Pyrolysis/GC/MS as a Method to Rapidly Profile Pyrotechnic Formulations for Objectionable Gaseous Emissions

Dilger, Jonathan M.; Miklaszewski, Eric J.; Papenmeier, Douglas M.; Thoreson, Kelly M.; Fedick, Patrick W.; Coleman, Jessica E.; Bohrer, Brian C.

doi:10.1021/acssuschemeng.8b04342

Cited by 5 publications

(6 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Pyro‐GC/MS was performed for comparison with the AI‐MS methods. Following the procedures found in Dilger et al, 23 GC/MS measurements of pyrolyzed samples were performed via a Pyroprobe 2000 (CDS Analytical, Inc., Oxford, PA) connected in‐line to a Finnigan PolarisQ GC/MSn ion trap mass spectrometer (Thermo Fisher Scientific, Waltham, MA). The quartz fire tube was placed within the pyrolysis probe and then was inserted into a chamber filled with helium carrier gas.…”

Section: Methodsmentioning

confidence: 99%

“…Mass spectrometry (MS) is one of the most prominent molecular identification instrumental techniques due to its sensitivity, specificity, and selectivity 18–20 . Pyrolysis gas chromatography mass spectrometry (Pyro‐GC/MS) is a current method utilized to characterize the side products and chemical reactions occurring when functioning a pyrotechnic 21–24 . This method easily identifies the chemical species in the pyrotechnic composition with any side products that are generated from deploying the devices 25 .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

From the laboratory to the field: Chemical analysis of colored smoke pyrotechnic formulations via mass spectrometry techniques

et al. 2023

Self Cite

View full text Add to dashboard Cite

Smoke dyes are complex molecular systems that have the potential to form many molecular derivatives and fragments when deployed. The chemical analysis of smoke samples is challenging due to the adiabatic temperature of the pyrotechnic combustion and the molecular complexity of the physically dispersed reaction products. Presented here is the characterization of the reaction byproducts of a simulant Mk124 smoke signal on a multigram scale, which contain the dye disperse red 9 (1-(methylamino)anthraquinone), by ambient ionization mass spectrometry. Our previous work has examined the thermal decomposition of a simplified smoke system consisting of disperse red 9, potassium chlorate, and sucrose by anaerobic pyrolysis gas chromatography mass spectrometry performed at the laboratory milligram scale. The results from the lab scale test were compared with a fully functioned Mk124 in the field. To achieve this, Mk124 smokes were functioned in the presence of sampling swabs that collected byproduct residues from the smoke plume in the ambient environment. These swabs were then analyzed using ambient ionization mass spectrometry to identify the expended pyrotechnic residues, with particular interest in halogenated species. Previous work determined the toxicity of unforeseen byproducts identified on the laboratory scale, which were also detected in the field demonstrating the correlation of the laboratory testing to the fielded systems. By understanding the chemical composition of smokes and their reaction products, potential toxicity effects can be easily assessed, leading to safer formulations with improved performance. These results can help assess how smoke byproducts may impact Warfighter performance, personnel health, and the environment.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

From the laboratory to the field: Chemical analysis of colored smoke pyrotechnic formulations via mass spectrometry techniques

et al. 2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…In comparison to pyrolysis-GC-MS approaches, 55 TD-pyro-DART-MS yields simplified mass spectra and shorter analysis times, whereas pyrolysis-GC-MS generates multiple MS peaks and relies on spectral libraries for analyte identification in complex matrices. 55,56 The extent to which PFAS-laden materials are incinerated is inadequately documented. Comprehensive characterization of thermal decomposition byproducts is limited due to the lack of standardized measurement protocols, which precludes our understanding of subsequent emissions under operational settings.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Thermal desorption–pyrolysis–direct analysis in real time–mass spectrometry (TD-pyro-DART-MS) , is a robust high-throughput ambient ionization technique for semiquantifying products of pyrolysis and incomplete combustion (PICs) under ambient conditions with few to no sample preparation requirements. , Rapid profiling of PFAS and their pyrolysis products on the TD-pyro-DART-MS platform enables soft ionization and characterization based on the differential volatilities of the constituents in the heated sample. In comparison to pyrolysis-GC-MS approaches, TD-pyro-DART-MS yields simplified mass spectra and shorter analysis times, whereas pyrolysis-GC-MS generates multiple MS peaks and relies on spectral libraries for analyte identification in complex matrices. , …”

