NASA/CP-1998-10156

Sixth Symposium on Chemical Evolution and the Origin

and Evolution of Life

Sara E. Acevedo, Donald L. DeVincenzi, and Sherwood Chang, Editors

National Aeronautics and

Space Administration

Ames Research Center

Moffett Field, California 94035-1000

September 1998
Available from:

NASA Center for AeroSpace Information

7121 Standard Drive

Hanover, MD 21076-1320

National Technical Information Service

5285 Port Royal Road

Springfield, VA 22161

_1 :If I"
PREFACE

This report contains session summaries and abstracts from the Sixth Symposium on Chemical

Evolution and the Origin and Evolution of Life, organized on behalf of NASA's Exobiology

Program and held November 17-20, 1997 at NASA's Ames Research Center, Moffett Field,

California.

The Exobiology Program is a key element of NASA's nascent Astrobiology Initiative;

=Astrobiology is defined as the study of life in the universe, and the chemical and physical forces

and adaptations that influences life's origins, evolution, and destiny."

The goal of NASA's Exobiology Program is to understand the origin, evolution, and distribution

of life in the universe. The Exobiology Program is therefore quite broad in scope and subject areas

covered during the Symposium included: Cosmic Evolution of the Biogenic Compounds,

Prebiotic Evolution, Early Evolution of Life, Evolution of Advanced Life, and Space Exploration

For Exobiology.

The Symposium provided an opportunity for NASA's Exobiology principal investigators to

present their most recent research results. In addition, the symposium helped foster increased

communication across disciplinary lines, formulate a more integrated program approach, review

progress in all tasks, and increase visibility of the Exobiology Program.

The more than 200 participants included Exobiology grantees, NASA Ames Research Center

staff, graduate students, and invited guests. Current plans are to continue to schedule this

symposium every three years. Further information about NASA's Exobiology Program can be

found at:

http://exobiology.nasa.gov/Exobiology_Program/program.htmt

Michael Meyer

Astrobiology Discipline Scientist

NASA Headquarters
'Ill
TABLE OF CONTENTS

Agenda .................................................................................................................................. iii

Session Summaries ................................................................................................................ 1

Abstracts of Oral Presentations "_ ........................................................................................... 17

Abstracts of Poster Presentations .......................................................................................... 77

Attendees Roster ................................................................................................................. 91

Index of Speakers ............................................................................................................... 105

The abstracts for the oral presentations appear in order of presentation. The page number for any

individual abstract can be found by the speaker's name in the Speaker's Index at the back of this

document.

AGENDA

................. MONDAY NOVEMBER 17, 1997

8:30 am

8:40 am

8:50 am

SYMPOSIUM SESSION I (OPENING REMARKS)

Introduction & Logistics (Donald DeVincenzi and Sara Acevedo)

Welcome (Henry McDonald)

Astrobiology & Exobiology (Michael Meyer)

9:10 am

9:30 am

9:50 am

10:10 am

10:30 am

10:50 am

11:10 am

11:30 am

11:50 am

12:10 pm

SYMPOSIUM SESSION II

Co-Chairs: J. Farmer and D. Deamer

INFRARED CAVITY RINGDOWN LASER ABSORPTION SPECTROSCOPY OF

CARBON CLUSTERS

(Robert Provencal, Joshua Paul, and Richard Saykally*)

HYDROGENATED PAH (AN AROMATIC & ALIPHATIC SPECIES) AS A

COMPONENT OF THE INTERSTELLAR AND CIRCUMSTELLAR MEDIUMS

(Thomas J. Wdowiak*, Kenneth M. Arnoult, and Luther W. Beegle)

IDENTIFICATION OF ORGANIC CARBON IN INTERPLANETARY DUST

(G.J. Flynn*, L.P. Keller, and M.A. Miller)

ADDITIONAL EVIDENCE FOR POSSIBLE BIOGENIC ACTIVITY IN THE MARTIAN

METEORITE ALH84001

(D.S. McKay*, E.K. Gibson, K. Thomas-Keptra, and C.S. Romanek)

Coffee Break

THE SEARCH FOR LIFE ON MARS

(John F. Kerridge*)

=

RADAR DETECTABILITY OF A SUBSURFACE OCEAN ON EUROPA

(Christopher F. Chyba*)

EARLY LIFE ENVIRONMENTS ON EARTH AND MARS (ELEEM)

(G. Arrhenius, S.J. Mojzsis*, T.M. Harrison, K.D. McKeegan, A.P. Nutman, and

C.R.L. Friend)

IN VITRO EVOLUTION OF NOVEL RNA AND DNA ENZYMES

. =

(Gerald F. Joyce*, Martin C. Wright, and Richard K. Bruick)

Lunch Break

* speaker; to find the abstract of a particular presentation, check the Speakers' Index at the back of this

report for the page number.
1:30pm

1:50 pm

2:10 pm

2:30 pm

2:50 pm

3:10 pm

3:30 pm

3:50 pm

4:10 pm

4:30 pm

4:50 pm

5:10 pm

SYMPOSIUM SESSION m

Co-Chairs: Y. Pendleton and D. Lies

CHEMISTRY OF THE BIOGENIC ELEMENTS IN DENSE INTERSTELLAR CLOUDS

AND RELATIONS TO THE SOLAR SYSTEM

(W.M. Irvine and J.E. Dickens*)

PHOTOCHEMICAL EVOLUTION OF THE BIOGENIC ELEMENTS IN PRECOMETARY/INTERSTELLAR ICE ANALOGS

(L.J. Allamandola*)

IS MOTHER EARTH THE MOTHER OF LIFE? THE SEARCH FOR ORGANIC

MOLECULES INSIDE MINERALS AND ROCKS

(Friedemann Freund* and Alka Gupta)

MOLECULAR MODELING OF PROTOCELLULAR STRUCTURES AND FUNCTIONS

(Andrew Pohorille*, Michael A. Wilson, Michael H. New, and Christopher Chipot)

STRUCTURE AND FUNCTION OF ENCAPSULATED REPLICATING SYSTEMS

(David W. Deamer*)

Coffee Break

PHOTOSYNTHESIS AND IRON IN HIGH IRON MICROBIAL MATS

(Beverly K. Pierson*)

SPECIES COMPOSITION OF HOT SPRING CYANOBACTERIAL MATS

(David M. Ward* and Thane Papke)

BIOGEOCHEMISTRY OF CARBON IN THE ANCIENT BIOSPHERE:

PERSPECTIVES FROM MODERN MICROBIAL COMMUNITIES AND THE ANCIENT

CARBON ISOTOPIC RECORD

(David J. DesMarais*, A. Tharpe, and J. Thompson)

THE DISTRIBUTION OF PROTEROZOIC FOSSILS IN TIME AND SPACE

(Andrew H. Knoll*)

THE BIOLOGICAL POTENTIAL OF MARS (AND MARS MISSIONS)

(Bruce Jakosky*)

Adjoum for the day

................ TUESDAY NOVEMBER 18, 1997

8:30 am

SYMPOSIUM SESSION IV

Co-Chairs: L. Allamandola and B. Pierson

THE NASA SPECIALIZED CENTER OF RESEARCH AND TRAINING (NSCORT) IN

EXOBIOLOGY

(Jeffrey L. Bada*, Stanley L. Miller, Gustaf Arrhenius, Russell F. Doolittle, Christopher

Wills, Gerald Joyce, and Leslie Orgel)

iv
8:50 am

9:10 am

9:30 am

9:50 am

10:10 am

10:30 am

10:50 am

11:10 am

11:30 am

11:50 am

12:10 am

ENANTIOMERIC EXCESSES IN THE AMINO ACIDS OF CARBONACEOUS

CHONDRITES

(John Cronin* and Sandra Pizzarello)

MODIFICATION OF AMINO ACIDS AT SHOCK PRESSURES OF 3.5 TO 32 GPa

(Etta Peterson, Friedrich Horz, George Cooper, and Sherwood Chang*)

AN INVESTIGATION OF SUGARS AND OTHER POSSIBLE FORMALDEHYDE

PRODUCTS IN THE MURCHISON METEORITE

(George Cooper*)

CO-ORIGIN OF METABOLISM AND BIOPOLYMER SYNTHESIS USING FORMOSE

SUGAR SUBSTRATES

(Arthur L. Weber*)

Coffee Break

THE ORIGIN AND EVOLUTION OF OXYGENIC PHOTOSYNTHESIS

(Robert E. Blankenship* and Hyman Hartman)

HORIZONTAL GENE TRANSFER: PITFALLS AND PROMISES

(J. Peter Gogarten*, Elena Hilario, and Lorraine Olendzenski)

GENES AND ENZYMES OF ANAEROBIC METABOLISM IN SHEWANELLA

PUTREFACIENS

(Kenneth H. Nealson, Doug Lies*, Sasha Tsapin, and James Scott)

VIABLE BACTERIA IN SIBERtAN AND ANTARCTIC PERMAFROST

(E.I. Friedmann*, A.D. Gilichinsky, T. Shi, G.S. Wilson, R.H. Reeves, V.E. Ostroumov,

E.A. Vorobyova, V.S. Soina, V.A. Shcherbakova, T.A. Vishnivetskaya, J.P. Chanton,

R.O. Friedmann, C.P. McKay, and E.M. Rivkina)

POLAR ANALOGS TO MARS

(C. McKay*, D. Andersen, W. Davis, and E.I. Friedmann)

Lunch Break

1:30 pm

1:50 pm

2:10 pm

SYMPOSIUM SESSION V

Co-Chairs: S. Cady and C. Chyba

THE END PERMIAN MASS EXTINCTION: GEOCHRONOLOGY AND PA'FIERNS OF

EXTINCTION

(Douglas H. Erwin*, Samuel A. Bowring, Mark Martin, Kathy Davidek, and Jin Yugan)

ORDOVICIAN BIODIVERSITY: GEOGRAPHY AND ENVIRONMENT

(Arnold I. Miller*)

WAS HIGH OBLIQUITY THE CAUSE OF LOW-LATITUDE PRECAMBRIAN

GLACIATION?

