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Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents

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Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents TECHNICAL PAPER ISSN 1047-3289 J. Air & Waste Manage. Assoc. 56:1503–1517 Copyright 2006 Air & Waste Management Association Ozone Artifacts and Carbonyl Measurements Using Tenax GR, Tenax TA, Carbopack B, and Carbopack X Adsorbents Jae Hwan Lee Samsung Co. Ltd., Chungcheongnam-do, Korea Stuart A. Batterman, Chunrong Jia, and Sergei Chernyak School of Public Health, University of Michigan, Ann Arbor, MI ABSTRACT 23% for Tenax GR, 101 Ϯ 24% for Carbopack B, and 79 Ϯ Four popular thermally desorbable adsorbents used for air 25% (91 Ϯ 9% for n-aldehydes) for Carbopack X. Ben- sampling (Tenax TA, Tenax GR, Carbopack B, and Car- zeneacetaldehyde recovery was notably poorer (22–63% bopack X) are examined for the potential to form artifacts across the four adsorbents). MDLs for several compounds with ozone (O3) at environmental concentrations. The were relatively high, up to 5 ng. By accounting for both performance of these adsorbents for the ketone and alde- artifact formation and method performance, this work hyde species identified as O3-adsorbent artifacts was also helps to identify which carbonyl compounds can be mea- characterized, including recovery, linearity, and method sured using thermally desorbable adsorbents and which detection limits (MDLs). Using gas chromatography/mass may be prone to bias because of the formation of O3- spectrometry, 13 different artifacts were identified and adsorbent artifacts. confirmed for both Tenax TA and Tenax GR, 9 for Car- bopack B, but none for Carbopack X. Several O3 artifacts not reported previously were identified, including: pen- INTRODUCTION tanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, Sampling of airborne volatile organic compounds (VOCs) and heptanal with Tenax TA; pentanal, 3-hexanone, using thermally desorbable solid adsorbents has proven 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and its usefulness in many environmental applications and 1-octene and 1-nonene with Carbopack B. Levels of has become a routine technique1 with compelling advan- straight-chain aldehyde artifacts rapidly diminished after tages over canisters, especially when a large sample vol- ume or sample transport is needed.2 Many adsorbents are a few cycles of adsorbent conditioning/O3 exposure, and concentrations could be predicted using a first-order available, and users are faced with the difficulty of select- model. Phenyl-substituted carbonyl artifacts (benzalde- ing materials appropriate for specific applications.3 The hyde and acetophenone) persisted on Tenax TA and GR ideal adsorbent would have the following characteristics: even after 10 O3 exposure-conditioning cycles. O3 break- (1) efficient adsorption and desorption of target com- through through the adsorbent bed was most rapid in pounds, potentially including very volatile, semivolatile, adsorbents that yielded the highest levels of artifacts. polar, and nonpolar compounds; (2) thermal stability; (3) Overall, artifact composition and concentration are low background levels of contaminants; (4) unaffected by shown to depend on O3 concentration and dose, condi- storage; (5) capable of sampling at very low concentra- tioning method, and adsorbent type and age. Calibrations tions; (6) uninfluenced by humidity4; (7) high capacity showed good linearity, and most compounds had reason- and breakthrough volume; (8) limited back diffusion able recoveries, for example, 90 Ϯ 15% for Tenax TA, 97 Ϯ losses (especially important for passive and low-flow sam- pling); (9) minimal water uptake; (10) longevity, allowing numerous conditioning/sampling/desorption cycles; and IMPLICATIONS (11) minimal adsorbent-oxidant reactions that yield arti- The formation of artifacts in air sampling can lead to biases, facts. No single adsorbent fulfils all of these requirements especially for carbonyl compounds that may be both and, increasingly, multisorbent tubes are used. formed and destroyed by reactions between O and adsor- 3 Air constituents like ozone (O ) and nitrogen oxides bents Tenax TA, Tenax GR, and Carbopack B. No positive 3 (NOx) can react with the adsorbent bed and analytes to O3-adsorbent artifacts were identified with Carbopack X, although this adsorbent had poorer recoveries of carbonyls form unwanted artifacts that can cause positive artifacts, (other than n-aldehydes) and higher detection limits than whereas reactions with previously adsorbed compounds the three other adsorbents. Concentrations of several arti- on the surface of the adsorbent can cause negative bias- fact compounds will diminish with repeated adsorbent use; es.3,5–8 The most recognized and significant interference 5 however, other compounds can be persistent. Thermally occurs because of reactions