Gas Chromatography with In Situ Catalytic Hydrogenolysis and Flame

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Gas Chromatography with In-situ Catalytic Hydrogenolysis and Flame Ionization Detection for the Direct Measurement of Formaldehyde and Acetaldehyde in Challenging Matrices Jim Luong, Xiuhan Yang, Yujuan Hua, Peilin Yang, and Ronda Gras Anal. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.analchem.8b04563 • Publication Date (Web): 09 Nov 2018 Downloaded from http://pubs.acs.org on November 13, 2018

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Analytical Chemistry

Gas Chromatography with In-situ Catalytic Hydrogenolysis and Flame Ionization Detection for the Direct Measurement of Formaldehyde and Acetaldehyde in Challenging Matrices Jim Luong1,2*, Xiuhan Yang3, Yujuan Hua1, Peilin Yang4, Ronda Gras1,2 Dow Chemical Canada ULC, Highway 15, Fort Saskatchewan, Alberta, T8L 2P4, Canada. Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag 75 Hobart 7001 Australia. 3 Dow Chemical China Investment Co., Ltd., No. 936 Zhangheng Road, Shanghai, 201203, China. 1

2 Australian

4

Dow Chemical USA, Analytical Science, Collegeville, PA 19426, USA.

ABSTRACT: A gas chromatographic strategy to advance the direct detection and quantification of volatile aliphatic aldehydes such as formaldehyde and acetaldehyde in gas phase matrices without the need for sample pre-treatment or concentration has been successfully developed. The catalytic hydrogenolysis of aldehydes to alkanes is conducted in-situ within the 3D printed steel jet assembly of the flame ionization detector and without any additional hardware required. Reliable conversion efficiencies of greater than 90% with respectable peak symmetries for the analytes were attained at 400 °C. Quantification of formaldehyde and acetaldehyde at parts-per-million level over a range of 0.5-300 ppm (v/v) for formaldehyde and 0.2-430 ppm (v/v) for acetaldehyde with a respectable precision of less than 5% RSD (n = 10) was achieved. Total analysis time is less than 10 min. Linearity with a correlation coefficient of R2 greater than 0.9997 and measured recoveries of >99% for spike tests under the specified conditions were achieved. The 3D printed steel jet assembly was found to be reliable and resilient to matrices such as air, water, hydrocarbons, and aromatics. An additional benefit realized with this analytical strategy is that the slight restriction induced by the presence of the catalyst in the 3D printed jet assembly enables backflush via the inlet split vent without the need for additional pressure control and inter-column connection devices. The utility of this technique was demonstrated with important aldehyde applications from various segments.

Volatile aliphatic aldehydes are chemicals of significance. For instance formaldehyde, the simplest form of aldehydes, is being used extensively in the production of industrial resins employed in particle board, coatings, and automotive materials [1-4]. Acetaldehyde is a feedstock for the production of acetic acid and can be used as a precursor to the formation of alkyd resins [5-8]. All of these compounds can exist either as residual reactants, impurities or undesired by-products from various processes and segments such as food and beverage, alternative feedstock, environmental, industrial hygiene, and pharmaceutical to name a few. The presence of aliphatic aldehydes is considered a ubiquitous feature of atmospheric environmental pollutants through several sources such as internal combustion engines, ozonolysis of hydrocarbons, and hydroxyl radical reactions. Given their volatility, toxicity, and widespread use, these aldehydes can also have negative impacts on human health. The emission of formaldehyde, the most prevalent aldehyde, has triggered intense concern because formaldehyde is a known irritant and it possesses the potential to react with hydrochloric acid to form bis-chloromethyl ether which is a known human carcinogen [7-10]. Acetaldehyde is classified as a Group I carcinogen by the International Agency for Research on Cancer

