Use of a solution cathode glow discharge for cold vapor generation of mercury with determination by ICP-atomic emission spectrometry

A novel vapor-generation technique is described for mercury determination in aqueous solutions. Without need for a chemical reducing agent, dissolved mercury species are converted to volatile Hg vapor in a solution cathode glow discharge. The generated Hg vapor is then transported to an inductively coupled plasma for determination by atomic emission spectrometry. Mercury vapor is readily generated from a background electrolyte containing 0.1 M HNO 3. Vapor generation efficiency was found to be higher by a factor of 2-3 in the presence of low molecular weight organic acids (formic or acetic acids) or alcohols (ethanol). Optimal conditions for discharge-induced vapor generation and reduced interference from concomitant inorganic ions were also identified. However, the presence of chloride ion reduces the efficiency of Hg-vapor generation. In the continuous sample introduction mode, the detection limit was found to be 0.7 microg L (-1), and repeatability was 1.2% RSD ( n = 11) for a 20 microg L (-1) standard. In comparison with other vapor generation methods, it offers several advantages: First, it is applicable to both inorganic and organic Hg determination; organic mercury (thiomersal) can be directly transformed into volatile Hg species without the need for prior oxidation. Second, the vapor-generation efficiency is high; the efficiency (with formic acid as a promoter) is superior to that of conventional SnCl 2-HCl reduction. Third, the vapor generation is extremely rapid and therefore is easy to couple with flow injection. The method is sensitive and simple in operation, requires no auxiliary reagents, and serves as a useful alternative to conventional vapor generation for ultratrace Hg determination.     

Microplasma source based on a dielectric barrier discharge for the determination of mercury by atomic emission spectrometry

A low-power, atmospheric-pressure microplasma source based on a dielectric barrier discharge (DBD) has been developed for use in atomic emission spectrometry. The small plasma (0.6 mm x 1 mm x 10 mm) is generated within a glass cell by using electrodes that do not contact the plasma. Powered by an inexpensive ozone generator, the discharge ignites spontaneously, can be easily sustained in Ar or He at gas flow rates ranging from 5 to 200 mL min(-1), and requires less than 1 W of power. The effect of operating parameters such as plasma gas identity, plasma gas flow rate, and residual water vapor on the DBD source performance has been investigated. The plasma can be operated without removal of residual water vapor, permitting it to be directly coupled with cold vapor generation sample introduction. The spectral background of the source is quite clean in the range from 200 to 260 nm with low continuum and structured components. The DBD source has been applied to the determination of Hg by continuous-flow, cold vapor generation and offers detection limits from 14 (He-DBD) to 43 pg mL(-1) (Ar-DBD) without removal of the residual moisture. The use of flow injection with the He-DBD permits measurement of Hg with a 7.2 pg limit of detection, and with repetitive injections having an RSD of <2% for a 10 ng mL(-1) standard.     

Equilibrium discharge from a nozzle of a mixture of an ideal gas and a condensing vapor

Within the framework of the theory of ideal gases, an examination is made of equilibrium discharge of a mixture of a gas and a condensing vapor from a nozzle. The basic equations describing discharge are presented, as well as the results of calculations of the discharge from a nozzle of a mixture of air and water vapor.     

Ultrasound-promoted cold vapor generation in the presence of formic acid for determination of mercury by atomic absorption spectrometry

A new cold vapor technique within the context of green chemistry is described for determination of mercury in liquid samples following high-intensity ultrasonication. Volatile Hg evolved in a sonoreactor without the use of a chemical reducing agent is carried to a quartz cell kept at room temperature for measurement of the atomic absorption. The mechanism involved lies in the reduction of Hg(II) to Hg(0) by reducing gases formed upon sonication and subsequent volatilization of Hg(0) due to the degassing effect caused by the cavitation phenomenon. Addition of a low molecular weight organic acid such as formic acid favors the process, but vapor generation also occurs from Hg solutions in ultrapure water. The detection limit of Hg was 0.1 microg/L, and the repeatability, expressed as relative standard deviation, was 4.4% (peak height). Addition of small amounts of oxidizing substances such as the permanganate or dichromate anions completely suppressed the formation of Hg(0), which confirms the above mechanism. Effect of other factors such as ultrasound irradiation time, ultrasound amplitude, and the presence of concomitants are also investigated. Some complexing anions such as chloride favored the stabilization of Hg(II) in solution, hence causing an interference effect on the ultrasound-assisted reduction/volatilization process.     

