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[Music]

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[Applause]

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all right so today I'm going to talk to

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you about corals which is a laser

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desorption / ablation mass spectrometer

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if you had the opportunity to go to the

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workshop yesterday you would have heard

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me describe it grandly in one minute

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using arm wavy movements but today

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you're gonna actually see that it's a

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it's a real instrument so I normally

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start off when I try to talk about this

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particular instrument concept by

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advocating for mass spectrometry but

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Peter did that for me so I don't really

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have to do that right now I will kind of

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introduce maybe the evolutionary arc of

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mass analyzers so there's our variety of

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options when you want when you know you

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want to fly a mass spectrometer of types

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of mass filters that you can fly I'm a

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product of NASA Goddard so I'm

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intimately familiar with quadrupole mass

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spectrometry which has been surveying

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the solar system since pioneer Venus but

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we have sector field instruments that

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were before then in the Apollo era

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time-of-flight instruments from Vega

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Giotto Rosetta and then most more

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recently are the Paul type ion traps

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that were flown on Rosetta and then we

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heard a little bit about the Mars

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organic molecule analyzer the moma

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instrument onboard the ExoMars Rover so

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all of these systems have been qualified

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or have successfully successfully been

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deployed to a number of planetary

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environments so they're by definition

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heritage or legacy analyzers and they

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still bring a lot to the table and

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they're viable instruments for

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progressive future mission concepts

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they're relatively low cost because once

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you've flown at once you have a heritage

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designed to pull from they're relatively

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low risk because they've been shown to

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survive launch cruise deployment and we

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know what we get from them from a

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performance perspective however since

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the Apollo era for sector field

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instruments for example on there's been

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a lot of time and a lot of investment in

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advancing what I'm gonna call

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next-generation technologies that kind

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of are are pushing the forefront of the

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field forward this is my arbitrary way

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of designating how those technologies

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might be classified there are those that

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maybe use heritage analyzers but add

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something new to them to enhance the

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performance

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to extend the mass range to increase one

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performance metric or another but what

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I'm going to talk to you today about it

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are two key capabilities that I think we

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really need to focus in on especially in

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the astrobiology context and that's

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molecular disambiguation and when we're

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talking about a Europa Lander mission we

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need innovative sampling and ionization

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sources so here's a traditional mass

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spectrum those who have seen my

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presentations before notice I always

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seem to pick on this one but once you

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make an animation you want to kind of

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stick with it so this is a spectrum from

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one of the inbound flybys of the Cassini

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Asst this is Cassini I and M s and we

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have matched to charge ratio on the x

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axis and we have intensity on the Y and

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we see there are a bunch of features

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here and we have a good idea of what the

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primary constituents of these Peaks are

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because you know we can one way we can

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do is we can try to rebuild reproduce

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the relative abundances of these Peaks

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looking at diagnostic fragmentation

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patterns or isotopic abundances of

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plausible species underneath each of

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these some people in the room do this

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there are also you know when you're a

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spaceflight instrument usually you don't

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fly a single analytical instrument so

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you can have corroborated measurements

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from other complimentary payload

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instruments that can give you some

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insight into what these Peaks might be

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but we can't with 100% certainty say

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that there aren't at least some minor

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component of these Peaks could be a

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variety of molecular signatures as I

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said I'm kind of pushing for a laser

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ablation mass spectrometer so once you

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start adding more novel ionization

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sources then you start adding in organic

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isobaric interferences that you have to

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account for so the problems not going

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away it's actually getting a little bit

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more complicated with these advanced

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technologies so we have a bunch of ways

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that we can try to separate these

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signals that are potentially competing

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with one another we've done this

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historically by using things like gas

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chromatography which will use the

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affinity of competing molecules their

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affinity for the stationary phase to

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separate them out through time that's

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still viable

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the

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MoMA instrument uses a kind of a neat

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little tool called tandem mass

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spectrometry and that's where you can

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this one there you go

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you can see a peak of interest you may