[11-13]. As such these compounds in various matrices require close monitoring. A variety of techniques for the measurement of highly volatile aliphatic aldehydes have been reported in the literature including high-performance liquid chromatography (HPLC), gas chromatography (GC), ion chromatography, spectrophotometry, fluorometry, piezoresistivity, amperometry, conductive measurements, and chemical sensors to name a few [14-25]. Each technique has its strengths and constraints. With an inherent advantage of the separation process, chromatography-based methods can provide more selective and accurate quantification for these aldehydes. Challenges remained for both GC and HPLC to perform direct detection, particularly for formaldehyde. As a result, an extra step involving either pre-column or post-column derivatization is usually required to improve method performance. Of the many available derivatization methods for carbonylic compounds, one of the most popular one is to react aldehydes with 2,4-dinitrophenyl hydrazine (DNPH) to form hydrazones for following HPLC-UV detection [26,27]. There are several constraints with this approach. For instance, the conversion efficiency could vary especially when there exists competitive reactions, measurement variability could be wide due to the

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multiple-step sample preparations particularly when using solid phase DNPH cartridges, and the cost of time, labour or consumables could be high. Gas chromatography is a logical choice due to the volatility of the analytes involved. While flame ionization detection (FID) can be employed effectively for the measurement of longer chain aldehydes, this detection strategy is not suitable for molecules such as formaldehyde. With formaldehyde, an insufficient amount of CHO+ ions is generated when combusted in the FID hydrogen flame, resulting in a high detection limit of more than 50 ppm (v/v) as demonstrated later in this article. Our efforts to detect low levels of formaldehyde and acetaldehyde include the use of a number of gas phase detectors such as photoionization detector (PID) equipped with an 11.7 eV lamp, helium pulsed discharge detector (He-PDD), and dielectric barrier detector (DBD) in helium mode. But these detectors were found to be either impractical or easily contaminated or difficult for in-field service [28,29]. It has been reported in the literature that under the right conditions, hydrogenolysis can be employed to convert oxygenated compounds to alkanes [30,31]. Leveraging this knowledge, we had also attempted to detect and quantify low levels of formaldehyde and acetaldehyde using post-column reaction gas chromatography with an appropriate catalyst substrate such as nickel on alumina with mixed results [32]. Here, while a reliable conversion rate of greater than 75% efficiency was achieved, the mechanical structure of the device, a 1.5-inch × ¼ inch stainless steel 304 tubular embodiment coupled to several Swagelok™ tees and union fittings, generated substantial void volume. The lack of an effective surface passivation strategy, much needed for active compounds such as formaldehyde and acetaldehyde, further exacerbated the problem. As a result, significant peak tailing was observed with an average peak width at base of more than 20 sec, making this approach not a viable solution for capillary gas chromatography. As such, there exists a critical unmet need for an effective, reliable, and accurate analytical strategy for the direct measurement of formaldehyde and acetaldehyde, particularly in gas phase matrices. Recent advances in 3D printing technology resulted in the fabrication of devices via an additive process having a geometry that is not possible by conventional means such as mechanical machining. A prototype 3D printed FID jet incorporated with a catalyst substrate suitable for hydrogenolysis was employed to advance the measurements for the analytes described. In this article, we introduce an analytical strategy for the direct measurement of formaldehyde and acetaldehyde in gas phase matrices without the need for sample pre-treatment or concentration. Hydrogenolysis of aldehydes was conducted insitu within the FID jet assembly without any additional hardware. Formaldehyde and acetaldehyde can be efficiently converted to methane and ethane respectively with an appropriate catalyst at an elevated temperature in a hydrogen atmosphere as shown in equations below: CH2O + 2H2 → CH4 + H2O [1] C2H4O + 2H2 → C2H6 + H2O [2]

We believe this is a first to report on the use of post-column reaction gas chromatography with in-situ catalytic hydrogenolysis using a 3D printed FID jet acting as a singlestage micro-reactor for the measurement of trace levels of formaldehyde and acetaldehyde in gas phase matrices. We prove that the concept for the determination of the analytes mentioned is a highly reliable and effective approach.

