Semivolatile Organic Compounds In Air Research Articles

Green methodology based on active air sampling followed by solid phase microextraction and gas chromatography-tandem mass spectrometry analysis to determine hazardous substances in different environments related to tire rubber

A fast, efficient, and simple air sampling methodology was developed to study a high number of volatile and semivolatile organic compounds in air above tire rubber materials and surfaces made of recycled tire rubber. The proposed method, based on active sampling (solid-phase extraction, SPE) using a small quantity of sorbent material (25 mg) followed by solid-phase microextraction (SPME) and gas chromatography-tandem mass spectrometry analysis, was developed with the aim of determining 40 organics substances including polycyclic aromatic hydrocarbons (PAHs), plasticizers, antioxidants, and vulcanization agents. An experimental design was carried out to study the influence of main factors such as type of SPME fibre, solvent addition, headspace volume, stirring, as well as the factor interactions. Method performance showed good linearity in a broad concentration range (0.05 to 200 ng m−3, for most compounds), with coefficients of determination (R2) higher than 0.9900. Whole method precision (≤ 16 %) and accuracy were also satisfactory, obtaining quantitative recoveries (mean values between 80 and 110 % in most cases). Limits of detection and quantification have also been calculated, yielding values of sub ng m−3 for most compounds. The validated method was applied to outdoor and indoor air environments including playgrounds, football pitches and warehouses showing the presence of most target compounds in the samples achieving high levels for some PAHs (concentrations up to 51 ng m−3), benzothiazole (BTZ), diisobutyl- dibutyl- and di-(2-ethylhexyl)- phthalate, among others, reaching concentrations up to hundreds of ng m−3 (BTZ). This is the first time that the combination of techniques SPE and SPME is applied for these families of chemicals, and it is also the first time that this approach is proposed for the simultaneous multiclass compound extraction of substances of different chemical families. The whole sampling and extraction procedure is performed in a short period of time (61 min) allowing high throughput. The elimination of the use of organic solvents and waste generation by using only 25 mg of sorbent and a SPME fibre than are both reused makes the method sustainable and in consonance with the principles of the green chemistry. The method can be implemented in any routine lab and easily automated using a SPME autosampler.

Global intercomparison of polyurethane foam passive air samplers evaluating sources of variability in SVOC measurements

Polyurethane foam passive air samplers (PUF-PAS) are the most common type of passive air sampler used for a range of semi-volatile organic compounds (SVOCs), including regulated persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs), and emerging contaminants (e.g., novel flame retardants, phthalates, current-use pesticides). Data from PUF-PAS are key indicators of effectiveness of global regulatory actions on SVOCs, such as the Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants. While most PUF-PAS use similar double-dome metal shielding, there is no standardized dome size, shape, or deployment configuration, with many different PUF-PAS designs used in regional and global monitoring. Yet, no information is available on the comparability of data from studies using different PUF-PAS designs. We brought together 12 types of PUF-PAS used by different research groups around the world and deployed them in a multi-part intercomparison to evaluate the variability in reported concentrations introduced by different elements of PAS monitoring. PUF-PAS were deployed for 3 months in outdoor air in Kjeller, Norway in 2015–2016 in three phases to capture (1) the influence of sampler design on data comparability, (2) the influence of analytical variability when samplers are analyzed at different laboratories, and (3) the overall variability in global monitoring data introduced by differences in sampler configurations and analytical methods. Results indicate that while differences in sampler design (in particular, the spacing between the upper and lower sampler bowls) account for up to 50 % differences in masses collected by samplers, the variability introduced by analysis in different laboratories far exceeds this amount, resulting in differences spanning orders of magnitude for POPs and PAHs. The high level of variability due to analysis in different laboratories indicates that current SVOC air sampling data (i.e., not just for PUF-PAS but likely also for active air sampling) are not directly comparable between laboratories/monitoring programs. To support on-going efforts to mobilize more SVOC data to contribute to effectiveness evaluation, intercalibration exercises to account for uncertainties in air sampling, repeated at regular intervals, must be established to ensure analytical comparability and avoid biases in global-scale assessments of SVOCs in air caused by differences in laboratory performance.

