A Novel Pretreatment Device Integrating Magnetic-Assisted Dispersive Extraction and Ultrasonic Spray Separation for Speciation Analysis of Arsenic in Whole Blood by Ion Chromatography-Inductively Coupled Plasma-Mass Spectrometry

Abstract

Speciation analysis of arsenic in blood is essential for identifying and quantifying the exposure of arsenic and studying the metabolism and toxicity of arsenic. Herein, a novel pretreatment device is rationally designed and used for speciation analysis of arsenic in whole blood by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS). The sample centrifuge tubes containing blood, reagents, and a magnetic stir bar are placed on the fidget spinner of the pretreatment device. When flicking the fidget spinner rotation with the finger, the magnetic stir bar in the tube rotates in three dimensions under the magnetic field, thereby assisting dispersive extraction of arsenic species by the mixing of blood with reagents. Afterward, the arsenic extract is separated in situ from the blood matrix using an ultrasonic spray sheet covered with a filter and ultrafiltration membrane, which is directly used for subsequent IC-ICP-MS analysis. For 100 μL of blood, the whole pretreatment operation can be completed within 10 min. With As­(III), As­(V), MMA, and DMA in blood as analytes, the use of the present pretreatment device will hardly lead to the loss and transformation of arsenic species, and the extraction efficiency of the total arsenic is more than 96%. When the pretreatment device is coupled to IC-ICP-MS, the detection limits of four arsenic species in whole blood are 0.017–0.023 μg L–1, and precisions are within 2.3–4.2%. This pretreatment device provides a simple, fast, efficient, and low-cost tool for extraction and separation of arsenic species in whole blood, opening a new idea for the pretreatment of complex samples.

Atomic spectrometry update: review of advances in the analysis of clinical and biological materials, foods and beverages

“…In this work, twelve samples, randomly chosen from the batch of candidate RMs, were used for certication and homogeneity studies. Measurements were carried out by SF-ICP-MS. For the determination of the 42 Ca : 44 Ca and 25 Mg : 24 Mg isotope ratios, the instrument was operated at medium resolution, using a standard cyclonic spray chamber with a MicroMist concentric nebuliser, whereas the determination of the 41 K : 39 K isotope ratio required an Aridus II membrane desolvator (CETAC Technologies, Omaha, USA), a microow nebuliser and operation in HR mode. The sample blend was prepared gravimetrically, by spiking an amount of about 0.5 g of each CRM, and placed in a modied PTFE microwave digestion vessel with an appropriate amount of a solution of the enriched isotopes ( 42 Ca, 41 K and 25 Mg), designed to obtain optimal isotope ratios for all three elements.…”

“…For the determination of As species in whole blood by HPLC-ICP-MS, Zhang et al 44 constructed a new sample preparation device based on magnet-assisted dispersive extraction and ultrasonic spray separation . In the first stage of the procedure, 100 μL of blood, 10 μL of 0.2% (v/v) Triton X-100 (cell disruption agent), and 100 μL of 12 g L −1 N -ethylmaleimide (thiol masking agent) were added to a 2 mL centrifuge tube together with a magnetic stir bar and placed in a suitably modified fidget spinner (supplier not given) that had been mounted on a base to which several magnets had been strategically placed so that when flicked once with a finger, the magnetic stir bar rotated for about 5 s inside the centrifuge tube under the action of the “relatively changing magnetic force, forming a crushing mechanical movement”.…”

“…The speciation of As in biological fluids was the subject of three interesting papers in this year’s Update. Zhang and co-workers 44 explored a novel extraction procedure, based on magnetic-assisted dispersive extraction, followed by ultrasonic spray separation, to assist the identification and quantification of As species (As III , As V , DMA, and MMA) in blood , as an aid to investigate As metabolism and biomarkers of exposure. Blood (100 μL) was mixed with 10 μL of 0.2% (v/v) Triton X-100 and 100 μL of 12 g L −1 N -ethylmaleimide with the aid of a magnetic stirrer.…”

Facile Lego-Spinner Pretreatment Device for Analysis of Arsenic Species in Dried Blood Spots by Ion Chromatography-Inductively Coupled Plasma-Mass Spectrometry

“…Due to the small blood collection, the DBS is heavily diluted during the conventional preprocessing, and the hematocrit effect leads to the uneven distribution of analytes, reducing the reliability of the quantitative data. Most studies of TAs in the DBS not only require the extraction of arsenic using the expensive and bulky instruments such as centrifuges and microwave digesters but also require the pretreatment for 90 min or more, which may be detrimental to the study of the unstable arsenic species in air. − ,, Currently, a few small mixing and centrifugation units have been designed to simplify the analytical workflows, including egg beaters, paper gyroscopes, , fidget spinners, , centrifugal microfluidic devices, and ultrasonic devices, , opening up a new idea for the pretreatment of complex samples. The Lego-based devices have the advantages of small size, low cost, and flexible configuration and can be designed for different analysis tasks such as microscope and capillary electrophoresis. − Therefore, it is promising to develop a Lego-based pretreatment device for the extraction and separation of arsenic species in the DBS through the rational configuration of Lego components, so as to achieve the fast and efficient analysis of arsenic species in the DBS by IC-ICP-MS.…”

“…Most studies of TAs in the DBS not only require the extraction of arsenic using the expensive and bulky instruments such as centrifuges and microwave digesters but also require the pretreatment for 90 min or more, which may be detrimental to the study of the unstable arsenic species in air. [22][23][24]26,27 Currently, a few small mixing and centrifugation units have been designed to simplify the analytical workflows, including egg beaters, 28 paper gyroscopes, 29,30 fidget spinners, 31,32 centrifugal microfluidic devices, 33 and ultrasonic devices, 34,35 opening up a new idea for the pretreatment of complex samples. The Lego-based devices have the advantages of small size, low cost, and flexible configuration and can be designed for different analysis tasks such as microscope and capillary electrophoresis.…”