EXPERIMENTAL An Agilent 7890A GC (Agilent Technologies, Wilmington, USA), equipped with a split/splitless inlet operating in split mode and an FID was employed for all analyses. A prototype, 3D printed steel jet assembly printed with an appropriate catalyst was provided by Activated Research Company (Minnesota, USA). The 3D printed jet technology has recently been commercialized by Activated Research Company as the jetanizer™, part number JT-CAP-PK1 for Agilent 7890A and 7890B series FIDs. The jet provided has dimensions equivalent to those of a classical FID jet employed by the 7890A gas chromatograph with a length of 43 mm and a jet orifice of 0.29 mm. A conventional jet (Agilent) having the same physical dimensions was also employed in this study for comparison purpose. For the gas samples, one mL manual injections were conducted using a one mL Hamilton Gastight Syringe (Hamilton Company, Reno, NV, USA). To eliminate the potential of overpressurization of the inlet which could result in the sample contacting the septum or being diverted through the septum vent stream, a steady injection technique was used. For the separation of the aldehydes from other components in the various matrices, a 50 m × 0.32 mm-id × 5 µm DB-1 (Agilent) column was used. The column was connected to a 0.5 m × 0.53 mm-id ProSteel (Agilent) uncoated deactivated metal tubing with an Ultimate union (Agilent) and Siltite (Trajan Medical, Melbourne, Australia) ferrules. The carrier gas was hydrogen, at a column flow rate of 5 mL/min. A split/splitless inlet was equipped with a 4 mm ultra-inert liner, operating at 200 °C in split mode at a split ratio of 5:1. The inlet pressure was 18.7 psig at 40 °C. The FID temperature was 400 °C. The temperature of the detector block was measured and controlled by electronics on board the gas chromatograph. Hydrogen flow was at 30 mL/min and air flow at 350 mL/min. The temperature was programmed from 40 °C (2 min) to 200 °C @ 15 °C/min and maintained at 200 °C for 2 min. When backflush was conducted, the hydrogen flow rate was increased from 30 mL/min to 45 mL/min and the inlet pressure reduced to 1 psig during the duration of backflush. Data were collected with Agilent ChemStation software version B.04.03SP1. Carrier and utility gases such as nitrogen, hydrogen, and air used for system performance studies were acquired from Linde (Edmonton, Canada). A test mixture that contains 0.1% of straight-chain hydrocarbons including methane, ethane, propane, butane, pentane, and hexane was used for method development. Formaldehyde as formalin solution (37 wt % in H2O, contains 10-15% Methanol as stabilizer) and acetaldehyde were purchased from Sigma-Aldrich (Oakville, Canada). The stock standards were prepared by injecting1 µL of the analyte into a 1,000 mL nitrogen purged glass vessel (Sigma-Aldrich). The standards were heated to 50 °C to facilitate complete


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analyte evaporation and the vessel was allowed to reach equilibrium at ambient temperature for one hour prior to analysis. With this method, a standard of 298 ppm (v/v) formaldehyde in nitrogen and 433 ppm (v/v) acetaldehyde in nitrogen can be prepared. Serial dilution with nitrogen was used to generate standards for calibration and detection limit studies. Cigarette smoke was generated by igniting a cigarette with its filter removed. The cigarette was attached to a SKC pump (Eighty Four, PA, USA) with the pump outlet connected to a 100 mL Tedlar bag. Beverages were obtained from a local grocery store in Edmonton, Alberta, Canada. Immediately upon opening the cans, ten mL aliquots of each of the samples were transferred into 20 mL headspace vials. The vials were capped with Teflon-backed silicone septa/aluminum caps and allowed to equilibrate for 30 min at room temperature. One mL of the headspace of the samples was extracted and analyzed.

constant, at an average rate of 90% (+/-2%) from 375 °C to 450 °C.