(Darren M. Williams*, James F. Kasting, and Lawrence Frekes)
2:30 pm

2:50 pm

3:10 pm

3:30 pm

3:50 pm

4:10 pm

4:30 pm

4:50 pm

5:10 pm

PALEOBIOLOGY OF THE TERMINAL PROTEROZOIC: PRELUDE TO THE

CAMBRIAN EXPLOSION

(Bruce Runnegar*)

CO2 GREENHOUSE IN THE EARLY MARTIAN ATMOSPHERE: SO2 INHIBITS

CONDENSATION

(Y.L. Yung*, H. Nair, and M.F. Gerstell)

Coffee Break

DIFFUSION OF PHOTOCHEMICALLY PRODUCED HYDROGEN PEROXIDE IN THE

MARTIAN REGOLITH

(Richard C. Quinn and Aaron P. Zent*)

THE SUDBURY IMPACT CRATER: EFFECTS ON CARBONACEOUS MA'I-FER

(T.E. Bunch*, L. Becker, J. Bada, D. Glavin, D. Des Marais, P. Schultz, F. Rietmeijer,

and W. Wolbach)

METEORITE IMPACT PRODUCTION OF VOLATILES AND THEIR BIOSPHERIC

EFFECTS AT THE CRETACEOUS/TERTIARY BOUNDARY

(Kevin O. Pope*, Kevin H. Baines, and Adriana C. Ocampo)

SHOCK SYNTHESIS OF ORGANICS IN COMETARY IMPACTS

(C.P. McKay* and B. Borucki)

DEVELOPMENT OF A LASER RAMAN SPECTROMETER FOR IN SITU

EXOBIOLOGY EXPLORATION

(Thomas J. Wdowiak*, David G. Agresti, Sergey B. Mirov, and Anatoly B. Kudryavtsev)

Adjourn for the day

WEDNESDAY NOVEMBER 19, 1997 ................

8:30 am

8:50 am

9:10 am

9:30 am

SYMPOSIUM SESSION VI

Co-Chairs: T. Kanavarioti and D. Lowe

NON-ENZYMATIC OLIGOMERIZATION OF MONONUCLEOTIDES USING

NON-STANDARD OLIGONUCLEOTIDE TEMPLATES

(Christopher Switzer*, Thazha P. Prakash, Rajanikanth Bandaru, Christopher

Roberts, and John Chaput)

TEMPLATE-DIRECTED SYNTHESIS OF DNA-PNA CHIMERAS

(Leslie E. Orgel* and Marcus Koppitz)

TITAN HAZE: CYANOACETYLENE AND CYANOACETYLENE-ACETYLENE

PHOTOPOLYMERS

(James P. Ferris* and David Clarke)

ABIOTIC ORGANIC SYNTHESIS UNDER SIMULATED HYDROTHERMAL

CONDITIONS

(Bernd R.ToSimoneit*, T.M. McCollum, and G. Ritter)

vi
9:50am

10:10am

10:30am

10:50am

11:10am

11:30am

11:50am

12:10am

HYDROTHERMAL ECOSYSTEMS IN A PLANETARY CONTEXT

(Everett L. Shock* and William B. McKinnon)

Coffee Break

ANOXIA AND EVOLUTIONARY PATI-ERNS IN THE SEA: ON-SHORE/OFF-SHORE

TRENDS AND RECENT RECRUITMENT OF THE DEEP-SEA AND

HYDROTHERMAL VENT FAUNAS

(David K. Jacobs* and David R. Lindberg)

MOSSBAUER SIGNATURES THAT MAY BE USEFUL IN IDENTIFYING RESIDUES

OF ANCIENT MARTIAN HYDROTHERMAL SYSTEMS

(-rhomas J. Wdowiak*, David G. Agresti, Manson L. Wade, Lawrence P. Armendarez,

and Jack D. Farmer)

EXPLORATION OF MONO LAKE USING TROV: APPLICATION OF

TELEPRESENCE TECHNOLOGY TO EXOBIOLOGY STUDIES

(C.R. Stoker*)

RECOGNIZING BIOGENIC SIGNATURES NEAR LIFE'S UPPER TEMPERATURE

LIMIT THE ROLE OF HYPERTHERMOPHILIC BIOFILMS IN SPICULAR GEYSERITE

MORPHOGENESIS

(Sherry L. Cady*, David J. Des Marais, Jack D. Farmer, Malcolm R. Walter, Carrine E.

Blank, and Norman R. Pace)

FOSSILIZATION PROCESSES IN THERMAL SPRINGS: COMPARATIVE STUDIES

OF MODERN AND ANCIENT SILICEOUS SPRING SYSTEMS

(Jack Farmer*, Brad Bebout, Linda Jahnke, David Des Marais, and Matcolm Watter)

Lunch Break

1:30 pm

1:50 pm

2:10 pm

2:30 pm

2:50 pm

3:10 pm

SYMPOSIUM SESSION VII

Co-Chairs: L.P. Knauth and A. Weber

THE IKIRYU SINTER (500,000-300,000 YRS.), KYUSHU, JAPAN

(Donald R. Lowe* and Eiji Izawa)

PRESERVATION OF HALOARCHAEA AND THEIR MACROMOLECULAR

CONSTITUENTS IN BRINE INCLUSIONS FROM BEDDED SALT DEPOSITS

(J.K. Fredrickson*, T.C. Onstott, T.J. Bailey, and D.P. Chandler)

EXPOSURE OF OSMOPHILIC MICROBES TO THE SPACE ENVIRONMENT ON

BIOPAN: UV-RADIATION, THE EFFECT OF ANHYDROBIOSIS AND PROTECTION

MECHANISMS

(R.L. Mancinelli* and M.R. White)

THE ORIGINS OF THE TRANSLATION MACHINERY

(Deana C. Larkin, Susan A. Martinis, and George E. Fox*)

THE CASE AGAINST COMETARY ORIGIN OF THE OCEANS

(K.J. Zahnle*)

Coffee Break

vii
3:30 pm

3:50 pm

4:10 pm

4:30 pm

4:50 pm

5:10 pm

5:30 pm

6:00 pm

ORGANICS IN SPACE: FROM STARDUST TO PLANETESIMALS

(Y. Pendleton*)

INTERSTELLAR PRECURSORS OF METEORITIC ORGANIC MOLECULES

(S.B. Chamley*)

WHAT BIOPOLYMERS ARE EXPECTED IN EXTRATERRESTRIAL

ENVIRONMENTS

(S.A. Benner*)

TOWARD RNA - THE MINERAL INDUCED PHOSPHORYLATION OF

GLYCOALDEHYDE

(G. Arrhenius, R. Krishnamurthy*, and S. Pitsch)

MARS SAMPLE RETURN QUARANTINE PROTOCOL WORKSHOP

(Donald L. DeVincenzi*)

PLANETARY PROTECTION AND MARS SAMPLE RETURN: FROM NOW

THROUGH LAUNCH AND BEYOND

(Margaret S. Race*)

Adjoum for the day

Poster Session

................. THURSDAY NOVEMBER 20, 1997 .................

8:30 am

8:50 am

9:10 am

9:30 am

9:50 am

10:10 am

SYMPOSIUM SESSION VIII

Co-Chairs: T. Wdowiak and L. Jahnke

THE ABUNDANCE OF 130 IN MARINE ORGANIC MATTER AND ISOTOPIC

FRACTIONATION IN THE GLOBAL BIOGEOCHEMICAL CYCLE OF CARBON

DURING THE PAST 800 MA

(John M. Hayes*, Harald Strauss, and A.J. Kaufman)

MOLECULAR BIOMARKERS FOR CYANOBACTERIA

(Linda L. Jahnke*, Roger E. Summons, and Harold P. Klein)

THE MARTIAN CARBON CYCLE AND IMPLICATIONS FOR THE _130 VALUE OF

THE ATMOSPHERE

(David Kass* and Yuk Yung)

DETECTION, FORMATION, AND EVOLUTION OF COMPLEX HYDROCARBONS IN

PROTOSTELLAR CORES

(Thangasamy Velusamy*, William D. Langer, and Steven Levin)

ANALYSIS OF THE CARBONACEOUS COMPONENT OF COMET HALLEY DUST

(Marina N. Fomenkova* and Sherwood Chang)

Coffee Break

viii

7-i I _
10:30 am

10:50 am

11:10 am

11:30 am

11:50 am

12:10 am

THE STRUCTURE OF EXTRATERRESTRIAL WATER ICE

(David Blake*, Peter Jenniskens, and Lance Delzeit)

THE MECHANISM OF AMINE-CATALYZED HYDROLYSIS OF RNA

(David A. Usher* and John R. Townsend)

INORGANIC SOLIDS AND THE ORIGINS OF LIFE

(Paul S. Braterman*, Kevin Shannon, and Joseph Boclair)

THE CHEMISTRY, MINERALOGY, AND SPECTROSCOPY OF THE BIOGENIC

ELEMENTS IN MARS SOIL ANALOGS

(J. Orenberg*, A. Banin, T. Rousch, and S. White)

EARLY EVOLUTION OF LIFE IN NON-MARINE ENVIRONMENTS

(L. Paul Knauth*)

Lunch Break

1:30 pm

1:50 pm

2:10 pm

2:30 pm

2:50 pm

3:10 pm

3:30 pm

3:50 pm

4:10 pm

4:30 pm

SYMPOSIUM SESSION IX

Co-Chairs: T. Bunch and J. Orenberg

THE DIVERSITY OF THE OUTER PLANETARY SYSTEM

(H. Levison* and J. Lissauer)

FORMATION OF THE ASTEROID BELT

(George W. Wetherill*, Stephen Kortenkamp, and John E. Chambers)

THE ROUTE FROM INTERSTELLAR TO PROTOSTELLAR ABUNDANCES:

EVIDENCE OF VARIABILITY IN THE INTERSTELLAR MEDIUM

(P. Wannier*, P. Schloerb, and G. Moriarty-Schieven)

SPECTROSCOPIC STUDIES OF PRE-BIOTIC CARBON CHEMISTRY

(Geoffrey A. Blake*)

THEORETICAL STUDIES OF THE EXTRATERRESTRIAL CHEMISTRY OF

BIOGENIC ELEMENTS AND COMPOUNDS

(David E. Woon*)

