Multichannel autosampler for Curie-point pyrolysis capillary gas chromatography

A multichannel autosampler which can automatically analyze up to 20 samples in sequence has been developed for on-line Curie-point pyrolysis – capillary GC. The results obtained from the system show that the analysis of thermally labile samples could be performed without either thermal degradation or reaction during the waiting time before the final pyrolysis. The reproducibilities of the relative peak areas and retention times of the characteristic pyrolysates of a tricomponent copolymer were significantly better than those obtained by manual sample manipulation.     

“Badge-type” passive sampler for monitoring ambient ammonia concentrations

A passive “badge-type” sampling device for the determination of gaseous ammonia was developed. The collection substrate is phosphoric acid. The sampler can be used for outdoor and indoor sampling of ammonia in the concentration range from 0.05 μg/m³ to 10 mg/m³. The performance was tested in the laboratory and in the field against an annualar denuder, a filter pack and an impinger technique. The intercalibration showed that the passive sampler compares very well with active samplers (r²=0.99; k=1.05). The average reproducibility of the sampler was 8%. Hence the badge sampler is well suited for the determination of ammonia in a wide range of concentrations and particularly for application under rural background conditions. The sampling rate of the device was calculated according to a simple multi-layer model.     

Solid-phase microextraction under controlled agitation conditions for rapid on-site sampling of organic pollutants in water

An electric drill coupled with a solid-phase microextraction (SPME) polydimethylsiloxane (PDMS) fiber or a PDMS thin film was used for rapid sampling of polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Laboratory experiments demonstrated that the sampling rates of SPME fiber and thin film can be predicted theoretically. Compared with the SPME fiber, the PDMS thin film active sampler exhibited a higher sampling rate and much better sensitivity due to its higher surface-to-volume ratio and its larger extraction phase volume. The amount of the analytes extracted by the thin film was around 100 times higher than those obtained by fiber, for both 5 min rapid sampling and equilibrium extraction. A new thin film active sampler was then developed for rapid on-site water sampling. The sampling kit included a portable electric drill, a copper mesh pocket, a piece of thin film, and a liner. Laboratory experiments indicated that the sampling remained in the linear uptake phase with this sampler to 8 min for the PAHs. Field test illustrated that this novel sampler was excellent for rapid on-site water sampling due to its short sampling period, high sampling efficiency and durability The thin film sampling kit facilitates on-site sampling, sample preparation, storage and transport. This new sampler is more user-friendly and easier to commercialize than previous samplers.     

Instrumental neutron activation analysis of dry atmospheric fall-out and rain-water

An automated precipitation sampler and an instrumental neutron activation analysis (i.n.a.a.) method for the determination of some major and trace elements in dry atmospheric fall-out and rain-water are presented. The sampler features a rain detector which makes separate collection of dry atmospheric fall-out and rain-water possible. The sampler is equipped with u.v. lamps in order to avoid algal growth during extended collection periods. After collection, the samples are separated into water-soluble and insoluble fractions. The soluble fraction is preconcentrated before analysis by freeze-drying. The i.n.a.a. method involves the measurement of both short- and long-lived radioactivities so that a total of 35 elements can be determined. The possibility of losses during freezedrying and the accuracy of the i.n.a.a. method were investigated for 7 elements by analysis of a soluble fraction with an independent method, viz. inductively coupled plasma atomic emission spectrometry.     

Development of the infrared hollow waveguide sampler for the detection of chlorophenols in aqueous solutions

A method based on the infrared hollow waveguide sampler was developed for sensing chlorophenols in aqueous solutions. This sampler was constructed by coating a suitable hydrophobic film onto the inner surface of an infrared hollow waveguide. By passing the aqueous solution through the hollow waveguide sampler, analytes can be absorbed into the hydrophobic layer. The adsorbed analytes can be sensed later by using Fourier transform infrared spectrometry. Six hydrophobic polymers were investigated for their performance in conjunction with the infrared hollow waveguide sampler for the detection of chlorophenols. Results indicated that poly(acrylonitrile-co-butadiene) was a most suitable hydrophobic material for absorption of chlorophenols in aqueous solutions. To further increase the detection sensitivity, factors such as sampling flow rate, sampling time, and thickness of the hydrophobic film were also investigated. Results indicated that the infrared signals were similar in the examined flow rates (2-30 mL/min), but that a higher flow rate tended to produce a higher analytical signal. Fast detection speed was an advantage of this method for the detection of chlorophenols, and the sampling/detection time can be <10 min. In addition, analytical signals were nearly proportional to the thickness of the hydrophobic film coating the inside of the hollow waveguide. With the optimal conditions found in this work, detection limits based on 3 times the peak-to-peak noise level were around 300 ppb for the chlorophenols examined. A high degree of linearity in the standard curves was also observed for this method in the concentration range of 10-100 ppm. The typical regression coefficients were >0.994 for the chlorophenols examined.     

