Rapid on-site identification of hazardous organic compounds at fire scenes using person-portable gas chromatography-mass spectrometry (GC-MS)–part 2: water sampling and analysis

Figures & data

Table 1. Run-off water samples collected from controlled fires. Ten mL of run-off water was placed into each vial. Each set of four vials was collected for each controlled fire, including for the fires containing only paper and cardboard.

Vial No.	Preparation	Sample extraction method	Analysis method	Location of sampling and analysis
1	Unfiltered samples added to vial containing 2 g salt	HS-SPME	Portable GC-MS	In-field
2	Sample filtered into vial with stirrer bar	DI-SPME	Portable GC-MS	In-field
3	Sample filtered into vial with stirrer bar	DI-SPME	Benchtop GC-MS	Laboratory
4	Unfiltered sample added to empty vial	Liquid-liquid extraction	Benchtop GC-MS	Laboratory

HS-SPME: headspace sampling-solid phase microextraction sampling; GC-MS: gas chromatography-mass spectrometry; DI-SPME: direct immersion sampling-solid phase microextraction sampling.

Figure 1. Representative portable gas chromatography-mass spectrometry (GC-MS) chromatograms of water run-off samples collected after extinguishment of fires consisting of (A) background paper and cardboard (max temp. ∼600 °C), (B) particle board (max temp. ∼500 °C), (C) melamine coated particle board (max temp. ∼500 °C), (D) laminated wood (max temp. ∼600 °C), (E) carpet (max temp. ∼300 °C), (F) rubber (max temp. ∼550 °C) and (G) underlay (max temp. ∼650 °C). Samples were extracted using both headspace sampling-solid phase microextraction sampling (HS-SPME) and direct immersion sampling-solid phase microextraction sampling (DI-SPME). Chromatograms have been adjusted to the same scale for direct comparison between the two extraction methods.

Table 2. Target compound list for in-field fire run-off water sampling and analysis.