Coffee Break

REDUCED NITROGEN ON THE EARLY EARTH

(D.P. Summers and N. Lemer*)

PREFERENCE FOR INTERNUCLEOTIDE LINKAGES AS A FUNCTION OF THE

NUMBER OF CONSTITUENTS IN A MIXTURE

(Anastassia Kanavarioti*)

INTERACTIONS OF CARBON COMPOUNDS AND PHOSPHATE WITH PYRITE IN

AQUEOUS SOLUTIONS

(Martin Schoonen* and Joakim Bebie)

THE MEENTHEENA CARBONATE, ANCIENT LAKES, FACIES, AND EXOBIOLOGY

(Stanley M. Awramik* and H. Paul Buchheim)

ix
4:50pm MARSSTUDIES

(H.P.Klein*)

5:10pm Adjourn Symposium

POSTERS

IGNEOUS ROCKS THAT SPARKLE, CRACKLE AND GLOW OXIDIZING RADICALS ACTIVATED BY

LOW VELOCITY IMPACTS (Jerome G. Borucki*, Steven J. Butow, Marshall Lis_, and Friedemann

Freund)

FAMILY CALONYMPHIDAE: TERMITE PROTISTS RELEVANT TO EARLY EUKARYOTIC

EVOLUTION (Michael Dolan and Lynn Margulis*)

HYDROTHERMAL PROSPECTING ON MARS (Jack D. Farmer*)

ORGANIC CARBON ASSOCIATED WITH CARBONATE IN ALH84001 (G.J. Flynn*, L.P. Keller, and

M.A. Miller)

THE EFFECTS OF AMONG SITE RATE VARIATION ON PHYLOGENETIC RECONSTRUCTION

FROM AMINO ACID SEQUENCES (J. Peter Gogarten* and Oiga Zhaxybayeva)

ABUNDANT VIRUSES IN ANTARCTIC LAKES (Ray Kepner* and Bob Wharton)

EFFECT OF LEAVING GROUP ON THE DIMERIZATION OF PHOSPHOIMIDAZOLIDE-ACTIVATED

NUCLEOTIDES (Lynn F. Lee* and Anastassia Kanavarioti)

HORIZONTAL GENE TRANSFER OF ARCHAEAL GENES INTO THE DEINOCOCCACEAE (Ryan

Murphy, Lorraine Olendzenski, Scott MacNamara, and J. Peter Gogarten*)

CHICXULUB IMPACT EJECTA IN BELIZE: INSIGHTS INTO THE ROLE OF ATMOSPHERES AND

VOLATILES IN LARGE IMPACTS (Adriana C. Ocampo*, Kevin O. Pope, Alfred G. Fischer, and John

R. Marshall)

THE PHYLOGENETIC POSITION OF THE MICROSPORIDIA: DEATH OF AN EARLY BRANCHING

LINEAGE? (Lorraine Olendzenski, Elena Hilario, and J. Peter Gogarten*)

METABOLIC ACTIVITY OF MICROORGANISMS IN PERMAFROST (E.M. Rivkina, E.I. Friedmann*,

C.P. McKay, and A.D. Gilichinsky)

WHAT ARE THE CARRIERS OF THE UIRS? SINGLE PHOTON INFRARED EMISSION

SPECTROSCOPY (SPIRES) OF UV-EXCITED PAHs (D.R. Wagner, D.J. Cook, and R.J. Saykally*)

STABLE CARBON ISOTOPE COMPOSITION OF CYANOBACTERIAL AND CHLOROFLEXUS

BIOMARKERS IN HOT SPRING MATS CONSTRUCTED BY OXYGENIC AND/OR ANOXYGENIC

PHOTOTROPHS (David M. Ward*, Marcel van der Meer, and Jan de Leeuw)

MARTIAN PALEOLAKE SEDIMENTS AND TERRESTRIAL ANALOGS: EXTANT AND EXTINCT ICECOVERED LAKES (Robert A. Wharton Jr.* and Peter T. Doran)

THE OXIDATIVE STRATIGRAPHY OF THE MARTIAN REGOLITH (Aaron Zent*)

X
SESSION SUMMARIES

The following summaries were compiled by the co-chairs of each session.

Individual abstracts from each paper or poster presented can be found in

subsequent sections of this report.

SESSION I

Welcome and Opening Remarks

The Symposium opened with the welcome address by Michael Meyer, NASA's Astrobiology

Discipline Scientist, who discussed the relationship between the extant exobiology program and

NASA's nascent endeavor in Astrobiology.

The Exobiology Program is a key element of the Astrobiology Initiative, as "Astrobiology is defined as

the study of life in the universe, and the chemical and physical forces and adaptations that influences

life's origins, evolution, and destiny."

SESSION II

D. Deamer and J. Farmer, Co-Chairs

The carbon chemistry of interstellar space provides potentially important information about the nature

of prebiotic chemical processes and their role in the nucleation of solid materials. R. Provencal

(UC Berkeley) et al. discussed the results of an astrophysical study to evaluate the importance of

previously unstudied pure carbon clusters in the interstellar environment using infrared diode laser

absorption spectroscopy. With this technique they were able to characterize the structure, bonding,

and other properties for carbon clusters containing as many as 13 carbon atoms. They supplemented

their IR diode laser observations with far infrared measurements (10-200 cm-1) to help design

astronomical searches for SOPHIA (and previously for the Kuiper Airborne Observatory). A new

technique called "cavity ringdown detection" was also developed for measuring infrared spectra of

carbon clusters. This method permits the measurement of very small absorption features at Dopplerlimited precision over the entire mid-IR.

T. Wdowiak (Univ. Alabama, Birmingham) et al. reported on the astronomical importance of polycyclic

aromatic hydrocarbons (PAHs) in interstellar and circumstellar environments. Previous studies have

focused on the importance of large aromatic carbon structures thought to explain emission bands in

unidentified infrared (UIR) spectra. However, based on a 2175 angstrom extinction feature, it now

appears that some fraction of the multi-ring structures in these environments could also include

aliphatic compounds. The aliphatic/cycloalkane fraction of large hydrogenated PAHs can undergo

cracking to form small chains, or be polymerized into kerogen-like structures similar to those found in

carbonaceous chondrites. Thus, the aliphatic component of PAHs is a potentially important source of

prebiotic compounds of the kind that could have_lead to life on Earth.

It has been suggested previously that the major prebiotic building blocks for life originated from

external sources, mostly being delivered to Earth on interplanetary dust particles (IDPs). G. Flynn et al.

(Plattsburgh State Univ. of New York) reported results from a spectral study of IDPs which combined

high resolution Fourier Transform Infrared (FTIR) Spectroscopy with Scanning Transmission X-Ray

Microscope (STXM) observations on ultramicrotomed samples. The techniques discussed can detect

and resolve weak C-H features in IDPs not observable by conventional laboratory methods.

Combining these two techniques enabled determination of both the bulk and relative abundances of

carbon-bearing spectes in samples, as well as their spatial distribution within samples. Results

indicated that IDPs contain significant abundances of long'chained aliphatic hydrocarbons,

suggesting that IDPs could have contributed important prebiotic compounds to the early Earth.

The announcement in August of 1996 of possible evidence for fossil life in martian meteorite,

ALH84001 (D. McKay et al. 1996 Science), has intensified NASA's interest in exploring for ancient life

during the upcoming Mars Global Surveyor Program. In this talk, McKay (NASA JSC) et al. provided an

update of recent progress in assessing their biological hypothesis for ALH84001. Additional

observations since the '96 report strengthen the case for 1) light carbon isotopic values in the
carbonateglobulesthatcontaintheputativebiosignatures(-55to-65 %),interpretedto bedueto

biologicalfractionation, 2) biofilm-like textures in the carbonates, 3) chains of magnetite grains similar

to those produced by terrestrial magnetotactic bacteria, and 4) oxygen isotope values indicative of low

temperatures. Although it was noted that individually each of these lines of evidence can be

explained by abiogenic processes, taken together, they provide a compelling argument for the

presence of life. Recent work by other authors has challenged the biogenicity of features identified by

McKay et al. as indicative of past life. However, based on a systematic review of recent work, McKay et

al. concluded that the case for their original biological interpretations for the meteorite and for the

existence of early life on Mars as been strengthened.

J.Kerridge (UC San Diego) provided a counter-argument to the proposal from D. McKay et al. that

ALH84001 contains evidence of ancient biogenic activity on Mars. Kerridge noted that every line of

evidence presented by McKay to support the biological hypothesis can also be explained by

inorganic processes. And although multiple lines of evidence are certainly desirable, in his judgment,

the evidence presented in favor of a biogenic origin fails to meet the stringent criteria required for a

convincing case. Because of the uncertainties intrinsic to analysis of trace organics and potential

contamination from long exposures to the Antarctic environment, Kerridge also argued that further

investigations of martian meteorites are unlikely to provide more satisfactory evidence. Robotic

missions to Mars are therefore essential, in which selected samples of sedimentary rocks are returned

to the Earth for analysis. A realistic estimate of the first such sample return missionsis 2008.

C. Chyba (Univ. Arizona) presented an analysis of possible liquid oceans beneath the ice sheet of the

Galilean satellite, Europa. He noted that the presence of liquid water elsewhere in the solar system

would be highly significant as a model of the early Earth at the time of life's origin. Chyba described a

potential future Europan mission to test the hypothesis of an ocean, focusing on the ability of radar to

provide evidence of liquid water. There are several unknown factors related to the transparency of ice

to radar and how to best select a wavelength most likely to penetrate several kilometers of ice. Given

the assumptions required by our present knowledge, it is possible to set a constraint of 10 km as the

maximum ice depth beneath which water could be detected using radar.

