NASA Technical Reports Server (NTRS) 20150008980: A Compact Tandem Two-Step Laser Time-of-Flight Mass Spectrometer for In Situ Analysis of Non-Volatile Organics on Planetary Surfaces

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by  NASA Technical Reports Server (NTRS)

A Compact Tandem Two-Step Laser Time-of-Flight
Mass Spectrometer for In Situ Analysis of Non-
Volatile Organics on Planetary Surfaces

Stephanie A. Gety, Wiliam B. Brisckerhoft, Xing Li Jamie Ella, Timothy Comibh,
‘Scott Ecebberger. Qingluo Wu, and Richad Zane

Absa Two-tep laser dsorton mass specremety Is
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INTRODUCTION

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science as well as aso. We wl pesca seen: work
{o develop + compat ser tow Plght mes sponte
that opti for detecting and anal 2 the nonvokte
‘rgniccompostion of srfice mater as pat of aur
tlt ebsnn to an moon, coma. ce cabonaecos ate.
Thorley eer” desorioninmiation mast specimen
(02318) fx pancuar has proven to be a wsefil aol ie
terest stole to Meniy reluced cuton, putty
‘wot space. in morc ad returned priv slat
{elem mato [Io] We have nent demonstmted IMS
Sia ighh-compact tnwaght ess ana tht 5
bean prosouek developed fer sngedaterdacortion and
Tnnation stds ea plane analog natal (8

2M employs fo arr pues to sequential devon by
en infil ple) apd ews (by an utavas pale) ante
ptinid forthe geometry at dimensions ofthe Stent.
In eur system the desorption lser wavelength i ker 16)
‘y-ray in 3 tunable mange Dewees 27 um and
‘SU gm. The =Sum wavelength i especialy suitable for
fepbbing the slrng sition atures of many ormanic
Species as well asthe Waterce mac ig ths range. The
Jnnaion ser wavelength is coment 26 nm which
‘ntoduces instru seit e armatc species thru &
sonateecrharcal muliphotos iotbaonmxchanism,
Inpieatons and plans for Hght-qoabl lser choos?
{inet thee natn nate vl be duce

‘Additonal sestures ofthe insrumant have been deveped
to enable advanced sss specromerie echniquss na stall
rachage. Thescineuge presion pulsed om gate that als
the sebum of 3 wane mass range of ners fr iegoved
Sensi to mligate adverse detector saturation effets when
incrogatng (nee sane consivents in the presesce of
loinant spe. Coupe wh the on gating capable the
‘scant iplecnation of induced dsoiaton toshnigace
{box for moby fon select aed targeted arent
nabs sieh can provide dete situa infomation.
Here. me desere heve ect strane dovclopnents. and
resent the perfomance ef the instrament (ecnkqucs 38
Epplec to rekvant plantar anaiog sales.

2. Monvation

Ins know rom ramote spectroscopy tha the Ot Solar
Sysiom husbos. = uivese populion of macronmbeul
Snes tha re aly ode rad cningatod
incorporation [0]. ite expoatioy of Tan's upper
susp ee 8 mess and psa spectre his ever 3
fennies wire of gant with a mae deol eoatc

‘hater than prod fm cheview meling ad rere

Sse, omg) lfuenoed the predton of benzene
die oer aout spocks [1.2 Si uel
‘pesado he padieed wth ee hints theron and

nr Cate Sola System modes, hers bam subvententy
epost wots sure is [1] Amrit at
‘ould devpher ems toal contrition omnes
{ough shor! isesigatin wf ange a Tees!
yet unewpace plactay bed: (ton ABO. sonet. or

onpared teresa ivethntone. of
fests Kimalioa and. histo of aeones and chem
sherti,

user desontin niin sans spect DMS
oneep. uly sine technique tht can preview sorpnstcna
Sali ain the norgaic and ese esos eset
sol mueral ih babes le ned or sample
Preparation. ul pulse appsch uo MS. as ussetbed hoe
Silesia of spectral mrnces by eoining
Jekike tors inlaioe ledhague ait & tnd MS
fagcity to Boke and see pent masses wi soe
sie spies, ca be Ae with big sonfseoes hi

