Establishing SI traceability for measurements of mercury vapour

The majority of measurements of mercury vapour, for example those to determine mass concentration in air, are currently ultimately traceable to the vapour pressure of mercury, usually via a bell-jar calibration apparatus. This allows a saturated concentration of mercury vapour in air to develop in a confined space in equilibrium with ambient conditions, from which a known mass of mercury can be removed for calibration purposes. Several empirical equations are available to describe the vapour pressure of mercury at a given temperature, but the agreement between them is not good, with data from different equations sometimes differing by 5% or more. In order to remove the dependence of mercury vapour measurement on these empirical equations, and to provide stability, comparability and coherence for mercury vapour measurements, this paper describes work undertaken to link directly mercury vapour measurements to standards of mass, and therefore to establish traceability for these measurements to the SI system of units. This has been achieved by measuring the mass output rate of a dynamic mercury vapour generator gravimetrically, and linking this to the expected mass concentration in the bell-jar apparatus. The SI traceable mercury vapour measurements have been shown to agree with the predicted output from the bell-jar, as defined by the most commonly used empirical mercury vapour pressure equation, within the uncertainty of the measurement.     

Elemental mercury vapour in air: the origins and validation of the ‘Dumarey equation’ describing the mass concentration at saturation

The Dumarey equation has been the dominant relationship used to calculate the mass concentration of saturated elemental mercury vapour in air for the calibration of mercury vapour measurement equipment for over 25 years. However, the origin of the equation, and the validation data supporting its accuracy have never been published. This paper addresses that deficiency, compares the Dumarey equation with other data sets to which it has been wrongly attributed in the past, and describes why it remains superior to the use of mercury vapour pressure data in combination with the ideal gas law, for the purposes of calibrating mercury vapour measurement equipment.     

CO2-laser photoacoustic detection of heavy water vapour. Basic principles

A CO₂-laser cw system and a photoacoustic detection apparatus, based on a nonresonant gas cell, was constructed and built. Coincidences of D₂O absorption with several laser lines were observed. The strongest absorption was observed with the line at 9.26 m, which was used in the experiments. Samples of deuterated water in the range from 10 to 100% deuterium were used to examine the behaviour of the photoacoustic signal under conditions of varying deuterium content and total vapour pressure. A principal calibration procedure with respect to this is proposed. The behaviour of the system on buffer gas introduction was examined with hydrogen and dry air. Self-buffering of water vapour is also discussed on the basis of the results.     

Neues Quecksilber-Spektrometer zur Messung von Quecksilberdampf in Luft

Zusammenfassung Ein Atomabsorptions-Spektrometer wird beschrieben, das zur Bestimmung des Quecksilbergehaltes in Luft die Absorption der im vakuumultravioletten Spektralbereich gelegenen Hg-Resonanzlinie 184,9 nm benutzt. Die Kombination einer Hg-Niederdruckdampflampe mit einer Photozelle mit CsI-Kathode gestattet einen Spektrometer-Aufbau ohne Monochromator oder Filter. Zur Messung der HgKonzentration in Gasen wird das Quecksilber einer Probe zunächst auf einem Goldblech gesammelt, durch Ausheizen des Goldes wieder freigesetzt und die Absorption durch die Dampfwolke bestimmt. Das Eichverfahren und Meßbeispiele werden erläutert.

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New mercury spectrometer for the measurement of mercury vapour in air

Summary An atomic absorption spectrometer is described using the absorption of the vacuum ultraviolet resonance line 184.9 nm to determine the amount of mercury in air. The use of a mercury low-pressure discharge lamp combined with a CsI photocell makes it possible to omit monochromator or filter. For measuring the concentration of mercury in all sorts of gases the mercury of the sample is collected on sheet gold. By heating the sheet mercury is set free and the absorption of the mercury vapour can then be measured. The calibration procedure and some analytical results are described.

     

A new apparatus for measuring the vapour pressure of liquid mixtures excess Gibbs free energy of octamethylcyclotetrasiloxane + cyclohexane at 308.15 K

A new apparatus for measuring the vapour pressure of liquid mixtures is described. In conjunction with an automatic pressure controller, a capacitance manometer is used as a null device to isolate the liquid and vapour. The vapour pressure is measured with a precision mercury manometer. The continuous-dilution technique for sample introduction has been incorporated in the new apparatus, so that the composition range of a mixture can be covered in two runs. The accuracy of each measured quantity is: pressure, 3 Pa; temperature (IPTS-68), 0.002 K; volume, 0.002 cm³. G^E for cyclohexane + octamethylcyclotetrasiloxane (abbreviated throughout this paper as omcts) at 308.15 K has been determined: the minimum value of ?68 J mol^?1 occurs near x₂(omcts) = 0.5.     