S. Mojzsis and G. Arrhenius (Scripps Inst.Oceanography) and colleagues, described recent results

that significantly push back the oldest record of biogenic activity on the Earth. In this research, high

grade metamorphic rocks of the Isua region of southern Greenland were investigated using stable

isotope analysis. It is generally considered that the Isua rocks are of early Archean age (3.6 - 3.9 Ga)

and contain the oldest evidence of madne sedimentary systems. The high grade meta-sedimentary

rocks studied include phosphatic mineral grains (apatite) Containing graphite inclusions. Carbon

isotopic analysis of the inclusions showed the graphite was isotopically lighter (by as much as -37%o)

than matrix graphite included in whole rock analyses of the same rocks. On Earth, the precipitation of

phosphate in sediments is thought to be biomediated and organic materials and organisms are often

incorporated into the mineral grains that form. The observed isotopic difference in the phosphate

hosted carbon and the matrix carbon was explained by the stability of phosphate during

metamorphism. Thus, the isotopic values of the phosphate carbon are interpreted to be closer to

primary, The depleted nature of the carbon isotope signatures is consistent with biological

fractionation. This implies that life was present at 3.9 Ga and that The prebiotic processes leading to

the origin of life on the Earth predate this estimate. These results support the case that the search for

phosphate mineral deposits on Mars is an important aspect of the strategy to explore for a martian

fossil record.

G. Joyce (Scripps Research Inst.) discussed a catalytic system which permits continuous evolution of

a population of RNA molecules. This system is characterized by a cyclic process in which DNA is

synthesized from an RNA template, and then RNA from the DNA in a second catalyzed polymerization

reaction. The system can be made to evolve by introducing errors into the resulting RNA polymers

followed by selective amplification of RNA molecules having a desired catalytic capability. In past work,

this cycle was carried out in batches, with ten or more batch steps required to produce changes in the

l:l I:
RNA function. More recently it was found possible to carry out the process in a continuous mode by

introducing a ligation reaction that allows newly synthesized RNAs to catalyze a reaction immediately.

In one example or continuous evolution, RNA with catalytic abilities were amplified by a factor of

10298, with new rounds of synthesis occurring every five minutes. Joyce reported the evolutionary

synthesis of a DNA enzyme that promotes a reaction analogous to the peptidyl transferase activity of

bacteria in which peptides such as gramicidin are synthesized.

SESSION UI

D. Lies and Y. Pendleton, Co-Chairs

J. Dickens and W. Irvine (Univ. Massachusetts, Amherst) are studying the molecular complexity and

evolution of gas phase interstellar molecules in dense molecular clouds. Dickens provided an

overview of the relation of the observed interstellar molecules to the chemistry of the primitive solar

system objects we observe today. The identification of new species in both the interstellar and

cometary environments provide additional links between the two regions. Important results include

the first detailed mapping of HCN and HCO + in cometary comae. The HNC/HCN abundance ratio is

much higher than that predicted by equilibrium chemistry, and is similar to the values found in the

interstellar medium, thus suggesting that some of the cometary HNC may be preserved interstellar

matter.

L. Allamandola (NASA Ames) presented a brief review of the role of infrared spectroscopy in the

identification of organic material and ices in the interstellar medium, and illustrated the connection

between those materials and planetary systems which form from the dust and gas around young stars.

The role of laboratory astrophysics in the identification of spectroscopic signatures observed from

interstellar dust has proven to be essential in understanding the composition, evolution, and

distribution of the basic building blocks which eventually led to life on Earth. This talk presented

results on the photochemistry of interstellar ices, and emphasized the potential prebiotic role of some

of these species. The formation of complex organics from simple starting mixtures in the laboratory

suggests that comets may have delivered these materials to the early forming Earth such that they

played a role in the evolution of life on this planet.

F. Freund (SETI Institute), with A. Gupta, discussed their work on the formation of complex

oxygenated organic molecules from water and carbon dioxide within minerals and rocks. Water and

carbon dioxide trapped in minerals breaks down to hydrogen gas, reduced carbon and peroxides,

which then can combine to form carbon-carbon, carbon-hydrogen, and carbon-oxygen bonds. They

showed that such processes can take place in artificially formed minerals in the lab and that the

products of these processes can be found in naturally occurring olivine crystals, providing a potentially

rich source of complex organic compounds for the evolution of early life.

A. Pohorilie (NASA Ames), with M. Wilson, M. New, and C. Chipot, spoke about the ability of small

synthetic peptides residing at interfaces between a nonpolar phase and water acting in functions

reminiscent of rudimentary membrane transport and signaling functions. Starting from disordered

structures, these peptides can organize into defined secondary structures, either in the nonpolar

phase or along the interface, depending on their primary sequences. Some of these ordered

structures can change orientation in response to electric fields and others, in pairs, can perform

unidirectional proton transport.

D. Deamer (UC Santa Cruz) discussed using liposomes containing catalytic nucleic acid-replicating

systems as mimics of early processes in the origin of cellular life. His group has been able to get lipids

representing those found in meteorites, as well as natural lipid material extracted from meteorites, to

form bilayer vesicles resembling membranes in many properties. By using lipids with appropriate chain

lengths, vesicles can be formed that are permeable to mononucleotides but not oligonucleotides.
The inclusion of nucleic acid-replicating enzymes in such vesicles allows the synthesis of nucleic

acids, which are retained inside the vesicles, from exogenously supplied mononucleotides.

B. Pierson (Univ. Puget Sound) spoke on the role of modern phototrophic microorganisms in the

oxidation of iron in hot springs as a model for such processes in the early history of the Earth and with

the goal of finding useful biogeochemical signatures due to this metabolism. Her group is examining

the effects of the phototrophic microorganisms in one particular thermal iron spring on oxidized iron

accumulation in the mats, and has been able to determine profiles for both oxygen concentration and

pH levels, with changes that depend on day/night cycles. They are also looking for evidence for

photoferrotrophy (direct photo-oxidation of iron by microorganisms) at this spring.

D. Ward (Montana State Univ.), with T. Papke, discussed studying cyanobacterial populations in

modem hot spring mats as models for stromatolites, the major extant fossils of Precambrian microbial

life. Morphology and culture alone are insufficient to define the populations in modem mats, so they

have been using molecular techniques to examine the relatively slowly evolving ribosomal RNAs and

more rapidly evolving rRNA intergenic spacers. They have seen distinguishable populations of

genetically very similar cyanobacteria across thermal gradients and vertical spacial gradients in these

mats, indicating that perhaps these may be different species inhabiting unique niches.

D. DesMarais (NASA Ames), with A. Tharpe and J. Thompson, discussed the use of _13C values to

follow biogeochemical carbon cycling and its application to ancient deposits. In addition to primary

production and bacterial degradation of carbon compounds, secondary production sustained by the

oxidation of organic carbon or inorganic sulfur was also shown to be important in affecting _13C values

in certain environments. Thermal alterations also affect these values, but affect the elemental H/C ratio

as well. Thus plotting H/C vs. 813C can help determine the extent of thermal alterations. Using this

approach, these investigators demonstrated that thermal alterations of mid-Proterozoic and

Neoproterozoic kerogens were lower than previous estimates.

A. Knoll (Harvard Univ.) spoke on using the current wealth of information about the Proterozoic fossil

record to predict general aspects of life prior to that period. For cyanobacteria, morphologic diversity is

predictive of speciation and had already occurred to a major extent by the early Proterozoic. For

eukaryotes, however, diversification occurred more during the Proterozoic and Mesoproterozoic

periods.

B. Jakosky (Univ. Colorado, Boulder) discussed the biological potential of Mars based on the

availability of energy necessary to drive living processes. Using the assumption that early life was

primarily hydrothermally driven, he estimates that Mars, which has been calculated to have only about

1% of the volcanic activity of Earth, probably only developed life over the 4 billion years of its

existence to a level comparable to 40 million years of Earth evolution. He also predicts a similar

situation for Europa, since it has been calculated to have slightly less energy than Mars.

SESSION IV

L. Allamandola and B. Pierson, Co-Chairs

In the paper on The NASA Specialized Center of Research and Training (NSCOFtT) in Exobiology,

J. Bada (UCSan Diego) et al. presented a global summary of the past 5 years of NSCORT activities in

San Diego. The program started in 1992, with an annual budget of about $1,000,000. The senior staff

now consists of six PIs and an Outreach Coordinator. The bulk of the money is used to support young

scientists in this new field of research. The main emphasis is on the origin of life. Activities span the

range from prebiotic chemistry (including extraterrestrial materials); to chemistry in the pre-RNA world;

as well as the eady chemistry of the RNA world extending to the formation of DNA and simple proteins.

Prior to the formation of the NSCORT program at San Diego, the Pl's citation impact factor was 290.

"*|_] i _
Several years into the NSCORT program, this rose to 480, attesting to the efficacy of the

collaborations and cross fertilization permitted under the auspices of the NSCORT program. The San

Diego NSCORT group also organizes meetings and sponsors internship programs.

Interesting results on the positive detection of small (less than 10%) enantiometric excesses of certain

amino acids in the Murchison and Murray meteorites were presented by J. Cronin (Arizona State Univ.)

and S. Pizzarello in their paper entitled Enantiometric Excesses in the Amino Acids of Carbonaceous

Chondrites. To minimize the possibility of confusion arising from contamination, the amino acids

selected for study were those not occurring in the Earth's biosphere. An important conclusion of this

work is that there exist extraterrestrial processes that can produce enantiometric excesses in amino

acids which contain alpha methyl groups. Amino acids which lack alpha methyl groups were found to

be racemic. The excesses seem to be consistent with production from irradiation processes by

neutron stars. This theory is at a very young stage.

In Modification of Amino Acids at Shock Pressures of 3.5 to 32 GPa, S. Chang (NASA Ames) et al.

investigated the effects of shocking amino acids under conditions which simulated the impacts

between these meteorites during their residence in the asteroid belt and with the Earth's surface.

A key question is to determine whether or not the compounds present in the meteorite could have

been altered or destroyed by these collisions. Some of the results showed that most amino acids

were destroyed in collisions with energies between 15 and 25 GPa. The small fraction of amino acids

that survive this energy retain their optical activity. Secondary products are formed, however, which

could have prebiotic significance. These include amino acids such as a!anine, glycine, and

_(- and l_-aminoisobutyric acid. It was found that alpha-amino isobutyric acid is one of the more stable

amino acids.