RESULTS AND DISCUSSION The novelties of the strategy involve the employment of postcolumn reaction gas chromatography based on in-situ catalytic hydrogenolysis reaction within a 3D printed steel jet assembly to convert formaldehyde and acetaldehyde to methane and ethane for sensitivity enhancements. The analytical approach has the capability to conduct backflushing without additional hardware. The double-duty of the jet which acts not only as a hydrogen burner but also a single-stage micro-reactor to facilitate in-situ hydrogenolysis represents yet another novelty. The 0.5 m × 0.53 mm-id ProSteel uncoated deactivated metal tubing was used to protect the analytical column stationary phase and column external coating from being damaged by prolong exposure to a temperature at 400 oC or higher. Decomposition materials from column stationary phase and polyimide coating can compromise chromatographic performance or cause a reduction in catalyst conversion efficiency. The hydrogen and air flow rates were set at 30 mL/min and 350 mL/min respectively as per manufacturer’s recommendations to achieve optimum performance for the detector with a detection limit of 0.5 to 1 pg C/sec. With the hydrogen and air flow rate selected, the peak symmetry of formaldehyde and acetaldehyde was studied over an FID temperature range from 300 °C to 450 °C using 298 ppm (v/v) of formaldehyde and 433 ppm (v/v) of acetaldehyde in nitrogen standards. Of note, 450 °C is the maximum temperature the FID can operate under. Figure 1 shows a plot of peak width at half height (PW1/2) over the temperature range described. As can be seen from Figure 1, PW1/2 of both analytes decreases substantially with an increase in detector temperature from 300 °C to 350 °C. The peak width remains relatively constant beyond 375 °C, consistent with earlier findings for the methanation of carbon monoxide and carbon dioxide to methane using a similar device as reported earlier [33]. Under the conditions used, very respectable PW1/2 of 2.4 s and 2.7 s for formaldehyde and acetaldehyde were achieved demonstrating the compatibility of the 3D printed device with capillary gas chromatography time scale. Conversion efficiencies of formaldehyde and acetaldehyde to methane and ethane respectively were found to be relatively

Figure 1. Peak width at half height (PW½) of formaldehyde and acetaldehyde over a temperature range from 300 °C to 450 °C. Based on the results obtained, the temperature of the FID detector was set at 400 °C to attain optimum chromatography performance both in terms of conversion efficiencies and chromatographic fidelity. At 400 °C, no deleterious effect or binding of the 3D printed steel jet assembly was observed when the jet was removed from the detector base in multiple occasions. Prolonged exposure of the jet assembly at an elevated temperature can cause galling between the jet thread and the detector base assembly. Figure 2 shows an overlay of formaldehyde and acetaldehyde standard at a concentration of 298 ppm (v/v) and 433 ppm (v/v) respectively demonstrating the excellent chromatographic fidelity with peak symmetry of 0.95 and 0.98 respectively. Methanol was detected in the formaldehyde standard as it is a stabilizing agent in the formalin solution used for standard preparation.

Figure 2. Overlay of chromatograms of 298 ppm (v/v) formaldehyde and 433 ppm (v/v) acetaldehyde in nitrogen. The enhancement of responses for the analytes with the addition of catalyst was demonstrated in Figure 3. Here, a comparison of performance between the 3D printed FID jet with catalyst versus a conventional FID jet was made. Both jets operated under identical gas chromatographic and detector conditions. A 298 ppm (v/v) formaldehyde in nitrogen and a 433 ppm (v/v) acetaldehyde in nitrogen standards were employed as benchmarks. For formaldehyde, an improvement of area count



of more than 35 times was realized. This clearly demonstrated the advantage of detecting formaldehyde with the 3D printed jet. As predicted, with an increase of carbon chain length of aldehydes which resulted in an increase in CHO+ ions formation, the effect of hydrogenolysis on the gain in FID response diminished. Nevertheless, a respectable response improvement for acetaldehyde of more than 1.6 times was observed. No significant change to the response for methanol was noted. This highlights the high degree of selectivity of the catalyst employed towards enhancing the overall sensitivity of the analytes by FID.

extinguish the flame, keeps the state of the catalyst intact without altering the reducing environment, and can be employed effectively to prevent carbonation of carbon-rich molecules such as unsaturates or aromatics. With this strategy, the operation of the 3D printed jet has been performed flawlessly for more than nine months without the need for replacement or maintenance. Analytical figures of merit for this approach are quite respectable especially with the manual injection technique used. Repeatability of RSD 99% (n = 3).

