Zhenli Zhu

Elemental determination of microsamples by liquid film dielectric barrier discharge atomic emission spectrometry.

In this study, a new liquid-film dielectric barrier discharge (LFDBD) atomic emission source was developed for microsample elemental determination. It consists of a copper electrode, a tungsten wire electrode, and a piece of glass slide between them, which serves as the dielectric barrier as well as the sample plate. The sample solution with 1 mol L(-1) nitric acid, when deposited onto the surface of the glass slide, forms a thin liquid film. The plasma is generated between the tip of the tungsten wire electrode and the liquid film surface when alternating-current (ac) high voltage (peak voltage ~3.7 kV, frequency ~30 kHz) is applied on the electrodes. Qualitative and quantitative determinations of metal ions in the sample solution were achieved by atomic emission measurements in the plasma and were demonstrated in this study with elements Na, K, Cu, Zn, and Cd. Detection limits were in the range from 0.6 ng (7 μg L(-1)) for Na to 6 ng (79 μg L(-1)) for Zn. Repeatability, expressed as relative standard deviation from seven repetitive analyses of samples with analyte concentrations at 1 mg L(-1), varied from 2.1% to 4.4%. Compared with other liquid discharge systems that operate at atmospheric pressure, the current system offers several advantages: First, it eliminates the use of a sample flow system (e.g., syringe or peristaltic pump); instead, a small aliquot of sample is directly pipetted onto the glass slide for analysis. Second, it is a microanalysis system and requires sample volume ≤80 μL, a benefit when a limited amount of sample is available. Third, because the sample is applied in aliquot, there is no washout time, and the analysis can be easily extended to sample array for high-throughput analysis. The proposed LFDBD is promising for in-field elemental determination because of its simplicity, cost effectiveness, low power supply, and no inert gas requirement.

Plasma Jet Desorption Atomization-Atomic Fluorescence Spectrometry and Its Application to Mercury Speciation by Coupling with Thin Layer Chromatography

A novel plasma jet desorption atomization (PJDA) source was developed for atomic fluorescence spectrometry (AFS) and coupled on line with thin layer chromatography (TLC) for mercury speciation. An argon dielectric barrier discharge plasma jet, which is generated inside a 300 μm quartz capillary, interacts directly with the sample being analyzed and is found to desorb and atomize surface mercury species rapidly. The effectiveness of this PJDA surface sampling technique was demonstrated by measuring AFS signals of inorganic Hg(2+), methylmercury (MeHg), and phenylmercury (PhHg) deposited directly on TLC plate. The detection limits of the proposed PJDA-AFS method for inorganic Hg(2+), MeHg, and PhHg were 0.51, 0.29, and 0.34 pg, respectively, and repeatability was 4.7%, 2.2%, and 4.3% for 10 pg Hg(2+), MeHg, and PhHg. The proposed PJDA-AFS was also successfully coupled to TLC for mercury speciation. Under optimized conditions, the measurements of mercury dithizonate (Hg-D), methylmercury dithizonate (MeHg-D), and phenylmercury dithizonate (PhHg-D) could be achieved within 3 min with detection limits as low as 8.7 pg. The combination of TLC with PJDA-AFS provides a simple, cost-effective, relatively high-throughput way for mercury speciation.

Flowing and Nonflowing Liquid Electrode Discharge Microplasma for Metal Ion Detection by Optical Emission Spectrometry

Abstract Liquid electrode discharge microplasma offers a simple, portable, and small platform for fast spectrochemical determination of metal ions in solution samples with lower consumption of consumables (e.g., working gases, electric current, and cooling water). Various liquid electrode discharge devices for metal ions determination with optical emission spectrometry have been developed in the past 20 years. We aim here to provide an overview of this field and to show the similarities and differences, and strengths and weaknesses of different flowing liquid electrode discharge systems and nonflowing liquid electrode discharge systems. We also discuss sample flow rates in flowing systems, required sample volume in nonflowing systems, and the two systems’ applications to real complex samples in this review.