Predicting the rate constants of semivolatile organic compounds with hydroxyl radicals and ozone in indoor air

Semivolatile organic compounds (SVOCs) in air can react with hydroxyl radicals (OH), nitrate radicals (NO3) and ozone (O3). Two questions regarding SVOC reactivity with OH, NO3 and O3 in the gas and particle phases remain to be addressed: according to the existing measurements in the literature, which are the most reactive SVOCs in air, and how can the SVOC reactivity in the gas and particle phases be predicted? In the present study, a literature review of the second-order rate constant (k) was carried out to determine the SVOC reactivity with OH, NO3 and O3 in the gas and particle phases in ambient and indoor air at room temperature. Measured k values were available in the literature for 90 polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphates, dioxins, di(2-ethylhexyl)phthalate (DEHP) and pesticides including pyrifenox, carbamates and terbuthylazine. PAHs and organophosphates were found to be more reactive than dioxins and PCBs. Based on the obtained data, quantitative structure-activity relationship (QSAR) models were developed to predict the k value using quantum chemical, molecular, physical property and environmental descriptors. Eight linear and nonlinear statistical models were employed, including regression models, bagging, random forest and gradient boosting. QSAR models were developed for SVOC/OH reactions in the gas and particle phases and SVOC/O3 reactions in the particle phase. Models for SVOC/NO3 and SVOC/O3 reactions in the gas phase could not be developed due to the lack of measured k values for model training. The least absolute shrinkage and selection operator (LASSO) regression and random forest models were identified as the most effective models for SVOC reactivity prediction according to a comparison of model performance metrics.

A needle trap device method for sampling and analysis of semi-volatile organic compounds in air

Semi-volatile organic compounds (SVOCs), such as phthalates, organophosphates, and polybrominated diphenyl ethers, are emerging as an important class of pollutants that are of serious health concerns. Determining concentrations of these pollutants is of great importance for environmental and exposure studies. In this work, a needle trap device (NTD) method was developed to measure the concentration of SVOCs in air samples. Sorbents were packed in the NTD to capture SVOCs with the aid of a sampling pump. NTD operational parameters, such as desorption temperature, desorption time, and sampling flow rate, were optimized for the target SVOCs. The limit of detection for air sampling by the NTD method ranged between 5 pg and 1 ng, depending on the SVOC compound. The variations in terms of NTD repeatability and reproducibility were lower than 14% for all cases. In addition, the influence of other experimental parameters, such as sampling temperature and humidity, breakthrough volume, NTD storage time, as well as carryover effect were examined. Finally, NTDs were used to determine emissions of gas-phase SVOCs from various consumer products in an emission cell and to collect total airborne SVOC samples (gas and particle phases) in an office. The results of NTD method were in an agreement with data obtained by conventional active sampling methods using Tenax® sorbent tubes and polyurethane foam samplers, but with improvements of relative standard deviation, sensitivity, and sampling time. The results demonstrated that the NTD method is a simple, sensitive, effective, reusable, and inexpensive technique for sampling and analyzing SVOCs in the concentration range from 2 ng m−3 to 100 μg m−3 in air.

Uncertainties in monitoring of SVOCs in air caused by within-sampler degradation during active and passive air sampling

Degradation of semivolatile organic compounds (SVOCs) occurs naturally in ambient air due to reactions with reactive trace gases (e.g., ozone, NOx). During air sampling there is also the possibility for degradation of SVOCs within the air sampler, leading to underestimates of ambient air concentrations. We investigated the possibility of this sampling artifact in commonly used active and passive air samplers for seven classes of SVOCs, including persistent organic pollutants (POPs) typically covered by air monitoring programs, as well as SVOCs of emerging concern. Two active air samplers were used, one equipped with an ozone denuder and one without, to compare relative differences in mass of collected compounds. Two sets of passive samplers were also deployed to determine the influence of degradation during longer deployment times in passive sampling. In active air samplers, comparison of the two sampling configurations suggested degradation of particle-bound polycyclic aromatic hydrocarbons (PAHs), with concentrations up to 2× higher in the denuder-equipped sampler, while halogenated POPs did not have clear evidence of degradation. In contrast, more polar, reactive compounds (e.g., organophosphate esters and current use pesticides) had evidence of losses in the sampler with denuder. This may be caused by the denuder itself, suggesting sampling bias for these compounds can be created when typical air sampling apparatuses are adapted to limit degradation. Passive air samplers recorded up to 4× higher concentrations when deployed for shorter consecutive sampling periods, suggesting that within-sampler degradation may also be relevant in passive air monitoring programs.