with O3. Although a number desorbable adsorbents can be used to measure carbonyls, of positive artifacts have been documented,9–12 the liter- although methods may require refinement to address sen- ature is limited and qualitative, and identifications of sitivity and artifact issues. many suspected artifacts have not been confirmed. The importance of artifact formation is likely to increase as Volume 56 November 2006 Journal of the Air & Waste Management Association 1503 Lee, Batterman, Jia, and Chernyak Table 1. Characteristics of the adsorbent materials in this study. Surface Density Maximum (Adsorbent Material Mesh Size (m2 g؊1) Temperature (؇C Tenax GR 2,6-Diphenyl-p-phenyleneoxide 60/80 24 375 with 23% graphitized carbon Tenax TA 2,6-Diphenyl-p-phenyleneoxide 60/80 35 375 Carbopack B Graphitized carbon black 60/80 100 Ͻ400 Carbopack X Graphitized carbon black 60/80 240 Ͻ400 method detection limits (MDLs) improve and as the num- retention.19 Tenax GR has a higher density (0.55 g mLϪ1) ber of polar compounds targeted as analytes grows. than Tenax TA (0.25 g mLϪ1) because of its graphite This work characterizes O3-adsorbent artifacts for content and a somewhat larger retention volume for very four popular adsorbents (Tenax GR, Tenax TA, Carbopack volatile compounds.20 On the other hand, higher back- B, and Carbopack X) using well-controlled laboratory ground has been claimed for Tenax GR than Tenax TA.18 tests. A quantitative assessment of artifacts is provided Currently, Tenax GR appears to be the most commonly using certified calibration standards and gas chromatog- used solid adsorbent for thermal desorption of air samples. raphy (GC)/mass spectrometry (MS) analysis, evaluating Artifact formation with Tenax has been studied or aging effects that result from repeated O exposure, and 16,21–24 3 reported for exposures to O3, nitrogen dioxide exploring some of the potentially causative mechanisms. 16,22,24 16,24 (NO2), nitrogen oxide (NO), sulfur dioxide, hy- Two relatively new materials are evaluated: Carbopack B, drogen peroxide,24 OH radical,24 limonene oxidation which has not been tested previously for O artifacts, and 22,24 3 products (with O3 and NO2), and halogens (Cl2 and Carbopack X, which has been examined recently by 25 Br2). Table 2 summarizes the O3-Tenax artifacts identi- 7 McClenny et al. O3 breakthrough curves developed for fied in the literature. Phenyl-substituted carbonyl com- the four adsorbents provide new information that helps pounds, especially benzaldehyde, acetophenone, benzo- to explain artifact formation. To quantify the artifacts, phenone, and benzeneacetaldehyde (Figure 1), have been analytical methods (including calibrations, MDLs, and reported as the principal O3-Tenax artifacts. Additional absorbent recoveries) were developed for the 15 carbonyls artifacts identified include phenol, benzonitrile, C9- and identified as O3-adsorbent artifacts and for each of the C10-aldehydes, and compounds tentatively identified as four adsorbents. 10 “alkylated phenols.” Using relatively large O3 doses (20 Lat50ppband2Lat1000 ppb), Klenø et al.24 identified BACKGROUND 16 the largest number of O3-Tenax artifacts. Pellizzari et al. Adsorbents used for thermal desorption can be classified noted that O3-Tenax GC artifacts decreased as adsorbents into polymers, graphitized carbon blacks (GCBs), carbon aged, for example, benzaldehyde declined from 670 to 65 molecular sieves, the carbon skeletal framework remain- ng and acetophenone from 300 to 20 ng from the first to ing after pyrolysis of a polymeric precursor, and other the fifth exposure cycle. NO2 exposure formed 2,6-diphe- materials. In this paper, two polymeric materials and two nyl-p-benzoquinone and 2,6-diphenyl-p-hydroquinone; GCB materials are evaluated. Characteristics of these ad- the latter compound was also found in the simultaneous sorbents are shown in Table 1. 22 presence of O3 and limonene. No significant differences between the two versions of Tenax have been reported.10 Polymer/Tenax Adsorbents However, the presence of graphite enhanced the decom- Tenax GC was the first adsorbent used for VOC analysis position of certain compounds, especially terpenes.26 with thermal desorption.13 This porous polymer is based Tenax GR was also associated with the catalytic break- on 2,6-diphenyl-p-phenylene oxide, a low bleed material down of some microbially related VOCs, for example, originally used as a GC column packing. Problems recog- 2-methylisoborneol, geosmin, and 1-octen-3-ol.4 Clausen nized with Tenax GC when used for air sampling include and Wolkoff22 have suggested that one artifact, phenyl- 14 a rather high background and chemical decomposition maleic anhydride, might be a good indicator of exposure in the presence of oxidants, such as O3 and NOx, that can of Tenax TA to O . 15,16 3 produce VOC artifacts. Often, however, no O3 arti-
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