Direct and rapid analysis of ambient air and exhaled air via electrostatic precipitation of aerosols in an atomizer furnace and Zeeman spectrometry

Techniques that allow the elements present in the air to be determined in a simple and rapid manner are very attractive. Direct aerosol sampling techniques avoid the need to pretreat the filter via wet digestion in order to remove any sources of contamination, and they decrease the precipitation time significantly. Analyzers based on this technique can also determine the concentrations of elements in the air automatically in situ. This paper is concerned with the development of a novel analytical system that is based on electrostatically precipitating aerosols from the air into a graphite furnace. The equipment includes a Zeeman spectrometer with high frequency modulation polarization (MGA-915), and an electrostatic precipitation system incorporated into the analyzer. The high sensitivity of the system developed here means that it can be used to determine element concentrations in the air exhaled by humans, as well as those in ambient air.     

Real-time monitoring of intravenous hypnotics propofol

A method for the determination of intravenous hypnotics in blood by monitoring of its concentration in exhaled air under clinical conditions is described. The results of propofol quantification in exhaled air are compared with those in blood collected by means of mass spectrometry. The possibility of the on-line noninvasive control of propofol in blood in the course of complex anesthesia using a mass spectrometer with electron ionization is demonstrated.     

A New Method for Standardless Analysis in ETA-AAS Applied to the Determination of Lead Associated with Air Aerosol

The analysis ofPbassociated with air aerosols by its accumulation through electrostatic precipitation directly in a graphite tube, which is subsequently used as an atomizer in electro thermal atomization-atomic absorption spectroscopy (ETA-AAS), has already been tested and found very convenient for its simplicity and speed. However, its use as a practical and useful method of analysis was hampered by the necessity of a laborious and difficult calibration with high risks of systematic errors. These difficulties can be bypassed by resorting to an absolute or standardless method of analysis. Standardless methods of analysis have been proposed for ETA-AAS measurements and recently applied toCdandHg.With the use of a new and more powerful power supply this method has been extended toPbso that a very easy, fast, and almost on line way of measuring the level ofPbin air aerosols is possible. The system presented in this paper is manually operated but its automation, in order to obtain an automatic control station, is only a matter of convenience.     

An optimized sampling and GC-MS analysis method for benzene in exhaled breath, as a biomarker for occupational exposure

Benzene is known to be toxic and carcinogenic: therefore, in case of exposure to benzene vapours, a reliable biological monitoring procedure is needed, particularly in the field of occupational hygiene. The determination of the concentration of benzene in the exhaled air 8 h after the exposure has been demonstrated to be a significant biomarker, even for low concentrations of airborne benzene vapours. This work presents a sampling and analysis method that optimizes previously described procedures: in the sampling phase, a double-step sample collection in Tedlar bags is used, in order to remove the breath moisture and to standardise the sample volumes. The analytical phase uses a cryogenic trap for the concentration of the air samples to be injected in the GC-MS, without the need for trapping materials, significantly reducing time and costs of the analysis and improving sensitivity. The presented method has been successfully applied to the biological monitoring of a mixed population (occupationally exposed and not exposed subjects, smokers and non-smokers), with a lower detection limit of 1.5 ng of benzene per litre of exhaled air, that is 1/200 of the biological exposure index recommended by the American Conference of Governmental Hygienists.     

New method for determination of trihalomethanes in exhaled breath: Applications to swimming pool and bath environments

A method for the estimation of the human intake of trihalomethanes (THMs), namely chloroform, bromodichloromethane, dibromochloromethane and bromoform, during showering and bathing is reported. The method is based on the determination of these compounds in exhaled breath that is collected by solid adsorption on Tenax using a device specifically designed for this purpose. Instrumental measurements were performed by automatic thermal desorption coupled to gas chromatography with electron capture detection. THMs in exhaled breath samples were determined during showering and swimming pool attendance. The levels of these compounds in indoor air and water were also determined as reference for interpretation of the exhaled breath results. The THM concentrations in exhaled breath of the volunteers measured before the exposure experiments showed a close correspondence with the THMs levels in indoor air where the sampler was located. Limits of detection in exhaled breath were dependent on THM analytes and experimental sites. They ranged between 170 and 710 ng m⁻³ in the swimming pool studies and between 97 and 460 ng m⁻³ in the showering studies. Application of this method to THMs determination during showering and swimming pool activities revealed statistically significant increases in THMs concentrations when comparing exhaled breath before and after exposure.     