Adjustment of a GC automatic liquid sampler for high-performance liquid chromatography

Summary An automatic liquid sampler for high-performance liquid chromatography is described.The sampler is based on a GC-injection system from Hewlett-Packard. The HPLC sampler has a unique cleaning system, excellent reproducibility and a plug-in compatibility for sample identification and computer control for Hewlett-Packard integrators and Laboratory Data Systems.     

Development and Calibration of a Portable Air Sampler

This paper describes the development and calibration of a portable air sampler for detecting chemical vapors. The air sampler is equipped with a preconcentrator, a battery operated mini-pump, a three-way valve, capacitive sensors housed in a sensing chamber, and a data acquisition and control circuit board. The preconcentrator is used to adsorb trace level chemicals and to thermally desorb them into the sensing chamber. The air sampler was calibrated using known concentrations of ethylbenzene vapor generated by an Environics gas mixing system. The air sampler was also tested using low concentration toluene and ethanol vapors generated by diffusion based vapor generation device. The concentration factor of the preconcentrator was experimentally determined.     

Evaluation of a passive air sampler for measuring indoor formaldehyde.

A passive air sampler, using 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole, was evaluated for the determination of formaldehyde in indoor environments. Chromatography paper cleaned using a 3% hydrogen peroxide solution was experimentally determined as being the optimum absorption filter for the collection of formaldehyde (0.05 microg cm(-2) formaldehyde). From a linear-regression analysis between the mass of formaldehyde time-collected on a passive air sampler and the formaldehyde concentration measured by an active sampler, the sampling rate of the passive air sampler was 1.52 L h(-1). The sampling rate, determined for the passive air sampler in relation to the temperature (19 - 28 degrees C) and the relative humidity (30 - 90%), were 1.56 +/- 0.04 and 1.58 +/- 0.07 L h(-1), respectively. The relationship between the sampling rate and the air velocity was a linear-regression within the observed range. In the case of exposed samplers, the stability of the collected formaldehyde decreased with increasing storage time (decrease of ca. 25% after 22 days); but with the unexposed samplers the stability of the blank remained relatively unchanged for 7 days (decrease of ca. 37% after 22 days). The detection limits for the passive air sampler with an exposure time of 1 day and 7 days were 10.4 and 1.48 microg m(-3), respectively.     

A radiofrequency glow-discharge-time-of-flight mass spectrometer for direct analysis of glasses

A radiofrequency (rf) glow-discharge (GD) ion source coupled to a commercial on-axis time-of-flight mass spectrometer (TOFMS) has been developed for the direct analysis of non-conducting samples. Different instrumental configurations of the rf-GD source, including the optional use of a sampler cone and the possibility of allowing electrical floating of the discharge, were evaluated first with a conducting sample. Higher ion signals were obtained when the GD was electrically floating and no sampler cone was used. A homogeneous glass was then analyzed using two different rf-GD configurations—with a sampler cone and discarding the use of the sampler cone. The atomic mass spectra obtained with the TOFMS using both configurations were compared. Analyte signals were systematically higher for the latest mode which avoids the sampler cone. The analytical capability of the proposed rf-GD–TOFMS system for the analysis of thick glasses, up to 6 mm, has been investigated in terms of sensitivity, isotopic ratio accuracy, and mass-resolving power. Different homogeneous glasses (including glasses as thick as 6 mm) have been analyzed and major and minor elements were detected. Isotope ratio accuracies of about ±1% and mass resolving powers of about 700 were observed.     