Figure 3. Comparison of response for formaldehyde and acetaldehyde between FID jet with catalyst and standard FID jet. Recently, we introduced a novel approach in backflushing by taking advantage of the additional pressure drop in the jet assembly [31]. This backflush approach can be conducted without the requirement of additional hardware. The design of the FID is such that hydrogen is fed tangentially down the side of the jet with its threads partially cut out on one side while air is fed to the top of the jet to facilitate the burning of hydrogen. With the added flow restriction of the jet assembly induced by the catalyst, backflush to inlet can occur if the inlet column pressure is substantially reduced, this results in hydrogen fuel of the FID flowing towards the inlet and eventually exiting through the inlet split vent. This backflush strategy is effective in protecting and extending the longevity of the catalyst used as well as improving system cleanliness. Further, with backflushing, the oven temperature that needs to be applied to eliminate or remove higher molecular weight compounds in the matrix can be reduced. The reduction in temperature increases column stationary phase life and overall system reliability and performance. Figure 4a shows an overlay of a blended mixture of 270 ppm (v/v) formaldehyde and 100 ppm (v/v) each of a hydrocarbon homologue in nitrogen. As stated earlier, methanol is present since it is one of the components in the formalin solution used. Figure 4b shows the same standard with backflushing conducted having an FID hydrogen flow rate increases from 30 to 45 mL/min and with the inlet pressure of the column dropped to 1 psig. As can be seen in Figure 4a, without backflush, all the model compounds in the test mixture were detected. In contrast, in Figure 4b, with a backflush carried out at 3.0 min, heavier hydrocarbons such as C4 to C6 were backflushed to the inlet vent. This approach of post-column backflushing does not

Figure 4. Impact of backflushing on analytes. Overlay of model compounds with (a) no backflush, (b) with backflush at 3.0 min. The utility of the analytical strategy was demonstrated with three relevant applications: 1. Volatile organic compounds (VOC) analysis: VOC analysis is a common analysis being conducted for many applications including environmental, fugitive emission, indoor and outdoor air quality. Figure S1 shows a chromatogram of popular VOC compounds such as methane, ethane, ethylene, cyclopropane, formaldehyde, ethylene oxide, and acetaldehyde. Without derivatization, formaldehyde and acetaldehyde can easily be detected in less than 10 min. The analytical strategy helped in improving sample throughput and providing near realtime data which is critical for data-driven decision making. 2. Determination of acetaldehyde in wines: Acetaldehyde is a known by-product in the fermentation process. Acetaldehyde can have a significant influence on odour and flavour in the food/flavour/beverage industries. Figure S2 shows a headspace of a white wine sample. With polydimethylsiloxane as a stationary phase, acetaldehyde and methanol will co-elute. The identification of the peak of interest was confirmed to be acetaldehyde by GC/MS. The level of


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acetaldehyde in the headspace sample was found to be at approximately 300 ppb (v/v) demonstrating the effectiveness of the approach applied.

3.

Rapid and direct measurement of formaldehyde in cigarette smoke: Conclusive medical evidence of the negative human health effects of tobacco consumption and second-hand smoke was realized in the early 70s. Cigarette smoke is a complex chemical mixture further exacerbated by chemicals and flavouring compounds added to the process by the producers. The presence of formaldehyde is monitored closely for product quality improvement and to improve the effectiveness of cigarette filter design. Figure S3 shows a chromatogram of smoke generated by a cigarette with its filter removed. The presence of formaldehyde can easily be detected. While positive identification of the analyte would require a complementary technique such as mass spectrometry, this approach can provide high throughput screening for product optimization and improvement. CONCLUSIONS An effective analytical strategy that employs in-situ hydrogenolysis with flame ionization detection for the measurement of formaldehyde and acetaldehyde in various matrices has been developed. Catalytic hydrogenolysis was conducted in-situ within the 3D printed FID jet assembly without any additional hardware. This approach resulted in a high conversion efficiency for the analytes and chromatographic fidelity suitable for use with capillary gas chromatography. Leveraging the additional back pressure generated by the 3D printed jet assembly, a strategy of postcolumn backflushing with the detector fuel gas and without additional hardware was successfully developed to improve the reliability and throughput of the analytical system. The novelty of the technique used was successfully demonstrated with relevant formaldehyde and acetaldehyde applications in various sectors including beverage, environmental, and chemical industries.

AUTHOR INFORMATION

acknowledged for providing the prototype modified jet assembly for technology development.

