Annual Committee Meeting Annual Committee Meeting

Taryn M. Lopez Taryn M. Lopez

May 8, 2008May 8, 2008

Environmental Chemistry ProgramEnvironmental Chemistry ProgramUniversity of Alaska FairbanksUniversity of Alaska Fairbanks

Department of Chemistry & Department of Chemistry & BiochemistryBiochemistry

Committee MembersCommittee MembersCathy Cahill:Cathy Cahill: Dept. of Chemistry/UAF Geophysical Institute/AVODept. of Chemistry/UAF Geophysical Institute/AVO

Specialties: Atmospheric chemistry, atmospheric aerosolsSpecialties: Atmospheric chemistry, atmospheric aerosols

Cindy Werner:Cindy Werner: USGS Volcano Emissions Project, Project Chief USGS Volcano Emissions Project, Project Chief

Specialties: Volcanic gas chemistry, monitoring of volcanic emissionsSpecialties: Volcanic gas chemistry, monitoring of volcanic emissions

Jon Dehn:Jon Dehn: UAF Geophysical Institute/AVO UAF Geophysical Institute/AVO

Specialties: Physical volcanology, remote sensing of volcanoesSpecialties: Physical volcanology, remote sensing of volcanoes

Bill Simpson:Bill Simpson: Dept. of Chemistry/UAF Geophysical Institute Dept. of Chemistry/UAF Geophysical Institute

Specialties: Physical and atmospheric chemistry, spectroscopySpecialties: Physical and atmospheric chemistry, spectroscopy

Rainer Newberry:Rainer Newberry: Dept. of Geology and Geophysics Dept. of Geology and Geophysics

Specialties: Geochemistry, genesis of ores, exploration of ore depositsSpecialties: Geochemistry, genesis of ores, exploration of ore deposits

Why study volcanic gases?Why study volcanic gases?

By collecting repeated gas measurements over By collecting repeated gas measurements over time scientists can use these chemical time scientists can use these chemical signatures to elucidate subsurface processes signatures to elucidate subsurface processes and help forecast volcanic activity.and help forecast volcanic activity.

Volcanic gases can provide insight into Volcanic gases can provide insight into subsurface volcanic processes through their subsurface volcanic processes through their chemical signatures:chemical signatures:– Magma solubilityMagma solubility– Water solubilityWater solubility– Pressure/TemperaturePressure/Temperature– Oxidation stateOxidation state

Research GoalsResearch Goals

1) Use the chemical signatures of volcanic gases 1) Use the chemical signatures of volcanic gases to elucidate subsurface volcanic processesto elucidate subsurface volcanic processes

2) Utilize, expand on, and validate ground and satellite-2) Utilize, expand on, and validate ground and satellite-based remote sensing techniques for volcano monitoring based remote sensing techniques for volcano monitoring to make it safer and more efficient for scientists to to make it safer and more efficient for scientists to measure volcanic gasesmeasure volcanic gases

3) Investigate the atmospheric evolution and fate of 3) Investigate the atmospheric evolution and fate of volcanic gases, specifically how volcanic gases react in volcanic gases, specifically how volcanic gases react in the atmosphere and what the implications of these the atmosphere and what the implications of these reactions are with respect to volcano monitoring and the reactions are with respect to volcano monitoring and the environmentenvironment

Current ProjectsCurrent Projects

• Chemistry and emission Chemistry and emission rates of volcanic gases from rates of volcanic gases from Bezymianny volcano, Bezymianny volcano, Kamchatka (Contribution to Kamchatka (Contribution to PIRE project)PIRE project)

• OMI (Ozone Monitoring OMI (Ozone Monitoring Instrument) validation for Instrument) validation for high latitude volcanic sulfur high latitude volcanic sulfur dioxide emissionsdioxide emissions

Image produced by Dimitry MelnikovImage produced by Dimitry Melnikov

I. Bezymianny Gas ChemistryI. Bezymianny Gas ChemistryProject goals:Project goals:

1)1) Collect repeated direct and remote measurements of Collect repeated direct and remote measurements of Bezymianny’s volcanic emissions over 3-4 field seasonsBezymianny’s volcanic emissions over 3-4 field seasons

• Ground (and air) based remote sensing of plume SOGround (and air) based remote sensing of plume SO22 (and BrO?) (and BrO?) column densities using UV spectroscopy (FLYSPEC)column densities using UV spectroscopy (FLYSPEC)