Validation and modelling of a novel diffusive sampler for determining concentrations of volatile organic compounds in air

A novel diffusive sampler that combines radial and axial diffusion has been developed that improves upon existing commercially available designs. The POcket Diffusive (POD) sampler has been validated under laboratory and field conditions for the measurements of VOCs in ambient air. Laboratory tests varied sampling conditions of temperature (−30–40 C), humidity (10–80%), wind velocity (0.1–4 m s⁻¹), and concentration (0.5–50 μg m⁻³) for a number of specific VOCs. An overall uncertainty of circa 9% for the measurement of benzene is calculated for the validation tests, in compliance with the data quality objectives of the EU air quality directive 2008/50/EC. A semi-empirical diffusion model has been developed to estimate sampling rates for compounds that were not tested, and for conditions outside of tested ranges during validation. The diffusion model (and validation tests) shows a low influence of environmental conditions on the sampling rate for the POD sampler. Average reproducibility values of circa 3% are reported with overall sampling uncertainties ranging from 9% to 15%, for the whole range of tested conditions, depending on the compound. The adsorbent cartridge is compatible with existing thermal desorption systems in the market. The diffusive sampler can modify the sampling rate by changing the diffusive body within a range of different porosities. Field tests, conducted in parallel with independent quality controlled canister sampling, confirmed the ease of use and quality of VOC measurements with the POD sampler, for compounds that were, and were not, evaluated during laboratory tests.     

一种便携式有毒气体被动采样检测装置的研制

以甲醛作为目标物,提出了一种基于扩散原理的具有大面积表面暴露的快速被动采样器及快速测定装置。该采样器不要求任何辅助采样泵使用该采样器研发的快速测定装置适用于现场气体样品的采集与测定。     

Convective transport in diffusive samplers

Convective transport in diffusive samplers was determined by the loss of a dilute dye solution from these samplers while held in a water bath. The water flow in the bath was adjusted to give the same Reynolds number had the diffusive sampler been exposed to an airborne analyte at a predetermined flow velocity. By numerical analysis, estimates were made of the degree of interference of convection on sampler performance. The results indicate an enormous difference between commercial diffusive samplers with respect to the effect of convection on the transport of analyte into the sampler.     

Correlation of mass transfer rates for a diffusive sampler with air speed and incidence angle

An accurate measurement of a gas concentration in air by diffusive sampling requires knowing the sampling rate. Both the boundary layer between turbulent ambient air and the sampler and the stagnant air layer inside the sampler impose resistance to the transport of analyte into the sampler. As the boundary layer mass transfer resistance is a function of the air speed and direction of the air movement, the sampling rate also depends on these variables. By the procedure developed here, the boundary layer mass transfer resistance was accurately measured as a function of wind speed and direction, and from these data a basic correlation with dimensionless parameters describing mass transfer was obtained. Deviation of air incidence angle and speed during sampling from the calibration conditions may produce a small positive bias, probably not in excess of 10%. Random variation of incidence angle and air speed while the sampler is in use may also contribute to the variability of this sampling method.     

Determination of sodium dodecylbenzene sulfonate in ternary mixtures by curie-point pyrolysis gas chromatography coupled to multivariate analysis

Summary Multivariate analysis was used to develop a viable method for determination of sodium dodecylbenzene sulfonate (DBS) by Curie-point pyrolysis gas chromatography. The pyrograms obtained were normalized against a maximum peak area and peak height. Normalized values were used for Quantification IV, which is one of the multivariate analysis methods, to select useful values initially. Then cluster analysis was carried out using both the selected values and their deviations. This method corresponds to qualitative analysis and indicates which data-base is similar to the sample. On the basis of this data-base, calibration data-bases are chosen. Principal component analysis (PCA) was performed using the calibration data-base and a set of sample data simultaneously. The principal component scores and contribution coefficients obtained were used to construct a calibration curve from which the DBS content of the sample was calculated. The results are in fair agreement with theoretical values.     

