Skip to main content
Key Specialties
Cardiology Diabetology Endocrinology Gastroenterology Geriatrics and Gerontology Gynecology and Obstetrics Hematology Infectious Disease Internal Medicine Nephrology Neurology Oncology Pediatrics Respiratory Medicine Rheumatology Surgery
Congress Coverage
2024 ACC Congress 2023 ESMO Congress 2023 EASD Congress 2023 ERS Congress 2023 ESC Congress
Clinical Collections
Advances in Alzheimer’s

Keynote webinar | Spotlight on medication adherence

LIVE: Thursday 27th June 2024, 18:00-19:30 (CEST)
Join our expert panel to discover why you need to understand the drivers of non-adherence in your patients, and how you can optimize medication adherence in your clinics to drastically improve patient outcomes.
ADVANCED SEARCH
Log in
Top
Forensic Toxicology
Published in: Forensic Toxicology 2/2019

01-07-2019 | Intoxication | Original Article

Rapid and robust speciation/quantitative analysis of arsenous acid and related metabolites in serum by liquid chromatography–inductively coupled plasma-tandem mass spectrometry

Authors: Yuko Kazui, Hikoto Ohta, Daisuke Watanabe, Takao Igawa, Masaaki Kasamatsu, Yasuhiro Suzuki, Yasuo Seto

Published in: Forensic Toxicology | Issue 2/2019

Login to get access

Abstract

Purpose

Arsenic, especially inorganic trivalent species, is one of the most important poisons in the field of forensic toxicology. There are many reports on the speciation analysis of arsenic species in biological specimens by liquid chromatography–inductively coupled plasma-mass spectrometry (LC–ICP-MS). The aim of this study was to develop a rapid and robust analytical method for speciation/quantitative analysis of arsenic species in serum by LC–ICP-tandem mass spectrometry (MS/MS).

Methods

An analytical method for arsenous acid and its metabolites, dimethylarsinic acid, monomethylarsonic acid, and arsenic acid in serum was tested through the analysis of serum samples by an LC–ICP-MS/MS system consisting of different anion exchange columns and different mobile phases. Rapid pretreatment of serum samples by ultrafiltration was also tested.

Results

Robust speciation/quantitative analysis of arsenic in serum samples with LC–ICP-MS/MS was achieved by using a mildly acidic mobile phase. The limits of detection for the four arsenic species were in the range 0.19–0.68 ngAs/mL, and the well-known interference by argon chloride ion was removed by the MS/MS apparatus. This method was precise enough for quantitative analysis of four arsenic compounds in serum (0.24–3.68% precision; 97.0–104% accuracy; and 101–112% recovery for all analytes at 5 and 50 ngAs/mL). The total analytical time was 30 min (20-min pretreatment and 10-min analysis), and multiple serum samples could be pretreated simultaneously.