Over the years, the organic inventory of potentially important prebiotic molecules in meteorites has

shown that many of these species are indeed present. Notably absent however are sugars, very

important molecules in living systems due to their energy content. Their absence from the list arises in

part because they are not as readily detected with the usual techniques. Simple sugars have been

postulated to be formed extraterrestrially by reactions involving formaldehyde in a slightly basic

solution. In the paper, An Investigation of Sugars and Other Possible Formaldehyde Products in the

Murchison Meteorite, G. Cooper (SE'I-I Institute) presented a targeted search for sugars, seeking to

ascertain the importance of the formaldehyde reactions. A variety of simple sugars were found,

supporting the importance of these reactions in the Murchison meteorite's history. Isotopic studies

showed that these sugars (polyols) are indigenous to the meteorite and not due to contamination.

However, the cyclic sugars - so important in today's metabolism - were not reported.

In Co-Origin of Metabolism and Biopolymer Synthesis Using Formose Sugar Substrates, A. Weber

(SETI Institute) presented a new perspective on the prebiotic processes that could have been

involved in the origin of metabolism and biopolymer synthesis. Considering the thermodynamics of a

wide variety of prebiotic molecules, it was shown that sugars are the most reduced substrate possible

for biosynthetic processes. This makes sugars a very attractive driver of many important reactions. For

example, it was demonstrated that viewed from the thermodynamic perspective, redox

disproportionation of sugar carbon accounted for about 90% of the total energy amino acid and lipid

biosynthesis whereas ATP accounted for less than 10 %. Thus, the author postulates that redox

disproportionation of carbon, and not ATP, is the primary energy source driving important

biosynthesis from glucose. An excellent case was made that since sugars are strong reducing agents,

they can be almost viewed as "batteries," powering these important processes.

R. Blankenship (Arizona State Univ.) presented a talk co-authored with H. Hartman on The Origin and

Evolution of Oxygenic Photosynthesis in which they presented a model for the origin of the

contemporary oxygen-oxidizing tetranuclear Mn complex from an ancestral binuclear Mn catalase that

may have used H202 as a reductant for a purple bacterial type of reaction center.

7
J.P.Gogarten(Univ.ofConnecticut)presentedapaperco-authoredwithE.Hilarioand

L.Olendzenski,Horizontal Gene Transfer: Pitfalls and Promises in which they presented ancient

horizontal gene transfer events from Bacteria into Archaea as an explanation for many of the

homologies occurring between metabolic genes from these two groups. The genes involved in the

essential core activities of genome structure and expression and chemiosmotic coupling were less

prone to horizontal transfer and therefore form the backbone of current phylogenies.

D. Lies presented a paper co-authored with A. Tsapin, J. Scott, and K. Nealson (Genes andEnzymes

of Anaerobic Metabolism in Shewanella outrefaciens) in which they demonstrated techniques for

isolating and characterizing the diverse electron carriers and reductases used by Shewanella

putrefaciens which can grow on a wide range of electron acceptors. A soluble multi-heme c-type

cytochrome with a range of redox potentials was detected as well as a high degree of homology

among the diverse reductases making the sequencing of the whole genome of this extremely

versatile organism a high priority.

E.I. Friedmann (Florida State Univ.) and several co-authors presented a paper (Viable Bacteria in

Siberian and Antarctic Permafrost) in which they demonstrated viable bacteria in permafrost more than

a million years old. These mesophilic bacteria (including anaerobes) decreased in number and

diversity with depth but remained viable in the absence of growth.

C. McKay (NASA Ames) presented a paper co-authored with D.T. Anderson, W.L. Davis, and

E.I. Friedman on "Polar Analogs to Mars" in which they proposed that if early Mars has been cold, this

may have enhanced preservation of traces of life that existed in geothermally warmed permafrost.

SESSION V

S. Cady and C. Chyba, Co-Chairs

The End Permian Mass Extinction Geochronology and Patterns of Extinction was discussed by

D.H. Erwin (Smithsonian Institute). The mass extinction event at the end of the Permian was the most

extensive biotic crisis in the history of life. Determining its cause, however, has been hampered by a

lack of high precision ages. Discriminating between possible extinction patterns and causes of the

extinction requires high-resolution geochronological age determinations and precise stratigraphic

information on taxon occurrences. Erwin and colleagues reported new uranium-lead-zircon data from

Late Permian and Early Triassic rocks in South China (i.e., from volcanic ash beds interbedded within

numerous Permo-Triassic (P-T) marine boundary layer sections) that provide the first constraints on

the duration of the extinction. By demonstrating that the final pulse of extinction occurred in less than

1 million years, the author's findings provide insight with regard to the rates of paleontological and

geochemical change that occurred during the close of the Permian, and provide critical data needed

to test possible extinction scenarios.

A.I. Miller's (Univ. of Cincinnati) research addresses the extent to which the evolution, diversification,

and extinction of advanced life in the Ordovician Period may have been mediated by physical

processes and events. By compiling a database that depicts occurrences of the Ordovician genera in

strata worldwide, and including data concerning the paleogeographic, paleoenvironmental, and

geological settings of each occurrence, Miller can investigate, over scales ranging from local to global,

whether the proliferation event at the end of the Ordovician Radiation was focused geographically or

environmentally. In the paper entitled Ordovician Biodiversity: Geography and Environment, results

to date were reported which include recognition that most of the global diversity increase was

concentrated in the first half of the period, and that a geographic linkage exists between Ordovician

radiation and likely regions of tectonic activity. Proximity to tectonic activity has been found to affect

the diversification attributes differently for each paleocontinent. Although Ordovician genera

expanded their geographic environmental ranges with age, preliminary results indicate that the Late

-1-11 I-
Ordovician mass extinction may have selectively eliminated taxa within limited geographic ranges,

raising the possibility that this event was also selective with respect to taxon age.

Two possible causes of the apparent low-latitude glaciation in Earth history during the Huronian

(-2.2 billion years) and again in Late Proterozoic (- 750 - 550 million years) include either a shift in the

Earth's obliquity (> 54°) or the possibility that at those times the surface of the Earth was completely

frozen over. A strong argument against the later hypothesis is that a global ice blanket would likely

have eliminated all photosynthetic life on the planet, a phenomenon not supported by the fossil

record. To reconcile the geological and fossil record, D.M. Williams (Penn State Univ.) and colleagues

have developed a self-consistent model that can account for a rapid drop in obliquity during the last

glacial period as a consequence of climate friction and changes in the Earth's oblateness. The title of

their paper posed the pertinent question: Was High Obliquity the Cause of Low-Latitude Precambrian

Glaciation? Although changes in the Earth's oblateness (hence obliquity) due to massive water

displacement during glaciation are usually considered to be negligible, the authors have noted that

these effects were likely to have been significant during the late Proterozoic when the bulk of the

Earth's continents are thought to have been clustered around the South Pole. The authors calculate

that a decrease in the early Earth's obliquity from 55° to 25° could have occurred in under 150 million

years, and that such an event process would bring the Earth's obliquity close to its present value of

< 250 by 430 million years.

In Paleobiology Of The Terminal Proterozoic: Prelude To The CambtYan Explosion, B. Runnegar

(UCLA) et al. examine the geologically most obvious biological event in the history of the Earth, the

Cambrian explosion of complex life. Much of the research aimed at understanding this milestone in

the evolution of life has focused on evidence from well preserved fossils in the Cambrian such as the

Burgess Shale. Although many of the evolutionary innovations were underway before the beginning

of the Cambrian, the oldest metazoan trace fossils are n(_older than about 550 million years. Recent

discoveries of Ediacaran trace fossils and associated carbonate skeletons in late Proterozoic rocks in

Namibia and Nevada provide a glimpse of biodiversity at the close of the Proterozoic that cannot be

traced in the Metazoa. Runnegar's research into the evolutionary innovations displayed by Ediacaran

fossils at the terminal Proterozoic indicate that the synchronous appearance of distantly related clades

of megascopic organisms point to the poverty of intrinsic rather than extrinsic explanations for the

nature of the Cambrian explosion of multicellular life.

Y. Yung (Cal Tech) and co-workers reported on their studies of the effects of SO2 on the middle

atmosphere of early Mars in C02 Greenhouse in the Early Martian Atmosphere: S02 Inhibits

Condensation. Ten years ago the ancient climate on Mars was considered to have consisted of a

dense carbon dioxide atmosphere that would have kept the planet's surface temperatures above the

melting point of water. Subsequent models that also considered the effects of CO2 condensation,

however, revealed that the presence of CO2 by itself would have been inadequate to sustain liquid

water on Mars. By incorporating small amounts of SO2 in their preliminary one-dimensional radiative

model of an early Mars atmosphere, Yung and co-workers have found that the middle atmosphere of

early Mars may have been kept warm enough to inhibit the condensation of CO2. An intriguing

consequence of their model is that the presence of a small amount of SO2 in a martian atmosphere

may also have provided an effective UV shield for a hypothetical martian biosphere.

A. Zent (NASA Ames) and R. Quinn presented results from their work modeling the diffusion of

photochemically produced hydrogen peroxide in the martian atmosphere down into the martian

regolith. This question is important for future searches for life or organic molecules on Mars: For

organics to survive in the martian soil, they must lie beneath the depth to which oxidants such as

hydrogen peroxide will diffuse. Quinn and Zent's work suggests that regolith mixing rather than

diffusion may be the dominant mechanism of oxidant transport in the martian regolith, depending on

destruction rates for hydrogen peroxide in martian soils.

9
T.Bunch(NASAAmes),D.DesMarais,L.Becker,W.Wolbach,J.Bada,andD.Glavindiscussedthe

effectsof theSudburyimpacteventonorganicmatter.TheynotethattheSudburyOnaping

formationimpactdepositsareexceptionallycarbonrich.Thegoalsoftheirinvestigationsareto

characterizethecarbonaceous components and their distributions, identify their potential sources,

model pressure-temperature-time conditions in the impact and establish when life reappeared in the

region. Interestingly, they argue that the impact may actually have helped life to reestablish itself

rapidly in the region, by furnishing nutrients and favorable environments.