The formation of diffuse discharge by short-front nanosecond voltage pulses and the modification of dielectrics in this discharge

The dynamics of diffuse discharge formation under the action of nanosecond voltage pulses with short fronts (below 1 ns) in the absence of a source of additional preionization and the influence of a dielectric film on this process have been studied. It is established that the diffuse discharge is induced by the avalanche multiplication of charge initiated by high-energy electrons and then maintained due to secondary breakdowns propagating via ionized gas channels. If a dielectric film (polyethylene, Lavsan, etc.) is placed on the anode, then multiply repeated discharge will lead to surface and bulk modification of the film material. Discharge-treated polyethylene film exhibits a change in the optical absorption spectrum in the near-IR range.     

Determination of mercury in ash and soil samples by oxygen flask combustion method--cold vapor atomic fluorescence spectrometry (CVAFS)

A simple method was developed for the determination of mercury (Hg) in coal fly ash (CFA), waste incineration ash (WIA), and soil by use of oxygen flask combustion (OFC) followed by cold vapor atomic fluorescence spectrometry (CVAFS). A KMnO4 solution was used as an absorbent in the OFC method, and the sample containing a combustion agent and an ash or soil sample was combusted by the OFC method. By use of Hg-free graphite as the combustion agent, the determination of Hg in ash and soil was successfully carried out; the Hg-free graphite was prepared by use of a mild pyrolysis procedure at 500 degrees C. For six certified reference materials (three CFA samples and three soil samples), the values of Hg obtained by this method were in good agreement with the certified or reference values. In addition, real samples including nine CFAs collected from some coal-fired power plants, five WIAs collected from waste incineration plants, and two soils were analyzed by the present method, and the data were compared to those from microwave-acid digestion (MW-AD) method.     

Determination of mercury in water and fish samples by cold vapor atomic absorption spectrometry after solid phase extraction on agar modified with 2-mercaptobenzimidazole

Due to the consumption of chicken and chicken products in Turkey at high ratio, trace metal content of chicken and chicken products from Turkey were determined by atomic absorption spectrometry after microwave digestion. The accuracy of the method was confirmed by analysis of standard reference material (NIST SRM 1577b Bovine liver). Trace element content in various parts of chicken samples and chicken products were to be in the range of 0.10-114 microg/g for copper, 0.25-6.09 microg/kg for cadmium, 0.01-0.40 microg/g for lead, 0.10-0.91 microg/g for selenium, 0.05-3.91 microg/g for manganese, 0.06-0.10 microg/g for arsenic, 0.01-0.72 microg/g for chromium, 0.01-2.08 microg/g for nickel, 0.01-0.02 microg/g for cobalt, 0.10-1.90 microg/g for aluminium, 1.21-24.3 microg/g for zinc, 2.91-155 microg/g for iron. The levels of lead in some analyzed chicken products were higher than the recommended legal limits for human consumption.     

Microwave and rf excitation of a discharge in sulfur vapor with added neon

An experimental investigation was made of the transient emission of a discharge excited by microwave radiation in mixtures of sulfur and rare gases. Several typical spectral types of emission were identified which alternate over time. Pis’ma Zh. Tekh. Fiz. 25, 27–33 (July 12, 1999)     

Distributions of the electron concentration and the electrical field intensity in a discharge with transverse gas pumping

Computation formulas are obtained for the parameters of a gas discharge with a transverse gas flow.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 54, No. 1, pp. 98–103, January, 1988.     

Investigation of the processes of periodic plasma structure formation in transverse nanosecond discharge with a slotted cathode

A periodic standing-like plasmic striation in inert gases has been observed and investigated under transversal nanosecond electric discharges. The pressure limits relevant for formation of a periodic plasma structure have been established, and the critical values for the voltage amplitude and discharge current have been found corresponding to the upper boundary of the range in which the plasma structure is formed. The external magnetic field effect on the parameters of the periodic plasma structure has been studied. It is stated that the plasma structure is formed at the stage of steady-state discharge and that the lifetime of the periodic structure considerably increases when the transversal magnetic field is applied.     