Conclusions

A rapid, sensitive, interference-free and robust speciation/quantitative analysis of toxic arsenous acid and related metabolites in serum by LC–ICP-MS/MS was developed. To our knowledge, this is the first report to use LC–ICP-MS/MS for analysis of arsenic species in human blood/serum samples.
Literature
1.
Benramdane L, Bressolle F, Vallon JJ (1999) Arsenic speciation in humans and food products: a review. J Chromatogr Sci 37:330–344CrossRefPubMed
2.
Delafiori J, Ring G, Furey A (2016) Clinical applications of HPLC-ICP-MS element speciation: a review. Talanta 153:306–331CrossRefPubMed
3.
Marcinkowska M, Barałkiewicz D (2016) Multielemental speciation analysis by advanced hyphenated technique—HPLC/ICP-MS: a review. Talanta 161:177–204CrossRefPubMed
4.
Okina M, Yoshida K, Kuroda K, Wanibuchi H, Fukushima S, Endo G (2004) Determination of trivalent methylated arsenicals in rat urine by liquid chromatography-inductively coupled plasma mass spectrometry after solvent extraction. J Chromatogr B 799:209–215CrossRef
5.
Heitland P, Köster HD (2009) Comparison of different medical cases in urinary arsenic speciation by fast HPLC-ICP-MS. Int J Hyg Environ Health 212:432–438CrossRefPubMed
6.
Verdon CP, Caldwell KL, Fresquez MR, Jones RL (2009) Determination of seven arsenic compounds in urine by HPLC-ICP-DRC-MS: a CDC population biomonitoring method. Anal Bioanal Chem 393:939–947CrossRefPubMed
7.
Serrano IN, Ballesteros MTL, Pacheco SSF, Álvarez SI, Colón JLL (2016) Total and speciated urinary arsenic levels in the Spanish population. Sci Total Environ 571:164–171CrossRef
8.
Heitland H, Blohm M, Breuer C, Brinkert F, Achilles EG, Pukite I, Köster HD (2017) Application of ICP-MS and HPLC-ICP-MS for diagnosis and therapy of a severe intoxication with hexavalent chromium and inorganic arsenic. J Trace Elem Med Biol 41:36–40CrossRefPubMed
9.
10.
Carioni VMO, McElroy JA, Guthrie JM, Ngwenyama RA, Brockman JD (2017) Fast and reliable method for As speciation in urine samples containing low levels of As by LC-ICP-MS: focus on epidemiological studies. Talanta 165:76–83CrossRefPubMed
11.
Yuan C, Lu X, Oro N, Wang Z, Xia Y, Wade TJ, Mumford J, Le XC (2008) Arsenic speciation analysis in human saliva. Clin Chem 54:163–171CrossRefPubMed
12.
Kintz P, Ginet M, Marques N, Cirimele V (2007) Arsenic speciation of two specimens of Napoleon’s hair. Forensic Sci Int 170:204–206CrossRefPubMed
13.
Contreras-Acuña M, García-Barrera T, García-Sevillano MA, Gómez-Ariza JL (2014) Arsenic metabolites in human serum and urine after seafood (Anemonia sulcata) consumption and bioaccessibility assessment using liquid chromatography coupled to inorganic and organic mass spectrometry. Microchem J 112:56–64CrossRef
14.
Fukai Y, Hirata M, Ueno M, Ichikawa N, Kobayashi H, Saito H, Sakurai T, Kinoshita K, Kaise T, Ohta S (2006) Clinical pharmacokinetic study of arsenic trioxide in an acute promyelocytic leukemia (APL) patient: speciation of arsenic metabolites in serum and urine. Biol Pharm Bull 29:1022–1027CrossRefPubMed
15.
Ito K, Goessler W, Gürleyük H, Wels B, Palmer CD, Verostek MF, Parsons PJ (2011) An interlaboratory study of arsenic speciation analysis of whole blood. J Anal At Spectrom 26:1740–1745CrossRef
16.
Araujo-Barbosa U, Peña-Vazquez E, Barciela-Alonso MC, Costa Ferreira SL, Pinto Dos Santos AM, Bermejo-Barrera P (2017) Simultaneous determination and speciation analysis of arsenic and chromium in iron supplements used for iron-deficiency anemia treatment by HPLC-ICP-MS. Talanta 170:523–529CrossRefPubMed
17.
Yigzaw Y, Hinckley P, Hewig A, Vedantham G (2009) Ion exchange chromatography of proteins and clearance of aggregates. Current Pharm Biotechnol 10:421–426CrossRef
18.
Goheen SC, Gibbins BM (2000) Protein losses in ion-exchange and hydrophobic interaction high-performance liquid chromatography. J Chromatogr A 890:73–80CrossRefPubMed
19.
Muca R, Marek W, Żurawski M, Piątkowski W, Antos D (2017) Effect of mass overloading on binding and elution of unstable proteins in hydrophobic interaction chromatography. J Chromatogr A 1492:79–88CrossRefPubMed
20.
Bandura DR, Baranov VI, Tanner SD (2002) Detection of ultratrace phosphorus and sulfur by quadrupole ICPMS with dynamic reaction cell. Anal Chem 74:1497–1502CrossRefPubMed
21.
Schaumlöffel D, Giusti P, Preud’Homme H, Szpunar J, Łobiński R (2007) Precolumn isotope dilution analysis in nanoHPLC-ICPMS for absolute quantification of sulfur-containing peptides. Anal Chem 79:2859–2868CrossRefPubMed
22.