K. Pope (Geo Eco Arc), K. Baines, and A. Ocampo examined meteorite impact production of volatiles

and their biospheric effects at the Cretaceous/Tertiary (K/T) boundary. In order to assess global

average environmental results of the K/T impact, they use estimates of volatiles in the projectile and

target rocks at the Chicxulub site to predict the mass of carbon dioxide, sulfur dioxide, and water vapor

globally distributed in the stratosphere by the impact. They conclude that global warming due to

carbondioxide generation was less than 1 degree centigrade, insignificant compared to cooling due

to sulfates.

C. McKay (NASA Ames) and B. Borucki used numerical and experimental techniques to model the

composition of an atmosphere dominated by cometary volatiles. They find that comet collisions on

early Earth should yield carbon dioxide and methane about equally, but little carbon monoxide. Comet

shocks do not produce ammonia, so that nitrogen will be in the form of molecular nitrogen rather than

ammonia. These results have obvious implications for the chemical composition of the early terrestrial

atmosphere, were that atmosphere in fact dominated by impacts.

Finally, T. Wdowiak (Univ. Alabama, Birmingham), D. Agresti, S. Mirov, and A. Kudryavtsev described

their development of a laser Raman spectrometer for in situ exobiology exploration. They have

demonstrated that the spectrometer may be cplibrated using Fraunhofer lines of the solar spectrum

obtained from atmospherically scattered sunlight, and that their laser signal will transmit through an

optical fiber cooled to as low as -132 degrees centigrade. Both these demonstrations are important

for the use of such an instrument on Mars. The group continues to obtain laser Raman spectral

signatures of particular interest to planetary exploration and exobiology.

SESSION VI

T. Kanavarioti and D. Lowe, Co-Chairs

The presentations in Session Vl focused on models for prebiotic self-replicating systems based on

nucleotides or nucleotide analogs, on simulation experiments to mimic Titan's atmospheric chemistry

and hydrothermal vent conditions, and on the identification of biomarkers associated with

hydrothermal vents, spring systems and lake formations.

C. Switzer (UC Riverside) opened the session by reporting on the ability of 2'-5'-linked RNAs to act as

templates and successfully direct the synthesis of a mixture of natural and non-natural

oligonucleotides. Work on non-natural nucleobases, such as iso-cytosine and iso-guanine, which

could potentially be used in place of the natural nucleobases was also presented.

L. Orgel (Salk Institute), with co-author M. Koppitz, discussed experiments which showed that peptide

nucleic acids, PNA, can act as templates for RNA synthesis and vice versa. In addition, the chemistry

was explored so that a PNA or DNA template can successfully direct the ligation between a DNA and a

PNA (chimera).

J. Ferris (Rensselaer Polytechnic Inst.) and co-author D. Clarke, described experiments which

simulate Titan's atmosphere and will be instrumental in helping explain the data returned from the

Huygens probe of the Cassini mission. Photolysis experiments with acetylene and cyanoacetyiene

10

1111'
resulting in polymerization and characterization of the products was done with scanning electron

microscopy (SEM) as well as with chemical methods.

B. Simoneit (Oregon State Univ.) and co-authors T.M. McCollm and G. Ritter described laboratory

experiments that simulate the tentative chemistry involved in prebiotic hydrothermal systems. Formic

acid and oxalic acid were exploited as the carbon source and during Fisher-Tropsch-type synthesis

yielded a number of organic compounds ranging from C 2 to C 35.

Research from E.L Shock's group (Washington Univ.) argues in favor of the existence of hydrothermal

vents in a planetary context and addresses the possibility that they existed in Europa and that they

might have fostered life.

In Anoxia and Evolutionary Patterns in the Deep Sea: On-Shore/Off-Shore Trends and Recent

Recruitment of the Deep-Sea and Hydrothermal Vent Faunas, D.K. Jacobs (UCLA) and D.R. Lindberg

emphasized the importance of anoxic events in the deep oceans in regulating biological evolution.

They note that the observed tendency for higher biological taxa to originate onshore and diversify

offshore is not uniform over time. Onshore origination of higher taxa is more characteristic of intervals

when there is strong deep-water anoxia, such as the middle to late Mesozoic, but an offshore origin is

favored in the Cenozoic, when the deep oceans have been more highly oxygenated. Periodic deepocean anoxia should also affect deep-water hydrothermal vent organisms, which are either oxygen

users or require redox gradients to survive.

T. Wdowiak (Univ. Alabama, Birmingham) and colleagues reported on a study in which a M6ssbauer

spectrometer was used to identify nanophase iron-bearing materials in hot springs in Yellowstone

National Park and Colorado. In MOssbauer Signatures that may be Useful in Identifying Residues of

Ancient Martian Hydrothermal Systems, nanophases detected included siderite and nontronite. Both

should be easily detectable in martian materials using MSssbauer techniques and could serve as keys

to identifying martian hot spring deposits.

In Exploration of Mono Lake Using TROV: Application of Telepresence Technology to Exobiology

Studies, C.R. Stoker (NASA Ames) reported on use of the TROV (Telepresence-Controlled

Remotely Operated Vehicle) in Mono Lake to examine tufa towers and the chemistry of the

subsurface springs that formed them. A number of sites were visited, including some tower-like

features that were not tufa towers.

S.L. Cady (SETI Institute) and colleagues reported on a study aimed at recognizing hyperthermophilic

biogenic signatures that might be preserved in the rock record on either the Earth or Mars. The

studies reported on in Recognizing Biogenic Signatures Near Life's Upper Temperature Limit: The

Role of Hyperthermophilic Biofilms in Spicular Geyserite Morphogenesis, demonstrate that the

morphology and deposition of spicular geyserite in the high temperature parts of hot springs are

controlled by hyperthermophilic biofilms and that different biofilm communities exist in subaerial and

subaqueous parts of the hot spring system.

Early organisms may have not only lived in and around hydrothermal springs but also evolved there. In

Fossilization Processes in Thermal Springs: Comparative Studies of Modem and Ancient Siliceous

Spring Systems, J. Farmer (NASA Ames), B. Bebout, L. Jahnke, D. Des Marais, and M. Walter, studies

of modern hot springs systems show that microbial signatures are preserved in a number of ways,

including cellular fossils, biofabrics, and biosedimentary structures. In both modern and ancient

deposits studied, organically preserved microfossils are rare: most organic matter is quickly removed

by oxidation. More common are silica coatings on organic grains and morphological structures formed

by biological activities.

11
SESSION VII

P. Knauth and A.L. Weber, Co-Chairs

D. Lowe (Stanford Univ.) described the Ikiryu sinter, a siliceous hot-spring deposit near Kuju Volcano,

Japan. The deposit includes: (1) a lower member composed of dense, recrystallized largely

structureless chert and (2) an upper member consisting of white siliceous sinter showing well

preserved layers of conical strornatolites, and silicifiedfilaments, streamers and sheet-like mats.

J. Fredrickson (Pacific NW National Lab.) reported on the preservation of haloarchaea and their

16S rDNA in brine inclusions from bedded salt deposits. Viable haloarchaea and their 16S rDNA were

found in four-year-old (modern) Laguna Grande de la Sal salt, but not 200 m.y. polyhalite from the

Salado Formation in New Mexico.

R. Mancinelli (SETI Institute) presented data on the survivability of osmophilic microbes exposed to

the space environment for two weeks aboard BIOPAN (a biological facility developed to fly in Earth

orbit on recoverable satellites). The osmophilic microbes survived the two week exposure. The major

cause of cell death was DNA damage which was greater in vacuum-UV exposed cells compared to

vacuum-only exposed cells.

G. Fox (Univ. Houston) described his studies of the origin of the translation machinery that involved

testing the ability of aminoacylated-tRNA molecules to form peptides in the absence of ribosomes. He

reported that aminoacylated-tRNAs yielded dipeptides in the absence of both synthetase and

ribosomes when Ala-His was used as a catalyst/cofactor.

K. Zahnle (NASA Ames) presented a case against the cometary origin of the oceans. He argued that

late-accreting volatile-rich veneers (either asteroids or comets) appear to be quantitatively inadequate.

He proposed that the water of the inner solar system could have come from objects falling from an

augmented ancient asteroid belt, or scattered planetesimals associated with the accretion of Jupiter.

Y. Pendleton (NASA Ames) reviewed studies of organic solid-state materials in space that show

remarkably similar absorption features (attributed to aliphatic hydrocarbons) amongst interstellar dust

clouds in our galaxy, dust-embedded distant galaxies, and the Murchison meteorite. Comparison of

these infrared observations with laboratory processed organic residues suggests that energetic

processing of simple ices results in materials similar to those seen in space.

S. Charnley (UC Berkeley) showed that the observed gas phase interstellar D/H ratios in CH2DOH and

CH3OD are lower than expected solely from formation on grains, and that chemical reactions must also

be forming CH3OD in the gas phase. He also extended the general surface reaction scheme (based

on organic radical stability) to oxygen and nitrogen atom additions to carbon chain radicals.

S. Benner (Univ. Florida) speculated on the identification of structures of modern terrestrial

biochemistry that are unique solutions to challenges faced by living systems in general. Since these

structures would be required for life, they would also be found in extraterrestrial life. His analysis

indicated that nucleic acids show some structural features that are likely to be universal, and others

that are not.

R. Krishnamurthy (UC San Diego) described the mineral induced phosphorylation of glycolaldehyde

to give glycolaldehyde phosphate. Gycolaldehyde phosphate and glyceraldehyde-2-phosphate have

been shown to condense under prebiotic conditions to give ribose-2,4-diphosphate which is

considered a precursor of primitive p-RNA (an RNA analog containing the pyranose form of ribose and

2' -, 4' linkages).

12
D. DeVincenzi (NASA Ames) reviewed the requirements for Planetary Protection that might be

imposed on a Mars Sample Return Mission. In light of the recommendation of the Space Studies

Board that the samples returned form Mars should be contained and treated as though potentially

hazardous until proven otherwise, he discussed the need to: (1) assure sample containment,

(2) quarantine and detect possible biological entities and/or organics in the sample, and (3) determine

if the Mars samples are hazardous.

M. Race (SETI Institute) reviewed the legal and public concerns about the environmental impact and

potentially hazardous nature of samples returned from Mars. She stressed that planetary protection

must be integrated early into all phases of the sample-return mission design and that NASA must keep

other government agencies and the public informed of the decision making and review process.

