CHARACTERIZATION OF EXOGENOUS ORGANIC MATTER ON THE GANYMEDE SURFACE. M. A. Zaitsev 1, M. V....

CHARACTERIZATION CHARACTERIZATION OF EXOGENOUS OF EXOGENOUS

ORGANIC MATTER ON ORGANIC MATTER ON THE GANYMEDE THE GANYMEDE

SURFACE.SURFACE.

M. A. ZaitsevM. A. Zaitsev11, M. V. Gerasimov, M. V. Gerasimov11, E. N. Safonova, E. N. Safonova11, M. A. Ivanova, M. A. Ivanova22, C. A. , C. A. LorenzLorenz22, A. V. Korochantsev, A. V. Korochantsev22, Yu. P. Dikov, Yu. P. Dikov3,13,1

11Space Research Institute (IKI), Space Research Institute (IKI), 22Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKHI)Vernadsky Institute of Geochemistry and Analytical Chemistry (GEOKHI)33Institute of Geology of Ore Deposits, Petrography, Mineralogy and Institute of Geology of Ore Deposits, Petrography, Mineralogy and GeochemistryGeochemistry (IGEM)(IGEM)

International Colloquium and Workshop

"Ganymede Lander: scientific goals and experiments“

IKI, Moscow, 06.03.2013

oceanocean

icy crusticy crust

stony and stony and

metallic coremetallic core

• What is the Habitability of the Ganymede Ocean?What is the Habitability of the Ganymede Ocean?

• What Organic Compounds (What Organic Compounds (OCOC) and Biomarkers are Present in the Ocean?) and Biomarkers are Present in the Ocean?

• What is the Signature of the Ocean Organics in the Surface Ice?What is the Signature of the Ocean Organics in the Surface Ice?

Cratered terrain of the GanymedeCratered terrain of the Ganymede

OCOC

OCOC

T, P (synthesis)T, P (synthesis)

rocky corerocky core

iceice

OCOC

UV, X-ray, UV, X-ray, γγ

OCOC

OCOCOCOC

Impacts of meteorites Impacts of meteorites

and cometsand comets

Dynamics of exogenous (Dynamics of exogenous (OCOC) and endogenous () and endogenous (OCOC) organic compounds) organic compounds

OCOC

crackcrack

Important questions to Important questions to answeranswer::

What is the proportion between What is the proportion between

endogenous and exogenous OC in the endogenous and exogenous OC in the

upper ~1 m layer of surface ice upper ~1 m layer of surface ice

(available for analysis by a lander)?(available for analysis by a lander)?

How to discriminate endogenous OC How to discriminate endogenous OC

from exogenous?from exogenous?

Given the different isomers for organic molecules with the same composition Murchison should contain several million different carbon-, hydrogen-, nitrogen-, oxygen-, and sulfur-based organic chemicals (Philippe Schmitt-Kopplin et al. (PNAS, 2010, 107, no. 7, 2763–2768).

What is the fate of OC during impact processing?

Delivery of biologically important OC by meteorites.Delivery of biologically important OC by meteorites.

Numerous studies of Murchison by different researches had revealed a complex mixture of large and small organic chemicals, including amino acids, sugar related compounds, carboxylic acids and nucleobases (Botta & Bada, 2002).

Composition of endogenous OC is unknownComposition of endogenous OC is unknown

Composition of OC in falling bodies can be Composition of OC in falling bodies can be characterized by OC in meteorites of characterized by OC in meteorites of different classesdifferent classes

Hypervelocity impact-induced modification of Hypervelocity impact-induced modification of OC can be simulated in laboratoryOC can be simulated in laboratory

The aim of the work:The aim of the work:

Characterization ofCharacterization of OC in carbonaceous OC in carbonaceous chondrites of different types and to chondrites of different types and to investigate modification trends of these OC investigate modification trends of these OC during simulated impact-induced high-during simulated impact-induced high-temperature processing.temperature processing.