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not know what it is exactly but you can

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eject the peaks that you're not

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interested in focus in on this one and

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intentionally break it apart to look at

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the structure of that molecule and to

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provide confidence and what you think it

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is and what I'm going to be pushing for

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today is what's called ultra-high mass

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resolution and that's where those Peaks

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that you saw on the previous slide

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becomes so skinny

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that you can actually elucidate the

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different components that might be

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competing with them so this is a

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Murchison sample we've heard you know

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number of talks have highlighted the

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complexity of Murchison sample but it

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just shows that within what looks like a

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single peak are a multitude of Peaks so

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if you're able to tickle out that that's

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dead at complexity than it really

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provides something so paul Mahaffey gave

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another kind of visual so I'm gonna give

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a different concept he he talked about a

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monatomic isobaric interference here we

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have a polyatomic so we have two organic

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compounds since we're talking about

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europa and with a lot of traditional

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instruments two peaks two distinct

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organic compounds might overlap with one

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another but as we progress towards

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higher and higher resolution instruments

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we're able to effectively separate them

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out without requiring an additional sub

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system like a chromatography system so

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the type of analyzer that I'm fighting

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you know advocating for here is called

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an orbit trap mass analyzer and the way

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it works is a little bit different than

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all of those heritage analyzers you have

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a source of ions and a pulse gets

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injected into this analyzer and they

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oscillate around this football-shaped

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electrode and the rate at which they

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oscillate maps to the mass-to-charge

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ratio of those species it's kind of neat

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for spaceflight not just because of the

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science products which is are these

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high-resolution mass spectra but there

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are no heavy magnets there are no RF

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supplies and there's actually no

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traditional detector assembly which is

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off

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considered a consumable for spaceflight

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applications and so you're able to start

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identifying what were previously

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isobaric species with the same nominal

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mass-to-charge ratio separating them out

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and that allows you to do you know some

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more quantitative metrics so what I want

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to do is to take that type of mass

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analyzer and integrate it with a laser

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source why a laser well there are a

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variety of reasons for it specific to

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Europa laser is access the less volatile

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the more refractory organics that may be

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embedded in the sample but they also

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allow us to break apart the inorganic

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phases so the salts and the other you

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know geological phases that may have

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been brought to the surface from ocean

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exchange can be accessed with these with

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these laser sources it doesn't require

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physical contact with the sample it

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provides spatially resolved measurements

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so you're limited the spatial resolution

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is only limited to the size of your your

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laser beam and a good example of some

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you know other benefits that it brings

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to the table are are highlighted by the

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moma instrument which will fly the first

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laser enabled mass spectrometry to space

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and so here we can see you know these

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are synthetic Mars analog samples but

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we've doped it with an organic compound

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and regardless of what the matrix is

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whether it's a single mineral of

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basaltic matrix or a phyllosilicate we

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can also add potentially degradation

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oxidative compounds in there and what

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otherwise might be you know might have

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induced the combustion of this organic

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because the pulse-width of a laser is so

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short we don't actually thermally alter

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the sample as much as a pyrolysis

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technique and so we're able to see that

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the primary molecule on top of that

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laser processing requires orders of

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magnitude less sample than traditional

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pyrolysis techniques and if you have the

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mass and available to fly maybe I'll

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call it an overqualified laser system if

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you have a high-energy laser system more

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than you need to maybe desorb some of

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these organics that also allows you to

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do a kind of pseudo tandem mass

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spectrometry

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so you can identify your organic at a

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low fluence and if you want to derive

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some of the structure if you want to try

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to identify if it's an isomer which

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which isomer it might be you can

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inundate it with more energy than you

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need to just see it intentionally break

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it up that way and give yourself some

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pseudo tandem mass spectrum so this

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orbit trap mass analyzer there's been a

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prototype in the in an overly oil France

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operational since maybe 2012 and so I

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had the opportunity to go out there a

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little over a year ago and that kind of

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serves as the proof of concept for the