The effect of the wind velocity on the uptake rates of various diffusive samplers

This paper examines the results of experiments carried out in an exposure chamber to determine the wind effects on the performance of various diffusive sampler types commonly used for measuring gaseous pollutants in air. The resistance to wind of six diffusive samplers, two Palmes tubes, a badge with diffusion membrane, the EMD sampler and two radial diffusive samplers for different pollutants was compared in a range of velocities from 0 to 300?cm?s^?1. For all diffusive samplers tested, an increase in uptake rate was observed with increased air velocity usually following a logarithmic function. The consequences are an underestimation in the concentration measured by the diffusive samplers for low wind velocities below 30?cm?s^?1 and conversely an overestimation from 60?cm?s^?1. The magnitude of wind effects depends on diffusive sampler type and exceeds an uptake rate variation of ±20% for the axial diffusion tubes and the EMD sampler. With regard to the characteristics of each diffusive sampler, the dependence of uptake rate on wind velocity was analysed and discussed. The radial diffusive samplers for benzene and particularly the ones having a large and thick porous membrane appear to be the most effective design to minimise the influence of air velocity on passive sampling.     

Passive sampling of ambient ozone by solid phase microextraction with on-fiber derivatization

The solid phase microextraction (SPME) device with the polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used as a passive sampler for ambient ozone. Both O-2,3,4,5,6-(pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and 1,2-di-(4-pyridyl)ethylene (DPE) were loaded onto the fiber before sampling. The SPME fiber assembly was then inserted into a PTFE tubing as a passive sampler. Known concentrations of ozone around the ambient ground level were generated by a calibrated ozone generator. Laboratory validations of the SPME passive sampler with the direct-reading ozone monitor were performed side-by-side in an exposure chamber at 25 °C. After exposures, pyriden-4-aldehyde was formed due to the reaction between DPE and ozone. Further on-fiber derivatizations between pyriden-4-aldehyde and PFBHA were followed and the derivatives, oximes, were then determined by portable gas chromatography with electron capture detector. The experimental sampling rate of the SPME ozone passive sampler was found to be 1.10 × 10⁻⁴ cm³ s⁻¹ with detection limit of 58.8 μg m⁻³ h⁻¹. Field validations with both SPME device and the direct-reading ozone monitor were also performed. The correlations between the results from both methods were found to be consistent with r = 0.9837. Compared with other methods, the current designed sampler provides a convenient and sensitive tool for the exposure assessments of ozone.     

Determination of passive-sampled sulphur dioxide in ambient air as sulphate ion by flow injection analysis with an in-line reaction column

A modified FIA method was developed for the determination of sulphur dioxide (SO(2)) in ambient air collected by a passive sampler. SO(2) was oxidized by hydrogen peroxide and determined as sulphate ion in solution. Barium-dimethylsulfoazo-III complex was used as spectrophotometric reagent. A BaSO(4)-immobilized in-line reaction column was introduced into the flow system to increase the sensitivity and reproducibility. An in-line cation exchange column was used to eliminate triethanolamine, which was used as the absorbent reagent in the passive sampler. Sulphate ions can be analyzed in the range of 0.08-10.00 mg l(-1) with the R.S.D. less than 1.6% at the rate of 15 samples h(-1). It was satisfactory to apply this method to the analysis of sulphur dioxide in ambient air and the results agreed with those obtained by ion chromatography.     

Modification of Amaya-Sugiura passive sampling spectrophotometric method of nitrogen dioxide determination in ambient air

Summary On the example of the previously tested method of nitrogen dioxide determination in ambient air two aspects of wind influence on the badge-type sampler performance were discussed: an appropriate design of the sampler eliminating any open recess over the face of the sampler and so called starvation effect i.e. decrease in the mass of analyte absorbed by the sampler at wind velocities below 20 cm/s. The wind effect on the performance of the passive sampler has been diminished from about 150% to maximum 20%.     

The evaluation of a tenax GR diffusive sampler for the determination of benzene and other volatile aromatics in outdoor air

The applicability of a tube-type diffusive sampler as an environmental monitor for benzene, toluene, ethylbenzene and xylene (BTEX) is reported. Uptake rates have been experimentally determined for a novel type adsorbent, Tenax GR, and compared to theoretical values. It is shown, that the uptake rates are virtually independent of environmental parameters within the experimental conditions studied. The response of the sampler to transient changes in concentrations has been determined in the laboratory. It is found that the sampler is capable of following an extreme concentration profile. Field comparisons with pumped samplers have been performed and good agreement is observed between the results of the two independent methods. The samplers have also been applied as environmental monitors at different locations.