ExperimentExperiment

Samples:Samples:o carbonaceous chondrites – Murchison (CM2) and Kainsaz carbonaceous chondrites – Murchison (CM2) and Kainsaz

(CO3)(CO3)o starting meteorites - selection of fresh pieces (~20 mg) and starting meteorites - selection of fresh pieces (~20 mg) and

their powdering their powdering o condensed material (~20 mg) collected after simulated condensed material (~20 mg) collected after simulated

impact-induced evaporation by means of a pulse laserimpact-induced evaporation by means of a pulse laser

Extraction of OC:Extraction of OC:o thermodesorption at thermodesorption at 460460°°СС/pyrolysis at /pyrolysis at 900900°°СС

Analysis of OCAnalysis of OC::o collection of OC in a cold trap at liquid nitrogen collection of OC in a cold trap at liquid nitrogen

temperature, then pulse heating to ~250-300°temperature, then pulse heating to ~250-300°СС and and transfer of volatile species to GC-MStransfer of volatile species to GC-MS

RT: 2.94 - 14.01 SM: 3B

3 4 5 6 7 8 9 10 11 12 13 14Time (min)

0

5000000

10000000

15000000

20000000

25000000

30000000

35000000

40000000

45000000

50000000

55000000

60000000

65000000

70000000

75000000

80000000

85000000

90000000

95000000

100000000

105000000

110000000

115000000

120000000

125000000

130000000

Re

lative

Ab

un

da

nce

8.88

4.40

7.09

9.00

5.21 5.32

7.26

5.50 9.196.20 10.86 13.3111.35

5.10 5.663.87 11.4113.80

12.6410.70 12.5012.85

12.107.523.48 8.826.47 7.60 9.38 10.408.62

8.52 9.796.83

3.30

NL:9.96E8TIC MS Murchison-1-des

RT: 13.93 - 24.99 SM: 3B

14 15 16 17 18 19 20 21 22 23 24Time (min)

0

20000000

40000000

60000000

80000000

100000000

120000000

140000000

160000000

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200000000

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300000000

320000000

340000000

360000000

380000000

400000000

Re

lative

Ab

un

da

nce

18.10

19.59

17.60

16.4919.1917.21

16.66

20.99

20.39

19.05

18.95

19.68 20.4716.3515.8614.76 15.15 21.07

14.41 21.37 21.5922.34

22.66 23.69 23.99 24.49

NL:4.08E8TIC MS Murchison-1-des

Typical chromatogram of thermodesorption products of Murchison at 460°Сand mass-spectra of some OC

Murchison-1-des #474-489 RT: 3.99-4.12 AV: 16 NL: 9.03E8T: + c Full ms [35.00-450.00]

35 40 45 50 55 60 65 70 75 80 85 90 95m/z

0

50000000

100000000

150000000

200000000

250000000

300000000

350000000

400000000

450000000

500000000

550000000

600000000

650000000

700000000

750000000

800000000

850000000

900000000

Re

lativ

e A

bu

nd

an

ce

44.00

45.1042.1539.08 47.11 56.11 72.0160.00 78.0351.05 67.13 84.0281.14 96.0661.95 75.09 91.20 98.1988.11

Murchison-1-des #519-527 RT: 4.37-4.44 AV: 9 SB: 17 4.30-4.36 , 4.44-4.50 NL: 8.99E6T: + c Full ms [35.00-450.00]

35 40 45 50 55 60 65 70 75 80 85 90 95m/z

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

4500000

5000000

5500000

6000000

6500000

7000000

7500000

8000000

8500000

Re

lativ

e A

bu

nd

an

ce

41.08

39.07

56.07

44.04

55.08

38.10

50.0537.08 57.1053.0649.06 63.9645.06 66.0259.11 78.1269.07 72.04 91.12 97.4488.8883.13 93.2575.11

Murchison-1-des #843-847 RT: 7.08-7.11 AV: 5 SB: 2 7.04 , 7.13 NL: 1.94E7T: + c Full ms [35.00-450.00]

35 40 45 50 55 60 65 70 75 80 85 90 95m/z

0

1000000

2000000

3000000

4000000

5000000

6000000

7000000

8000000

9000000

10000000

11000000

12000000

13000000

14000000

15000000

16000000

17000000

18000000

19000000

Re

lativ

e A

bu

nd

an

ce

78.07

50.05

77.0852.05

39.07

79.1038.08 63.03 76.0949.06

73.0662.0453.0748.05 64.05 80.0940.06 67.08 86.26 94.1584.86 91.14


35 40 45 50 55 60 65 70 75 80 85 90 95m/z

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

4500000

5000000

5500000

6000000

6500000

7000000

7500000

Re

lativ

e A

bu

nd

an

ce

58.00

83.99

45.03

39.07

57.02

38.08

37.08 41.09 69.01 83.0485.0556.08 59.0349.06 81.03

67.0855.0870.06 80.06 98.0887.1064.07 91.08 96.43


35 40 45 50 55 60 65 70 75 80 85 90 95m/z

0

2000000

4000000

6000000

8000000

10000000

12000000

14000000

16000000

18000000

20000000

22000000

24000000

26000000

28000000

30000000

Re

lativ

e A

bu

nd

an

ce

91.06

92.09

39.08

65.04

63.03

45.11 51.06 93.0962.0338.09 89.0841.0861.03 66.0655.07 70.09 97.0474.03 86.0481.0949.07