Sey of aninchernealy knprtnt chases oT onsnis.
suskohaes
3. INSTRUMENT DisieN
Ihe Seelipnt ot mise oes ne

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oli snes sonore Se wihir a ersnonccote Dube
‘ill ding Loui as exohale serra buned
Libosto-sale LSS fs bso shots tbe seve

snd sstrive. oul in determing, the ywesence and
Sonpocian of msromssclaranemais materel i
fetvonies [ith ‘Tier ve snl (Hand ued
Sonata samples fom Sinise [15} The aaa a the
TBS tectguc wil be val capeiiy fy ature Pu aie

inectgtiny ofelted plenary ha.

Tn LIS the ents oan nee Ker st Bethe
Tonia estas io ger panics seule
fhe sample, & converse snl (10 er 5728 et
eles opoalad ule Eraneccome dehy gepeadng
etgant ih shi degre arbassy i Le Seta

Peake ar (7 een hb pene ingen
‘minature LD-TOFAS nsmnt ik caved ed
refer [1] has en fed to plone the twodset

Sorin tvhniqu. x sown in Fite ail pol
taeneph the Mbt nie eadsmonal Runes ofa Pulsed
NuVAtiova toto sor neal ants toate spe
sie. Aller dele of 0 n6 7, depending on sample
Poston, an athozoral 2 pulse (eguene ea pe
fom a secone NEVAG) lances the eatelts aia
let nz the ae gh reson nba a
Ph ROMP, Mest rte. the WEL
Mesoyi tasers oe alced by a tyable opi!
Darn wssilatr (PO) protucing pulsed IRs the range

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stostiy-ssle megs omens el
fave fen foe polonred ing LIS Ss a Saad
[ives te cote the asssement of rine 128
pecormanee Inthe L2MS at Sala ubed CO: ase

Tig Alice CH, Slogel AL SD AS) Way ape to
eveuteibe ieter rae. Ti beans fcusedtowspot a
ij in lanl fesonh ths sample hv cae batt
Th aoutal phne thes estes prensa hy ie
AU utp ot the uh ie an) of
INENAG face ‘Spout Mises, DCH Uy, The fos ae
nas amayed in bull FORMS posing ar
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Mleplnciy “ant in ntaso Tian tune
omnes oF he srl eke ude sh
FF qmuntanah coupon 8 ela

Teco prtofconey demesne of IMS [and
essen in ping Bl Sar shone fasta ot
Ipemenig thse essa ai mas
spect low we tithe cb cnn te
TENS cn ming compact insert oye fra
‘mteofcais stan ite ed fener ri

4, EXPERIMENTAL METHODS

“The PAIL citi mi (Sime-AUrsh) conmting 16
ongmie stndanls os Kl Te where 10 pte. ech
‘Sheponcnt olen acetone. The pophan and 24-
arinopurine sanpes are soil power purchased fom
SpmrAtlssh, For the espeimuns done by the mints!
instrument the hyiphate PAI mare Ups oo
2 anil stetsanple probe tha allons the sample beheld
2 tne nsocesary votagedurmg TOF-MS anas. The samp
‘rope abled 1 form a fle and he sample probes
intoduced into the vaccum chanber for purpslown and
analy, The powdered sales wee de pcssedont the
ample probe frase colesheatlahment without he use
{saat and tanstened ino the chamber fr pump. dsm and

The sample stub sre uns carmion eve,
andthe Untnce of the sunple fom the instrument it ad
the imerection of th lonation lser pute eon be ell
dpsed. The dehy etwsen Inser poles wae peste
Comvoled wih dehy genentor: (Dé Stanford Reserch
System. Sunnyvale CA USA) coupled wo the everal Q-
svc tigguts ofeach her urine the eprinent the I
[User fat at oust Blow the prompt natin then
inthe absence the IVs orton pe Then dey
botineen the > lies i set at an aver stating val,
‘gpa 13s andthe UY lser ener seul incase
By ineements of tons af uY unl 9 Iweestep Ber mess
scrim observed anrecode! Both The energy of hee
|b and the dla ean be timo daring each exert
‘mane the Sn inonsts of the spocks of itest a
‘sce,

fh the L2MS cxerinents at Stanford. 2 24 drop of he
‘anyple soon sap sptteente 4 ghss pater and did
fnder abit condiions, Thos the lass plaer wos
‘finstened nto the s3coum char thysjgh at nto
Fach eo spstrum avenged over 20 fsersn0