• Direct sampling of volcanic gases from dome (and elsewhere?) Direct sampling of volcanic gases from dome (and elsewhere?) using evacuated (Giggenbach) bottle techniqueusing evacuated (Giggenbach) bottle technique

2)2) Use these data (and geochemical modeling software?) to Use these data (and geochemical modeling software?) to deduce subsurface environmental conditionsdeduce subsurface environmental conditions

3)3) Compare gas chemistry with seismic, deformation, and Compare gas chemistry with seismic, deformation, and petrologic data to generate a model explaining petrologic data to generate a model explaining Bezymianny’s volcanic system (PIRE Project Goal)Bezymianny’s volcanic system (PIRE Project Goal)

Bezymianny Sample Locations, 2007Bezymianny Sample Locations, 2007

ASTER image from 2/4/2007ASTER image from 2/4/2007

I. Bezymianny Gas ChemistryI. Bezymianny Gas Chemistry

Methods:Methods:

FLYSPECFLYSPEC Giggenbach BottlesGiggenbach Bottles

FLYSPEC SpecificationsFLYSPEC Specifications

• Ocean Optics USB2000 UV Ocean Optics USB2000 UV Spectrometer, integrated Spectrometer, integrated GPS & data processing GPS & data processing softwaresoftware

• Measures light intensities Measures light intensities from 177 to 330 nm at 0.25 from 177 to 330 nm at 0.25 nm spectral resolutionnm spectral resolution

• Software uses SOSoftware uses SO22 absorption feature from 300 absorption feature from 300 – 315 nm, as well as clear – 315 nm, as well as clear sky, and plume FLYSPEC sky, and plume FLYSPEC measurements to calculate measurements to calculate SOSO22 column densities, column densities, according to Beer’s Lawaccording to Beer’s Law

www.oceanoptics.com

Figure from Figure from KeithKeith Horton Horton

FLYSPEC TheoryFLYSPEC Theory

UV Source

Volcanic Plume

Io(λ) I (λ) FLYSPEC

FLYSPECIo(λ)

UV Source

Volcanic Plume

Io(λ) I (λ) FLYSPECFLYSPEC

FLYSPECFLYSPECIo(λ)

I(λ) = transmitted radiation Io (λ) = incident radiationσ = molar absorptivity n = concentration l = pathlength of plume

Beer’s Law: ln (Iλ / Ioλ) = - σλnl

Giggenbach SamplingGiggenbach Sampling

Direct samples were collected Direct samples were collected using 300 ml pre-weighed, using 300 ml pre-weighed, evacuated bottles evacuated bottles (Giggenbach bottles) (Giggenbach bottles) containing a 4 M KOH and containing a 4 M KOH and Cd(CHCd(CH33COOH)COOH)22 absorbing absorbing

solutionsolution

I. Bezymianny Gas ChemistryI. Bezymianny Gas Chemistry

Preliminary Results:Preliminary Results:

№ sampl. Temper. H2O CO2 H2S SO2 HCl CO CH4 H2 N2 O2 Ar He C2H6 C2H4 C3H8 C3H6 C4H10 (н) C4 (i) S\Cl

dome 1 301 95.872618 1.4984703 0.0021972 0.3078716 0.9232342 4.144E-05 4.166E-05 0.021501 1.3383623 0.0215239 0.014133 0 9.393E-08 1.962E-06 5.922E-08 3.605E-07 2.193E-07 2.742E-06 0.306PF 2 201 99.683343 0.09682 0.000071 0.0343179 0.0085728 0 8.887E-07 0.000138 0.1403459 0.0347655 0.001624 0 6.542E-09 1.043E-08 5.113E-09 2.971E-08 1.059E-09 7.055E-08 3.34dome 3 301 97.320346 0.9892997 0.0003954 0.1618316 0.475826 3.124E-05 3.14E-05 0.0050735 1.0193507 0.0169784 0.0108318 0 7.394E-08 1.419E-06 4.88E-08 2.541E-07 1.778E-07 2.046E-06 0.308

FLYSPECFLYSPEC

Giggenbach BottlesGiggenbach Bottles

II. OMI Validation for Volcanic SOII. OMI Validation for Volcanic SO22

Project Goals:Project Goals:

1)1) Compare direct and ground/air-based remote Compare direct and ground/air-based remote sensing SOsensing SO22 measurements from high latitude measurements from high latitude

volcanoes to OMI SOvolcanoes to OMI SO22 product product

2) Determine strengths and weaknesses of OMI 2) Determine strengths and weaknesses of OMI product for high latitude volcano monitoring product for high latitude volcano monitoring and formulate method to make data and formulate method to make data comparablecomparable