35 40 45 50 55 60 65 70 75 80 85 90 95m/z

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

4500000

5000000

5500000

6000000

6500000

7000000

7500000

8000000

8500000

9000000

9500000

10000000

10500000

11000000

11500000

12000000

12500000

13000000

13500000

Re

lativ

e A

bu

nd

an

ce

97.01

98.03

45.03

39.06

69.02 91.0753.06 58.01 99.0592.0855.0738.08 41.08 70.0765.05

63.0347.02 49.05 81.07 95.0783.0868.0642.12 89.0972.06

11

11 22

22

3333 44

44

55

55 66

66

((11)) - CO - CO22, , ((22))-isobutene-isobutene, (3)-, (3)-benzenebenzene,,

(4) – (4) – thiophenethiophene, (5) – , (5) – toluenetoluene, ,

(6)-(6)-methyl thiophene, (7) – nmethyl thiophene, (7) – n--dodecanedodecane, ,

(8)(8) – – nn--tridecanetridecane

Murchison-1-des #1967-1970 RT: 16,48-16,50 AV: 4 SB: 12 16,40-16,46 , 16,50-16,53 NL: 3,77E7T: + c Full ms [35,00-450,00]

40 60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

70

80

90

100

Re

lativ

e A

bu

nd

an

ce

43,09

57,09

71,10

85,1156,10

70,11

98,1484,14 170,23112,14 127,16 141,19 162,16 182,25 207,06 224,99 251,02

77

77

Murchison-1-des #2159-2164 RT: 18,09-18,13 AV: 6 SB: 14 18,00-18,07 , 18,12-18,15 NL: 5,37E7T: + c Full ms [35,00-450,00]

40 60 80 100 120 140 160 180 200 220 240m/z

0

10

20

30

40

50

60

70

80

90

100

Rel

ativ

e A

bund

ance

43,1057,09

71,11

85,10

55,0770,12

99,1384,14 184,23127,16 141,18 155,20 182,22 191,17 206,29 251,04225,25

8888

OC in the products of thermodesorption of MurchisonOC in the products of thermodesorption of Murchison

Results of identificationResults of identificationAbun-Abun-dancedance,,

%%ClassesClasses of OCof OC

Subclasses of Subclasses of OCOC

Groups of compounds and individual substancesGroups of compounds and individual substances

Hydro-Hydro-carbonscarbons

Alkanes > CAlkanes > C1010

NN--dodecanedodecane ( (CC1212HH2626), ), nn--tridecane tridecane ((CC1133HH2828), , ), , nn--tetradecane tetradecane ((CC1144HH230230), , н-), , н-

pentadecanepentadecane ( (CC1155HH3232), ), structural isomers of structural isomers of СС1111-С-С1919 alkanesalkanes. . Main Main

components arecomponents are nn--alkanesalkanes С С1111-С-С1818

56,556,5

Unsaturated Unsaturated hydrocarbonshydrocarbons

Isobutene (CIsobutene (C44HH88)), , isomers ofisomers of С С66-С-С1010 alkenesalkenes , С, С44-С-С77 alkadyenesalkadyenes, , alkynesalkynes 3,33,3

Alicyclic Alicyclic hydrocarbonshydrocarbons

Isomerides of alkylcyclopropanesIsomerides of alkylcyclopropanes,, cyclopentene (C cyclopentene (C55HH88)), ,

alkylcyclopentenesalkylcyclopentenes, , alkylcyclohexanesalkylcyclohexanes, , decahydronaphthalene decahydronaphthalene derivativesderivatives

1,21,2

Benzene and Benzene and aklylbenzenesaklylbenzenes

BenzeneBenzene (С (С66HH66), ), toluenetoluene (С (С77HH88), ), xylenexylene (С (С88HH1010), ), styrenestyrene (С (С88HH88), ), cumenecumene