Tor the GSFC ply pe els given bleh 104
nase eng ange for 75 190 comesponding 3
fangs of peak power dsnoy ban and BY MWe

las’ enemies rings fom 40 to HO 2, comespondng 19 &
rage of peak power donsy towween 77 and 430 MWe
[OPO tar ence ranged fom 1010259. consaponding
1 arange ofpevk power density bee 2 and 9 MWiem
For esr spt sar estate 4 be = 30qun ase, Each
pernumrsprscne un average of 1629 ler shots

"Tae UV laser caer) im Sinlord LMS ited 1010 md,
for a bean spot of 6 a in diameter without Geusin
comspanding te posh paver deny of appmsinaaly 18
‘Mien The nergy ofthe CO her ea sll no,
It iroperted nl he thes Hr

5. Results

Hee we pert ul of L2MS memuraments of theoe
orgie "elance | whvautt0.plnaianyatochorst
Tokeseli™ stonatic Redwewbaes. anion ace and
ruckobses. Figures 22nd 3 shove a conparion of mss
{sing diferent thre finn IK ser wavelets! FE. 2)
To pa at Stentd. (ig. 3 cop! 064 am at GSFC wih the
rinature poise and ig. 3 Botan) 29 pm st CSEC- aso
‘lh he mnie proto

‘Conor, Gas Siracnre_]

TS-PAIT Nee

PAT

Nahe m | ©
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Foxe w | oe
Phra m |
eons
eworgpyre
Indo. 23-py ree
Beets
eno(eh pone

Trypan

‘acid

Ti Daaoparine
1m ak tice measucents, sulle peaks are sean
soresponding fa beet nf the Pais contened hin he
frre "The Shani us shown in Te 2 ph we
Shs using a 10 ym desorption ls. apd mass peaks ae
Snot mz 166,178,202, 28 22.296 and 278, Comparing
to Table I ve canarigr there peaks to th eamponett PAHS
raphe (mat. = 12 Da) acenaphiby lone fms. 152
Di and seenapbone an. ~ 158 Da

[seer on
Alias 7
be o
rf 4h
5 oy

Fert art ta
wancoarhecboon snliecering the boron 1288 isan

aes 20m
030) oatene

Signal rtenity (a..)

me

esl for te mite prongs down Figure 2
coe 2 a enn er
ibvsstnmlcour weight PAlte —decled” are orm
Morena apse m= 22 Dh er omc
Figure 2 ation) shows the sme prety siunent
‘haunt we he OND out ned hese 029
Sim savlength The san 265 nation wasnt os
Bred. A broods ange of PAlts seen for he 29 um

esomlion st, inching. tomers phenanthrene and
fanihecene at m= 178 wd Uhh the igh molecu wight
Spares te miuure. We prove pauibe eshanlsns Tor
ince bance stew bobexn tans a entguns Ia
‘te dicuesin section belo

Repeconiatve spies lnm he amino aid and neceokase
cases of maces beer anal! sing LMS to ist he
deecton epabisicy, for cheney et rice eyued
poberct rom hydcubuns. As shore it Fire 4 the

horton L2MS hstumen: a Stanfrd eon rend dtc the
rmakcubr x of 26 daminoparinn st m= 130 using &
Gesorpton laser pube at 10m and ovzation a 266mm.
Uikoetse. tplopkan can be deleted using the sate se
sonfiguration. The stongest peak inthe typlopian spectra,
however. then tap at 1: 13.

inchecaiartersnnen ng frame tnt
Tia ps arn fossa

For sompaison, we show anabek af these standard
‘organics wih the GSFC pray inthe wide desir
‘algun. ih desorpon 999m and nation at 256
fin The noise hn of 26 daninopsins 9 naceobase.
readily Scot at iz 80g 3 taph The moor fen a
fms 130s tne dominant feu in the mass specie
Upuophan (igs bot. Abo saen in hese spss the
lec fon ef cronene a ar= 30, Covent Was aed
these sanphs as amiss cata