OMI Background/SpecificationsOMI Background/Specifications

• Flown on the EOS-Aura Spacecraft Flown 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 radiation Measures solar backscatter radiation • 1560 wavelength bands from 270-500 nm with a spectral 1560 wavelength bands from 270-500 nm with a spectral

resolution of 0.5 nmresolution of 0.5 nm• Measures trace gases including: OMeasures trace gases including: O33, NO, NO22, HCHO, BrO, , HCHO, BrO,

OClO, and SOOClO, and SO22

• Also measures aerosol characteristics, cloud top heights, Also measures aerosol characteristics, cloud top heights, cloud coverage, and surface UV irradiance.cloud coverage, and surface UV irradiance.

Schobert et al., 2006 & Ahmad et al., 2003Schobert et al., 2006 & Ahmad et al., 2003

II. OMI Validation for Volcanic SOII. OMI Validation for Volcanic SO22

Preliminary Results:Preliminary Results:

Fourpeaked Case StudyFourpeaked Case Study

Image produced by Simon CarnImage produced by Simon Carn

Gas flight data provided by USGS-VEPGas flight data provided by USGS-VEP

II. OMI Validation for Volcanic SOII. OMI Validation for Volcanic SO22

Current work:Current work:• Compare OMI SOCompare OMI SO22 product to USGS-VEP gas flight measurements product to USGS-VEP gas flight measurements

for Fourpeaked and Augustine 2006 eruptionsfor Fourpeaked and Augustine 2006 eruptions

• Compare OMI SOCompare OMI SO22 product to ground-based measurements at product to ground-based measurements at

Bezymianny and other volcanoes (Shiveluch? Stromboli?)Bezymianny and other volcanoes (Shiveluch? Stromboli?)

• Attended OMI Workshop led by Simon Carn (University of Maryland Attended OMI Workshop led by Simon Carn (University of Maryland Baltimore County & NASA Goddard Space Flight Center) at the Baltimore County & NASA Goddard Space Flight Center) at the Cascades Volcano Observatory (Feb. 2008)Cascades Volcano Observatory (Feb. 2008)

• Obtained IDL code to produce images and calculate SOObtained IDL code to produce images and calculate SO2 2 mass mass

Future WorkFuture Work

• Continue measurements at Bezy; expand sampling Continue measurements at Bezy; expand sampling techniques to get a more thorough dataset (Stream techniques to get a more thorough dataset (Stream sampling? Sublimates? BrO absorption?)sampling? Sublimates? BrO absorption?)

• Compare OMI to gas measurements (continue work Compare OMI to gas measurements (continue work on Fourpeaked and Augustine 2006 VEP on Fourpeaked and Augustine 2006 VEP measurements)measurements)

• Obtain funding to for gas sampling instrumentation Obtain funding to for gas sampling instrumentation (electrochemical sensors/infrared analyzers) and (electrochemical sensors/infrared analyzers) and field money to conduct aerial traverse of plume to: field money to conduct aerial traverse of plume to: 1) validate OMI and 2) see how gases evolve with 1) validate OMI and 2) see how gases evolve with time (homo & heterogeneous reactions & formation time (homo & heterogeneous reactions & formation of aerosols)of aerosols)

First Year HighlightsFirst Year Highlights

Spring 2007:Spring 2007: TA for Chem 106; took Environmental TA for Chem 106; took Environmental Geochemistry, IR Remote Sensing; Accepted into PIRE Geochemistry, IR Remote Sensing; Accepted into PIRE programprogram

Summer 2007:Summer 2007: Participated in PIRE program (PK, Bezymianny, Participated in PIRE program (PK, Bezymianny, CVO/MSH), collected gas measurements from Bezymianny & CVO/MSH), collected gas measurements from Bezymianny & MSHMSH

Fall 2007:Fall 2007: TA for Chem 105; took Intro to Geochemistry, TA for Chem 105; took Intro to Geochemistry, Fundamentals of Environmental Chemistry; Participated in Fundamentals of Environmental Chemistry; Participated in AVO eruption response at Pavlof Volcano (measured volcanic AVO eruption response at Pavlof Volcano (measured volcanic SOSO22); Presented preliminary results from Bezymianny SO); Presented preliminary results from Bezymianny SO22 measurements at AGU Fall Meetingmeasurements at AGU Fall Meeting