Section: Introductionmentioning

confidence: 99%

“…53,54 Rapid profiling of PFAS and their pyrolysis products on the TD-pyro-DART-MS platform enables soft ionization and characterization based on the differential volatilities of the constituents in the heated sample. In comparison to pyrolysis-GC-MS approaches, 55 TD-pyro-DART-MS yields simplified mass spectra and shorter analysis times, whereas pyrolysis-GC-MS generates multiple MS peaks and relies on spectral libraries for analyte identification in complex matrices. 55,56 The extent to which PFAS-laden materials are incinerated is inadequately documented.…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Molecular Characterization of the Thermal Degradation of Per- and Polyfluoroalkyl Substances in Aqueous Film-Forming Foams via Temperature-Programmed Thermal Desorption–Pyrolysis–Direct Analysis in Real Time–Mass Spectrometry

West

Brown

Fedick

2023

Environ. Sci. Technol. Lett.

Self Cite

View full text Add to dashboard Cite

The release of aqueous film-forming foam (AFFF), containing per-and polyfluoroalkyl substances (PFAS), from Department of Defense activities has received attention over the years due to the environmental persistence and bioaccumulation of PFAS. As a result, the National Defense Act established that the removal of PFAS-containing waste is critical. Thermal destruction methods are commonly used techniques, yet the fate of degraded PFAS remains poorly understood. In this study, we employ thermal desorption−pyrolysis−direct analysis in real time−mass spectrometry (TD-pyro-DART-MS) to characterize products of pyrolysis and determine the extent of degradation from 25 to 600 °C. PFAS ranging from 4−14 carbon atoms were monitored in situ, followed by legacy AFFF. Headgroup scission was observed, followed by carbon−carbon bond cleavages in the structures resulting in [C x F y ] − fragments differing by -CF 2 (50 Da) and -C 2 F 4 (100 Da). High-molecular weight PFAS resulted in more detectable pyrolytic fragments than low-molecular weight counterparts. AFFF concentrate thermal degradation analysis was more complex and was determined to require higher-resolution mass spectrometers for molecular assignment. This study demonstrates the development of a robust analytical methodology for in situ characterization of the products of thermal degradation of PFAS related to thermal remediation or when PFAS are used to extinguish fuel fires.

show abstract

Determination of Particulate Matter Emission Factors of Common Pyrotechnic Articles

Keller

Schragen

2021

Propellants Explo Pyrotec

View full text Add to dashboard Cite

The measurement of particulate matter (TSP, PM 10, and PM 2.5 ) emitted by pyrotechnic articles is described. For this purpose, pyrotechnic articles for entertainment purposes of category F2 (i. e. consumer fireworks according to European legislation) are examined exemplarily. The aim was to determine reliable emission factors (EF). Different types of pyrotechnic articles were used to obtain a more representative database. Commonly used analytical methods, like impactor technology, are accompanied by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy to obtain a better insight into the nature of the emissions. Specific emission factors are determined for each pyrotechnic article. In the absence of activity rates, an average specific emission factor can be used to assess emission inventories. The average emission factors for investigated articles are 253 g PM 10 per kg net explosive content (NEC) and 200 g PM 2.5 per kg NEC. The highest emission is found for a battery of shot tubes, the lowest emission of particulate matter is found for a fountain-like pyrotechnic article. Furthermore, the hypothesis is assessed whether it makes a difference to determine emission data based on pyrotechnic mixtures or pyrotechnic articles. It is demonstrated that the combustion of pyrotechnic articles generates a higher amount of particulate matter than the combustion of pyrotechnic mixtures.

show abstract

Pyrolysis/GC/MS as a Method to Rapidly Profile Pyrotechnic Formulations for Objectionable Gaseous Emissions

Cited by 5 publications

References 35 publications

From the laboratory to the field: Chemical analysis of colored smoke pyrotechnic formulations via mass spectrometry techniques

From the laboratory to the field: Chemical analysis of colored smoke pyrotechnic formulations via mass spectrometry techniques

Molecular Characterization of the Thermal Degradation of Per- and Polyfluoroalkyl Substances in Aqueous Film-Forming Foams via Temperature-Programmed Thermal Desorption–Pyrolysis–Direct Analysis in Real Time–Mass Spectrometry

Determination of Particulate Matter Emission Factors of Common Pyrotechnic Articles

Contact Info

Product

Resources

About