6. Discussios

The rests shown above slew us 10 compare the
lnsinenentperinmunee using a range of desorption
‘aveegths fm 14 am to 3 yen TD ym. Al alses
twee pete using 266m fr Snitin- 10s came
{he mas spt othe 1GPAH mizue we observe tat he
25 undseerption wavelength produces mre presente
‘eas speceurn he PAU cntaned within hemi: The
re spctrm obizd forthe ease of 3 ne dssonton|
Isr shows an apparent bis foward: her macula wight
foneunds, la etpirton the mass sperm tained ah
the hbormtory samen. ung 19pm desorplan shows the
modest ange of PAs forte kaon mite

Signal Intensity (a.u.)

Fine 26min ond apn tom) anni er

Imijaisicemor hong ec Coonan ao

The comparison between 1964 aan and 22 yen sults i
sorparatel stighorsr, given that these spect ws
Iakor on the same prcotype muss spectrometer. with onl he
Ue hser configuesion nodifad, Beeuse the PAH source
rises ere aie fomthe sa vendor i sonal
to draw compaduns Retwcen he GSFC priype resus and
those oblaned sin the borin stent. Tha
marion suggests tat he counting of the desorption
Imcchanism maybe. poor at 1968 nm snd exbanead at
incre desopion Waveenths

‘We eutnot ele ot owe sample ne insta lets
that may aio phy a rok these dns. Tor esnple, he
Source igus alhough supped fom the same vendo.
‘vee rot igang os the sie pou. There bate
‘ferences cook lead te quai dirences i the mass
Spectrum though we argue tat these ess weal Be sal
‘ompirl 10 (he ess bits thal te sen these
eum A inher eypfienal Btor that old act
‘he aval reuse he eebtive Nolily of the By
Fcc wight PAHS seniied hin the rkgans An
poe that is cpened under stephens condone can
Cpurense pre xml vobilaion of the fee molecular
SSeahe spots the PAIL miu. ‘his cou Bet
Jsount fr he bss ve high eleva pnt al ree

doa of the rasoncnent betwcen the lbomton) L2MS
fnabrar andthe compact prolly cold ko warions i
‘esuls._ For pls we have prvbusly Jesbed a mss+
‘epenent ees he opinion oF edly tie ets
‘the desorption and lntaten pulses (8) We en sheer
fale tut tht sau shi othe dey ey cou abu ge

While these experimen laces cans pa a contains
rol othe cbservedeirencesin spectra we suggest thatthe
arclar viral eurgtes ofthe pees understudy ae
feo ingomant to the desomtion saelmgth depends
reented Ree, The ne wavelet dependence eas
arcu pogress até eur dalled “cigs willbe he
topic ofe faa ssp.

‘Wher the muckubse 24 dlminepurne Is easly seen
sing desorplon ut bth 1Opmand a 23 jm yang des
ppei tee swale depenlence tia quately
Jn prc th the PAT re: that he mela i
se rei detected fr hs tartan configton
11 teporant to note that tpophon t less subeet to
‘olttaton efits than the PAI mire gen i ably
in sud arm under arb conditions, The care of
{typtophan ie supportthe cancion ha tnger sorption
‘Sstlengh i ingorant te the deletion of conan =p

7. Concusion

We have demnstated hwostep soe mass spectrometric
anabses va compact mseurentation that vould be
‘compile wth ior mf platy sian oppomunies
The wnstep iis spo of sue oF erent standin
reponed here ibarate Ine semsilviy of L2MS to Sey
oma spusio.ivlaing pollo Hysrearbens:
Duckebase alanine acts. Detecting and chartering
these specie il be ipporant 3 9a wf Laue exleton
higsons 0 understanding the astro and P
fnvenny high pry sok epsom angels, Whore our
inventions suggest thet longer deromtion wavelengths
provide the mt esi dteton of coin pane specie
{Sr lar pus ean produce meaning anal f bead

linea chemi an
Fnerament package Tain he weave sabia
patiy = titre desi scence pstoad designed tor
Sudsing an is orpriaive bo

REFERENCES

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