Target Organic Contaminant Target Organic Contaminant g gg gLibrary Development in Support Library Development in Support

of Sample Analysis at Mars (SAM)of Sample Analysis at Mars (SAM)Raul Garcia Sanchez

Research Mentor: Dr. Prabhakar MisraDepartment of Physics & Astronomy Howard UniversityDepartment of Physics & Astronomy, Howard University

Research Investigator: Dr. Paul R. MahaffyCode 699, NASA Goddard Space Flight Center

OverviewThe primary purpose of the research is to develop an organic

d b f h h h

Overview

contaminants database for the SAM project that supports the MarsScience Laboratory (MSL).

k l h d l fOur work involves the development of an organic contaminantsdatabase that will allow us to determine what compounds are foundhere on Earth and would be inadvertently detected in the Mars soiland gaseous samples as impuritiesand gaseous samples as impurities.

In order to develop a comprehensive target database, we utilize theNational Institute of Standards & Technology (NIST) Automated MassNational Institute of Standards & Technology (NIST) Automated MassSpectral Deconvolution and Identification System (AMDIS) and IonFingerprint Deconvolution (IFD) software to analyze the GC/MSdata.

Research PurposeAnalyze data from the rover environment using Gas

Research Purpose

Chromatography-Mass Spectroscopy (GC-MS).

D l i i d b f h S lDevelop an organic contaminants database for the SampleAnalysis at Mars (SAM) utilizing GC-MS analysis tools.

Utilize this database to identify compounds from actualmission samples.p

Research QuestionsWhat organic compounds can be found in the rover

Research Questions

structure?Where in the rover can they be found?

H l d i h d fHow accurately can we determine the compounds from teststo those on the actual rover?

How will identifying these compounds help when the timecomes for the actual mission analysis?y

NASA Mars Exploration TimelineNASA Mars Exploration Timeline2001:

2001 Mars Odyssey - 7 April 2001 - Mars Orbitery y po Still in orbit as of March 2008, and the ending date was

extended to September 2008.o Odyssey's Gamma Ray Spectrometer detected significantg

amounts of hydrogen, which was thought to be containedin large deposits of water ice.

2003:Mars Express - 2 June 2003 - Mars Orbiter and Lander

Lander failed during descent andwas declared lost in early February 2004.

In early 2004 the Planetary FourierSpectrometer team announced it haddetected methane in the Martianatmosphere. ESA announced in June2006 the discovery of aurorae on Mars.

NASA Mars Exploration TimelineNASA Mars Exploration Timeline

• 2003:– Spirit (MER-A) - 10 June 2003 - Mars Rover– Opportunity (MER-B) - 7 July 2003 - Mars Rover

• Both missions landed successfully in January 2004 and• have met or exceeded all their targets.• Among the most significant scientific returns has been conclusive evidence

that liquid water existed at some time in the past at both landing sites.M i d d il d i d h i ll l d b h '• Martian dust devils and windstorms have occasionally cleaned both rovers'solar panels, and thus increased their lifespan.

• 2005:– Mars Reconnaissance Orbiter - 10 August 2005 - Mars Orbiter

• The Mars Reconnaissance Orbiter snapped the first image of a series of activeavalanches near the planet's north pole, scientists said March 3, 2008.

NASA Mars Exploration TimelineNASA Mars Exploration Timeline2007

Ph i 04 A 2007 M S L dPhoenix - 04 August 2007 - Mars Scout LanderThe Lander has a robotic arm with a2.5 m reach and capable of digging a

h lmeter into the Martian soil.It also has a microscopic camera capable of resolving toone-thousandth the width of a human hair, and discovered asubstance at its landing site on June 15 2008 which wassubstance at its landing site on June 15, 2008, which wasconfirmed to be water ice on June 20.

Mars Science Laboratory (MSL)Mars Science Laboratory (MSL)“Curiosity” is the newest rover in NASA’s Mars ExplorationProgram expected to launch in 2011.