Electrical and optical characteristics of nanosecond discharge confined between dielectric walls in a diode with a slit cathode

The electrical and optical characteristics of a transverse nanosecond pulsed electric discharge confined between dielectric walls in a helium-filled diode with a hollow (slit) cathode has been experimentally studied in the range of gas pressures of 1–100 Torr. It is shown that the cathode current density in the anomalous glow discharge regime is several orders of magnitude greater than the anode current density. A relationship is established between the characteristic radiation relaxation time and the fast diffusion cooling of electron gas after the jump in the near-wall potential.     

微波消解-氢化物发生原子荧光光谱法同时测定蔬菜中汞、砷

本文建立了一种梯度升压微波消解样品,氢化物发生双道原子荧光光谱法同时测定蔬菜样品中汞、砷的方法。在优化实验条件下,蔬菜样品中Hg、As回收率分别为98.9%-109.3%和91.1%-96.1%;检出限分别为0.0094μg/L、0.0331μg/L。并对其相讨标准偏差(RSD)、精密度和准确度进行了评估,结果表明该方法用于蔬菜中Hg、As的同时测定是可行的。     

Experimental study of the process of film condensation of nitrogen vapor from a mixture with helium

On the basis of an experimental study of the process of film condensation of nitrogen vapor from a mixture with helium and of the hydrodynamics of the film, data are obtained which make it possible to calculate counterflow condensers for cryogenic installations.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 32, No. 1, pp. 24–29, January, 1977.     

The formation of accelerated electrons and their effect on the structure of nanosecond discharge with slot cathode

Experimental investigations are performed of the current-voltage characteristics and spatial distribution of optical radiation of plasma within the cathode cavity and in the discharge gap under conditions of transverse nanosecond electric discharge with a slot cathode. The investigations are performed in helium in the gas pressure range from 1 to 100 torr. It is demonstrated that the cathode layer is formed at the initial stage of discharge and that the electrons accelerated in the narrow cathode region pick up energy of the order of 1 keV. The efficiency of electron beam generation is estimated, and the mechanisms of generation of fast electrons are identified. The free paths of accelerated electrons in plasma under different initial conditions are determined, and the mechanisms of relaxation of energy of this group of electrons are analyzed. The correlation is established between the special features of relaxation of energy of fast electrons and the formation of the structure of beam-plasma discharge with a slot cathode.     

Mechanism of carbon film formation in a discharge with crossed electric and magnetic fields in neon and argon

The process of carbon-film formation in a discharge with crossed electric and magnetic fields in neon and argon has been studied in a system with a cylindrical geometry of electrodes. Radial profiles of the film thickness on an edge substrate have been measured using an interferometric technique. A diffusion model of film formation is proposed, which takes into account the inert gas ion charge exchange and gas heating processes. Experimental data are compared to the results of model calculations.     

建立一种准确测定氢气、氖气和氩气三元混合气含量的方法

介绍利用热导气相色谱分析仪测定氢气、氖气和氩气三元混合气中各组分含量的分析方法,试验结果计算表明,该分析方法能够满足电子芯片保护气产品质量检测的要求。     

Preconcentration, speciation and determination of ultra trace amounts of mercury by modified octadecyl silica membrane disk/electron beam irradiation and cold vapor atomic absorption spectrometry

Mercury (II) and methyl mercury cations at the Sub-ppb level were adsorbed quantitatively from aqueous solution onto an octadecyl-bonded silica membrane disk modified by 2-[(2-mercaptophyenylimino)methyl] phenol (MPMP). The trapped mercury was then eluted with 3ml ethanol and Hg2+ ion was directly measured by cold vapor atomic absorption spectrometry, utilizing tin (II) chloride. Total mercury (Hgt) was determined after conversion of MeHg+ into Hg2+ ion by electron beam irradiation. A sample volume of 1500ml resulted in a preconcentration factor of 500 and the precision for a sampling volume of 500ml at a concentration of 2.5microgl(-1) (n=7) was 3.1%. The limit of detection of the proposed method is 3.8ngl(-1). The method was successfully applied to analysis of water samples, and the accuracy was assessed via recovery experiment.