Direct measurement of the mercury content of exhaled air: a new approach for determination of the mercury dose received

A new rapid technique is presented for determination of the dose of mercury inhaled; it is based on direct measurement of the concentration of mercury in exhaled air by use of a Zeeman mercury spectrometer RA-915+. It has been demonstrated experimentally that the dose received during short-term exposure to mercury vapor is determined more reliably by this method rather than by conventional techniques based on measurement of the mercury content in blood or urine.     

Exhaled breath condensate: Determination of non-volatile compounds and their potential for clinical diagnosis and monitoring. A review

Exhaled breath condensate is a promising, non-invasive, diagnostic sample obtained by condensation of exhaled breath. Starting from a historical perspective of early attempts of breath testing towards the contemporary state-of-the-art breath analysis, this review article focuses mainly on the progress in determination of non-volatile compounds in exhaled breath condensate. The mechanisms by which the aerosols/droplets of non-volatile compounds are formed in the airways are discussed with methodological consequences for sampling. Dilution of respiratory droplets is a major problem for correct clinical interpretation of the measured data and there is an urgent need for standardization of EBC. This applies also for collection instrumentation and therefore various commercial and in-house built devices are described and compared with regard to their design, function and collection parameters. The analytical techniques and methods for determination of non-volatile compounds as potential markers of oxidative stress and lung inflammation are scrutinized with an emphasis on method suitability, sensitivity and appropriateness. The relevance of clinical findings for each group of possible non-volatile markers of selected pulmonary diseases and methodological recommendations with emphasis on interdisciplinary collaboration that is essential for future development into a fully validated clinical diagnostic tool are given.     

Determination of the Efficiencies of Filter Media Using Atmospheric Aerosols

Aerosol refers to an assembly of liquid or solid particles suspended in a gaseous medium long enough to enable observation or measurement. Aerosol concentration is one of index for evaluating environmental quality. Filtration by filter media is usually used to collect aerosols, where the efficiency of the filter should be known. A convenience method has been developed for determination of the filter efficiency as aerosol size and air velocity.     

Stepwise injection photometric determination of nickel in air aerosols

A procedure is developed for the automated determination of nickel in air aerosols; it involves the adhesive separation of aerosols on a fiberglass column in the on-site mode followed by the photometric determination of analytes with dimethyl glyoxime under the conditions of stepwise injection analysis of aerosol concentrates. The analytical range for nickel is 1.5–38 μg/m³; the detection limit of the method is 0.5 μg/m³ at an air sample volume of 30 L. The duration of sampling to an adhesive column and concentrate analysis were 15 and 10 min, respectively.     

Gas-chromatographic determination of chlorostyrene and dichlorostyrene isomers in workplace air

Conditions for a gas-chromatographic determination of vapors and aerosols of p-chlorostyrene and 2,6-dichlorostyrene contained in workplace air samples were determined. The method is based on the adsorption of p-chlorostyrene and 2,6-dichlorostyrene on activated charcoal and fiberglass, desorption with toluene and analysis of the obtained solution by capillary gas chromatography with flame ionization detection (FID). The determination limit of the method is 5 mg m(-3) for each substance.     

Radionuclide variations in the air over Monaco

Radionuclides in aerosols and precipitation have been analyzed by IAEA-MEL in Monaco since 1987 and 1999, respectively, to identify their behavior in the atmosphere and delivery into the northwestern Mediterranean Sea. While the concentration of ⁷Be in aerosols has been affected by the stratospheric-tropospheric mixing and precipitation, the concentration of ¹³⁷Cs in aerosols has been influenced by a combination of local meteorological conditions and re-suspension of ¹³⁷Cs from soil. Higher concentrations of ⁷Be, ¹³⁷Cs, ^239,240Pu and ²⁴¹Am in precipitation occurred during spring and summer. The highest deposition rates of these radionuclides were observed in spring and autumn during periods of high precipitation. A good correlation was found between the amount of precipitation and depositional flux for ⁷Be, but not for ¹³⁷Cs, ^239,240Pu and ²⁴¹Am. This indicates that the wet process as well as the dry process seem to be important factors in determining the annual deposition for transuranic radionuclides and ¹³⁷Cs.     

