Optimal design of diffusive samplers

Some commercially available diffusive samplers use two layers of adsorbent placed in series. After sampling is completed, the time weighted average concentration of analyte is estimated from the weighted sum of the uptake of analyte on these two layers. It is known that such a division into layers can increase the permissible sampling time. Here the principles underlying this sampling procedure are analyzed through a fundamental application of the theory of diffusion. Using a trial and error procedure, the optimal division of adsorbent was calculated, and the increase in sampling time that such a division can give was confirmed theoretically. Also, should the uptake in the backup layer exceed a predetermined fraction of the total uptake, this will indicate misuse of the diffusive sampler.     

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.     

Theoretical approach to non-constant uptake rates for tube-type diffusive samplers

A simple theoretical model was developed for evaluating the validity of the simplified uptake model of diffusive sampling. In the model based on the plate theory diffusion to the adsorbent surface, phase equilibrium of the adsorbate and mass transport in the adsorbent bed were considered. It was found that in the early stage of sampling, the rate of sampling is close to its theoretical value. As sampling progresses, the concentration increases and the mass transfer front gradually moves into the adsorbent layer. Above a certain threshold limit, the mass uptake becomes a steady state process in which the diffusion in the air gap and the mass transport in the adsorbent bed are balanced. As uptake is a cumulative process, sampling should continue long enough to render the effects of these initial changes negligible. That is why constant uptake rates can still be obtained above a critical exposure dose. This critical exposure dose should be exceeded both in the determination of uptake rates and outdoor measurements, to obtain consistent and reliable analytical data. Evaluation of the time and concentration dependence of uptake rate in laboratory experiments and the time dependence of uptake rate in filed test was performed to justify the model results. Since the determination of uptake rates always takes places in the laboratory, where the exposure time is much shorter and the concentration is much higher than in the environment, the uptake rates are thus overestimated by 10-30%. Therefore, the uptake rates should be determined in the field under ambient conditions by means of an independent reference method.     

Badge-type diffusive sampler using 3-methyl-2-benzothiazolinone hydrazone for measuring formaldehyde in indoor air.

The evaluation of a badge-type diffusive sampler for measuring formaldehyde using 3-methyl-2-benzothiazolinone hydrazone (MBTH) was investigated. On average, the formaldehyde concentration in blanks was reduced by approximately 31% by cleaning procedures. The cleaning techniques did not significantly differ in effectiveness. The maximum sampling rate was 22.4 +/- 3.5 mL min(-1) at MBTH concentrations of 0.05%. The formaldehyde concentration in blanks did not appreciably increase over a period of about 1 month at room temperature, and was 0.36 +/- 0.03 microg, with a relative standard deviation of 8%. The diffusive sampler had good precision and accuracy for measuring formaldehyde in indoor environments. For a 24-h exposure time, the limits of detection and quantification calculated with the field blanks were 9.7 and 13.8 ppb, respectively. The minimum exposure times were calculated based on the measured and calculated limits of quantification, the sampling rate, and the atmospheric formaldehyde concentration. The capacity of the diffusive sampler with 0.5% MBTH was 3 ppm h(-1), approximately 1.5-times the capacity when the MBTH concentrations were 0.05%.     

Determination of indoor air quality of a phytosanitary plant

Effective fermentation monitoring is a growing need due to the rapid pace of change in the wine industry, which calls for fast methods providing real time information in order to assure the quality of the final product. The objective of this work is to investigate the potential of non-destructive techniques associated with chemometric data analysis, to monitor time-related changes that occur during red wine fermentation. Eight micro-fermentation trials conducted in the Valtellina region (Northern Italy) during the 2009 vintage, were monitored by a FT-NIR and a FT-IR spectrometer and by an electronic nose and tongue. The spectroscopic technique was used to investigate molecular changes, while electronic nose and electronic tongue evaluated the evolution of the aroma and taste profile during the must-wine fermentation. Must-wine samples were also analysed by traditional chemical methods in order to determine sugars (glucose and fructose) consumption and alcohol (ethanol and glycerol) production. Principal Component Analysis was applied to spectral, electronic nose and electronic tongue data, as an exploratory tool, to uncover molecular, aroma and taste modifications during the fermentation process. Furthermore, the chemical data and the PC1 scores from spectral, electronic nose and electronic tongue data were modelled as a function of time to identify critical points during fermentation. The results showed that NIR and MIR spectroscopies are useful to investigate molecular changes involved in wine fermentation while electronic nose and electronic tongue can be applied to detect the evolution of taste and aroma profile. Moreover, as demonstrated through the modeling of NIR, MIR, electronic nose and electronic tongue data, these non destructive methods are suitable for the monitoring of must-wine fermentation giving crucial information about the quality of the final product in agreement with chemical parameters. Although in this study the measurements were carried out in off-line mode, in future these non destructive techniques could be valid and simple tools, able to provide in-time information about the fermentation process and to assure the quality of wine.     