REFERENCES (1) Tang, X.; Bai, Y.; Duong, A.; Smith, M. T.; Li, L.; Zhang, L. Formaldehyde in China: Production, consumption, exposure levels, and health effect Environ. Int. 2009, 35, 1210–1224. (2) Akyuz, K. C.; Nemli, G.; Baharoglu, M.; Zekhovic, E. Effects of acidity of the particles and amount of hardener on the physical and mechanical properties of particleboard composite bonded with urea formaldehyde Int. J. Adhes. Adhes. 2010, 30, 166–169. (3) Chang, C.; Lin, K. Assessment of the strategies for reducing VOCs emission from polyurea-formaldehyde resin synthetic fiber leather industry in Taiwan Resour. Conserv. Recycl. 2006, 46, 321–334. (4) Greenfield, S. A.; Dupont, J. A. Formaldehyde stabilized coating compositions, US patent 4129448A, 1973. (5) Yoneda, N.; Kusano, S.; Yasui, M.; Pujado, P.; Wilcher, S. Recent advances in processes and catalysts for the production of acetic acid Appl. Catal., A 2001, 221, 253–265. (6) Jones, J. H. The Cativa™ Process for the Manufacture of Acetic Acid Platinum Metals Rev. 2000, 44, 94–105. (7) Salthammer, T. The formaldehyde dilemma Int. J. Hyg. Environ. Health 2015, 218, 433–436 (8) Duong, A.; Steinmaus, C.; McHale, C. M.; Vaughan, C. M; Zhang, L. Reproductive and developmental toxicity of formaldehyde: a system review Mutat. Res. 2018, 728, 118–138. (9) Nurmakov, U. B.; Tagiyeva, N.; Semple, S.; Devereux, G.; Sheikh, A. Volatile organic compounds and risk of asthma and allergy: A system review Eur. Respir. Rev. 2015, 24, 92–101. (10)Liebling, T.; Kenneth, K. D.; Pastides, H.; Griffith, R. G.; Lemeshow, S. Cancer mortality among workers exposed to formaldehyde Am. J. Ind. Med. 1984, 5, 423–428. (11)Salaspuro, M. Acetaldehyde and gastric cancer J. Dig. Dis. 2011, 12, 51–59. (12)Soffritti, M.; Belpoggi, F.; Lambertin, L.; Lauriola, M.; Padovain, M.; Maltoni, C. Results of long-term experimental studies on the carcinogenicity of formaldehyde and acetaldehydes in rats Ann. N. Y. Acad. Sci. 2002, 982, 87–105. (13)Lachenmeier, D.W.; Kanteres, F.; Rehm, J. Carcinogenicity of acetaldehyde in alcoholic beverages: risk assessment outside ethanol metabolism Addiction 2009, 104, 533–550. (14)Heck, H. D’a.; White, E. L; Casanova-Schmitz, M. Determination of formaldehyde in biological tissues by gas chromatography/mass spectrometry Biomed. Mass Spectrom. 1982, 9, 347–353.

*Jim Luong, PhD, FRSC (UK) E-mail: [email protected] ORCID: 0000-0003-4120-1207 Telephone: 1-780-998-8668

(15)Rocha, F. R.; Coelho, L. H. G.; Lopes, M. L. A.; Carvalho, L. R. F.; da Silva, J. A. F.; do Lago, C. L; Gutz, I. G. R. Environmental formaldehyde analysis by active diffusive sampling with a bundle of polyethylene porous capillaries followed by capillary zone electrophoretic separation, and contactless conductivity detection Talanta 2008, 76, 271–275.

ACKNOWLEDGMENT

(16)Chung, P.; Tzeng, C.; Ke, M.; Lee, C. Formaldehyde gas sensors: A review Sensors 2013, 13, 4468–4484.