Separation and quantitation of monovalent anionic and cationic species in mainstream cigarette smoke aerosols by high-performance ion chromatography

A simple method has been developed to separate and quantitate monovalent ionic species in mainstream cigarette smoke aerosols based on ion chromatography (IC) with conductivity detection. The method entails collecting the smoke aerosol particulate phase by electrostatic precipitation, dissolving the smoke condensate in methanol (MeOH), and separating the ionic species on either a cation- or anion-exchange column. The method has been applied to the analysis of smoke aerosols from two cigarettes, 1R4F Kentucky Reference cigarettes and a new cigarette that heats but does not burn tobacco. The predominant cations in smoke aerosols from 1R4F Kentucky Reference and the new cigarettes are sodium (Na+), ammonium (NH4+), and potassium (K+) ions; the predominant anions are acetate (AcO-) and formate (HCOO-). Trace amounts of chloride (Cl-), nitrite (NO2-), and nitrate (NO3-) ions are also present.     

Determination of lead in atmospheric particulates by flameless atomic absorption spectrometry with a graphite tube

A procedure for the determination of atmospheric particulate lead by flameless atomic absorption spectrometry is described. Aerosols are collected on 10-cm Whatman 41 filters with high-volume pumps. The lead is removed from a one-eighth sector of the filter by two ultrasonic treatments in 0.1 M nitric acid for 10 and 5 min, respectively. Investigations, including comparison with samples pre-ashed at low temperature, indicated that the lead was completely recovered. Routinely 20-μ1 amounts of the solution are injected into a graphite tube and the % absorption at 283.3 nm is measured. The elements normally encountered in atmospheric aerosols do not interfere. The sensitivity for 24-h samples is 0.01 μg m^?3 of air. Sampling time can be reduced to a few minutes in urban air when a larger segment of the filter is used and a larger volume is injected. The reproducibility of the complete procedure is 3% for a typical lead concentration of 0.35 μg m^?3. The method was applied to short-period variations of the lead concentration in urban air.     

Application of solid-phase microextraction and gas chromatography-mass spectrometry to the determination of volatile organic compounds in end-exhaled breath samples

Analysis of exhaled air is of particular interest as an indicator of health as well as a tool for the diagnosis of diseases. It is also a very attractive procedure for the biological control of the exposition to hazardous solvents. This kind of analysis presents numerous advantages over other methods, the most important being that it is not an invasive procedure and, therefore, it is well accepted and can be applied to a wide range of compounds. Furthermore, the analysis is simplified since the matrix is less complex that in the case of blood or urine. In spite of these obvious advantages and the good results obtained, analysis of exhaled air is not in daily use, probably due to the fact that there are no normalized systems of sampling, thus making the interpretation of the results difficult. In this paper, a method for the determination of tetrachloroethylene in exhaled air using solid-phase microextraction is presented. This method, which can be applied to other volatile organic compounds, was developed with special emphasis of end-exhaled breath sampling. The sample is collected in a glass tube whose ends are closed once the exhalation is finished. The tube has an orifice sealed with a septum through which the fiber is inserted. Then, the fiber is desorbed in the injector of a gas chromatograph and the analysis is accomplished using mass spectrometry for the identification and quantification of the components. The proposed system avoids the need of complex sampling equipment and allows analysis of the alveolar fraction. Additionally, the system is economical and easy to handle, thus facilitating the development of normalized methods and its routine use in field studies.     

Adsorption, association and precipitation in hexadecyltrimethylammonium bromide/sodium dodecyl sulfate mixtures

The phase equilibria of surfactant aqueous mixtures, hexadecyltrimethylammonium bromide and sodium dodecyl sulfate, have been studied by polarizing microscopy, quasielastic light scattering, conductivity, potentiometric, electrophoretic, and surface tension measurements. Adsorption at the air/solution interface, association and precipitation in bulk solution strongly depended on the molar ratio and the concentration of surfactants. Catanionic vesicles coexisted with crystalline catanionic salts in a broad concentration range. The relative proportions of crystallites and vesicles varied according to the concentration and the molar ratio of the surfactants. The solid crystalline phase was progressively converted to catanionic vesicles with increasing surfactant molar ratio. At the highest excess of one of the surfactants transition from catanionic vesicles to mixed micelles occurred. The formation and stability of different phases are discussed in terms of surfactant molecular packing constraints and electrostatic interactions in the headgroup region. Surfactant tail-length asymmetry and the change of electrostatic interactions in the headgroup region from attractive to repulsive are governing factors for the transition from planar to curved bilayers. Received: 9 June 1998 Accepted: 18 August 1998     