(С(С99HH1212), ), cymenescymenes (С (С1010HH1414), ), trimethylbenzenestrimethylbenzenes (С (С99HH1212), ), alkylbenzenes alkylbenzenes

containig containig СС44÷÷<<СС77 side chainsside chains20,420,4

Naphthalene, its Naphthalene, its derivatives and derivatives and other aromaticsother aromatics

NaphthaleneNaphthalene (С (С1010HH88),), methylnaphthalenesmethylnaphthalenes (С (С1111HH1010), ),

dimethylnaphthalenesdimethylnaphthalenes (С (С1212HH1212))9,19,1

O-O-containincontainin

gg compoundcompound

ss

Carbonyl Carbonyl compoundscompounds

AldehydesAldehydes: : acetaldehydeacetaldehyde ( (CHCH33CHOCHO) ) and othersand others, , cetonescetones: : acetoneacetone (С (С33HH66OO) )

andand othersothers. . 2,22,2

OtherOther O-O-containing containing compoundscompounds

AlcoholsAlcohols, , furanfuran (С (С44HH44OO) ) and its derivativesand its derivatives 2,42,4

S- S- containincontainin

gg compoundcompound

ss

--Thiophene Thiophene (С(С44HH44SS) ) andand alkylthiophenesalkylthiophenes withwith С С22÷÷>C>C4 4 side chains,side chains,

benzothiophenebenzothiophene,, dimethyldisulfide dimethyldisulfide CHCH33S-SCHS-SCH334,04,0

N-N-containincontainin

gg compoundcompound

ss

--NitrilesNitriles (acetonitrile CH(acetonitrile CH33CNCN, , benzonitrile Cbenzonitrile C66HH55CNCN), ), pyridine (Cpyridine (C55HH55N)N) and and

its derivatives its derivatives 0,90,9

TotalTotal::

100100

Comparison of abundances of different subclasses of OC in Comparison of abundances of different subclasses of OC in products of thermodesorption at products of thermodesorption at 460460°°С С of Murchison and of Murchison and

KainsazKainsaz

Con

cent

ratio

n, w

t.%

0

10

20

30

40

50

60

KainsazMurrchison

carb

onyl

s

othe

r O

-con

tain

ing

OC

nitr

ils

unsa

tura

ted

hydr

ocar

bons

alic

yclic

hyd

roca

rbon

s

alca

nes

>C

10

thio

phen

es

benz

ene

and

akly

lben

zene

s

naph

thal

ene

and

its d

eriv

ativ

es

Comparison of products which are produced during Comparison of products which are produced during pyrolysis (at pyrolysis (at 900900°°СС) of) of Murchison and Kainsaz Murchison and Kainsaz

meteorites meteorites

Components and Components and groups of groups of

componentscomponentsMurchisonMurchison KainsazKainsaz

COCO22 ++ ++

SOSO22 ++ --

MethylmercaptaneMethylmercaptane CHCH33SHSH ++ --

IsopreneIsoprene (С (С55HH88)) ++ --

AcetonitrileAcetonitrile ( (CHCH33CNCN)) ++ --

BenzeneBenzene (С (С66HH66)) ++ ++

Toluene (CToluene (C77HH88)) ++ ++

Xylenes and other Xylenes and other alkylbenzenesalkylbenzenes ++ ++

NaphthaleneNaphthalene (С (С1010HH88)) ++ ++

AlkanesAlkanes >C>C1010 ++ ++

Summary:Summary:

We have measured ~200 organic compounds in products of We have measured ~200 organic compounds in products of thermodesorption thermodesorption (460(460ººСС) ) of Murchison (CM2) and Kainsaz (CO3) of Murchison (CM2) and Kainsaz (CO3) carbonaceous chondrites. Some biochemically important compounds carbonaceous chondrites. Some biochemically important compounds (e.g. amino acids) were not targeted in this step of investigation.(e.g. amino acids) were not targeted in this step of investigation.

OC are qualitatively similar in composition for both Murchison and OC are qualitatively similar in composition for both Murchison and Kainsaz, though Murchison has higher abundance and diversity of OC Kainsaz, though Murchison has higher abundance and diversity of OC rather than Kainsaz. This is consistent with the higher metamorphic rather than Kainsaz. This is consistent with the higher metamorphic temperatures of the Kainsaz temperatures of the Kainsaz ((453453±29ºC±29ºC) ) compared to the Murchison compared to the Murchison (96(96±±65 65 ººСС)) which which resulted in depletion of volatile organics. resulted in depletion of volatile organics.

