ABSTRACT
Objective: To establish a high performance liquid chromatography-inductively coupled plasma mass spectrometry(HPLC-ICP-MS)method for the determination of trivalent arsenic(AsIII),pentavalent arsenic(As), methyl arsenic(MA),dimethyl arsenic(DMA),arsenical choline(AsC)and arsenical betaine(AsB)in traditional Chi- nese medicine Cordyceps. Methods: The arsenic species in Cordyceps were extracted with hot 0.15 mol/L nitric acid so- lution,separated by HPLC on a Dionex IonPacTM AS7 column(4 mm×250 mm,5 μm)with aqueous 5 mmol/L and 100 mmol/L ammonium carbonate solutions in a gradient elution as mobile phase,and quantitatively determined by ICP-MS. Results: The six kinds of arsenic species showed a good linearity within the range of 5-200 μg/kg. The average recovery was 83.3-115.9%,and the relative standard deviation was less than 5%. The main form of arsenic species in C ordyceps was inorganic arsenic(AsIIIand As),and the total content of ASIII+Asvaried around 1 mg/kg in the three tested batches of samples. Conclusion: The established HPLC-ICP-MS method is convenient,accurate and reliable for the analysis of different arsenic species in Cordyceps. In addition,the present work on the determination of six arsenic species in Cordy- ceps could be used as reference for improvement of the limitation standard of arsenic in Cordyceps.
ABSTRACT
The element speciation analysis for heavy metals in herbal medicines is still in the beginning stage. In this study,the total amount of arsenic( As) in 103 batches of 17 commonly used Chinese medicines( including 16 plant medicines and 1 medicinal fungus) was detected by inductively coupled plasma mass spectrometry( ICP-MS). Furthermore,based on HPLC-ICP-MS,the simultaneous detection methods of six As speciation kinds in traditional Chinese medicines were established. An AS7 anion exchange column was selected and the As forms in 17 traditional Chinese medicines was systematically analyzed. The results showed that the method of pretreatment of medicinal materials by microwave digestion and the detection of total amount of As by ICP-MS was stable and reliable. As for the speciation analysis of As,the high-speed ultrasonic extraction method was adopted,and it showed that the linear relationship of the six As speciation was satisfied with the correlation coefficient R2>0. 999 9. The LOQ of six kinds of As speciation were 0. 20,0. 10,0. 15,0. 10,0. 25,0. 10 μg·L~(-1) for arsenic betaine( As B),arsenious acid [As( Ⅲ) ],dimethyl arsenic( DMA),arsenic choline( As C),monomethyl arsenic( MMA),arsenic acid[As( Ⅴ) ],respectively. The recoveries were between 84. 24% and 121. 5%,and the relative standard deviations were 2. 7% to 11%. Among the 103 batches of medicinal materials,only one batch of sample As exceeded the Chinese Pharmacopoeia limit standard; As( Ⅲ) and As( Ⅴ) had high detection rate in 103 batches of Chinese herbal medicines,within which As( Ⅴ) was the main detected form,and inorganic As accounted for the ratio reached 80. 90%-98. 73%; some samples detected DMA,MMA and As B,As C was not detected in any batch. This study established an analytical method suitable for the speciation of As in Chinese herbal medicines,and provided basic data for As residual residue in Chinese herbal medicines,which can provide important reference for the risk assessment and quality standards.
Subject(s)
Arsenic , Chromatography, High Pressure Liquid , Drugs, Chinese Herbal , Reference Standards , Mass SpectrometryABSTRACT
Objective To establish an analysis method for the detection of 6 arsenic compounds [AsC, AsB, As(Ⅲ), DMA, MMA and As(V)] in blood and urine by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry(HPLC-ICP-MS), and apply it to real cases. Methods Triton was used to damage cells, and then EDTA·2Na·2H2O was used to complex arsenic compounds in cells, and sonication and protein deposition by acetonitrile were performed for sample pretreatment. With the mobile phase consisted of ammonium carbonate and ultrapure water, gradient elution was per-formed for obtaining the arsenic compounds in samples, which were analysed by ICP-MS with Hamilton PRP-X100 column. Results The limits of detection in blood were 1.66-10 ng/mL, while the lower limits of quantitation in blood ranged from 5 to 30 ng/mL. The limits of detection in urine were 0.5-10 ng/mL, while the lower limits of quantitation in urine were 5-30 ng/mL. The relative standard deviation of inter-day and intra-day precisions was less than 10%. This method had been successfully applied to 3 cases. Conclusion This study has established an analysis method for detecting 6 common arsenic compounds in blood and urine, which can be used to detect the arsenic compounds in the blood and urine from ar-senic poisoning cases as well as the patients under arsenic treatment.
ABSTRACT
OBJECTIVES: The purpose of this study was to determine a separation method for each arsenic metabolite in urine by using a high performance liquid chromatography (HPLC)- inductively coupled plasma-mass spectrometer (ICP-MS). METHODS: Separation of the arsenic metabolites was conducted in urine by using a polymeric anion-exchange (Hamilton PRP X-100, 4.6 mm x 150 mm, 5 mum) column on Agilent Technologies 1260 Infinity LC system coupled to Agilent Technologies 7700 series ICP/MS equipment using argon as the plasma gas. RESULTS: All five important arsenic metabolites in urine were separated within 16 minutes in the order of arsenobetaine, arsenite, dimethylarsinate, monomethylarsonate and arsenate with detection limits ranging from 0.15 to 0.27 mug/L (40 muL injection). We used GEQUAS No. 52, the German external quality assessment scheme and standard reference material 2669, National Institute of Standard and Technology, to validate our analyses. CONCLUSIONS: The method for separation of arsenic metabolites in urine was established by using HPLC-ICP-MS. This method contributes to the evaluation of arsenic exposure, health effect assessment and other bio-monitoring studies for arsenic exposure in South Korea.