1. Annual Committee Meeting Taryn M. Lopez May 8, 2008 Environmental Chemistry Program University of Alaska Fairbanks Department of Chemistry & Biochemistry

2. Committee Members Cathy Cahill: Dept. of Chemistry/UAF Geophysical Institute/AVO Specialties: Atmospheric chemistry, atmospheric aerosols Cindy Werner: USGS Volcano Emissions Project, Project Chief Specialties: Volcanic gas chemistry, monitoring of volcanic emissions Jon Dehn: UAF Geophysical Institute/AVO Specialties: Physical volcanology, remote sensing of volcanoes Bill Simpson: Dept. of Chemistry/UAF Geophysical Institute Specialties: Physical and atmospheric chemistry, spectroscopy Rainer Newberry: Dept. of Geology and Geophysics Specialties: Geochemistry, genesis of ores, exploration of ore deposits

3. Why study volcanic gases? By collecting repeated gas measurements over time scientists can use these chemical signatures to elucidate subsurface processes and help forecast volcanic activity. Volcanic gases can provide insight into subsurface volcanic processes through their chemical signatures: –Magma solubility –Water solubility –Pressure/Temperature –Oxidation state

4. Research Goals 1) Use the chemical signatures of volcanic gases to elucidate subsurface volcanic processes 2) Utilize, expand on, and validate ground and satellite- based remote sensing techniques for volcano monitoring to make it safer and more efficient for scientists to measure volcanic gases 3) Investigate the atmospheric evolution and fate of volcanic gases, specifically how volcanic gases react in the atmosphere and what the implications of these reactions are with respect to volcano monitoring and the environment

5. Current Projects Chemistry and emission rates of volcanic gases from Bezymianny volcano, Kamchatka (Contribution to PIRE project)Chemistry and emission rates of volcanic gases from Bezymianny volcano, Kamchatka (Contribution to PIRE project) OMI (Ozone Monitoring Instrument) validation for high latitude volcanic sulfur dioxide emissionsOMI (Ozone Monitoring Instrument) validation for high latitude volcanic sulfur dioxide emissions Image produced by Dimitry Melnikov

6. I. Bezymianny Gas Chemistry Project goals: 1)Collect repeated direct and remote measurements of Bezymianny’s volcanic emissions over 3-4 field seasons Ground (and air) based remote sensing of plume SO 2 (and BrO?) column densities using UV spectroscopy (FLYSPEC)Ground (and air) based remote sensing of plume SO 2 (and BrO?) column densities using UV spectroscopy (FLYSPEC) Direct sampling of volcanic gases from dome (and elsewhere?) using evacuated (Giggenbach) bottle techniqueDirect sampling of volcanic gases from dome (and elsewhere?) using evacuated (Giggenbach) bottle technique 2)Use these data (and geochemical modeling software?) to deduce subsurface environmental conditions 3)Compare gas chemistry with seismic, deformation, and petrologic data to generate a model explaining Bezymianny’s volcanic system (PIRE Project Goal)

7. Bezymianny Sample Locations, 2007 ASTER image from 2/4/2007

8. I. Bezymianny Gas Chemistry Methods: FLYSPECGiggenbach Bottles

9. FLYSPEC Specifications Ocean Optics USB2000 UV Spectrometer, integrated GPS & data processing softwareOcean Optics USB2000 UV Spectrometer, integrated GPS & data processing software Measures light intensities from 177 to 330 nm at 0.25 nm spectral resolutionMeasures light intensities from 177 to 330 nm at 0.25 nm spectral resolution Software uses SO 2 absorption feature from 300 – 315 nm, as well as clear sky, and plume FLYSPEC measurements to calculate SO 2 column densities, according to Beer’s LawSoftware uses SO 2 absorption feature from 300 – 315 nm, as well as clear sky, and plume FLYSPEC measurements to calculate SO 2 column densities, according to Beer’s Law www.oceanoptics.com Figure from Keith Horton

10. FLYSPEC Theory I(λ) = transmitted radiation Io (λ) = incident radiation σ = molar absorptivity n = concentration l = pathlength of plume Beer’s Law: ln (Iλ / Ioλ) = - σλnl

11. Giggenbach Sampling Direct samples were collected using 300 ml pre-weighed, evacuated bottles (Giggenbach bottles) containing a 4 M KOH and Cd(CH 3 COOH) 2 absorbing solution

12. I. Bezymianny Gas Chemistry Preliminary Results: FLYSPEC Giggenbach Bottles

13. II. OMI Validation for Volcanic SO 2 Project Goals: 1)Compare direct and ground/air-based remote sensing SO 2 measurements from high latitude volcanoes to OMI SO 2 product 2) Determine strengths and weaknesses of OMI product for high latitude volcano monitoring and formulate method to make data comparable

14. OMI Background/Specifications Flown on the EOS-Aura SpacecraftFlown on the EOS-Aura Spacecraft Aura was launched on July 15, 2004Aura was launched on July 15, 2004 Daily global coverage (14 orbits)Daily global coverage (14 orbits) 2600 Km swath width2600 Km swath width 13 x 24 Km spatial resolution at nadir13 x 24 Km spatial resolution at nadir Hyperspectral UV/VIS spectrometerHyperspectral UV/VIS spectrometer Measures solar backscatter radiationMeasures solar backscatter radiation 1560 wavelength bands from 270-500 nm with a spectral resolution of 0.5 nm1560 wavelength bands from 270-500 nm with a spectral resolution of 0.5 nm Measures trace gases including: O 3, NO 2, HCHO, BrO, OClO, and SO 2Measures trace gases including: O 3, NO 2, HCHO, BrO, OClO, and SO 2 Also measures aerosol characteristics, cloud top heights, cloud coverage, and surface UV irradiance.Also measures aerosol characteristics, cloud top heights, cloud coverage, and surface UV irradiance. Schobert et al., 2006 & Ahmad et al., 2003