It is larger and can travel farther than previous rovers such asSpirit and OpportunitySpirit and Opportunity.

C i h d d i f i ( h SAM)Contains the most advanced suite of instruments (such as SAM)to date. It will also make use of innovative technologies forlanding.

MSL GoalsMSL GoalsAssess the biological potential by determining the nature andinventory of organic carbon compounds, etc.

I h b b l M b dInvestigate past habitability on Mars by determininginformation about carbon dioxide and water.

Characterize the geology of the landing region andinterpreting the processes that have formed rocks and soils.p g p

Characterize the broad spectrum of surface radiation.p

Sample Analysis at Mars (SAM)Sample Analysis at Mars (SAM)It consists mainly of three devices for chemical analysis:

G Ch hGas ChromatographMass SpectrometerTunable Laser Spectrometeru a e ase Spect o ete

I ill l h i i f il d kIt will analyze the composition of soil and rock onMars with the intention of findingcompounds that are associated withplife.

SAM ProcessSAM ProcessThe mass spectrometer will divide the sample and itsl t belements by mass.

The gas chromatograph will heat the sample until theyvaporize, and will separate the gases so the compounds arrivep , p g pat different intervals.The laser spectrometer will measure the abundance of

i i t h b h d d i thorganic isotopes such as carbon, hydrogen and oxygen in thecompounds.

ToolsToolsSoftware

Automated Mass Spectral Deconvolution and Identification System (AMDIS)

National Institute for Standards and Technology (NIST) MS Search

Ion Fingerprint Deconvolution (IFD)

Automated Mass Spectral Deconvolution and f S SIdentification System (AMDIS)

AMDIS is a free software used to extract clean spectrafrom complex GC MS analysisfrom complex GC-MS analysis.It allows you to build your own target compound library.This allows you to analyze the samples and match them

i h hwith the components you want.It is useful when you have noisy Total Ion Current (TIC)spectra files.pIt allows you to search components in the NIST librarythrough the NIST MS Search program.It deconvolutes the data matching the compounds andIt deconvolutes the data, matching the compounds andfinding target compounds from the selected library.It accepts large data files in different formats.

AMDIS ProcedureAMDIS analyzes the background and calculates a noise l l f l i level for later processing. It then analyzes the data for an increase of a special ion trace. trace. If there is maxima for other traces at the same time, it assumes there is a peak and shapes a model peak. From there, it calculates clean spectra for each peak. Lastly, it identifies the compound via a library search.

AMDIS InterfaceAMDIS Interface

The confirm window in manual mode: Above is the GC data and b l h MS d f h l d GC i ibelow the MS data for the selected GC retention time.

AMDIS Interface: D l ti A l iDeconvolution Analysis

Confirm window after deconvolution analysis: The upperConfirm window after deconvolution analysis: The upperwindow is the GC data. The graph depicts the TIC over a period oftime for the chosen component. The analysis identifies with anarrow the compounds found in the GC data, and with a T thosep ,compounds it found in the search library. The lower windows arethe compound spectra.

National Institute for Standards and T h l g (NIST) MS S hTechnology (NIST) MS Search

When you have the MS for a compound at a certain retentiontime in the GC, you can run a search command to see if thecompound matches an entry in the NIST library.

The NIST library search program returns the compoundsthat are most likely the identity of the compound you arey y p ysearching for.

It can search by structure or spectra.

NIST MS Search InterfaceNIST MS Search Interface

Compound to identify from the AMDIS Program

Mass spectra for searched compound and the selected possible compound.

The possible identity of the compounds sorted by probability.

Ion Signature Quantitative D l ti (ISQD) S ftDeconvolution (ISQD) Software

Features a set of advanced deconvolution algorithms thatid tif t t d t i diffi lt didentify target compounds present even in difficult andcomplex mixtures.

The software extracts each compound's characteristic signature,untangling it from the surrounding sample matrix.

Will be able to identify compounds “ultra-fast”.