A differential photoacoustic mercury detector

A sensitive instrument for the detection of mercury is described. The difference in mercury concentration between two identical flow-through silica cells is measured by means of the photoacoustic effect. The cells are illuminated laterally by a 20-W germicidal mercury discharge lamp. A microphone in each cell detects pressure changes produced when mercury vapour absorbs resonance radiation from the lamp and releases the energy to nitrogen flowing in the partially closed cells, as heat derived from quenched fluorescence. A differential microphone connection discriminates against ambient noise and contributes to a detection limit of less than 0.02 ng of mercury with a linear response up to 70 ng. Variables such as gold collector design and heating rate, inlet filters and traps, changes in carrier gas flow, carrier gas composition, lamp operating current and modulation frequency which all affect instrument performance are discussed. Photochemical loss of mercury can be avoided if dry nitrogen, carbon dioxide, or air is used as the carrier gas provided contamination by avid vapours and water is prevented by a calcium oxide trap at the inlet.     

A sensitive photo-acoustic mercury detector

Apparatus for the photo-acoustic determination of mercury vapour is described. A detection limit of better than 0.2 ng of mercury and a linear working range up to 150 ng can be realised in the presence of substantial levels of ambient noise. Nitrogen carrier gas effectively quenches the mercury fluorescence in a tubular cell attached alongside a modulated germicidal mercury discharge lamp. The released heat results in pressure fluctuations, in a partially closed cell, which are detected by using a microphone and simple electronics. A narrow-band amplifier and a lock-in detector allow signals to be recorded. Very low cost and simplicity are important features. A gold foil collection system is used to increase selectivity. The apparatus is suitable for laboratory and field applications.     

Determination of the partial pressure of single low volatile compounds in mixtures

A new measuring system for the determination of the vapour pressure of single compounds in mixtures is introduced. A coupling system consisting of a quadrupol mass spectrometer and a vapour pressure balance was used for these measurements. Some calibration measurements and investigations of mixtures are discussed.     

Determination of the partial pressure of single low volatile compounds in mixtures

A new measuring system for the determination of the vapour pressure of single compounds in mixtures is introduced. A coupling system consisting of a quadrupol mass spectrometer and a vapour pressure balance was used for these measurements. Some calibration measurements and investigations of mixtures are discussed.     

Mercury determination in sediments by CVAAS after on line preconcentration by solid phase extraction with a sol-gel sorbent containing CYANEX 471X®

The development of a preconcentration method for the measurement of trace levels of mercury in digested sediments is described. Solid phase extraction (SPE) was used for the preconcentration of mercury coupled on-line by means of a flow injection (FI) system followed by cold vapour atomic absorption spectrometry (CVAAS) detection. The SPE was carried out through a column packed with a sorbent material containing triisobutylphosphine sulfide (CYANEX 471X®) as mercury extractant and prepared by the sol-gel process. The effects of FI variables (argon, eluent, and reductant flow rates, loading and elution times) as well as the eluent concentration on the analytical performance of the method were evaluated. The proposed method was validated under the optimum conditions. The calibration graph was linear from 0.05?µg?L^?1 to 3.0 µg?L^?1 of Hg. The detection limit (DL), based on three times the standard deviation of the blank measurement criterion, was 24?ng^?L^?1. The repeatability was 1.5% and 1.8% RSD (n?=?10) at concentrations of 0.5 and 1 µg?L^?1 of Hg, respectively. Method enrichment factors of 16 with a productivity of 30 samples h^?1 or 32 with a productivity of 17 samples h^?1 were achieved under selected conditions. Certified reference materials, inductively coupled plasma mass spectroscopy (ICP-MS) and cold vapour atomic fluorescence spectrometry (CVAFS), were used to evaluate the accuracy of the proposed method.     

Flow system device for the on-line determination of total mercury in seawater

The instrumental set-up for the on-line sampling, digestion and quantification of total mercury in seawater is described. Based on a flow system and cold vapour atomic absorption spectrometry (CVAAS) detection limit was improved by a gold amalgam preconcentration to 0.5 ng l(-1). The manifold design was optimized by the variation of the gas flow, length of reaction coils, shape and material of the gas-liquid separator and flow rate of the reductant. A calibration following the equations p=0.039c+0.0813 (p, peak area; c, concentration) and a correlation coefficient of r=0.9996 was obtained. The relative standard deviation of three measurements of 0.5 ng l(-1) Hg(2+) was 3.8%. The long-time (12 h) reproducibility was 6.2% RSD (n=25) of 0.5 ng l(-1) Hg(2+). With a recovery rate >90% mercury can be determined after on-line UV digestion. For a complete analysis, 6 min is required. The technique is fast, simple to handle and robust. The apparatus is designed for the use on research vessels under sea conditions.     

Radio-release determination of mercury vapour in air using radioactive kryptonate of selenium sulfide

Radioactive kryptonate of selenium sulfide is suggested for the determination of the concentration of mercury vapour in air. Selenium sulfide was applied as a coating to paper; upon the exposure to an atmosphere containing mercury vapor, a black color of mercuric sulfide and mercuric selenide developed. The fractional decrease in the radioactivity of the paper (related to the original specific activity) was found to be proportional to the concentration of mercury vapor and time of exposure. Other factors which can be controlled were found to be affecting the determination significantly.     