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corrals instrument so I'm gonna say when

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you need to conform to the form fit and

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function of a flight instrument it

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certainly met the function we're

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building up this is a breadboard we have

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in operation now at NASA Goddard only

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brought online within the last couple of

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weeks and this the inside of this

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instrument looks just like with the

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corrals instrument wheel so this meets

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the form and the function but with this

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IC to opportunity and with negotiations

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going on with at JPL pre project team

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were designing this and we will be

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building and qualifying the an

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engineering test unit that meets the

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form fit and function of a flight model

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so we've we have a prototype of the

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laser operational so here's you know

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some of the performance metrics of that

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laser system it's hot again it's highly

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capable so it brings three times the

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energy per pulse that the moma laser

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does because we are interested in that

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in source decay and all of this put

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together should allow us to again

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measure the organic and the inorganic

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composition of samples delivered from

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the europa surface and so I just wanted

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to go over some of the data that we've

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collected recently so here's an example

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of a type of experiment we could run

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this is at the in the French laboratory

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so here we have magnesium sulfate salt

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before and after irradiation

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this salt was doped with an amino acid

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and so the power of this spectrum shows

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that this instrument meets our mass

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resolution requirements you can see our

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parts per million mass accuracy which is

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also critical because that gives you the

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molecular

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soit geometry but what I really like

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about this spectrum is that it shows the

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organics the primary molecule the the

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quintessential fragment you'll find this

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on the NIST database for an e i--

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spectrum - as the dominant fragment and

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then the inorganic fraction you can even

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if you're a geologist you'll even see

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that we can get the isotopic composition

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of magnesium as well so we were curious

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you know what what are our limits of

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detection for example can we see organic

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compounds at the level that the moment

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instrument does which is at the one Pico

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mole per millimeter squared

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concentration level because it's a

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surface technique and so we kind of

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simulated a Europa Lander situation

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where we had in our case it was a

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solution that was allowed to dry down

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rather than an ice to sublimate but

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looking at the residue we were able to

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see a variety of organics this is just

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in positive mode but we're able to see

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the molecular ions of amino acids in

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this kind of context at the Pico mole

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per millimeter square mole so highly

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sensitive and again we're able to get

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isotopic abundances we heard that that's

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maybe not the top priority of a Europa

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Lander mission but it's something that

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we're able to deliver on as well so more

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work is being done looking at the

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capabilities of these progressive

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instruments that we're building with

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progressive levels of fidelity we're

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looking at how our fragmentation

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patterns they said if you over if you

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inundate the sample with excess energy

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you can intentionally fragment so we're

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looking at correlations between our

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fragmentation patterns with a laser

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source and how they map to the

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traditional misty eye mass spectrum

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we're looking at a variety of different

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you know compositions sample matrices so

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here's a an example for Thole ins which

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is apt given the announcement just an

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hour ago looking at inorganic phases so

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here we're looking at major and minor

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elements in a basaltic phase for example

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and doped with that's good it's also a

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pathfinder for more advanced instruments

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but with that I'll leave the conclusion

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slide up there

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[Applause]

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[Music]

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[Applause]

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[Music]

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so the high-mass range can be tuned for

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what is so with this type of mass

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analyzer you have windows that you can

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look at and the window is about 40 x

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from your lowest mass to your highest

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mass we can certainly see higher so our

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our corrals STM has a couple of modes

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defined so when we're looking at the

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inorganic fraction which might overwhelm

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the signal of trace organics we would

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look at from you know sodium Mass 23 up

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to maybe cut it off at 74 so we don't

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have glycine in there and then we could

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go from 75 up to 40 X that but it's

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actually tunable where you want but it

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needs to be 40 X the lowest mass is your

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where's the turnoff yeah so we had this

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conversation about what how large of a

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macro molecule can you analyze without a

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multi matrix and so that yeah without

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fragmenting it beyond recognition and so

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I think I told you this that we were

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measuring dye and tripeptides

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we haven't tested beyond that as of yet