Application of solid-phase microextraction to monitoring indoor air quality

Practical application of Solid-Phase Microextraction (SPME) for the assessment of the quality of indoor air is presented. SPME was used to sample selected organic pollutants (carbon tetrachloride, benzene, toluene, chlorobenzene, p-xylene and n-decane). An SPME fiber was coated with a 100 μm film of polydimethylsiloxane. The analytes extracted were analysed with a gas chromatograph directly coupled with a mass spectrometer (GC-MS). The method was used to assess the indoor air quality in a few selected flats. The concentrations ranged from below detection limits to 6.9 mg/m³ for benzene depending on the flat; they were relatively high for newly built or freshly renovated flats. Received: 14 July 1998 / Revised: 17 November 1998 / Accepted: 21 November 1998     

Monitoring the air quality around an oil refinery through the use of diffusive sampling

Diffusive sampling has been used to study the spatial distribution of SO₂, NO₂, NO_x, NH₃ and BTX (benzene, toluene and xylenes) near an oil refinery located in Falconara, Italy, over the period from March to October 2001. Three different categories of sampling sites (roadside, residential and background) were studied. In total, 56 sites were monitored. The results were evaluated on the basis of the limit values found in the European Directives. The results of the defined study indicate that the measured concentrations were substantially lower than the ambient air quality standard with the maximum concentrations being generally found much closer to emission sources. The monitoring method described here can be used to assess integrated concentration levels over long periods of time and to identify pollution hotspots where concentrations are likely to be consistently high. Identification of these hotspots may help to assess air quality and to implement proper action plans, especially in locations where industrial and urban pollution coexist.     

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     

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.     

Air monitoring of volatile aromatic compounds by means of long-term exposure diffusive samplers

Results obtained by using "Analyst", a long-term diffusive sampler, in some monitoring campaigns, performed for the determination of benzene and the volatile aromatic pollutants, in five cities of the Italian Umbria Region and at the city of Forlì, are presented and discussed. First results of an inter comparison between the "Analyst" and "radial-type" diffusive samplers, carried out by the Regional Agency for the Ambient Protection (ARPA) of Forlì, point out substantial advantages with the long-time sampling devices.     

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.     

Monitoring of tropospheric ozone in the ambient air with passive samplers

Two sampling campaigns in suburban places in the north zone of Santa Clara city, Cuba, have been carried out on a weekly base with the use of Radiello passive diffusion tubes in order to monitor the tropospheric ozone (O₃) levels in 2010. The first campaign was scheduled from February to April (cold season) and the second one in August and October (warm season), both of them at two sampling sites, i.e., Farm and School of Art Instructors. After aqueous extraction, the samples were analyzed by UV–VIS spectrophotometry.A seasonal trend was observed with the maximum O₃ concentrations in the cold season and the minimum levels in the warm season. Samples collected during the cold season showed the highest O₃ levels. Higher levels were reached at the Farm site with average values of about 58 ± 12 μg/m³, which exceeded the limit of the Cuban Standard 99:1999. In the warm season, the O₃ concentrations were similar for both sites, but lower than those observed in the cold season. The overall, seasonal average value was found to be 24 μg/m³. Despite the higher weekly average temperatures in August, the O₃ concentrations during this month showed the lowest values of the whole sampling period, which finding is in agreement with that reported by the Meteorological Institute of Cuba.Mathematical models, based on the Cochrane-Orcutt algorithm, were fitted to the acquired data set to explain the change in the tropospheric ozone concentrations under various meteorological conditions during the two campaigns. The correlation coefficients for both the cold and the warm seasons demonstrated a strong correlation, i.e., 0.779 and 0.951, respectively. The high correlation of wind speed in the model from the first sampling campaign explains the sharp decrease in O₃ concentrations at the SAI sampling site from the sixth week of sampling.     