Atmospheric gas-particle partitioning versus gaseous/particle-bound deposition of SVOCs: Why they are not equivalent

Semi-volatile organic compounds (SVOCs) can be particle-bound or in the gas phase in the atmosphere, depending on the (temperature dependent) gas-particle partitioning of the chemicals and the fraction of particles in air. Several studies linked gas-particle partitioning of SVOCs in the atmosphere directly to the gaseous/particle-bound deposition of these chemicals, i.e. in cases of compounds occurring mainly in the gas phase, the deposition was also assumed to be mainly in gaseous form. In this study, we apply a multi-media fate model to point out that gas-particle partitioning of SVOCs in air and gaseous/particle-bound deposition of SVOCs are driven by different mechanism and, thus, cannot be deduced from each other. We apply our calculations to polychlorinated biphenyls (PCBs), as model SVOCs. We show that the fraction of particle-bound deposition to deciduous forest is 1.5–190 times higher in winter and between 5 and 1000 times higher in summer than the particle-bound fraction of these chemicals in air. The fraction of particle-bound deposition to coniferous forest is 1.5–172 times higher in winter and between 5 and 1000 times higher in summer than the particle-bound fraction of PCBs in air. In addition to the fractions of particle-bound SVOCs in air and particle-bound deposition, we recalculated particle-bound and gaseous deposition velocities to coniferous and deciduous forest for PCBs. The deposition velocities obtained for dry gaseous deposition (<1 m/h) are much lower than the existing values in the literature (10–200 m/h) because earlier studies assumed that for PCBs occurring predominantly in the gas phase, interception was also completely due to dry gaseous deposition.

Influence of Sampler Configuration on the Uptake Kinetics of a Passive Air Sampler

Passive air samplers (PAS) are simple and cost-effective tools to monitor semivolatile organic compounds in air. Chemical uptake occurs by molecular diffusion from ambient air to a passive sampling medium (PSM). Previous calibration studies indicate that even for the same type of PAS, passive air sampling rates (R, m(3)(air)/d) can be highly variable due to the influence of a number of factors. Earlier studies mainly focused on factors (e.g., wind speed and temperature) influencing R via the kinetic resistance posed by the air boundary layer surrounding the PSM because that layer was deemed to be the main factor determining the uptake kinetics. Whereas recent calibration studies suggest that the PAS configuration can influence R, so far few studies have specifically focused on this factor. In this study, with the objective to understand the effect of PAS configurations on R, we applied a gravimetrical approach to study the kinetics of water vapor uptake from indoor air by silica gel placed inside cylindrical PAS of various configurations. We also conducted an indoor calibration for polychlorinated biphenyls on the same type of PAS using XAD-resin as the PSM. R was found to be proportional to the interfacial transfer area of the PSM but not the amount of the PSM because chemicals mainly accumulated in the outer layer of the PSM during the deployment time of the PAS. The sampler housing and the PSM can introduce kinetic resistance to chemical uptake as indicated by changes in R caused by positioning the PSM at different distances from the opening of the sampler housing and by using PSM of different diameters. Information gained from this study is useful for optimizing the PAS design with the objective to reduce the material and shipping costs without sacrificing sampling efficiency.

Integral assessment of pollution in the Suquía River (Córdoba, Argentina) as a contribution to lotic ecosystem restoration programs

The Suquía River lower–middle basin (Córdoba, Argentina) is subject to a strong anthropic impact because it receives pollutants from different sources (industries, wastewaters, heavy traffic, agricultural land use, etc.) We have assessed the degree of watershed degradation of Suquía River lower–middle sections through the analysis of different ecosystem compartments (air, water, riparian soil, sediments and biota), in order to provide useful data to be considered in future river restoration programs. Four study sites were selected along the river (La Calera city, Córdoba city, Corazón de María village and Río Primero city) which were sampled during the low- and high-water flow periods. We analyzed: a) chemical and physical characteristics of water, sediments, and riparian soil; b) heavy metal content of water and sediments, and c) semi-volatile organic compounds in air. Besides, pollutant bioindicators such as fish assemblages, lichens ( Usnea amblyoclada), vascular plants ( Tradescantia pallida), and microorganisms (fecal coliform and Escherichia coli) were used to further assess the status of the river. All analyzed ecological compartments were affected by water pollution, particularly, fish assemblages, sediments and riparian soils by heavy metal and coliform bacteria. Moreover, we detected a possible contribution of sulfur and a high pollutant content in air that merit further research about other air–water exchanges. Accordingly, we strongly suggest that an action to restore or remediate the anthropic effect on the Suquía River be extended to all possible compartments along the river.

