Development and field evaluation of a new diffusive sampler for Hydrogen Sulphide in the ambient air

A diffusive sampler for the determination of hydrogen sulphide (H₂S) based on collection on a paper filter coated with silver nitrate followed by optical densitometric determination of the metal sulphide was developed. Laboratory tests were conducted in controlled atmosphere to evaluate linearity, uptake rate, face velocity effects, sample stability, influence of relative humidity and of interferents, precision and accuracy. The measured uptake rate for H₂S was determined in experiments involving sampling at different concentration levels in comparison to a wet standard colorimetric technique. The precision of the measurements for co-located passive samplers was lower than 15%. The accuracy of the data collected is within 20% of the actual value measured by the wet method. The sampler is capable of reliable measurements of H₂S at common levels of a polluted atmosphere in urban settings yielding average concentration levels over one month and beyond. Diffusive sampling can be adopted to analyse in detail the temporal and spatial trends of H₂S concentration in ambient air and in specific historic buildings or in museums. Figure At the end of sampling cap #2 is removed and optical density is measured     

Laboratory and field measurements of a badge type passive sampler for the determination of ambient sulfur dioxide concentrations

The performance of a badge type passive sampler for the determination of sulfur dioxide is described. The trapping agent is triethanolamine. Analysis is performed by ion chromatography. Thus, the method allows the simultaneous detection of sulfur dioxide and nitrogen dioxide. The sampler was tested in the laboratory and in the field. The intercomparison with independent methods in the field showed very good agreement against two active sampling methods. Regression analyses (the results of the passive sampler always represent the y-axes) gave r² = 0.81 and k = 1.07 ± 0.01 for the intercomparison with an annular denuder technique and r² = 0.92 and k = 0.96 ± 0.01 for the intercomparison with a commercial fluorescence sulfur dioxide analyzer. The average reproducibility in the field was 7% (RSD). The detection limit was 0.18 μg SO₂/m³ for an exposure time of two weeks. Received: 9 February 1998 / Revised: 22 June 1998 / Accepted: 26 June 1998     

Laboratory and field measurements of a badge type passive sampler for the determination of ambient sulfur dioxide concentrations

The performance of a badge type passive sampler for the determination of sulfur dioxide is described. The trapping agent is triethanolamine. Analysis is performed by ion chromatography. Thus, the method allows the simultaneous detection of sulfur dioxide and nitrogen dioxide. The sampler was tested in the laboratory and in the field. The intercomparison with independent methods in the field showed very good agreement against two active sampling methods. Regression analyses (the results of the passive sampler always represent the y-axes) gave r² = 0.81 and k = 1.07 ± 0.01 for the intercomparison with an annular denuder technique and r² = 0.92 and k = 0.96 ± 0.01 for the intercomparison with a commercial fluorescence sulfur dioxide analyzer. The average reproducibility in the field was 7% (RSD). The detection limit was 0.18 μg SO₂/m³ for an exposure time of two weeks. Received: 9 February 1998 / Revised: 22 June 1998 / Accepted: 26 June 1998     

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.     

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.     

Validation of the Willems badge diffusive sampler for nitrogen dioxide determinations in occupational environments

The Willems badge, a diffusive sampler for nitrogen dioxide, has previously been validated for ambient air measurements. This paper describes the laboratory and field validation of the Willems badge for personal sampling under working environment conditions. The mean sampling rate in the laboratory tests was 46 ml min(-1), with an RSD of 12%. No statistically significant effects on sampling rate of the sampling time, concentration of NO2 or relative humidity were found. A slightly decreased sampling rate was observed at low wind velocity. This was also confirmed during static sampling, which makes the sampler less appropriate for static sampling indoors. No back diffusion was observed. Storage of the samplers for two weeks before or after exposure did not affect the sampling rate. Our analysis is based on a modified colorimetric method, performed by FIA (flow injection analysis). This technique was compared to ion chromatography analysis. The use of ion chromatography lowered the detection limit from 11 to 2 microg m(-3) for an 8 h sample, and furthermore enabled the detection of other anions. In conclusion, the diffusive sampler was found to perform well for personal measurements in industrial environments.     

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.     