Non-chromatographic determination of inorganic and total mercury by atomic absorption spectrometry based on a dielectric barrier discharge atomizer

A novel, fast and simple non-chromatographic approach for determination of inorganic and total mercury has been developed by cold vapor atomic absorption spectrometry based on dielectric barrier discharge (DBD) atomizer. The determination of inorganic mercury and total mercury can be achieved in a fast sequential fashion (1 min sample−1). In the proposed method, with 0.01% (m/v) NaBH4 used as reductant, inorganic mercury is reduced to elemental mercury, whereas the methylmercury forms an intermediate volatile methylmercury hydride (CH3HgH). A low temperature DBD atomizer was employed for the atomization of CH3HgH. Only inorganic mercury can be measured in the absence of the DBD plasma. However, in addition to inorganic mercury, CH3HgH can be atomized and total mercury is determined in the presence of the plasma. The methylmercury concentration can then be obtained from the difference. The effects of several experimental parameters, such as NaBH4 concentration, HCl concentration, discharge gas and gas flow rate on the analytical performance were investigated. The method provided good reproducibility (<3% RSD) and the detection limits of Hg2+ and CH3Hg+ were found to be 0.35 ng mL−1 and 0.54 ng mL−1, respectively. The proposed method was validated by the analysis of a certified reference material (tuna fish). In addition, it was successfully applied to the analysis of fish samples. The method is excellent for mercury speciation measurements as it provides short analysis time and good reproducibility.

Significant sensitivity improvement of alternating current driven-liquid discharge by using formic acid medium for optical determination of elements.

A method has been developed to improve the performance of alternating-current electrolyte atmospheric liquid discharge (ac-EALD) optical emission spectrometry for the determination of elements. Significant enhancement of emission intensity was achieved by adding organic substance into the nitric acid electrolyte solutions. Under the optimized conditions, 3% (v/v) formic acid in nitric acid (pH 1.0) produced 13 times enhancement for Ag and 7% (v/v) formic acid resulted in 17 times enhancement for Cd. The emission of Pb was even enhanced 78 times in the presence of 3% formic acid. In addition, the signal stability was also improved compared with that in the absence of organic substances. Repeatability was 0.8% for 0.1 mg L(-1) Ag, 0.7% for 0.2 mg L(-1) Cd and 2.6% for 1 mg L(-1) Pb standard solutions (n=5). The limits of detection of Ag, Cd and Pb were 1, 17 and 45 μg L(-1), respectively. The accuracy of the method was demonstrated by determination of elements in simulated natural water samples (GBW(E)080402 and GBW(E)080399).

Dielectric Barrier Discharge for High Efficiency Plasma-Chemical Vapor Generation of Cadmium

A novel approach for Cd vapor generation was developed on the basis of a plasma-assisted chemical process. The generated Cd vapor was subsequently measured by atomic fluorescence spectrometry. Dissolved Cd species were readily converted into volatile species by reaction with hydrogen in a coaxial thin-film dielectric barrier discharge (DBD) plasma reactor. Both atomic and molecular Cd species were produced when a solution containing Cd(2+) was exposed to hydrogen-containing DBD plasma. Fast and efficient vapor generation of Cd was achieved simply in plain (neutral) water medium. Optimal conditions for the DBD-plasma Cd vapor generator were identified. The performance of this thin-film DBD plasma-chemical vapor generation (CVG) was evaluated through comparison with that arising from the conventional HCl-KBH4 system. The vapor generation efficiency of the proposed method (He-DBD) was found to be superior to the conventional CVG approach. Under the optimized conditions, the detection limits of Cd were found to be from 0.03 ng mL(-1) (Ar-DBD) to 0.008 ng mL(-1) (He-DBD) with a heated quartz tube atomizer (QTA); good repeatability (relative standard deviation (RSD) = 1.4%, n = 5) was obtained for a 1 ng mL(-1) standard. The new thin-film DBD plasma-CVG provides several additional advantages including simple setup, easy coupling with flow injection, low power consumption (≤18 W), cost-effectiveness, and long operation lifetime. The accuracy of the proposed method was validated through analysis of cadmium in reference material of simulated natural water sample GBW(E)080402 and rice reference material GBW10045. The concentration of cadmium determined by the present method agreed well with the reference values.