Areas that have recently received special attention are: (1) consideration of the environmental impact

statement, (2) identification of legal ambiguities and scientific uncertainties, (3) development of a

systematic biohazard testing protocol for returned martian samples, and (4) studying public risk

perceptions and responses.

SESSION VIII

L. Jahnke and T. Wdowiak, Co-Chairs

J. Hayes (Woods Hole Oceanographic Inst.), with colleagues H. Strauss and A.J. Kaufman, described

their examination of the global biogeochemical cycle of carbon as inferred by 13C abundances.

Except for declines between 550 and 520 Ma, and about 29 Ma ago, the fraction of 13C can be

accounted for by the maximum set by the physiology and enzymology of marine algae. The observed

declines can be attributed to increased rates of planktonic growth and a decreased abundance of

CO2.

L. Jahnke (NASA Ames), R.E. Summons, and H.P. Klein have studied mid-chain, methyl-branched

alkanes as a group-specific biomarker for cyanobacteria for the purpose of providing data of use in

interpreting the ancient carbon record. They find that dimethyl alkane synthesis is linked to

environmental factors in the case of contemporary thermal springs. This points to the utility of pure

culture studies in interpretation of the fossil record.

Retuming to 13C, D. Kass (Cal Tech) and Y. Yung argue that on Mars carbon does not cycle through

the environment as for Earth. It remains in the atmosphere-cap-regolith reservoir until lost from the

planet by exospheric processes or conversion to carbonate. Unlike Earth, the carbonate is not

subducted, making it a permanent sink. This difference argues against applying the terrestrial 813C

isotopic system to Mars. Unlike Earth, the 813C of th_ atmospheric reservoir can change with time.

They have initiated models and find the martianatmosphere "started out quite light and has

progressively gotten heavier."

Using the 70 m Deep Space Network antenna at Goldstone, California, T. Velusamy (JPL), W. Langer,

and S. Levin probed protostellar cores for long chain hydrocarbon molecules: cumulene carbenes

(H2C=(C=)nC), acetylenes, and linear carbon chain radicals. The data allow tracking down the gas

phase chemical pathways by which these species are formed as star formation proceeds.

M. Fomenkova (UC San Diego) and S. Chang have been mining the mass spectroscopy data base

obtained during the Comet Halley fly-bys of more than a decade ago. They have been able to go

beyond elemental abundances and have established the outlines of the molecular groups for the

carbonaceous grain component of Comet Halley. Included are polymers of formaldehyde, HCN, and

unsaturated nitriles. The nitrogen abundance in mixed grains (inorganic plus organic) is enhanced.

This work provides a beginning bridge between interstellar matter and what is cometary/solar system.

13
D.Blake(NASAAmes),P.Jenniskens,andL. Delzeitenaciouslycontinuetheirdissectionofthe

solidformsofthemostexobiologicallyrelevantmolecule(youmayrecalltheircoverphotofor

Science). These researchers have mastered the transferable cold finger technique to track down all

the varieties of transitions that can occur after water molecules alight on a cold interstellar surface

(grain). The objective: to correlate things such as a comet outburst with structure defined by electron

diffraction, etc.

The research of D. Usher (Comell Univ.) focuses on the mechanism of the de novo formation of RNA

in prebiotic times. This reaction is known to be catalyzed by amines, particularly alkanediamines, yet

the mechanism of this catalysis has been a subject of controversy in recent years. The reported recent

results show that the mechanism of amine-catalyzed cleavage of RNA appears to be simple generalbase catalysis, however earlier work suggested that the actual mechanism of amine-catalyzed hydroxyl

attack on a phosphate diester involves the kinetically equivalent protonated amine plus the

deprotonated hydroxyl group. Their search continues for amine catalysts that can improve the yield of

RNA oligomers in the de novo formation of FINA from nucleoside 2',3'-cyclic phosphates under

simulated prebiotic conditions.

The ion exchange and catalytic properties of layered double hydroxides, along with solid state photoreduction of carbonate through a ferrous iron presence commanded the attention of P. Braterman

(Univ. of North Texas), K. Shannon, and J. Boclair. They find that conversion of carbonate to

formaldehyde is not significant when 10 atom % iron(ll) containing layered double hydroxides with

carbonate are subjected to UV radiation. Iron(ll) carbonate converts to a green rust of iron(ll), iron(Ill)

hydroxide carbonate. The layered double hydroxides do absorb the possible prebiotic ferrocyanide,

and investigation of the reaction of ammonium magnesium ferrocyanide and formaldehyde shows

evidence for a wide range of products, which are the study's next target.

For a long time to come, most of what we are going to learn about Mars will be through remote sensing

from orbit. After all, the martian surface to be roved/walked upon is equivalent to the dry surface of

Earth, and that took a little time to explore on foot. J. Orenberg (San Francisco State Univ.), A. Banin,

T. Roush, and S. White continue their effort to produce laboratory analogs of martian soil and

characterize them with reflectance spectroscopy and other physical methods, including x-ray

diffraction. The precursor material for the analogs is partly palagonized volcanic tephra. The analogs

are "weathered" with acids (H2SO4, HNO3, and HCI). In the visible and near IR (250-2500 nm), an

increase in overall reflectance is noted and attributed to sulfate and salt mixtures. For the 2.5-25

micron IR region, the carbonate and sulfate bands are distinct; however, neither nitrate nor phosphate

can be detected.

L.P. Knauth. (Arizona State Univ.) reported on his studies of the early evolution of life in non-marine

environments. Some non-marine deposits contain microfossils, as until oceanic salinity decreased to

acceptable levels, early evolution of life may have been especially active in the lower salinity, nonmarine waters in lakes, rivers, and soils. Microfossils of probable cyanobacteria have been found in the

associated secondary silica in paleokarsts as old as 1200 m.y. Knauth et al. seek to identify silica and

carbonate that formed in'early subaerial and other non-marine environments and explore further the

newly emerging fossil record of life on land in the Precambrian. The preservation of organisms in this

type of silica is currently being examined and ancient examples are a new target material for exploring

the fossil record of life on land in the Precambrian and possibly on Mars. Calcite alteration veins in

terrestrial basaits are being similarly examined and may provide easily accessible target material for

future sample returns from Mars.

14
SESSION IX

T. Bunch and J. Orenberg, Co-Chairs

The session began with a presentation by H. Levison (Southwest Research Institute) and J. Lissauer

entitled The Diversity of the Outer Planetary System. The authors created a set of plausible outer

planetary systems using direct numerical integrations. Included in these simulations were the effects of

the solar nebula. This included the accretion of nebular gas in order to form Jupiter-like planets. It was

found that some sort of dissipation was required for time scales longer than 10 million years in order

to construct systems like ours. The number of planets can vary from one to seven. Systems with a

large number of planets never contain large, Jupiter-like planets, but instead are made up of Uranuslike planets. Stable planetary systems can include planets in mean motion resonances with one

another. Perhaps most surprisingly, it is possible to construct stable systems in which the planetary

orbits can undergo large, semi-periodic changes.

G. Wetherill (Carnegie Institution of Washington), S. Kortenkamp, and J. Chambers in a presentation

entitled Formation of the Asteroid Belt emphasized the importance of asteroids in meteorite formation

and their effect upon the earliest evolution of life on Earth. They presented a model of the formation

of bodies interior to giant planets which suggests an asteroid belt population of 25 bodies as large as

or more between Earth and Jupiter within a few million years. These bodies are removed from the

asteroid region in about 100 million years due to collisions with each other. It was concluded that gas

giants postdate the formation of Mars sized asteroidal bodies and asteroids interior to the gas giants

because these giants would preclude the formation of such bodies.

In a presentation by P. Wannier (JPL) and co-authors P. Schloerb and G. Moriarty-Schieven entitled

The Route from Interstellar to Protostellar Abundances: Evidence of Variability in the Interstellar

Medium, the assumption that there is a steady evolution of nuclear abundances in the Galaxy resulting

in a balanced enrichment of the elements considered essential for the evolution of life was tested.

Observations were made on the scale of a solar mass, in this case on Rho Oph, a nearby, molecular

cloud complex using the isotope pair O17/O 18, the most precisely determined extra-solar abundance

ratio. The group concluded tentatively that there are measurable variations in abundances on solar

mass scales. The study will be extended to an examination of the nearest known interstellar molecular

cloud, L1457, to allow confirmation of the tentative conclusion.

Spectroscopic Studies of Pre-Biotic Carbon Chemistry was the subject of a presentation by G. Blake

(Cal Tech). His group is attempting to constrain the overall chemical budget of the biogenic elements

during star formation processes. These studies are done using observational spectroscopy combined

with laboratory and theoretical components. Imaging with Millimeter Arrays is designed to probe the

cdtical coupling of phase and grain mantle in the prebiotic evolution of protoplanetary nebulae. Such

molecules as HCN, HC3 N, CH3CN, HNCO, CS, SO, SO2, OCS, HDO, CO, H2CO, CH3OH, and

HCOOH were detected in comet Hale-Bopp at spatial resolutions akin to optical astronomy. In the

lab, the extraordinarily complex prebiotic chemistry of carbon as reflected in interstellar and primitive

solar system materials is being studied as vinyl radical, benzyne diradical and carbenes.

D. Woon (Molecular Research Institute) spoke about Theoretical Studies of the Extraterrestrial

Chemistry of Biogenic Elements and Compounds as shown in gas-grain reactions which are thought

to form molecular species (e.g., alcohols, ketones, aldehydes, and carboxylic acids) in interstellar and

circumstellar clouds. The hydrogenation of CO to form the formyl radical HCO is important as a

precursor to the formation of larger organic species. The hydrogenation reaction is greatly enhanced

by icy surfaces comprised of water or other species. Theoretical ab initio calculations were conducted

to elucidate the modifying effect of water on the hydrogenation reaction. The conclusion was that

water has little impact on the energetics of the reaction, but does alter the potential energy surface of

the reaction.