Corresponding Author

Dr. Wayde Konze, Dr. Tonya Stockman, Dr. Jim Alexander Jr., and Dr. Lotus Huang of the Dow Chemical Company are acknowledged for their support. Dr. Matthias Pursch, also of the Dow Chemical Company is acknowledged for his help in reviewing the manuscript. Professor Dr. Robert A. Shellie of the University of Tasmania, Australia is acknowledged for the fruitful discussions and his advice on 3D printing technology. Dr. Andrew Jones of Activated Research Company is

(17)Thomas, C. L. P.; McGill, C. D.; Towill, R. Determination of formaldehyde by conversion to hexahydroxazolo [3,4-a] pyridine in denuder tube with recovery by thermal desorption, and analysis by gas chromatography-mass spectrometry Analyst 1997, 122, 1471–1476. (18)Yokelson, R. J.; Goode, J. G.; Ward, D. E.; Susott, R. A.; Babbitt, R. E.; Wade, D. D.; Bertschi, I.; Griffith, D. W. T.; Hao, W. M. Emissions of formaldehyde, acetic acid, methanol, and other trace gases from biomass fires in North Carolina measured by airborne



Fourier transform infrared spectroscopy J. Geophys. Res.: Atmos. 1999, 104, 30109–30125.

cigarette smoke by high-performance liquid chromatography Analyst 1989, 114, 355–360.

(19)Avigad, G. A simple spectrophotometric determination of formaldehyde and other aldehydes: Application to periodateoxidized glycol systems Anal. Biochem. 1983, 134, 499–504.

(28)Luong, J.; Sieben, L.; de Zeeuw, J. Formaldehyde and acetaldehyde analysis in hydrocarbon matrices, M. Lee Editor, proceedings of the Nineteenth International Symposium on Capillary Chromatography and Electrophoresis, Wintergreen, Virginia, USA, May 1997.

(20)Martos, P. A.; Pawliszyn, J. Sampling and determination of formaldehyde using solid-phase microextraction with on-fiber derivatization Anal. Chem. 1998, 70, 2311–2320. (21)Velikonja, S.; Zupacic-Kralj, I. J.; Marsel, J. Comparison of gas chromatographic and spectrometric techniques for the determination of formaldehyde in water J. Chromatogr. A, 1995, 704, 449–454. (22)Mohamed, A. A.; Mubarak, A. T.; Marestani, Z. M.; Fawy, K. F. Highly sensitive and selective catalytic determination of formaldehyde and acetaldehyde Talanta 2008, 74, 578–585. (23)United States Department of Labour, OSHA, formaldehyde in workplace atmospheres, OSHA method ID-205, December 1990. (24)Swarin, S.J.; Lipari, F. Determination of formaldehyde and other aldehydes by high performance liquid chromatography with fluorescence detection, J. Liq. Chromatogr. 1983, 6, 425-444. (25)Possanzini, M., Palo, V., Determination of formaldehyde and acetaldehyde in air by HPLC with fluorescence detection Chromatographia, 1997, 5, 235-240. (26)Lipari, F.; Swarin, S. J. Determination of formaldehyde and other aldehydes in automobile exhaust with an improved 2,4dinitrophenylhydrazine method J. Chromatogr. A 1982, 247, 297– 306.

(29)Luong, J.; Gras, R.; Sun, K.; Winniford, B.; Monagle, M. Analysis of formaldehyde and acetaldehyde in ambient air with helium pulsed discharged ionization detector and dielectric barrier detector in helium mode, proceedings from Gulf Coast Conference, Galveston, Texas, USA, September 2001. (30)Wojcik, B.; Adkins, H. Hydrogenolysis of alcohols to hydrocarbons, J. Am. Chem. Soc. 1933, 55, 1293-1294. (31)Gurbuz, E. I. ; Hibbitts, D. D.; Iglesia, E. Kinetic and mechanistic assessment of alkanol/alkanal decarbonylation and deoxygenation pathways on metal catalysts, J. Am. Chem. Soc. 2015, 137, 1198411995. (32)Luong, J.; Sieben, L.; Fairhurst, M. Determination of low levels of formaldehyde and acetaldehyde by gas chromatography/flame ionization detection with a nickel catalyst J. High Resolut. Chromatogr. 1996, 19, 591–594. (33)Luong, J.; Hua, Y.; Gras, R.; Hawryluk, M. In situ methanation with flame ionization detection for the determination of carbon dioxide in various matrices Anal. Methods 2018, 10, 1275–1279.

(27)Houldgate, P. R.; Dhingra, K. S.; Nash, S. J.; Evans, W. H. Determination of formaldehyde and acetaldehyde in mainstream

For TOC only:


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Gas Chromatography with In Situ Catalytic Hydrogenolysis and Flame

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