Alternating current driven atmospheric-pressure liquid discharge for the determination of elements with optical emission spectrometry

An atmospheric pressure plasma sustained by an alternating-current power supply was generated using the electrolyte solution as one electrode. The emission spectra of the plasma are related to the metal ions present in the solution and thus can be used for metal ion detection. The main advantage of this source is that it operates at low flow rates in the range of 0.1 to 0.8 mL/min. The effects of the discharge electrolyte anion, the pH and solution flow rate on emission signal were studied. The analytical response curves for Na and Cd demonstrated good linearity at least in the range of 0.5–100 mg L−1. The limit of detection of Na and Cd were determined to be 0.04 and 0.09 mg L−1, respectively. The method was applied for the determination of elements in simulated natural water samples (GBW(E)080408 and GBW(E)080402). The obtained results were in good agreement with the reference values. It provides an alternative analytical method for the determination of elements in water samples.

On line vapor generation of osmium based on solution cathode glow discharge for the determination by ICP-OES

A novel plasma induced vapor generation method is proposed to determine osmium in solutions. Without any chemical oxidizing agents, osmium ion can be readily converted to volatile osmium tetraoxide vapor in the solution cathode glow discharge (SCGD) system. The generated osmium vapor is then transported to inductively coupled plasma for determination by optical emission spectrometry. The influences of background electrolyte, carrier gas flow rate, sample flow rate, ICP power and discharge current were investigated. The analytical performances of this proposed technique were evaluated under optimized conditions. The detection limit of Os was calculated to be 0.51 ng mL(-1). The reproducibility, expressed as the relative standard deviation (n=11) of a 2.0 μg mL(-1) standard solution, was 1.9%. This SCGD induced vapor generation is sensitive and simple, oxidation reagents free, providing an alternative analytical method for measuring Os in geological or environmental water samples.

Dielectric barrier discharge-plasma induced vaporization for the determination of thiomersal in vaccines by atomic fluorescence spectrometry

Direct determination of thiomersal in vaccine by atomic fluorescence spectrometry with dielectric barrier discharge (DBD)-plasma induced vaporization was developed. No sample pretreatments other than dilution were needed in the measurement. The evaporation and atomization of thiomersal in vaccine samples was achieved rapidly in one step. The produced mercury vapor was transported to atomic fluorescence spectrometry for analysis. It is a green method that obviates the need of strong oxidization procedure for degradation of thiomersal to inorganic mercury and reduction agents such as sodium tetrahydroborate(III) or tin(II) chloride to generate Hg vapor. The DBD plasma was generated in a quartz tube (i.d. 5 mm and o.d. 6 mm) by a concentric circles model. The operating parameters such as discharge gas type, gas flow rate, and power were optimized. Possible interference by concomitant elements was also investigated. External calibration was achieved with aqueous standards solution of thiomersal. Under the optimal experimental condition, the detection limit was 0.03 μg L−1 for Hg, equivalent to 0.06 μg L−1 of thiomersal in solution. The analytical precision, represented by the relative standard deviation (RSD) from multiple measurements (n = 5) of 5 μg L−1 thiomersal (as Hg), was 2.5%. This method was also applied to measure thiomersal in five commercial vaccines. In the absence of CRMs for thiomersal in vaccine samples, it was validated by comparing with results from inductively coupled plasma mass spectroscopy (ICP-MS), which showed good correlation.

Solution cathode glow discharge induced vapor generation of mercury and its application to mercury speciation by high performance liquid chromatography–atomic fluorescence spectrometry

A novel solution cathode glow discharge (SCGD) induced vapor generation was developed as interface to on-line couple high-performance liquid chromatography (HPLC) with atomic fluorescence spectrometry (AFS) for the speciation of inorganic mercury (Hg(2+)), methyl-mercury (MeHg) and ethyl-mercury (EtHg). The decomposition of organic mercury species and the reduction of Hg(2+) could be completed in one step with this proposed SCGD induced vapor generation system. The vapor generation is extremely rapid and therefore is easy to couple with flow injection (FI) and HPLC. Compared with the conventional HPLC-CV-AFS hyphenated systems, the proposed HPLC-SCGD-AFS system is very simple in operation and eliminates auxiliary redox reagents. Parameters influencing mercury determination were optimized, such as concentration of formic acid, discharge current and argon flow rate. The method detection limits for HPLC-SCGD-AFS system were 0.67 μg L(-1) for Hg(2+), 0.55 μg L(-1) for MeHg and 1.19 μg L(-1) for EtHg, respectively. The developed method was validated by determination of certified reference material (GBW 10029, tuna fish) and was further applied for the determination of mercury in biological samples.