Development of a new passive sampler based on diffusive milligel beads for copper analysis in water

A new passive sampler was designed and characterized for the determination of free copper ion (Cu²⁺) concentration in aqueous solution. Each sampling device was composed of a set of about 30 diffusive milligel (DMG) beads. Milligel beads with incorporated cation exchange resin (Chelex) particles were synthetized using an adapted droplet-based millifluidic process. Beads were assumed to be prolate spheroids, with a diameter of 1.6 mm and an anisotropic factor of 1.4. The milligel was controlled in chemical composition of hydrogel (monomer, cross-linker, initiator and Chelex concentration) and characterized in pore size. Two types of sampling devices were developed containing 7.5% and 15% of Chelex, respectively, and 6 nm pore size. The kinetic curves obtained demonstrated the accumulation of copper in the DMG according to the process described in the literature as absorption (and/or adsorption) and release following the Fick's first law of diffusion. For their use in water monitoring, the typical physico-chemical characteristics of the samplers, i.e. the mass-transfer coefficient (k₀) and the sampler-water partition coefficient (K_sw), were determined based on a static exposure design. In order to determine the copper concentration in the samplers after their exposure, a method using DMG bead digestion combined to Inductively Coupled Plasma – Atomic Emission Spectrometry (ICP-AES) analysis was developed and optimized. The DMG devices proved to be capable to absorb free copper ions from an aqueous solution, which could be accurately quantified with a mean recovery of 99% and a repeatability of 7% (mean relative uncertainty).     

Fluorimetric determination of nitrogen oxides in the air by a novel red-region fluorescent reagent

A sensitive fluorimetric method for the determination of nitrogen oxides (NO(x): NO+NO(2)) in air is described. Nitrogen dioxide (nitrogen monoxide was previously converted to nitrogen dioxide in oxide tubes) was aspirated through a fritted glass bubble at a flow rate of 500 ml min(-1) for 120 min and fixed as nitrite, using 0.1 N NaOH as a trapping solution with the empirical absorption efficiency 0.74 and the stoichiometric factor 0.5. The method is based on the fluorescence quenching of a red-region fluorescent reagent, tetra-substituted amino aluminum phthalocyanine (TAAlPc), after being diazotized by nitrite. Under optimal conditions the linear range of the calibration curve for nitrite is 1-40 ng ml(-1) (NO(2) 0.24-9.6 ppb, v/v). The detection limit is 0.34 ng ml(-1) for nitrite (NO(2) 0.08 ppb, v/v) and the relative standard deviation for six replicate measurements of 15 ng ml(-1) nitrite is 3.2%. The method has been applied to the determination of nitrogen oxides in the air with satisfactory results. Typical gaseous co-pollutants such as SO(2), H(2)S and HCHO did not interference the determination.     

Production of nitrogen oxides in a positive column of a glow-type discharge in air flow

This paper deals with the investigations of a low-current glow-type discharge in air flow as applied to the problem of nitrogen oxide production. The electrode configurations correspond to the classical coaxial plasmatron and to the so-called gliding arc. The discharge burns in a regime of constricted positive column with a typical current density from 47 to 120 A/cm² and with the related electron density from 0.53?10¹⁴ to 2.3?10¹⁴ 1/cm³. The gas temperature changes from 3000 to 3610 K. The described conditions provide a flow of NO molecules from the plasma column with the energetic cost for production of one molecule of (30–50) eV. Maximum content of NO molecules [NO]?=?4 g/m³ (3500 ppm) was obtained. In spite of a rather high gas temperature, the plasma is still nonequilibrium. The high vibrational levels of the nitrogen molecules are populated, and the main channel of the nitric oxide production is associated with the reaction in which the vibrationally excited nitrogen interacts with atomic oxygen.

     

Laboratory and field evaluation of diffusive gradient in thin films (DGT) for monitoring levels of dissolved mercury in natural river water

