Identification of Gas-phase Pyrolysis Products in a Prescribed Fire: 
Seminal Detections Using Infrared Spectroscopy for Naphthalene, Methyl Nitrite, Allene, Acrolein and Acetaldehyde

Scharko, Nicole K.; Oeck, Ashley M.; Tonkyn, Russell G.; Baker, Stephen P.; Lincoln, Emily; Shu‐Chien, Alexander Chong; Corcoran, Bonni M.; Burke, Gloria M.; Weise, David R.; Myers, Tanya L.; Banach, Catherine A.; Johnson, Tim

doi:10.5194/amt-2018-346

Cited by 3 publications

(4 citation statements)

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“…One obvious instance is when performing remote standoff sensing where it is not the peak width of the condensed-phase analytes that may limit the sensitivity, but rather the linewidths of the gas-phase atmospheric interferents. 31,32,38 Most of the common interferents are small molecules (e.g., CO 2 , H 2 O) and have very narrow rotational-vibrational lines. Using higher resolution to better subtract or compensate for the lines as well as avoiding optical saturation is important.…”

Section: Discussionmentioning

confidence: 99%

“…Almost all the spectra were obtained from pure liquids (except for the aqueous solutions) or, in the case of solids, pure chemicals diluted in KBr pellets. Some of the spectra have been reported previously, some in open literature publications 4,30,[37][38][39][40] and/or as part of publicly available datasets, 1,5,37,41,42 adaptable to multiple experimental designs. The one common factor is that all of the data were acquired at high spectral resolution, i.e., 2.0 cm −1 for all samples.…”

Section: Pnnl Spectral Librariesmentioning

confidence: 99%

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Optimal Spectral Resolution for Infrared Studies of Solids and Liquids

Forland,

Hughey,

Wilhelm

et al. 2024

Appl Spectrosc

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Due to a legacy originating in the limited capability of early computers, the spectroscopic resolution used in Fourier transform infrared spectroscopy and other systems has largely been implemented using only powers of two for more than 50 years. In this study, we investigate debunking the spectroscopic lore of, e.g., using only 2, 4, 8, or 16 cm−1 resolution and determine the optimal resolution in terms of both (i) a desired signal-to-noise ratio and (ii) efficient use of acquisition time. The study is facilitated by the availability of solids and liquids reference spectral data recorded at 2.0 cm−1 resolution and is based on an examination in the 4000–400 cm−1 range of 61 liquids and 70 solids spectra, with a total analysis of 4237 peaks, each of which was also examined for being singlet/multiplet in nature. Of the 1765 liquid bands examined, only 27 had widths <5 cm−1. Of the 2472 solid bands examined, only 39 peaks have widths <5 cm−1. For both the liquid and solid bands, a skewed distribution of peak widths was observed: For liquids, the mean peak width was 24.7 cm−1 but the median peak width was 13.7 cm−1, and, similarly, for solids, the mean peak width was 22.2 cm−1 but the median peak width was 11.2 cm−1. While recognizing other studies may differ in scope and limiting the analysis to only room temperature data, we have found that a resolution to resolve 95% of all bands is 5.7 cm−1 for liquids and 5.3 cm−1 for solids; such a resolution would capture the native linewidth (not accounting for instrumental broadening) for 95% of all the solids and liquid bands, respectively. After decades of measuring liquids and solids at 4, 8, or 16 cm−1 resolution, we suggest that, when accounting only for intrinsic linewidths, an optimized resolution of 6.0 cm−1 will capture 91% of all condensed-phase bands, i.e., broadening of only 9% of the narrowest of bands, but yielding a large gain in signal-to-noise with minimal loss of specificity.

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Section: Discussionmentioning

confidence: 99%

Section: Pnnl Spectral Librariesmentioning

confidence: 99%

Optimal Spectral Resolution for Infrared Studies of Solids and Liquids

Forland,

Hughey,

Wilhelm

et al. 2024

Appl Spectrosc

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“…(Burling et al, 2010;Burling et al, 2011;Akagi et al, 2013;Akagi et al, 2014). Additionally, the program has been used for ground-based solar FTIR measurements (Griffith et al, 2003). "…”

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confidence: 99%

Responses to Referee 1

Johnson¹

2019

Preprint

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“…Referee Comments: Line 258 Figure 3 and accompanying text: The inclusion of naphthalene in the fit has not only improved the fit in the wavenumber range of the naphthalene peak (785 -775 cm-1) but also in the 770 -760 cm-1 range. While a minor point, it is probably worth commenting that the fitting process will result in poorer values for other species without all the contributors to the spectrum being included, as the intensities of those other components are distorted to try to compensate for the missing emission measurements, and it is defined as the change in the mixing ratio of the target compound relative to the change in mixing ratio of the reference species, generally either carbon monoxide or carbon dioxide (Urbanski et al, 2008). Here, carbon monoxide is used as the reference species since the present study focuses on pyrolysis, and prior fire studies generally provide emission ratios relative to carbon monoxide, which makes it a convenient quantity for comparison."…”

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confidence: 99%

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Johnson¹

2019

Preprint

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Referee Comments: Overall this paper presents a useful extension of FTIR analysis for VOCs in samples taken from challenging environments. The paper is well written and requires few, if any, typographical corrections. However, I do have some suggestions that I believe would increase the readability and utility of the paper. The term "Seminal Detections" is correct but, unfortunately, the term is much more commonly associated C1 AMTD Interactive commentPrinter-friendly version Discussion paper with seminal fluid detection and may reduce the "searchability" of the paper. Perhaps "First Detections" could be used in the title and in equivalent places within the body of the manuscript.Author Comments: We thank the referee for the constructive suggestions to improve the readability, utility and "searchability" of the paper. The term "seminal" has been replaced with "first" in the title and throughout the manuscript.Referee Comments: Lines 16/17 (first sentence in abstract): split into two sentences at the semicolon.Author Comments: Lines 16/17 have been corrected as suggested.Referee Comments: Line 29 "significantly": in a measurement and analysis paper the term "significantly" should be retained for use only in the statistical context. While clear enough here, it is best to avoid it and use, perhaps, "profoundly", "strongly", etc.Author Comments: The term "significantly" has been replaced with "profoundly" in the line 29. Referee Comments: Line 31 "however, prescribed ...": "however" implies "in contrast to", but this sentence seems more to be about additional sources of VOCs. Perhaps "Additionally, prescribed..." Author Comments: The term "however" has been replaced with "additionally" in the line 31.Referee Comments: Line 55 "thermal decomposition (pyrolysis)": the technical definition of pyrolysis seems to be something like physical and chemical transformation induced by high temperature INERT atmosphere (absence of oxygen). I am not sure that wildfire processes meet that definition. Perhaps the authors can expand upon this section slightly to make it clear that this is actually pyrolysis and not simply emission due to pressure increases (gas expansion), vapourisation, etc.

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Identification of Gas-phase Pyrolysis Products in a Prescribed Fire: Seminal Detections Using Infrared Spectroscopy for Naphthalene, Methyl Nitrite, Allene, Acrolein and Acetaldehyde

Cited by 3 publications

References 79 publications

Optimal Spectral Resolution for Infrared Studies of Solids and Liquids

Optimal Spectral Resolution for Infrared Studies of Solids and Liquids

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