GC × GC-MS HYPHENATED TECHNIQUES FOR THE ANALYSIS OF VOLATILE ORGANIC COMPOUNDS IN AIR

Comprehensive two-dimensional gas chromatography (GC × GC) and its direct applications to measurement of volatile and semivolatile organic compounds in air are reviewed and discussed. The paper includes a brief discussion of the instrumental set-up and theory for the comprehensive GC × GC hyphenated with different detection techniques. Several reviewed types of modulators demonstrate that the applications of comprehensive GC × GC are still under development, underlying the flexibility of the system as well. The fundamental differences between one-dimensional and two-dimensional gas chromatography, regarding their potential to provide both qualitative and quantitative information, are also presented. The present article focuses on reported applications dealing with the analysis of volatile and semivolatile organic compounds from air (gas and particles related), but some data related to other sample types analyzed with comprehensive GC × GC are also briefly presented. The paper supports the idea that there is a good reason for interest in comprehensive GC × GC, which seems to be a suitable technique for applications in the separation of complex mixtures of volatile and semivolatile compounds.

Field Testing a Flow-Through Sampler for Semivolatile Organic Compounds in Air

Even without access to the electrical grid, a flow-through sampler (FTS) can collect gaseous and particle-bound semivolatile organic compounds (SOCs) from large volumes of air by turning into the wind and having the wind blow through a porous sampling medium. To test its performance under field conditions, a FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were codeployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Quantitative relationships between the wind speed outside the sampler and after passage through the PUF were established and allow the accurate estimation of sampling volumes under conditions of low and high wind speed. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were quantified in the samples taken by both air samplers. Separate analysis of seven PUF disks arranged sequentially within the FTS, confirm that even relatively volatile SOCs do not experience serious break-through. Theoretical plate number analysis of the break-through curves yields an understanding of the effect of temperature and wind speed on FTS sampling efficiency, and reveals different behavior of gaseous and particle-bound-compounds on the PUF. Air concentrations of PCBs and PAHs obtained with the FTS compare favorably with those obtained by averaging the concentrations of several 24 h active high volume samples taken during the same time period.

A Flow-Through Sampler for Semivolatile Organic Compounds in Air

A widely acknowledged limitation of current passive air sampling designs for semivolatile organic chemicals is their relatively low sampling rate, severely constraining the temporal resolution that can be achieved. Addressing the need for an improved sampling design which achieves significantly faster uptake while maintaining the capability of providing quantitative information, a new sampler has been developed that provides greatly increased sampling rates by forcing the wind to blow through the sampling medium. The sampler consists of a horizontally oriented, aerodynamically shaped, stainless steel flow tube mounted on a post with ball bearings, which turns into the wind with the help of vanes. A series of polyurethane foam (PUF) discs with relatively large porosity mounted inside the flow tube serve as the sampling medium. The sampled air volume is calculated from wind speed, which is measured outside the sampler and after passage through the sampling medium using precalibrated vortex rotor and turbine anemometers mounted on top of the sampler and at the exit of the flow tube, respectively. Small battery-operated data loggers are used for data storage. Under typical wind speed conditions, the sampler can collect 100 m(3)/ day, which is approaching the sampling rates of conventional high volume samplers. Controlled experiments in the laboratory and frontal chromatography theory yield the theoretical plate number and breakthrough volumes for polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the PUF plugs and allow for the estimation of breakthrough levels for relatively volatile organic chemicals. After correction for breakthrough, the air concentration obtained with the new flow-through sampler are independent of sampling length and volume and compare favorably with those obtained from conventional pumped high volume samples.

A preliminary investigation of sorbent-impregnated filters (SIFs) as an alternative to polyurethane foam (PUF) for sampling gas-phase semivolatile organic compounds in air

Filters impregnated with XAD-4™ resin were used in a small series of high-volume air samples to compare their collection of gas-phase semivolatile toxic substances (organochlorine pesticides, OCs, and polycyclic aromatic hydrocarbons, PAHs) with that achieved by polyurethane foam (PUF). The advantages of the use of such sorbent-impregnated filters (SIFs) include a reduction in size which leads to numerous benefits. The latter include simplified sample handling, shipping and storage, and the potential for a decrease in solvent requirements for pre-cleaning and extraction. Furthermore, such SIFs could be used to measure combined particle/gas concentrations of target compounds. Gas concentrations derived from the SIFs in a filter-SIF–SIF–PUF configuration agreed well with values derived from the PUF plugs in a comparison filter-PUF configuration. The collection efficiency of a single SIF was ∼80% on average. As such, these SIFs are viewed as a promising alternative to PUF and further, more extensive study of their performance characteristics appears to be warranted.