Zinn N, Krüger R, Leonhard P, Bettmer J (2008) μLC coupled to ICP–SFMS with post-column isotope dilution analysis of sulfur for absolute protein quantification. Anal Bioanal Chem 391:537–543CrossRefPubMed
23.
Šlejkovec Z, Podgornik H, Černelč P, Falnoga I (2016) Exceptions in patterns of arsenic compounds in urine of acute promyelocytic leukaemia patients treated with As2O3. Biometals 29:107–118CrossRefPubMed
24.
Šlejkovec Z, Falnoga I, Goessler W, van Elteren JT, Raml R, Podgornik H, Černelč P (2008) Analytical artefacts in the speciation of arsenic in clinical samples. Anal Chim Acta 607:83–91CrossRefPubMed
25.
Guo M, Wang W, Hai X, Zhou J (2017) HPLC-HG-AFS determination of arsenic species in acute promyelocytic leukemia (APL) plasma and blood cells. J Pharm Biomed Anal 145:356–363CrossRefPubMed
26.
Chen YW, Belzile N (2010) High performance liquid chromatography coupled to atomic fluorescence spectrometry for the speciation of the hydride and chemical vapour-forming elements As, Se, Sb and Hg: a critical review. Anal Chim Acta 671:9–26CrossRefPubMed
27.
Schmidt L, Landero JA, Santos RF, Mesko MF, Mello PA, Flores EMM, Caruso JA (2017) Arsenic speciation in seafood by LC-ICP-MS/MS: method development and influence of culinary treatment. J Anal At Spectrom 32:1490–1499CrossRef
28.
Guimarães D, Roberts AA, Tehrani MW, Huang R, Smieska L, Woll AR, Lin S, Parsons PJ (2018) Characterization of arsenic in dried baby shrimp (Acetes sp.) using synchrotron-based X-ray spectrometry and LC coupled to ICP-MS/MS. J Anal At Spectrom 33:1616–1630CrossRef
29.
Schmidt L, Landero JA, La Rosa Novo D, Duarte FA, Mesko MF, Caruso JA, Flores EMM (2018) A feasible method for As speciation in several types of seafood by LC-ICP-MS/MS. Food Chem 255:340–347CrossRefPubMed
30.
Japanese Standards Association (2006) High frequency plasma mass spectrometry general notice, K0133. In: JIS Handbook. Japanese Standards Association, Tokyo, pp 371–388 (in Japanese)
31.
Higashikawa Y, Kazui Y, Suzuki S, Ohtsuru O (2008) Arsenic speciation of arsine-exposed blood samples by high-performance liquid chromatography-inductively coupled plasma mass spectrometry and As-adduct, a possible indicator of AsH3 exposure. J Anal Toxicol 32:344–348CrossRefPubMed
32.
Tan SH, Horlick G (1986) Background spectral features in inductively coupled plasma/mass spectrometry. Appl Spectrosc 40:445–460CrossRef
33.
Kaise T (2002) Speciation of arsenic compounds in biological samples by high performance liquid chromatography-inductively coupled plasma mass spectrometry system. J Plasma Fusion Res 78:646–652 (in Japanese with English abstract) CrossRef
34.
Ohwaki S, Matsuoka M, Sato T, Kikukawa K, Kobayashi M, Kaneko S (2018) Arsenic speciation analysis in seaweed and rice flour samples by ion chromatography combined with inductively coupled plasma-mass spectrometry. Studies Sci Technol 7:69–74 (in Japanese)
35.
Yoshinaga J, Chatterjee A, Shibata Y, Morita M, Edmonds JS (2000) Human urine certified reference material for arsenic speciation. Clin Chem 46:1781–1786PubMed
36.
Oliver LK (2009) Laboratory assessment of exposure to neurotoxic agents. In: Dobbs M (ed) Clinical neurotoxicology. Saunders, Philadelphia, pp 213–221CrossRef
Metadata
Title
Rapid and robust speciation/quantitative analysis of arsenous acid and related metabolites in serum by liquid chromatography–inductively coupled plasma-tandem mass spectrometry
Authors
Yuko Kazui
Hikoto Ohta
Daisuke Watanabe
Takao Igawa
Masaaki Kasamatsu
Yasuhiro Suzuki
Yasuo Seto
Publication date
01-07-2019
Publisher
Springer Singapore
Keyword
Intoxication
Published in
Forensic Toxicology / Issue 2/2019
Print ISSN: 1860-8965
Electronic ISSN: 1860-8973
DOI
https://doi.org/10.1007/s11419-019-00479-w

Other articles of this Issue 2/2019

Forensic Toxicology 2/2019 Go to the issue

Original Article

Quantification of clitidine in caps and stems of poisonous mushroom Paralepistopsis acromelalga by hydrophilic interaction liquid chromatography–tandem mass spectrometry

Original Article

Methylone and pentylone: structural analysis of new psychoactive substances

Case Report

Determination of ocfentanil and W-18 in a suspicious heroin-like powder in Belgium

Letter to the Editor

CYP2B6, ABCB1 and OPRM1 profile in a stillborn affected by chronic methadone intoxication

Original Article

Identification and structural characterization of synthetic cathinones: N-propylcathinone, 2,4-dimethylmethcathinone, 2,4-dimethylethcathinone, 2,4-dimethyl-α-pyrrolidinopropiophenone, 4-bromo-α-pyrrolidinopropiophenone, 1-(2,3-dihydro-1H-inden-5-yl)-2-(pyrrolidin-1-yl)hexan-1-one and 2,4-dimethylisocathinone

Review Article

Suicidal deaths due to helium inhalation