Determination of soluble and insoluble nickel compounds in airborne particulate matter by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry

An extraction procedure for the determination of soluble and insoluble nickel and its compounds in ambient air dust was investigated employing a special device for the generation of test aerosols and using water-soluble NiCl2, partly water-soluble NiCO3 and water-insoluble NiO as model compounds. Additionally, results of the separation and determination of different nickel species down to some ng/m3 in ambient aerosols are discussed. The extraction was carried out with a solution containing 0.01 mol/L EDTA in order to determine partly water-soluble compounds such as NiCO3 and water-soluble, non-toxic nickel compounds in one step. Airborne dust was sampled on filters at locations close to two metallurgical plants in Northrhine-Westphalia (Germany), and first results on the nickel concentration (mean (median) values over a period of 4 months: 8.6+/-6.5 ng/m3 (6.7 ng/m3) and 27.7+/-36 ng/m3 (10.8 ng/m3), respectively) in the collected dust are presented. For EDTA-soluble nickel compounds the maximum and mean fractions of total nickel were found to be 77.1% and 18.6+/-12%, respectively.     

Gas-chromatographic determination of chlorostyrene and dichlorostyrene isomers in workplace air

Conditions for a gas-chromatographic determination of vapors and aerosols of p-chlorostyrene and 2,6-dichlorostyrene contained in workplace air samples were determined. The method is based on the adsorption of p-chlorostyrene and 2,6-dichlorostyrene on activated charcoal and fiberglass, desorption with toluene and analysis of the obtained solution by capillary gas chromatography with flame ionization detection (FID). The determination limit of the method is 5 mg m^–3 for each substance. Received: 13 December 1999 / Revised: 6 March 2000 / Accepted: 7 March 2000     

Determination of ethane,pentane and isoprene in exhaled air using a multi-bed adsorbent and end-cut gas-solid chromatography

A method for the determination of exhaled ethane, pentane and isoprene was developed and validated. The method was based on pre-concentration of the analytes on a multi-bed solid adsorbent tube containing Tenax TA, Carboxen 569 and Carboxen 1000, thermal desorption and gas chromatography (GC) with flame ionisation detection (FID). A pre-column in an end-cut GC system was used to avoid problems with water and strongly retained substances. The detection limits were 5, 2 and 6 pmol per sample for ethane, pentane and isoprene, respectively, using a sample volume of 500 ml. The linearity was good for all analytes with correlation coefficients exceeding 0.999. The repeatability for exhaled air samples was 7, 10 and 12% for ethane, pentane and isoprene, respectively. Analysis of a certified reference material of ethane and pentane did not differ significantly from the certified values. Ethane and pentane levels were stable up to six days of storage in sample tubes. Isoprene levels were not stable during storage in the sample tubes used here, but using Carbopack X instead of Carboxen 569, levels were stable up to two days. The levels of exhaled ethane, pentane and isoprene in healthy subjects (n = 4) were 8.1+/-5.8 pmol l(-1), 11+/-5.8 pmol l(-1) and 2.4+/-0.90 mnol l(-1), respectively. The method could, with minor modifications, be used to determine other low-molecular hydrocarbons in exhaled air as well.     

On-line analysis of ambient air aerosols using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy is developed for the detection of aerosols in ambient air, including quantitative mass concentration measurements and size/composition measurements of individual aerosol particles. Data are reported for ambient air aerosols containing aluminum, calcium, magnesium and sodium for a 6-week sampling period spanning the Fourth of July holiday period. Measured mass concentrations for these four elements ranged from 1.7 parts per trillion (by mass) to 1.7 parts per billion. Ambient air concentrations of magnesium and aluminum revealed significant increases during the holiday period, which are concluded to arise from the discharge of fireworks in the lower atmosphere. Real-time conditional data analysis yielded increases in analyte spectral intensity approaching 3 orders of magnitude. Analysis of single particles yielded composition-based aerosol size distributions, with measured aerosol diameters ranging from 100 nm to 2 μm. The absolute mass detection limits for single particle analysis exceeded sub-femtogram values for calcium-containing particles, and was on the order of 2–3 femtograms for magnesium and sodium-based particles. Overall, LIBS-based analysis of ambient air aerosols is a promising technique for the challenging issues associated with the real-time collection and analysis of ambient air particulate matter data.