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In order to evaluate the composition and distribution characteristics of inorganic elements in Laminaria japonica, this study employed inductively coupled plasma mass spectrometry(ICP-MS) to detect the inorganic elements and used high performance liquid chromatography tandem ICP-MS(HPLC-ICP-MS) to determine the content of different arsenic species in L. japonica from diffe-rent origins. Micro X-ray fluorescence(Micro-XRF) was used to determine micro-area distribution of inorganic elements in L. japonica. The results showed that the average content of Mn, Fe, Sr, and Al was high, and that of As and Cr exceeded the limits of the national food safety standard. According to the results of HPLC-ICP-MS, arsenobetaine(AsB) was the main species of As contained in L. japonica. The more toxic inorganic arsenic accounts for a small proportion, whereas its content was 1-4 times of the limit in the national food safety standard. The results of Micro-XRF showed that As, Pb, Fe, Cu, Mn, and Ni were mainly distributed on the surface of L. japonica. Among them, As and Pb had a clear tendency to diffuse from the surface to the inside. The results of the study can provide a basis for the processing as well as the medicinal and edible safety evaluation of L. japonica.
Subject(s)
Arsenic/analysis , Chromatography, High Pressure Liquid/methods , Laminaria , Mass Spectrometry/methods , Spectrum Analysis , Trace Elements/analysisABSTRACT
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.
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Objective@#To establish a method for determination of arsenic species in blood with high performance liquid chromatography-atomic fluorescence spectrometry (HPLC-AFS) .@*Methods@#The effect of mobile phase about chromatography separation and sample pretreatment conditions and atomic fluorescence spectrometry detection parameters has been optimized to reliably measure the following four kinds of species arsenic compound including arsenic[As (III) ]、dimethylarsinic acid (DMA) 、monomethylarsonic acid (MMA) and arsenate[As (V) ] in acute intoxication human blood. The method of technical standard about within-run, between-run and recoveries of standard were optimized.@*Results@#The method showed As (III) linear relationship was 2.63-100.00 μg/L, The detection limit was 2.63 μg/L. The relative coefficient (r) was 0.9999; DMA linear relationship was 3.21-100.00 μg/L, The detection limit was 3.21 μg/L. The r was 0.9992; MMA linear relationship was 3.41-100.00 μg/L, The detection limit was 3.41 μg/L. The r was 0.9998; As (V) linear relationship was 3.90-100.00 μg/L, The detection limit was 3.90 μg/L. The r was 0.9996. The average recovery of four species arsenic in tested samples ranged from 91.3%-99.8% with the relative standard deviation (RSD) from 2.39% to 4.05%. The within-run and between-run relative standard deviations (RSD) of repetitive measurement at 10.00, 40.00, 80.00 μg/L concentration levels were 1.99%-4.59% and 2.72%-4.53%.@*Conclusion@#This method is low detection limit, good accurate and high sensitivity, proposed method had been applied to the analysis of arsenic species in blood samples those who acute intoxication or poisoning diagnosis.
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Objective Quantitative analysis of four arsenic species As (III), As (V), monomethyl arsenate (MMA), dimethyl arsenate (DMA) in rat serum, liver, kidney, and spleen was performed to compare their differences between realgar and realgar nanoparticles (NPs) groups. Methods SD rats were ig treated with blank solvent, realgar, and realgar NPs (800 mg/kg) respectively. After 28 d of continuous administration, serum and tissues were collected and four arsenic species were determined by high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Results Four arsenic species were detected in serum and kidney of rats, three were detected in the liver and two in the spleen. The content of arsenic species in the realgar NPs group was significantly higher than that in the realgar group. Conclusion Nanotechnology enhanced the bioavailability of realgar, and more arsenic was absorbed into the body and underwent metabolic transformation, which might lead to increased toxicity of realgar NPs.
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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 .
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BACKGROUND: Arsenic is a carcinogenic heavy metal that has a species-dependent health effects and abandoned metal mines are a source of significant arsenic exposure. Therefore, the aims of this study were to analyze urinary arsenic species and their concentration in residents living near abandoned metal mines and to monitor the environmental health effects of abandoned metal mines in Korea. METHODS: This study was performed in 2014 to assess urinary arsenic excretion patterns of residents living near abandoned metal mines in South Korea. Demographic data such as gender, age, mine working history, period of residency, dietary patterns, smoking and alcohol use, and type of potable water consumed were obtaining using a questionnaire. Informed consent was also obtained from all study subjects (n = 119). Urinary arsenic species were quantified using high performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP/MS). RESULTS: The geometric mean of urinary arsenic (sum of dimethylarsinic acid, monomethylarsonic acid, As3+, and As5+) concentration was determined to be 131.98 μg/L (geometric mean; 95% CI, 116.72–149.23) while urinary inorganic arsenic (As3+ and As5+) concentration was 0.81 μg/L (95% CI, 0.53–1.23). 66.3% (n = 79) and 21.8% (n = 26) of these samples exceeded ATSDR reference values for urinary arsenic (>100 μg/L) and inorganic arsenic (>10 μg/L), respectively. Mean urinary arsenic concentrations (geometric mean, GM) were higher in women then in men, and increased with age. Of the five regions evaluated, while four regions had inorganic arsenic concentrations less than 0.40 μg/L, one region showed a significantly higher concentration (GM 15.48 μg/L; 95% CI, 7.51–31.91) which investigates further studies to identify etiological factors. CONCLUSION: We propose that the observed elevation in urinary arsenic concentration in residents living near abandoned metal mines may be due to environmental contamination from the abandoned metal mine. TRIAL REGISTRATION: Not Applicable (We do not have health care intervention on human participants).