Direct quantitative analysis of organic compounds in the gas and particle phase using a modified atmospheric pressure chemical ionization source in combination with ion trap mass spectrometry.

A slightly modified atmospheric pressure chemical ionization source is employed for direct quantitative analysis of volatile or semivolatile organic compounds in air. The method described here is based on the direct introduction of an analyte in the gas or particle phase, or both, into the ion source of a commercial ion trap mass spectrometer. For quantitation, a standard solution is directly transferred into the vaporizer unit of the ion source via a deactivated fused-silica capillary by using the sheath liquid syringe pump, which is part of the mass spectrometer. The standard addition procedure is conducted by varying the pump rate of a diluted solution of the standard compound in methanol/water. A N2 sheath gas flow is applied for optimal vaporization and mixing with the analyte gas stream. By performing detailed reagent ion monitoring experiments, it is shown that the relative signal intensity of [M + H]+ ions is dependent on the relative humidity of the analyte gas stream as well as the composition and concentration of CI reagent ions. The method is validated by a comparison of the standard addition results with a calibration test gas of known concentration. To demonstrate the potential of atmospheric pressure chemical ionization mass spectrometry as a quantitative analytical technique for on-line investigations, a tropospherically relevant reaction is carried out in a 493-L reaction chamber at atmospheric pressure and 296 K in synthetic air at 50% relative humidity. Finally, the applicability of the technique to rapidly differentiate between analytes in the gas and particle phase is demonstrated.

Single-sided membrane introduction mass spectrometry for on-line determination of semi-volatile organic compounds in air.

Construction, optimization, and testing of a novel single-sided configuration for a semi-permeable [poly(dimethylsiloxane); PDMS] membrane introduction system for mass spectrometry is described. On-line detection of semi-volatile organic compounds of environmental interest is shown, including lindane (a pesticide), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) (an explosive), butylated hydroxytoluene (BHT) (an antioxidant), 1,2-dichlorobenzene, dimethylmethyl phosphonate (DMMP) (a chemical warfare agent simulant) and naphthalene. The technique has limits of detection in the sub-ppb range. with rise times of 4 to 7 s and fall times of 12 to 36 s and a response that is linear over 4 orders of magnitude (from 0.1 ppb to 1000 ppb for DMMP). The cycle time, from crude air sampling to acquisition of results, is approximately 1 min. No sample preparation is necessary.

Direct analysis of semivolatile organic compounds in air by atmospheric pressure chemical ionization mass spectrometry.

Atmospheric pressure chemical ionization is employed for direct air analysis, without ion source modification, by using the sheath gas as the sample transport agent. A simple modification of the sheath gas inlet line allows introduction of gaseous samples into a commercial atmospheric pressure chemical ionization source. Optimization and testing of this novel air sampling method are described and detection of semivolatile compounds is shown. The analytical performance of the technique is established with methyl salicylate, including a limit of quantification of 100 pptr, a limit of detection of 50 pptr, a linear response from 100 pptr to 20 ppb, and rise and fall times of 12 and 20 s, respectively. Using reagent ion monitoring, it is shown that the protonated methanol dimer is the principal CI reagent ion leading to protonated dimethyl methylphosphonate, while the monomer is mainly responsible for protonating methyl salicylate. Since the formation of the CI reagent (methanol clusters) can be controlled by simple variation of experimental parameters, the selectivity of the method can be easily adjusted to suit the targeted analyte. Performance is found to be independent of the choice of air or nitrogen as the sheath gas (and thus as the sample matrix) and this, together with the sensitivity and speed of the technique, make it promising for field studies.

Design of continuous‐monitoring device based on membrane extraction with sorbent interface and micro‐gas chromatograph

AbstractA device for the continuous monitoring of the volatile and semivolatile organic compounds in air by membrane extraction followed by sorbent concentration and gas chromatographic separation is discussed. The device samples headspace and makes automatic injections followed by rapid separation and quantification. The main components of the system include membrane module, microtrap, and transfer line. A membrane module, microtrap, and fan are mounted in a housing, together constituting a MESI (membrane‐extraction sorbent interface) sampling unit. A heated silicosteel capillary column was used as the transfer line, avoiding adsorption and condensation of analytes and performing separation of the analytes prior to detection. The device demonstrated potential for field monitoring of aromatic hydrocarbons, chlorinated compounds, and terpenoids. © 2001 John Wiley &amp; Sons, Inc. Field Analyt Chem Technol 5: 69–74, 2001