Field and Laboratory Measurements of Biomass Burning VOCs using High- Resolution Chemical Ionization Mass Spectrometry

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1 Field and Laboratory Measurements of Biomass Burning VOCs using High- Resolution Chemical Ionization Mass Spectrometry Matthew Coggon, Abigail Koss, Jessica Gilman, Kanako Sekimoto, Bin Yuan, Brian Lerner, Carsten Warneke, Joost de Gouw Outline Overview of NOAA VOC instrumentation deployed at the Fire Sciences Laboratory. Summary of recent work aimed at understanding lack of acetonitrile in ambient measurements of residential burning emissions.

2 VOC Instrumentation at Platform AMS I-CIMS ACES NO3-CIMS FTIR, PAX Cartridge Samplers Filter Samplers Wind Tunnel and Control Room On the web at NOAA VOC Group Instrumentation: GC-MS I CIMS H 3 O + -CIMS GC- H 3 O + -CIMS Ground Floor and Outdoors Teflon mini-chamber HR-AMS, SP-HR-AMS CAPS, PASS SP2, CLAP, POPS SMPS, WSOC-PILS H3O + -CIMS, I CIMS GC-MS, PAM CSU Chamber BrC-PiLs, BBCEAS, PiLs-ESI, CRDPAS, NEPH, Ny, NO Aerodyne Mobile Lab

3 VOC Instrumentation at Platform AMS I-CIMS ACES NO3-CIMS FTIR, PAX Cartridge Samplers Filter Samplers Wind Tunnel and Control Room On the web at NOAA VOC Group Instrumentation: GC-MS I CIMS H 3 O + -CIMS GC- H 3 O + -CIMS Ground Floor and Outdoors Teflon mini-chamber HR-AMS, SP-HR-AMS CAPS, PASS SP2, CLAP, POPS SMPS, WSOC-PILS H3O + -CIMS, I CIMS GC-MS, PAM CSU Chamber BrC-PiLs, BBCEAS, PiLs-ESI, CRDPAS, NEPH, Ny, NO Aerodyne Mobile Lab

4 VOC Instrumentation at H 3 O + -CIMS: Real Time Measurement GC-H 3 O + -CIMS: VOC Identification Hollow cathode VOCs drift Tube Ion guides time-of-flight mass analyzer H 2 O H 3 O + g) MCP H 3 O + Mode H 3 O + + VOC VOC-H + + H 2 O NO + Mode NO + + VOC-H VOC + + HNO NO + + VOC VOC-NO + GC H 3 O + -CIMS

5 VOC Instrumentation at VOC Identification by coupling GC with H 3 O + -CIMS H 3 O + m/z CIMS 85 detection C 5 H 9 O + m/z C 5 CH 10 O H + 5 H 10 O NO + NO + CIMS detection Abigail Koss, VOC Identification by GC-CIMS, in prep

6 VOC Instrumentation at VOC Identification by coupling GC with H 3 O + /NO + CIMS H 3 O + m/z CIMS 85 detection C 5 H 9 O + m/z C 5 CH 10 O H + 5 H 10 O NO + NO + CIMS detection (?) Abigail Koss, VOC Identification by GC-CIMS, in prep

7 VOC Instrumentation at VOC Identification by coupling GC with H 3 O + /NO + CIMS H 3 O + Ionization H 3 O + H + M m/z = M+1 H 3 O + m/z CIMS 85 detection C 5 H 9 O + m/z C 5 CH 10 O H + 5 H 10 O NO + M H 3 O + H + m/z = M+1 NO + CIMS detection (?) Abigail Koss, VOC Identification by GC-CIMS, in prep

8 VOC Instrumentation at VOC Identification by Coupling GC with H 3 O + /NO + CIMS H 3 O + Ionization H 3 O + H + Retention m/z 87 Time C 5 H 10 (s) O H + m/z H H 3 O + CIMS 3 O + 85 C CIMS detection 5 H 8 O H + M M H 3 O + m/z = M+1 H + m/z = M+1 NO + m/z 116 C CIMS detection 5 H 10 O NO + (?) Abigail Koss, VOC Identification by GC-CIMS, in prep

9 VOC Instrumentation at VOC Identification by Coupling GC with H 3 O + /NO + CIMS H 3 O + Ionization H 3 O + H + Retention m/z 87 Time C 5 H 10 (s) O H + m/z H H 3 O + CIMS 3 O + 85 C CIMS detection 5 H 8 O H + M M H 3 O + NO + Ionization m/z = M+1 H + m/z = M+1 NO + m/z 116 C CIMS detection 5 H 10 O NO + NO + + M m/z = M-1 NO + NO + Aldehyde ionization Ketone ionization (?) M m/z = M+30 Abigail Koss, VOC Identification by GC-CIMS, in prep

10 VOC Instrumentation at VOC Identification by Coupling GC with H 3 O + /NO + CIMS Advantages to GC-H 3 O + -CIMS Retention m/z 87 Time C 5 H 10 (s) O H + m/z H H 3 O + CIMS 3 O + 85 C CIMS detection 5 H 8 O H + GC front end allows for the separation of a VOC mixture. H 3 O + and NO + CIMS allows for the unambiguous assignment of molecular formula NO + m/z 116 C CIMS detection 5 H 10 O NO + Combining the techniques in series and in parallel allows us to gather in-depth detail of the chemical and temporal evolution of biomass burning emissions (?) Abigail Koss, VOC Identification by GC-CIMS, in prep

11 VOC Instrumentation at Ponderosa Pine Structure of Lignin 0 min 20min Furans Polyunsaturated OVOCs furan furfural catechol guaiacol phenol

12 VOC Instrumentation at Ponderosa Pine Flaming (High T) Smoldering (Low T) High temperature: exposure far away Low temperature: exposure for local residents 0 min 20min More to come in 2019 during FIREX Aircraft Campaign! Smoldering (Low T) Flaming (High T) Learn more at: OVOCs Unsubstituted

13 VOC Instrumentation at Ground Observations Mobile Laboratory You are here!

14 VOC Instrumentation at What VOCs are dominant in residential burning as measured by our mass spectrometer? Furfural Where is all the acetonitrile? Furfural Acetonitrile Time of Day (hr) Time of Day (hr)

15 VOC Instrumentation at Furfural is a good tracer for residential burning. Acetonitrile is not. Mobile Laboratory Furfural Distribution Acetonitrile Distribution Wood Stove Plumes Ag Fire

16 VOC Instrumentation at Composition Emissions (L) (H) (L) f NVOC = σ NVOCs σ VOCs (H) Coggon et al. (2016). Geophys. Res. Letters.

17 Primary VOC Emissions at Summary Deployment of the GC-H 3 O + -CIMS at has provided refined detail of the VOCs measurable by GC, H 3 O +, and NO + CIMS. Ambient measurements show that furans and substituted aromatics serve as good biomass burning tracers. Acetonitrile not suitable as a tracer for lownitrogen fuels (e.g. residential wood burning) Outlook Evaluate VOCs linked with smoldering vs flaming combustion (Kanako Sekimoto) Evaluate VOC emission factors (Casten Warneke/Matt Coggon) Identify biomass burning species that may serve as suitable tracers or chemical clocks (Jessica Gilman)