). Methods The contents of trace arsenic and mercury in drinking water were detected by HGAFS based on optimized working conditions in this assay. The influences of some factors, such as sample pretreatment, pH value and interfering ions in drinking water were analyzed also. Results The detection limit of arsenic, mercury was 0.29 ng/ml and 0.05 ng/ml respectively. The precision (relative standard deviation) of the method was less than 6.8% .The recovery rates ranged from 85.7%～112.6%. The detecting results for standard materials were very much close to the reference values. Conclusion This method was suitable for the detection of arsenic and mercury in drinking water.

Determination of Tellurium in Workplace Air by Microwave Digestion-HG-AFS / 环境与健康杂志

Objective To establish a method for determination of tellurium(Ti)in the air of workplace by microwave digestion-HG-AFS. Methods The air samples were collected by micropore filters and the concentration of tellurium was determined by microwave digestion-HG-AFS. Results In this method, the linear range was 0.11-40.0 ?g/L, the detection limit was 0.11 ?g/L, the lowest detected concentration of tellurium was 0.000 09 mg/m3(based on 30 L air sample), the rate of recovery was in the range of 95.5%-98.2%, the RSD was less than 3%. Conclusion The method is rapid, accurate, sensitive and suitable for the determination of tellurium in the air of workplace.

Determination of Total Selenium in Salt by HG-AFS / 环境与健康杂志

Objective To establish a sensitive ,reliable and convenient method for determination of total selenium(Se) in salt by HG-AFS. Methods The salt samples were dissolved and added hydrochloric acid (HCl),after heating by boiling water ,used HG-AFS to determinate Se. Results The linear range of the method was 0.5-400 ?g/L, The correlation coefficient was larger than 0.999 5, the recovery rates were 95.7%-102.8%. If 1 ml sample was collected, the detection limit was 0.08 ?g/L. Conclusion The method is sensitive, reliable, simple, less sample usage, and is an ideal method for determination of total selenium in salt.