Ion Signature Quantitative Deconvolution: TIC P k Id tifi tiPeak Identification

Peak #1

Peak #2

Peak #3 (selected)Peak #1 (selected)

Peak #4 and so on

Hi h t P k iHighest Peak in selected spectrum

Scan Number and Retention time of the spectrum selected.

MethodologyUtilize IFD to identify theTIC peaks, then select the most significant ones.

Methodology

Run a similarity (based for highest match/rmatch ratio) and an identitysearch (based on probability) using IFD.

Interpret the results between these searches.

Export theTIC peak spectra to NIST.

U NIST t id tif th t d t t if it ith IFD ltUse NIST to identify the spectra and test if it agrees with IFD results.

Insert entry into contaminants spreadsheet.

Project Timeline: Current WorkRetrieve and tabulate information regarding the data files andtheir run parameters rover location etc

Project Timeline: Current Work

their run parameters, rover location, etc.

Retrieve the temperatures for the data files based on the methodusedused.

Consult with other researchers to ensure that the results returnedby our analysis matches with their expectations of whatby our analysis matches with their expectations of whatcontaminants should be present.

Integrate the new data into the target library and monitor howIntegrate the new data into the target library and monitor howeffective it is in successfully identifying compounds found in therover’s environment to ensure correct contaminant detection.

File DatabaseFile DatabaseHyperlink to the filefile.

Column Information

Development of File DatabaseDevelopment of File DatabaseThe file database is a spreadsheet file that contains file locations

i h i f i h i d i iwith information on the runtime parameters and environment inwhich the tests were taken.

This database contains parameters such as: location of the file, thenumber by which it is identified in the material archive, location

l d h l don rover, sample name and Type, the GC Column Type used,temperatures and the date the run was done.

So far we have been able to obtain most of these parameters forover 1000 Finnigan Themo files. We are awaiting input from JPL todetermine the material archive number and the location on therover.

Contaminants DatabaseContaminants Database

Link to file database.

U k d h l b bilit dUnknown compounds have very low probability, do not meet user criteria and have a low match ratio.

Development of Contaminants DatabaseDevelopment of Contaminants DatabaseThe contaminants database is a reference spreadsheet file thatcontains the compounds found in each file and how they can beidentified by their library name.

It lists the name and formula of the most likely compoundaccording to the NIST search that matches an unknowngcompound. It also lists how similar the two compounds are interms of their peaks (match/rmatch) and their abundance(percentage).

B d h i il h h i l d iBased on how similar they are, they are appropriately named inthe library.

Target Compound LibraryTarget Compound Library

D l t f T g t C d LibDevelopment of Target Compound LibraryOn the upper side of the figure we have the name, spectral andother information regarding our unknown spectrum, in themiddle portion is a peak comparison and the lower part is thecompound that most likely matches your unknown compoundcompound that most likely matches your unknown compound.

We see that the spectra match very closely to each other and thep y ypeaks are similar as well in terms of abundance. After this, wego to our contaminants database, look for the component in thel b b f ll h f l h h d hlibrary by following the file path. Then we can determine whatthe known compound was identified as and how probable it is.

Project Timeline: Future WorkProject Timeline: Future WorkContinue analyzing more test data files as well as real-timedata as it becomes available.

C i d i h i d b f hContinue updating the contaminants database for theFinnigan data.

Develop a program prompt that will ease the retrieval of thefile information.

AcknowledgementsAcknowledgementsWe would like to acknowledge with appreciation thefinancial support from NASA GSFC and the DC Space GrantConsortium (DCSGC) that allowed Raul Garcia-Sanchez tospend the 2009 summer in the Atmospheric Experimentsspend the 2009 summer in the Atmospheric ExperimentsLaboratory (Code 699 GSFC) and the award of a FacultySummer Fellowship to Dr. Prabhakar Misra.

We would like to gratefully acknowledge the support andguidance of Dr. Paul Mahaffy and his research group in this

j tproject.