Subject(s)
Female , Humans , Male , Arsenic , Cacodylic Acid , Chromatography, Liquid , Delivery of Health Care , Drinking Water , Environmental Health , Informed Consent , Internship and Residency , Korea , Mass Spectrometry , Plasma , Reference Values , Smoke , SmokingABSTRACT
HPLC-ICP-MS method was established to separate AsB, As(Ⅲ), monmethyl arsenic ( MMA ) , dimethyl arsenic ( DMA ) and As(V) in rat viscera. Ultrasonic water bath extraction was used for sample pretreatment. Dionex IonPac AS19 anion-exchange column and 20 mmol/L (NH4)2CO3(pH=9. 7) were used to analyze arsenic species in rat liver and kidney after realgar infected. The results showed that the method was not interfered by 40 Ar35 Cl+ peak, the linear ranges for five arsenic species were all between 1 and 300 μg/L with linear coefficients more than 0. 9990, and the detection limits were between 0. 3 and 0. 5 μg/L. The relative standard deviations ( RSDs) for the determination of five species were less than 5% and the recoveries were between 83. 8% and 111. 7%. After speciation analysis, DMA, As(Ⅲ) and unknown compound 2 were found in liver;DMA, MMA, As(Ⅲ), unknown compound 1, unknown compound 2 and unknown compound 3 were found in the kidney. The results indicated that this method could be used for arsenic species analysis of realgar metabolism.
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Objective To explore the effects of exogenous methionine on arsenical distribution in liver,blood and brain of mice exposed to sodium arsenite through drinking water. Methods The female Kunming mice were randomly divided into control group, the alone arsenic exposure group , the low level methionine intervention group, the moderate level methionine intervention group and the high level methionine intervention group, eight mice in each group . The mice in the experimental groups were exposed to sodium arsenite through drinking water at 50 mg/L arsenic for four consecutive weeks. And at the fourth week the 5 groups were treated intraperitoneally with saline solution (control and As group),100 mg/kg b.w,200 mg/kg b.w or 400 mg/kg b.w methionine,respectively . Twenty-four hours after cessation of methionine administration,mice were anaesthetized and rapidly dissected. The samples of blood,liver and brain were removed immediately for arsenic species analysis. Levels of inorganic arsenic (iAs),monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA) were determined by HG-AAS method. Then total arsenic speciation( TAs), primary methylation ratio( PMR)and secondary methylation ratio( SMR)in each tissue were calculated. Results Compared with the control group, the levels of iAs, MMA, DMA and TAs in liver, brain and blood, were significantly higher in all experimental groups ( P
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Objective To explore the effects of exogenous glutathione on arsenic distribution and nitric oxide (NO) metabolism in the brain of mice exposed to arsenite through drinking water. Methods Female Kunming mice were randomly divided into 5 groups, eight in each, and the mice were exposed to sodium arsenite through drinking water at doses of 0 mg/L (control) and 50 mg/L arsenic for 4 consecutive weeks, on the fourth week, with the exposure of arsenic, glutathione was given through intraperitoneal injection at doses of 200 mg/kg b.w, 400 mg/kg b.w or 800 mg/kg b.w, respectively for 7 days. In the end of treatment, the samples of blood and brain were collected. Levels of inorganic arsenic (iAs), monomethylarsonic acid (MMA) and dimethylarsenic acid (DMA) were determined by HG-AAS method. Activities of nitric oxide synthase (NOS) and the concentrations of NO were determined with kits. Results Compared with those in single arsenic group, glutathione significantly decreased levels of iAs, MMA and total arsenic levels (TAs) in the blood and levels of DMA and TAs in the brain. Activities of NOS and levels of NO in As group were significantly lower than those in control, however administration of glutathione could ameliorate these toxic effects, and NOS activities in groups treated with 400 mg/kg b.w and 800 mg/kg b.w glutathione were significantly higher than those in single arsenic group. Conclusion Exogenous glutathione may promote methylation of arsenic, therefore reduce arsenic levels in both blood and brain. Moreover, it is proposed that administration of exogenous glutathione can ameliorate the adverse effects of arsenic on NO metabolism in the brain via decreasing the brain arsenic burden.
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Objective To establish the method of high performance liquid chromatography and hydrid genesis atomic fluorescence spectroscopy(HPLC-HGAFS) about arsenic species in urine of rats treated with sodium arsenite.Methods The solution containing 15 mmol/L(NH4)2HPO4(pH=6.0)was used as the chromatographic eluant,the flow rate of which was 1.0 ml/min.The parameters of HPLC-HGAFS consisted of multiplier negative high voltage,hollow-cathode lamp's joint current and co-current,the flow rate of carrier gas,the flow rate of barrier shield gas,supporting liquid and reducing agent,which were 285 V,80 mA,36 mA,400 ml/min,600 ml/min,7%HCl and the mixed liquor of 1.5%KBH4 and 0.35% KOH respectively.Results The linear range of method was 20-100 ?g/L,and the linearity of regression equation of iAs3+,iAs5+,DMA was better.The lowest detection concentration of iAs3 +,iAs5 +,DMA in urine were 12.03,6.67 and 8.66 ?g/L respectively and all of the coefficient correlation were ≥0.98.The average recovery rates of DMA were 96.5%-103.4% and RSDs were 0.39%-1.26%.Conclusion The method has been proved accurate,sensitive and is applicable to the determination of arsenic species in urine.