Vapour pressure of DSC calibration substances

For a large number of DSC calibration substances the vapour pressure at room temperature or at transition temperature (whichever is the highest) is given. It is important to know the vapour pressure of substances, because a DSC measurement on a substance with a high vapour pressure requires encapsulation of the substance in a hermetically sealed crucible to prevent evaporation. Because the calibration procedure must be performed using the same type of sample pan as will be used during the actual measurements, the presented information allows one to decide which calibration substances and/or what type of sample pan should be used for calibration.This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis of Al Nanopowders in an Anodic Arc

Nanopowders of metals and metal oxides have been produced using an arc operated between a refractory rod anode and a hollow cathode (J. Haidar in A method and apparatus for production of material vapour, Australian Patent No. 756273, 1999). the arc attachment to the anode is through a small region of molten metal located at the tip of the rod anode. Heat from the arc evaporates the molten metal and the vapour is passed through the arc plasma before condensing into sub-micron particles downstream of the cathode. A precursor metal is continuously fed onto the tip of the anode to maintain the molten metal region and compensate for losses of materials due to evaporation. The particle size of the produced powder depends on the pressure in the arc chamber and for production of nanoparticles in the range below 100 nm we use a pressure of 100 torr. Aluminium has been used as a precursor material, leading to production of aluminium metal nanopowders when the arc is operated in argon and to aluminium oxide nanopowders for operation in air. For operation in air, the products are made of γ-Al₂O₃.     

Effect of operating conditions on water transport during the concentration of sucrose solutions by osmotic distillation

A recent membrane technique, osmotic distillation (OD), is used to concentrate binary water–sucrose solutions at ambient temperature under atmospheric pressure. The principle is based on the extraction of water vapour from a dilute aqueous solution, which is put in contact with a hypertonic salt solution by means of a macroporous hydrophobic membrane. The concentration difference between both solutions translates into a transmembrane vapour pressure drop, that constitutes the driving force for mass transfer. An experimental device is designed at laboratory scale for this study, allowing achievement of vapour fluxes of 10 kg m⁻² h⁻¹ under standard conditions. The effect of various operating parameters on vapour flux is studied. The solute content results in the most influencing variable via water activity in brine and via viscosity in sugar solutions. The effect of concentration polarisation on the brine side is not negligible and would have to be taken into account for process optimisation. This phenomenon could not be quantified on the sugar solution side due to pressure drop limits of the pilot rig. Eventually, the vapour flux can be significantly increased by adding a temperature difference to the transmembrane concentration difference, when pure water is evaporated.     

Determination of Mercury at the Picogram per Milliliter Level Using Immobilized Horseradish Peroxidase

Abstract

New test method and test device for the mercury (II) determination at the pg/mL level were developed based on the mercury inhibitory action on horseradish peroxidase immobilized on solid supports – in the cells of the polystyrene plate and on the chromatographic paper. The reactions of o-dianisidine, 3,3′,5,5′-tetramethylbenzidine and o-phenylenediamine oxidation by hydrogen peroxide were used as the indicator reactions. The mercury inhibitory effect increased in the presence of thiourea. Under the elucidated optimal conditions the calibration curves for the mercury determination showed a linear relationship between the peroxidase inhibition degree and the mercury concentration in the range of 0,1–1000 pg/mL. The mercury detection limits were 0,1–10 pg/mL in dependence on the concrete indicator reaction. The analysis completed in 15 min. The proposed test device was applied to the mercury determination in underground waters of Moscow region. The mercury content obtained was coincident with that obtained by atomic-fluorescent method with cold vapour.     

Evaporation of a binary liquid mixture

An apparatus was designed to measure the evaporation rates of the components comprising a binary liquid mixture, from a horizontal surface, under condi Evaporation studies were conducted on the ethanol-water system. The effects on the evaporation rate of air velocity and liquid composition were investiThe experimental evaporation rates were shown to depend on vapour pressure driving force. For the pure component, the evaporation exhibited a direct li For ethanol-water mixtures the total and ethanol component evaporation increased with increasing ethanol concentration, while that of the water compone     

Simultaneous sampling and analysis for vapor mercury in ambient air using needle trap coupled with gas chromatography-mass spectrometry

A needle trap (NT) technique for simultaneous sampling and analysis of vapor and particle mercury in ambient air using gold wire filled in a syringe needle has been developed. This NT technique relies on gold amalgamation rather than adsorption/absorption to traditional solid-phase microextraction. Hg trapped by Au-amalgamation NT is thermally desorbed in a hot injection port of a gas chromatograph; desorbed Hg is then determined by the coupled mass spectrometer. This simultaneous sampling and analysis technique were optimized, tested, and used for the collection and accurate determination of elemental Hg in ambient air. Linear calibration curves were obtained for Hg sampling by NT when mass spectrometry (MS) was used for detection; they spanned over 4 orders of magnitude. MS offered excellent sensitivity and selectivity. Selected ion monitor (SIM) mode was used for the linear calibration curves. The selected quantitation ion was m/z 202, since m/z 202 was the strongest isotope of mercury mass spectrum. The method was verified with HgCl(2) spiked solution samples. An excellent agreement was found between the results obtained for the Hg-saturated air samples and HgCl(2) spiked solution samples. The use of the Au-amalgamation gas-sampling needle trap method, for the measurement of Hg in air and Hg(2+) water samples, is described herein.