Compound name	Paper/cardboard		PB		Mel		LW		Carpet		Rubber		Underlay
	HS	DI	HS	DI	HS	DI	HS	DI	HS	DI	HS	DI	HS	DI
Trimethylamine				✔		✔		✔
Pentane [28]							✔
Methylbutadiene isomer [29]											✔
Methylbutane isomer [30, 31]	✔	✔	✔				✔	✔	✔				✔
Dimethylbutane isomer	✔	✔	✔		✔			✔				✔
Methylene chloride							✔	✔
Pentenyne												✔
Methylbutadiene isomer											✔	✔
Methybutene isomer [31]		✔	✔					✔	✔			✔
Methylpentane isomer [32]	✔		✔		✔		✔	✔	✔				✔
Methylpentane isomer	✔	✔	✔		✔		✔	✔	✔				✔	✔
Hexane [31–33]	✔	✔					✔					✔
Dimethyloctane isomer				✔		✔		✔		✔				✔
Methylfuran isomer						✔		✔
Unknown 1		✔		✔		✔	✔	✔		✔		✔	✔	✔
Hexane			✔		✔		✔		✔				✔
Methyloctene isomer	✔				✔				✔				✔
Methylpentanol isomer	✔					✔	✔	✔						✔
Tetrahydrofuran			✔
Butanol [29]			✔				✔	✔
Benzene [28–38]	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔
Dimethylcyclopentane isomer	✔								✔
Chloromethylbutane isomer	✔	✔	✔
Trimethylpentane isomer [32]	✔	✔	✔		✔		✔	✔	✔				✔
Ethyldimethylpentane isomer	✔	✔			✔		✔	✔	✔				✔
Heptane [31]	✔	✔	✔		✔		✔	✔	✔				✔
Dimethylfuran isomer [29]	✔			✔		✔
Trimethylpentane isomer	✔						✔		✔
Methylpentanone isomer											✔
Methylpyrrole isomer				✔		✔
Trimethylpentane isomer	✔				✔		✔		✔
Dimethylbutane isomer	✔		✔
Methylhexanal isomer	✔						✔		✔
Trimethylpentene isomer	✔				✔		✔						✔
Toluene [28, 29, 31–40]	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔
Butanone [29]	✔		✔		✔		✔		✔				✔
Hexanal [29]						✔
Unknown 2						✔
Furfural [29, 35, 41, 42]		✔		✔		✔				✔		✔
Unknown 3											✔
Ethylbenzene [29, 35, 36, 38, 40]	✔		✔	✔	✔	✔	✔	✔	✔		✔	✔	✔	✔
Xylene isomer [28–31, 36, 40]		✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔	✔
Phenylethyne [29, 40]											✔	✔
Styrene [29, 32, 34, 35, 37, 40]		✔		✔		✔	✔	✔			✔	✔		✔
Xylene isomer	✔	✔	✔	✔	✔	✔	✔	✔	✔		✔	✔	✔
Cyclohexanone [42]												✔
Unknown 4				✔		✔								✔
ɑ-Pinene [29]				✔
Ethylhexanal isomer										✔
Trimethylbenzene isomer [36]		✔	✔	✔	✔		✔	✔	✔		✔		✔	✔
Unknown 5											✔
Trimethylbenzene isomer			✔	✔	✔				✔				✔
Methylfurancarboxyaldehyde isomer [40]										✔
Unknown 6				✔
Benzaldehyde [29, 40]		✔		✔		✔		✔		✔
Camphene [29]											✔	✔
Propylbenzene isomer [40]			✔	✔	✔				✔				✔
Phenol [29, 34, 35, 37]												✔
Aniline											✔	✔
Benzonitrile [29, 38, 40]										✔				✔
Trimethylbenzene isomer		✔	✔		✔		✔	✔	✔				✔	✔
Unknown 7											✔
Unknown 8								✔
Methylethylheptane isomer										✔
Trimethylbenzene isomer					✔				✔
Limonene [29, 36]			✔
Dimethylpyrrole isomer								✔
β-Pinene		✔						✔				✔
Unknown 9											✔
Methylphenol isomer										✔
Indene [29, 36, 37, 40]										✔		✔	✔
Unknown 10											✔
Acetophenone [29, 40]										✔
Methylbenzaldehyde isomer														✔
Methylphenol isomer										✔		✔
Methylbenzaldehyde isomer													✔	✔
Unknown 11											✔
Methoxyphenol isomer [29, 40, 42]				✔		✔				✔
Dimethylphenol isomer				✔						✔
Methylindene isomer										✔
Dimethylphenol isomer				✔
Methoxymethylbenzene isomer				✔
Unknown 12												✔
Unknown 13														✔
ɑ-ɑ-Trimethylcyclohexene-methanol isomer						✔
Methoxymethylphenol isomer				✔		✔	✔	✔		✔
Naphthalene [28, 29, 32–34, 36, 39, 40, 43]		✔		✔				✔		✔	✔	✔	✔	✔
Unknown 14														✔
Dimethoxytoluene isomer				✔			✔	✔
Unknown 15												✔
Benzothiazole											✔	✔		✔
o-(Methoxybenzoyl)-o'-(chlorobenzoyl)-benzenediol isomer												✔
Ethylmethoxyphenol isomer [35]				✔		✔	✔	✔		✔
Unknown 16										✔
Methylbenzothiazole isomer														✔
Methylnaphthalene isomer [35, 36, 40]												✔	✔	✔
Hydroxylmethylacetophenone isomer										✔
Methylnaphthalene isomer												✔		✔
Unknown 17										✔
Eugenol [41, 42]				✔		✔	✔	✔
Propenylmethoxyphenol isomer [42]				✔				✔		✔
Unknown 18										✔
Propylmethoxyphenol isomer [35]						✔	✔	✔
Tetradecane [40]				✔
Eugenol [41, 42]				✔
Eugenol						✔	✔	✔		✔
Dihydrotrimethylquinoline isomer												✔
Unknown 19												✔
Bis(dimethylethyl)phenol isomer		✔	✔	✔	✔	✔	✔	✔				✔	✔	✔
Unknown 20										✔
Unknown 21										✔
(Methylthio)-benzothiazole												✔
Unknown 22														✔
Benzophenone										✔
Bis(methylene)-benzamine isomer												✔
Butyl citrate										✔				✔

