Speciation of As(ΙΙΙ)/As(V) and Total Inorganic Arsenic in Biological Fluids Using New Mode of Liquid-Phase Microextraction and Electrothermal Atomic Absorption Spectrometry
In this paper, a new extraction method based on countercurrent liquid–liquid microextraction (CLLME) has been developed for the extraction and preconcentration of inorganic arsenic (iAs) in plasma and urine samples prior to their analysis by electrothermal atomic absorption spectrometry (ETAAS). In this method, firstly, 5 ml of water is added to the extraction vessel. Then 30.0 μl of the extracting solvent is added to it in order for the extracting solvent to be placed in the narrow-necked vessel. In total, 10 ml of a standard solution or a pretreated real sample is added to the sample container and it is connected to the extraction vessel via a connector. While opening the embedded valve at the bottom of the sample container and the one in the extraction vessel, the sample solution flows into the extracting solvent with the same flow rate, leading to the successful extraction of metal ligand into the extracting organic solvent. Under the optimum conditions, calibration curves are linear in the range of 0.1–50 μg l−1, and limit of detections (LODs) are in the range of 0.03–0.05 μg l−1. The enhancement factor and enrichment factor were in the range of 220–240 and 198–212, respectively. Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 5.0 μg l−1 of arsenic were in the range of 2.3–3.5% and 4.0–5.7%, respectively. The applicability of the proposed CLLME and ETAAS methods was demonstrated by analyzing the iAs in spiked urine and plasma samples. The obtained recoveries of the arsenic in the range of 92–107% indicated the excellent capability of the developed method for speciation of arsenic from plasma and urine samples.
KeywordsArsenic speciation Countercurrent liquid–liquid microextraction Extraction solvent lighter than water Biological analysis
The authors gratefully acknowledge the Research Council of Kermanshah University of Medical Sciences (Grant Number: 96422) for the financial support.
Compliance with Ethical Standards
Conflict of Interest
The authors declare that they have no conflict of interest.
All the participants were informed about the purpose of the study and gave informed consent.
- 1.Chen B, Hu B, He M, Mao X, Zu W (2012) Synthesis of mixed coating with multi-functional groups for in-tube hollow fiber solid phase microextraction–high performance liquid chromatography–inductively coupled plasma mass spectrometry speciation of arsenic in human urine. J Chromatogr A 1227:19–28CrossRefPubMedGoogle Scholar
- 4.Asadollahzadeh M, Tavakoli H, Torab-Mostaedi M, Hosseini G, Hemmati A (2014) Response surface methodology based on central composite design as a chemometric tool for optimization of dispersive-solidification liquid–liquid microextraction for speciation of inorganic arsenic in environmental water samples. Talanta 123:25–31CrossRefPubMedGoogle Scholar
- 10.Huang CZ, Hu B, Jiang ZC (2007) Simultaneous speciation of inorganic arsenic and antimony in natural waters by dimercaptosuccinic acid modified mesoporous titanium dioxide micro-column on-line separation and inductively coupled plasma optical emission spectrometry determination. Spectrochim Acta B 62:454–460CrossRefGoogle Scholar
- 14.Uluozlu OD, Tuzen M, Mendil D, Soylak M (2010) Determination of As(III) and As(V) species in some natural water and food samples by solid-phase extraction on Streptococcus pyogenes immobilized on Sepabeads SP 70 and hydride generation atomic absorption spectrometry. Food Chem Toxicol 48:1393–1398CrossRefPubMedGoogle Scholar
- 15.Shamsipur M, Fattahi N, Assadi Y, Sadeghi M, Sharafi K (2014) Speciation of As(III) and As(V) in water samples by graphite furnace atomic absorption spectrometry after solid phase extraction combined with dispersive liquid–liquid microextraction based on the solidification of floating organic drop. Talanta 130:26–32CrossRefPubMedGoogle Scholar
- 17.Majidi B, Shemirani F (2011) In situ solvent formation microextraction in the presence of ionic liquid for preconcentration and speciation of arsenic in saline samples and total arsenic in biological samples by electrothermal atomic absorption spectrometry. Biol Trace Elem Res 143:579–590CrossRefPubMedGoogle Scholar
- 25.Liu Y, He M, Chen B, Hu B (2015) Simultaneous speciation of inorganic arsenic, selenium and tellurium in environmental water samples by dispersive liquid liquid microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry. Talanta 142:213–220CrossRefPubMedGoogle Scholar
- 27.Ghambarian M, Khalili-Zanjani MR, Yamini Y, Esrafili A, Yazdanfar N (2010) Preconcentration and speciation of arsenic in water specimens by the combination of solidification of floating drop microextraction and electrothermal atomic absorption spectrometry. Talanta 81:197–201CrossRefPubMedGoogle Scholar
- 30.Ahmadi-Jouibari T, Fattahi N, Shamsipur M (2014) Rapid extraction and determination of amphetamines in human urinesamples using dispersive liquid–liquid microextraction andsolidification of floating organic drop followed by high performanceliquid chromatography. J Pharm Biomed Anal 95:145–151CrossRefGoogle Scholar
- 33.Shemirani F, Baghdadi M, Ramezani M (2005) Preconcentration and determination of ultra trace amounts of arsenic(III) and arsenic(V) in tap water and total arsenic in biological samples by cloud point extraction and electrothermal atomic absorption spectrometry. Talanta 65:882–887CrossRefPubMedGoogle Scholar