Organic sulfides (methylmercaptane and dimethylsulfide) were Organic sulfides (methylmercaptane and dimethylsulfide) were measured in the Murchison thermodesorption products but were absent measured in the Murchison thermodesorption products but were absent for Kainsaz. This observation may indicate the absence of sulfide and for Kainsaz. This observation may indicate the absence of sulfide and disulfide bridges in the Kainsaz OC, which bounds fragments of high-disulfide bridges in the Kainsaz OC, which bounds fragments of high-molecular OC (result of high metamorphic temperatures). Such OC as molecular OC (result of high metamorphic temperatures). Such OC as acetonitrile and isoprene were also absent in the Kainsaz pyrolysis acetonitrile and isoprene were also absent in the Kainsaz pyrolysis products contrary to that of the Murchison and are probably lost due to products contrary to that of the Murchison and are probably lost due to defragmentation of kerogen during thermal metamorphism. defragmentation of kerogen during thermal metamorphism.

Based on the pyrolysis results, high-molecular polymerized OC Based on the pyrolysis results, high-molecular polymerized OC (kerogen) of the carbonaceous chondrites can be characterized as (kerogen) of the carbonaceous chondrites can be characterized as blocks of high-condensed aromatic structures with functional groups, blocks of high-condensed aromatic structures with functional groups, which are bound by hydrocarbon- and sulfur-containing bridges.which are bound by hydrocarbon- and sulfur-containing bridges.

Co

nce

ntra

tion

, w

t.%

0

10

20

30

40

50

starting Kainsazcondensate

carb

on

yls

oth

er

O-c

on

tain

ing

OC

nitr

ils

un

satu

rate

d h

ydro

carb

on

s

alic

yclic

hyd

roca

rbo

ns

alc

an

es

>C

10

thio

ph

en

es

be

nze

ne

an

d a

klyl

ben

zen

es

na

ph

thal

en

e a

nd

its

de

riva

tive

s

Comparison of abundances of different subclasses of OC in Comparison of abundances of different subclasses of OC in products of thermodesorption at products of thermodesorption at 460460°°С С of Kainsazof Kainsaz and the and the condensate from its impact-simulated high-temperature condensate from its impact-simulated high-temperature

vaporizationvaporization

Main characteristics of high-temperature products of Main characteristics of high-temperature products of impact-simulated vaporization of Murchison and impact-simulated vaporization of Murchison and Kainsaz:Kainsaz:

• high qualitative similarity of OC in starting meteorites high qualitative similarity of OC in starting meteorites and in their experimentally produced condensates;and in their experimentally produced condensates;

• high abundance of COhigh abundance of CO22 and SO and SO22;;

• higher concentration of acetonitrile, furan group higher concentration of acetonitrile, furan group compounds, various thiophene derivatives, compared compounds, various thiophene derivatives, compared to starting meteorites thermodesorption products;to starting meteorites thermodesorption products;

Conclusions:Conclusions:

• endogenous OC delivered to the Ganymede surface by endogenous OC delivered to the Ganymede surface by falling meteorites can be represented by a wide diversity falling meteorites can be represented by a wide diversity of hydrocarbons, O-, S-, and N- containing compounds;of hydrocarbons, O-, S-, and N- containing compounds;

• being fragmented from a high-condensed kerogen-like being fragmented from a high-condensed kerogen-like material, OC can be presented by a sufficiently complex material, OC can be presented by a sufficiently complex molecules;molecules;

• biologically important molecules like amino acids and biologically important molecules like amino acids and nucleobases can be also delivered by carbonaceous nucleobases can be also delivered by carbonaceous chondrites/comets;chondrites/comets;

• impact-induced high-temperature processing of meteoritic impact-induced high-temperature processing of meteoritic material does not change qualitatively the pattern of material does not change qualitatively the pattern of delivered OC;delivered OC;

• we need to elaborate composition- and isotope- based we need to elaborate composition- and isotope- based criteria to discriminate between endogenous and criteria to discriminate between endogenous and exogenous OC;exogenous OC;

• try to find fresh ices to avoid exogenous contamination.try to find fresh ices to avoid exogenous contamination.

CHARACTERIZATION OF EXOGENOUS ORGANIC MATTER ON THE GANYMEDE SURFACE. M. A. Zaitsev 1, M. V....

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