PB: results obtained for particle board; Mel: results for melamine coated particle board; LW: laminated wood results; ✔: compound detected. HS: headspace; DI: direct immersion. Where a compound name has been underlined, these indicate USEPA priority pollutants [44]. Unknown compounds indicate that a clearly defined peak was present within the sample that could not be matched to either the on-board or NIST library. Citations indicate that a similar compound was previously identified as by-products of pyrolysis and combustion within the existing literature. Only the first isomer of each compound was referenced.

Figure 2. Representative benchtop gas chromatography-mass spectrometry (GC-MS) chromatogram compared to a portable GC-MS chromatogram of water run-off from a controlled burn of rubber after extraction using direct immersion sampling-solid phase microextraction sampling (DI-SPME), where (A) is a complete overview of the chromatogram and (B) is an expanded section of the baseline of the same result. The major peaks (1–7) present within the benchtop GC-MS results were also detected and identified on the portable GC-MS (see also Table 2); 1) Unknown 11, 2) naphthalene, 3) benzothaizole, 4) dihydrotrimethylquinoline, 5) bis(dimethylethyl)phenol, 6) (methylthio)-benzothiazole, 7) bis(methylene)-benzenamine.

Figure 3. Representative benchtop gas chromatography-mass spectrometry (GC-MS) chromatogram of run-off water from a controlled burn of rubber after liquid-liquid extraction (LLE) compared to a portable GC-MS chromatogram of water run-off from a controlled burn of rubber after extraction using direct immersion sampling-solid phase microextraction sampling (DI-SPME), where (A) is a complete overview of the chromatogram and (B) is an expanded section of the same result. Surrogate compounds and internal standards in the extracted sample are denoted with “S” and “IS”, respectively.

Table 3. Compounds detected and identified using conventional laboratory-based sampling and analysis of fire water run-off.

Compound name	PB	Mel	LW	Carpet	Rubber	Underlay
2(5H)-Furanone				✔		✔
1,2,3,3,4-pentamethylcyclopentene	✔	✔			✔
Benzaldehyde				✔		✔
1,2,3,4,5-pentamethylcyclopentene			✔
Phenol	✔	✔	✔	✔	✔	✔
2-hydroxy-3-methyl-2-cyclopenten-1-one				✔		✔
4-Methyl-5H-furan-2-one				✔		✔
2-Methylphenol	✔		✔	✔	✔	✔
3 + 4-Methylphenol	✔	✔	✔	✔	✔	✔
Methyl 2-furoate				✔		✔
2-methoxyphenol	✔	✔	✔
Maltol				✔
Benzoic acid [29]				✔		✔
2-methoxy-4-methylphenol				✔
Dimethyl ester pentanedioic acid					✔
2,4-Dimethylphenol			✔	✔
5-(hydroxymethyl)-2-furancarboxaldehyde	✔			✔		✔
Naphthalene					✔
Dimethyl ester hexanedioic acid					✔
Vanillin [41, 42]	✔			✔
N-phenyl-acetamide					✔
2,5-bis(1,1-dimethylethyl)-phenol						✔
1,2-dihydro-2,2,4-trimethyl-quinoline					✔
2,7-dichloro-naphthalene	✔
2,5-dimethylbenzenebutanoic acid			✔
2(3H)-Benzothiazolone					✔
1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone			✔
3-(4-hydroxy-3-methooxyphenyl)-2-propenal			✔
2-Mercaptobenzothiazole					✔
Octadecanoic acid				✔
Butyl citrate				✔

PB: results obtained for particle board; Mel: results for melamine coated particle board; LW: laminated wood results; ✔: compound detected; ✔: similar peak also detected in field-based results. Citations refer to compounds previously identified as by-products of pyrolysis and combustion in the existing literature. Compounds in italics indicate library matched identifications. All other compounds are method specific target compounds.

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