Laboratory development and field evaluation of a new diffusive sampler to collect nitrogen oxides in the ambient air

Diffusive samplers for the determination of NO(x) and NO2 based on collection on a coated carbon paper filter have been developed. NO is first oxidized to NO2 and then collected on the reactive surface. When NO2 and NOx samplers are exposed simultaneously, NO can be calculated by difference. The sampler has been derived from a Palmes design as recently modified by Bertoni et al. for the determination of BTX (benzene, toluene, xylenes). Laboratory tests were conducted in controlled atmosphere to evaluate linearity, uptake rate, face velocity effects, sample stability, influence of relative humidity, precision and accuracy. The samplers are capable of reliable measurements of the two species at common levels of a polluted atmosphere in urban settings yielding average concentration levels over 1 month and beyond.The uptake rate of NO2 was found to be 11.7 mL/min in a very good agreement (within 5%) with the value calculated from theory. The measured uptake rate for NO(x) was determined in experiments involving sampling at different concentration levels in comparison to chemiluminescence (CL) measurements. The precision of the measurements for co-located passive samplers was better than 5%. The accuracy of the data collected is within +/-20% of the actual value measured by CL. The laboratory and field results show that the NO(x) and NO2 samplers meet the data quality goal requested by the first EU Directive 1999/30/EU for these pollutants.     

Remote sensing measurements for evaluation of air quality in an urban area

The Differential Optical Absorption Spectrometry (DOAS) is a remote-sensing technique finding greater consents in these last years. The analytical principle of the DOAS system is based on the light absorption in the near-UV and Vis regions of those pollutants with fine vibrational structures such as SO2, NO2, O3, nitrous acid, formaldehyde, benzene, toluene, etc.. The relationship among the adsorbed light intensity and the xompound concentrations is ruled by the Lambert-Beer's law. The DOAS analysis allows to study and to interpretate the complex mechanisms of the formation and transformation of the pollutants and particularly of those of secondary origin. In this paper we have reported and discussed the behaviors of NO2, O3, HNO2, formaldehyde, benzene and toluene measured by this system during the 2000--2003 period in the Rome area (an area highly influenced by anthropogenic sources) and in Pietracupa (Molise) area (considered as remote site). The results show how the DOAS system highlight very well the secondary pollution evolution; this, described by the profiles of NO2 and O3 being at the same time products and precursors of the photochemical smog, is not influenced by the emission flow intensity and consequently assumes homogeneous values in the whole urban area.     

Modelling of toluene solid-phase microextraction for indoor air sampling

Solid-phase microextraction (SPME) is a convenient and efficient sampling technique recently applied to indoor air analysis. We propose here a theoretical model of the adsorption kinetics of toluene on SPME fibre under static extraction conditions. We discuss the effects of sampling volume and initial concentration of analyte on the adsorption kinetics. This model is used to estimate the limits of detection taking into account operating conditions and to calculate theoretical calibration curves. Results of comparison with experimental data are encouraging: only 11% difference for calibration curves and 30% for the estimation of the limit of detection. On the basis of this kinetics model, the solid concentration gradient in the Carboxen coating was modelled with Fick’s second law of diffusion in unsteady-state mass-transfer mode. Mass diffusion from the gas sample to the SPME fibre was also investigated. It was shown that diffusion is the limiting step of the mass-transfer process in the static mode. Thus, the model developed, allows a better understanding of adsorption on Carboxen fibre and in the future could be a useful tool for cheap and time-saving development of SPME methods and the estimation of sampling performance. Figure PDMS/Carboxen SPME fibre (scanning electron microscopy – magnification x 220)     

The trapping of indoor air contaminants

The removal of indoor air contaminants by reactivity with air filters coated with reagents has been found to be effective for aldehydes, acidic and basic vapours as well as isocyanates Coatings of polymeric amines were used for formaldehyde trapping as well as for the removal of acidic vapours and for the removal of isocyanates. The addition of glycerol as a plasticizer for the coating can also be an effective reagent.     

The use of leaves of Rosmarinus officinalis L. as samplers for polycyclic aromatic hydrocarbons. Assessment of air quality in the area of Palermo

The quantitative analysis of polycyclic aromatic hydrocarbons (PAHs) in vegetables and animals allows us to evaluate the quality of air, in a determined geographic area, without the need of making long samplers with complicate instrumentation. In this work, Rosmarinus officinalis leaves have been used as passive samplers. In particular, this plant was chosen because it is widespread in the Mediterranean area and it is commonly found both in the metropolitan and in the peripheral areas of the city of Palermo. Results for the concentration of total polycylic aromatic hydrocarbons (the sum of the 22 compounds) and the PAHs distribution in leaves from Rosmarinus officinalis are presented. Purified extracts were analyzed by GC-MS.