15. II. OMI Validation for Volcanic SO 2 Preliminary Results: Fourpeaked Case Study Image produced by Simon Carn Gas flight data provided by USGS-VEP

16. II. OMI Validation for Volcanic SO 2 Current work: Compare OMI SO 2 product to USGS-VEP gas flight measurements for Fourpeaked and Augustine 2006 eruptionsCompare OMI SO 2 product to USGS-VEP gas flight measurements for Fourpeaked and Augustine 2006 eruptions Compare OMI SO 2 product to ground-based measurements at Bezymianny and other volcanoes (Shiveluch? Stromboli?)Compare OMI SO 2 product to ground-based measurements at Bezymianny and other volcanoes (Shiveluch? Stromboli?) Attended OMI Workshop led by Simon Carn (University of Maryland Baltimore County & NASA Goddard Space Flight Center) at the Cascades Volcano Observatory (Feb. 2008)Attended OMI Workshop led by Simon Carn (University of Maryland Baltimore County & NASA Goddard Space Flight Center) at the Cascades Volcano Observatory (Feb. 2008) Obtained IDL code to produce images and calculate SO 2 massObtained IDL code to produce images and calculate SO 2 mass

17. Future Work Continue measurements at Bezy; expand sampling techniques to get a more thorough dataset (Stream sampling? Sublimates? BrO absorption?)Continue measurements at Bezy; expand sampling techniques to get a more thorough dataset (Stream sampling? Sublimates? BrO absorption?) Compare OMI to gas measurements (continue work on Fourpeaked and Augustine 2006 VEP measurements)Compare OMI to gas measurements (continue work on Fourpeaked and Augustine 2006 VEP measurements) Obtain funding to for gas sampling instrumentation (electrochemical sensors/infrared analyzers) and field money to conduct aerial traverse of plume to: 1) validate OMI and 2) see how gases evolve with time (homo & heterogeneous reactions & formation of aerosols)Obtain funding to for gas sampling instrumentation (electrochemical sensors/infrared analyzers) and field money to conduct aerial traverse of plume to: 1) validate OMI and 2) see how gases evolve with time (homo & heterogeneous reactions & formation of aerosols)

18. First Year Highlights Spring 2007: TA for Chem 106; took Environmental Geochemistry, IR Remote Sensing; Accepted into PIRE program Summer 2007: Participated in PIRE program (PK, Bezymianny, CVO/MSH), collected gas measurements from Bezymianny & MSH Fall 2007: TA for Chem 105; took Intro to Geochemistry, Fundamentals of Environmental Chemistry; Participated in AVO eruption response at Pavlof Volcano (measured volcanic SO 2 ); Presented preliminary results from Bezymianny SO 2 measurements at AGU Fall Meeting Spring 2008: TA for Chem 105; took P-Chem (Quantum Chemistry & Spectroscopy); High Temperature Geochemistry; attended OMI workshop at CVO

19. Future Work Timeline Summer 2008: Measure volcanic gases at Stromboli (May-June); Shiveluch (July); Bezymianny (July) volcanoes and process data to determine emission rates. Produce OMI images for dates with corresponding ground/air measurements; compare data. Fall 2008: Take P-Chem (Thermodynamics & Kinetics), Intro to Atmospheric Sciences, Chem Seminar; continue data processing & OMI comparison, attend IAVCEI-CCVG Volcanic Gas Workshop (Mexico, November), present on OMI validation results. Spring 2009: Take Remote Sensing of Volcanic Eruptions, Atmospheric Chemistry, Presentation Techniques; Prepare for comprehensive exams. Summer 2009: Comprehensive exams, present proposal; Field work at Bezymianny. Fall 2009: Take Physical Volcanology, continue research. Spring 2010: Take Molecular Spectroscopy, continue research.

20. Grades Received CHEM 609 Environmental Geochemistry: A GEOS 654 Visible/IR Remote Sensing: A CHEM 605 Fundamentals of Environmental Chemistry: A GEOS 618: Introduction to Geochemistry: A- CHEM 332: Quantum Chemistry & Spectroscopy ? GEOS 695: High Temperature Geochemistry ?

21. Thank you! Questions?

22. Discussion Points Comments on appropriateness of research goals Suggestions for more effectively meeting goals (new instrumentation, sampling techniques, modeling, etc.)Suggestions for more effectively meeting goals (new instrumentation, sampling techniques, modeling, etc.) BezymiannyBezymianny OMI validationOMI validation Appropriateness of course-selection and modification for degree course requirementsAppropriateness of course-selection and modification for degree course requirements Comments on timeline Comments on timeline Suggestions for 3 rd projectSuggestions for 3 rd project

23. Extra Slides…

25. Gas Flight Traverses 1, 5 & 7 Overlain on OMI Interpolation

26. Traverse 1: Assume Plume Area of 22.8 Km 2 For 32.8 DU = 747.84 DU*Km 2 Pixel Area (not at nadir) = 13 x 42 Km (546 Km 2 ) (assume 0 DU for remainder of Pixel) 747.84 DU*Km 2 + 0*534DU*Km 2 = 546X X = 1.37 DU = Average Pixel Value OMI Measured SO 2 = 0.24 DU 32.8 DU 0 DU 23.4 Km 4.77 Km