Spring 2008:Spring 2008: TA for Chem 105; took P-Chem (Quantum TA for Chem 105; took P-Chem (Quantum Chemistry & Spectroscopy); High Temperature Geochemistry; Chemistry & Spectroscopy); High Temperature Geochemistry; attended OMI workshop at CVOattended OMI workshop at CVO

Future Work TimelineFuture Work Timeline

Summer 2008:Summer 2008: Measure volcanic gases at Stromboli (May-June); Shiveluch Measure volcanic gases at Stromboli (May-June); Shiveluch (July); Bezymianny (July) volcanoes and process data to determine (July); Bezymianny (July) volcanoes and process data to determine emission rates. Produce OMI images for dates with corresponding emission rates. Produce OMI images for dates with corresponding ground/air measurements; compare data.ground/air measurements; compare data.

Fall 2008:Fall 2008: Take P-Chem (Thermodynamics & Kinetics), Intro to Atmospheric Take P-Chem (Thermodynamics & Kinetics), Intro to Atmospheric Sciences, Chem Seminar; continue data processing & OMI comparison, Sciences, Chem Seminar; continue data processing & OMI comparison, attend IAVCEI-CCVG Volcanic Gas Workshop (Mexico, November), attend IAVCEI-CCVG Volcanic Gas Workshop (Mexico, November), present on OMI validation results.present on OMI validation results.

Spring 2009:Spring 2009: Take Remote Sensing of Volcanic Eruptions, Atmospheric Take Remote Sensing of Volcanic Eruptions, Atmospheric Chemistry, Presentation Techniques; Prepare for comprehensive exams.Chemistry, Presentation Techniques; Prepare for comprehensive exams.

Summer 2009:Summer 2009: Comprehensive exams, present proposal; Field work at Comprehensive exams, present proposal; Field work at Bezymianny.Bezymianny.

Fall 2009:Fall 2009: Take Physical Volcanology, continue research. Take Physical Volcanology, continue research.

Spring 2010:Spring 2010: Take Molecular Spectroscopy, continue research. Take Molecular Spectroscopy, continue research.

Grades ReceivedGrades Received

CHEM 609 Environmental Geochemistry: ACHEM 609 Environmental Geochemistry: A

GEOS 654 Visible/IR Remote Sensing: AGEOS 654 Visible/IR Remote Sensing: A

CHEM 605 Fundamentals of Environmental Chemistry: ACHEM 605 Fundamentals of Environmental Chemistry: A

GEOS 618: Introduction to Geochemistry: A-GEOS 618: Introduction to Geochemistry: A-

CHEM 332: Quantum Chemistry & Spectroscopy ?CHEM 332: Quantum Chemistry & Spectroscopy ?

GEOS 695: High Temperature Geochemistry ?GEOS 695: High Temperature Geochemistry ?

Thank you!Thank you!

Questions?Questions?

Discussion PointsDiscussion Points• Comments on appropriateness of research goalsComments on appropriateness of research goals

•Suggestions for more effectively meeting goals (new Suggestions for more effectively meeting goals (new instrumentation, sampling techniques, modeling, etc.)instrumentation, sampling techniques, modeling, etc.)

•BezymiannyBezymianny

•OMI validationOMI validation

•Appropriateness of course-selection and modification for Appropriateness of course-selection and modification for degree course requirementsdegree course requirements

• Comments on timelineComments on timeline

•Suggestions for 3Suggestions for 3rdrd project project

Extra Slides…Extra Slides…

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

Traverse 1: Assume Plume Area of 22.8 KmTraverse 1: Assume Plume Area of 22.8 Km2 2

For 32.8 DU = 747.84 DU*KmFor 32.8 DU = 747.84 DU*Km22

Pixel Area (not at nadir) = 13 x 42 Km (546 KmPixel Area (not at nadir) = 13 x 42 Km (546 Km22) ) (assume 0 DU for remainder of Pixel)(assume 0 DU for remainder of Pixel)

747.84 DU*Km747.84 DU*Km22 + 0*534DU*Km + 0*534DU*Km2 2 = 546X= 546XX = 1.37 DU = Average Pixel ValueX = 1.37 DU = Average Pixel Value

OMI Measured SOOMI Measured SO22 = 0.24 DU = 0.24 DU

32.8 DU

0 DU

23.4 Km23.4 Km

4.77 4.77 KmKm