The use of multi-channel silicone rubber traps as denuders for polycyclic aromatic hydrocarbons

Atmospheric polycyclic aromatic hydrocarbons are ubiquitous environmental pollutants, which may be present both in the gaseous phase and adsorbed onto the surface of particles. Denuders are sampling devices which have been effectively employed in such partitioning applications. Here we describe and characterise a novel miniature denuder consisting of two multi-channel silicone rubber traps (each 178 mm long, 6 mm o.d. containing 22 silicone tubes), separated by a quartz fibre filter for particle phase collection. The denuder only requires a small portable personal sampling pump to provide sampling flow rates of ∼0.5 L min⁻¹. Theoretical considerations indicated that the air flow through the denuder was expected to be laminar, and the linear velocity arising from longitudinal diffusion was found to be negligible. The calculated particle transmission efficiency through the denuder was found to be essentially 100% for particles > 50 nm, whilst the experimental overall efficiency, as determined by CPC and SMPS measurements, was 92 ± 4%. The size resolved transmission efficiency was <60% for particles below 20 nm and 100% for particles larger than 200 nm. Losses could have been due to diffusion and electrostatic effects. Semi-volatile gaseous analytes are pre-concentrated in the silicone of the trap and may be thermally desorbed using a commercially available desorber, allowing for total transfer and detection of the collected analytes by GC–MS. This enhances detection limits and allows for lower sampling flow rates and shorter sampling times, which are advantageous for studies requiring high temporal resolution.     

Trace analysis of airborne haloacetates

Haloacetates in various environmental compartments can be determined by gas chromatography-negative-ion chemical-ionization mass spectrometry after derivatization with 1-pentafluorophenyl diazoethane. Detection limits in absolute amounts per injection are between 0.01 fg (chlorodifluoroacetate) and 80 fg (monofluoroacetate). Sampling of haloacetates in urban air was performed by means of cylindrical denuders coated with alkalized glycerol. The haloacetates detected are trifluoro-, monochloro-, dichloro-, trichloro-, monobromo-, and dibromoacetate. The concentrations in ambient air fluctuate strongly, e.g. between 20 and 3000 pg/m³ for TFA. Haloacetates are also found in river waters and tree foliage. A major problem is interference from contamination with trifluoro- and trichloroacetate.     

Determination of Ammonia/Air Diffusion Coefficient Using Nafion Lined Tube

Abstract

Trace gaseous ammonia in air was removed in a laminar flow Teflon tube lined with Nafion film. The ammonia deposition pattern was obtained by sectioning the Nafion lining, extracting with an aqueous solution, and measuring the concentration with an ammonia gas electrode. Mass transport analysis of the deposition pattern demonstrated that the ammonia was removed from the air stream at a rate controlled by gaseous diffusion. The ammonia/air diffusion coefficient equalled 0.228 ± 0.012 cm² s^?1 at 1 atm 25°C. No dependence on relative humidity was observed over the range 10–92%.     

Diffusion technique for the generation of gaseous halogen standards

Halogens are known to play an important role in the tropospheric ozone-depletion chemistry and are of special interest because of their influence on the atmospheric oxidation capacity. In this paper, we investigate the application of a capillary diffusion technique for the generation of gaseous halogen standards like Br₂, IBr, ICl and I₂. The influence of capillary dimension (i.e. length and inner diameter), ambient pressure and headspace volume of the diffusion vessel on the test gas output has been evaluated. The experimental output rates are determined from the mass loss of the analyte vessel on a regular schedule and compared with their respective theoretical predictions. We also demonstrate that a 1,3,5-trimethoxybenzene-coated diffusion denuder is capable of collecting gaseous ICl quantitatively, which provides an attractive alternative for the rapid determination of the output of test gas devices. The output rates of ICl measured by the denuder method are in close agreements with the data obtained by the gravimetric method.     

Novel method for determining DDT in vapour and particulate phases within contaminated indoor air in a malaria area of South Africa

The organochlorine insecticide DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane) is still used for malaria vector control in certain areas of South Africa. The strict Stockholm Convention on Persistent Organic Pollutants (POPs) allows spraying on the inside of traditional dwellings with DDT. In rural villages contaminated dust presents an additional pathway for exposure to DDT. We present a new method for the determination of DDT in indoor air where separate vapour and particulate samples are collected in a single step with a denuder configuration of a multi-channel open tubular silicone rubber (polydimethylsiloxane (PDMS)) trap combined with a micro quartz fibre filter. The multi-channel PDMS trap section of the denuder concentrates vapour phase insecticide whereas particle associated insecticide is transferred downstream where it is collected on a micro-fibre filter followed by a second multi-channel PDMS trap to capture the blow-off from the filter. The multi-channel PDMS trap and filter combination are designed to fit a commercial thermal desorber for direct introduction of samples into a GC–MS. The technique is solvent-free. Analyte extraction and sample clean-up is not required. Two fractions, vapour phase and particulate phase p,p′-DDT, o,p′-DDT; p,p′-DDD, o,p′-DDD; p,p′-DDE and o,p′-DDE in 4 L contaminated indoor air, were each quantitatively analysed by GC–MS using isotopically labelled ring substituted ¹³C₁₂ – p,p′-DDT as an internal standard. Limits of detection were 0.07–0.35 ng m⁻³ for p,p′-DDT, o,p′-DDT, p,p′-DDD, o,p′-DDD, p,p′-DDE and o,p′-DDE. Ratios of airborne p,p′-DDD/p,p′-DDT and of o,p′-DDT/p,p′-DDT are unusual and do not match the ideal certified ingredient composition required of commercial DDT. Results suggest that the DDT products used for indoor residual spraying (IRS) prior to, and during 2007, may have been compromised with regards to insecticidal efficacy, demonstrating the power of this new environmental forensics tool.