The diffusive gradient in the thin films (DGT) technique was tested to measure dissolved mercury (Hg) both in laboratory aqueous solutions and in situ in river water. For this purpose, a commercial ready-to-use and specific-for-Hg DGT device was used. Each sampler consisted of a filter membrane-agarose gel as the diffusive layer and a Spheron-Thiol resin in polyacrylamide gel as the binding agent. Basic performance assays at the laboratory with this type of DGT unit confirmed the applicability of Fick's first law for DGT measurements. The diffusion coefficient of MeHg in the agarose diffusive gel was 8.50?×?10^?6?cm² s^?1 at 25°C. Several field studies were also carried out in two different rivers of the Ebro River basin (NE Spain) affected by Hg wastes released by the chlor-alkali industry. Hg concentrations determined by DGT were generally much lower than the results obtained through direct measurements of the river water. In addition, the results of a time series experiment also performed in the field show that the amount of Hg accumulated in the resin does not increase at all with the exposure time. This may be explained by the underestimation of the truly dissolved Hg fraction due to the formation of a biofilm layer on the surface of the samplers, thus clogging the filter and preventing Hg species from diffusing through it. Consequently, it was demonstrated that the DGT technique presents important limitations for measuring Hg in polluted rivers characterised by a high biomass load (eutrophic), whereas its performance was demonstrated to be correct in oligotrophic waters.     

A specific spectrophotometric determination of ozone in air in the presence of sulfur dioxide and nitrogen oxides

A sensitive, specific spectrophotometric method for the determination of ozone in air by the ozonolysis of 1,1-di-phenylethylene (DPE) is described. The yield of formaldehyde from the ozonolysis of several terminal olefins was determined, and DPE was found to give the highest yield, 90%. The method was checked against the EPA iodimetric method, and gives a consistent yield of formaldehyde over the ozone range 0.05–5.00 μg g^-1 of air. As sulfur dioxide is used as a reagent, its presence in air does not interfere. Interference by nitrogen oxides and other free radical oxidants is prevented by the addition of mesitol (2,4,6-trimethylphenol). Formaldehyde in air interferes, but can be determined by using the method with DPE omitted from the sampling train, and so accounted for. In the procedure, formaldehyde is determined by the reverse of the West—Gaeke method for sulfur dioxide.     

A new fluorescence method for determination of ozone in ambient air

A new simple method for determination of ozone in ambient air is presented. The reaction employed is based on the known ozonolysis of indigo dye. The indigotrisulfonate molecule contains one carbon–carbon double bond (C═C), which reacts with ozone and generates isatinsulfonates and sulfoanthranilate. The quantitatively formed sulfoanthranilate presents fluorescence (λ_ex 245 nm, λ_em 400 nm). Ozone was collected using two cellulose filters coated with 40 μL of 1.0 × 10^{− 3} mol L^{− 1} of indigotrisulfonate. The analytical response was linear in the range 0–150 ppbv ozone, and a detection limit of 7 ppbv was achieved using a sampling time of 15 min and an optimum sampling air flow rate of 0.4 L min^{− 1}. There was no interference from sulfur dioxide, formaldehyde or nitrogen dioxide. The ozonolysis mechanism and the reaction products are discussed.     

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%.     

Sorption of nitrogen oxides in a nonporous crystal

The uptake of various nitrogen oxides was studied with the well known nonporous p-tert-butylcalix[4]arene under ambient conditions.     

Fullerenes-extracted soot: a new adsorbent for collecting volatile organic compounds in ambient air

Fullerenes-extracted soot (FES) is the by-product of fullerenes production. Retention characteristics at different temperatures for 17 volatile organic compounds (VOCs) on FES are measured. The adsorption and desorption efficiencies for VOCs on FES adsorbent tubes range from 40.8 to 117%, most of them being 100+/-20%. The values are compared with Tenax GR, an adsorbent commonly used in environmental analysis. FES can be used as an adsorbent of low cost to collect VOCs in environmental samples.     

Determination of small quantities of nitrogen oxides in air by ion chromatography using a chromatomembrane cell for preconcentration

Chromatomembrane (CM) cells operate in computer-aided FIA systems as unique manifolds for extraction and preconcentration procedures. By coupling with ion chromatography an instrumentation was obtained allowing sample preparation and detection of nitrogen oxides in air in a quick and automated way. The aim of this paper is to study the absorption of acid components from air inside the new devices.     

Determination of small quantities of nitrogen oxides in air by ion chromatography using a chromatomembrane cell for preconcentration

Chromatomembrane (CM) cells operate in computer-aided FIA systems as unique manifolds for extraction and preconcentration procedures. By coupling with ion chromatography an instrumentation was obtained allowing sample preparation and detection of nitrogen oxides in air in a quick and automated way. The aim of this paper is to study the absorption of acid components from air inside the new devices. Received: 11 September 1997 / Revised: 12 November 1997 / Accepted: 16 November 1997