15
N.Lemer(NASAAmes)and D. Summers discussed their research concerning Reduced Nitrogen on

the Early Earth. They suggested that one source of reduced nitrogen could be the fixation of nitrogen

to NO by shock heating, followed by photochemical conversion of the NO into nitrite. Utilizing the

ammonia by this reaction and non-reducing conditions could produce amino acids via the Strecker

synthesis. Additional studies show that the Strecker synthesis does not appear to be hampered by

the presence of iron. Thus the Strecker synthesis and the iron reduction of nitrite to ammonia can be

combined to form amino acids from nitrite, ferrous iron, cyanide and formaldehyde.

A. Kanavartoti (UC Santa Cruz) reported on the Preference for intemuceotide Linkages as a Function

of the number of constituents in a mixture. Phosphoimidazolide activated ribomononucleotides are

useful substrates for non-enzymatic synthesis of oligonucleotides. Product distributions were

obtained in reactions with one, two or three reactive components at the same total nucleotide

concentration. The most remarkable result of the experiments is that the nearly 2 fold increase of the

percent yield of intemucleotide-linked dimers is not due to a concentration effect, but to the

increased complexity of the system. These observations may provide an example of how increased

complexity in relatively simple chemical systems leads to organization of the material and

consequently to chemical evolution.

M. Schoonen (SUNY, Stoney Brook) and J. Bebie presented results on the Interactions of Carbon

and Phosphate with Pyrite in Aqueous Solutions. Pyrite plays a central role in the chemo-lithotrophic

model championed by Wachtershauser where the redox couple is assumed to have reduced CO2 or

CO to simple organic compounds. Thermodynamic calculations for a temperature range of 0 to 300° C

were made to evaluate the energetics of CO2 reduction. Results show that the FeS-H2S/FeS2 couple

drops with increasing temperature and the first step reduction of CO2 to HCOOH is energetically

unfavorable. In addition, FOT analysis indicates an energy barrier that prevents facile CO2 reduction.

Tests were also made to determine the effectiveness of pyrite as a scavenger of C-compounds and

phosphates. Little interaction was shown by acetate, alanine, and glycine whereas phosphates were

strongly retained on pyrite.

S. Awramik (UC Santa Barbara) and P. Buchheim discussed The Meentheena Carbonate, Ancient

Lakes, Facies and Exobiology. The Carbonate Member has abundant and diverse stromatolites and

rare microfossils that represents an important unit with significant exobiological implications for

understanding ancient life in lakes. The Meentheena and its stromatolites indicate that during the late

Archean microbial life thrived in lakes and, that despite higher atmospheric pCO2 levels, carbonates

preserving aspects of this fossil record can be widespread. The authors suggest that the search for

evidence of ancient life on Mars, include lacustrine deposits with repeated sequences that might

represent fluctuating water depths.

H.P. Klein (SETI Institute) presented Mars Studies about work that began as an outgrowth of

participation on the Russian '96 mission, and was initiallydirected toward two aspects of that mission:

involvement in the Mars Oxidant experiment (MOx), which was chosen to be flown on the small lander,

and involvement in establishing geological criteria of exobiology relevance. Since the loss of that

mission, Klein has continued work with other collaborators and extended the research to include

characterization of the Ma'Adim Vallis-Gusev Crater region and the Ares Vallis region (the landing site

for the Pathfinder spacecraft). Finding additional sites for exobiological study on Mars will be aided by

continued analysis of Viking orbiter data. While ships sailing the interplanetary sea do at times make a

safe transit (the Vikings, Pathfinder), some (Mars Observer, Mars '96) do not; Klein has experienced

both situations. Given the 20-year plus gap between the Vikings and Pathfinder, it's good to have

someone grounded on both sides.

16

i!_|1 "
ORAL

ABSTRACTS

of

PRESENTATIONS

The abstracts for the oral presentations appear in order of presentation. The page

number for any individual abstract can be found by the speaker's name in the

Speaker's Index at the back of this document. The abstracts for the poster

presentations are after those of the oral presentations and are in alphabetical

order by the first author's name.
-I- I I
INFRARED CAVITY RINGDOWN LASER ABSORPTION SPECTROSCOPY

OF CARBON CLUSTERS

Robert Provencal, Joshua Paul, and Richard Saykally*

Department of Chemistry, University of California at Berkeley

Pure carbon clusters are a virtually unexplored form of carbon that may be important in interstellar

chemistry and the nucleation of solid matter. To advance astrophysical study of these species is the

aim of this research.

We have previously studied carbon clusters are large as C13 by infrared diode laser absorption

spectroscopy 1, characterizJng their structures, bonding, and properties. These data, supplemented

by precise measurement of far infrared (10-200 cm-1) bending frequencies permit the design of

astronomical searches using Far-IR receivers aboard the KAO (or SOFIA) as recently demonstrated by

the detection of C3 in SgrB22.

Here we describe a new approach for measuring infrared spectra of carbon clusters using cavity

ringdown detection 3. This method permits the measurement of very small absorptions (~1 x 10-6

fractional absorption per pass) with Doppler-limited precision, and with complete coverage of the midinfrared. New results for carbon clusters will be presented.

Referenc_;:

1. T.F. Giesen, A. Van Orden, H.J. Hwang, R.S. Fellers, R.A. Provencal, and R.J. Saykally, Science

265:756 (1994).

2. A. Van Orden, J.D. Cruzan, R.A. Provencal, T.F. Giesen, R.J. Saykally, R.T. Boreiko, and A.L. Betz,

in Proceedings from the Airborne Astronomy Symposium on the Galactic Ecosystem: From Gas to

Stars to Dust, ed. M.R. Haas, J.A. Davidson, and E.F. Erickson, ASP San Francisco Conference

Proceedings, paper 103, (1994).

3. J.B. Paul and R.J. Saykally, Anal Chem 69:287 (1997); J.B. Paul, J.J. Scherer, A. O'Keefe, and

R.J. Saykally, Laser Focus World 33:71 (1997).

HYDROGENATED PAH (AN AROMATIC & ALIPHATIC SPECIES)

AS A COMPONENT OF THE INTERSTELLAR AND

CIRCUMSTELLAR MEDIUMS

Thomas J. Wdowiak*, Kenneth M. Arnoult

University of Alabama at Birmingham

Luther W. Beegle

Jet Propulsion Laboratory

While the multi-ring molecules called polycyclic aromatic hydrocarbons (PAH) are of demonstrated

astrophysical interest, is there relevance for exobiology? Very recent developments reveal the story

of multi-ring structures in the interstellar and circumstellar mediums to be a richer one than previously

imagined. Since its inception, the PAH hypothesis has been focused on large aromatic carbon

structures having a minimum of hydrogen atoms at the periphery. The concept was driven by

consideration of the necessary properties to explain the observed unidentified infrared (UIR) emission

bands.

19
Whatis new is the idea that a fraction of the multi-ring structure need not be aromatic! Indeed, the

aromatic portion may reside in the form of islands, which among other things could give rise to the

2175 _ interstellar extinction "bump." Other interesting aspects of hydrogenated PAH (or Hn-PAH)

are the correlations of laboratory infrared spectra with 3 micron region emission from Orion and the

proto-planetary nebula IRAS 05341+0852. It was this finding that initiated consideration of a molecular

species that might be described as a "hybrid of" or "link between" aromatic and aliphatic molecular

species. We have found additional evidence that the strength of the observed 6.2 micron (1600 cm 1)

UIR band, relative to others, may be a signature of an extensive hydrogenated PAH component of the

interstellar medium. Also, the interstellar absorption known as the "diamond" band, through previous

attribution to tertiary carbons at the surface of nanophase diamonds, can also be explained by

hydrogenated PAH structures having molecular weights >1000 amu.

From the viewpoint of exobiology, the attractive aspect of hydrogenated PAH, as a cosmic species, is

that the aliphatic fraction of these kinds of structures is a much more likely feedstock for processing

into species that, on the basis of the terrestrial model, are considered to be prebiotics. The extensive

aliphatic/cycloalkane fraction of large hydrogenated PAH structures can undergo cracking into smaller

linear forms or be polymerized into kerogen-like material such as that found in carbonaceous

chondrites. Hydrogenated PAH (Hn-PAH) can serve as an alternative (as compared to previous

models) reservoir of the kind of material that can be processed into prebiotics.

IDENTIFICATION OF ORGANIC CARBON IN INTERPLANETARY DUST

G.J. Flynn*

SUNY-Plattsburg

L.P. Keller and M.A. Miller

MVA Inc.

Modeling by Anders /1/ indicates interplanetary dust particles (IDPs) provided a significant amount of

prebiotic organic matter to the surface of the early Earth. IDPs, -10 microns in size, collected by NASA

from the Earth's stratosphere, have an average carbon content of -12%/2/. However, our Electron

Energy Loss and Carbon-XANES measurements indicate that graphite is common in IDPs, and the

ratio of organic to graphitic carbon has not been established.

Organic carbon in the form of polycyclic aromatic hydrocarbons (PAHs) has been detected in IDPs by

Clemett et al./3/and Swan eta;./4/have reported the Fourier Transform Infrared Spectroscopy ('FTIR)

detection of a "poorly resolved band around 2860 cm-1" accompanied by bands at 2926 cm-1 and

2960 cm -1, a region characteristic of C-H stretching vibrations, in several IDPs. To follow-up on their

report, we examined four IDPs using a Spectra-Tech u-FTIR installed on an infrared beamline at the

National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory. This instrument has a

signal to noise ratio -100 times better than conventional laboratory FTIR instruments/5/, providing the

sensitivity needed to detect and resolve the weak C-H features in IDPs.

Fragments, several microns thick, of three IDPs (L2008F13, L2008F16, and L2008G9) exhibited

three relatively strong absorptions, at 2960 cm-1 , 2926 cm-1, and 2854 cm -1, and the best spectrum

of L2008G9 also showed a weaker feature near 2870 cm -1. The pair of features at 2926 cm -1 and

2854 cm-1 are characteristic of the C-H2 symmetrical and asymmetrical stretching vibrations in an

aliphatic hydrocarbon, while the pair of features at 2960 cm-1 and 2870 cm-1 are characteristic of the

C-H3 symmetrical and asymmetrical stretching vibrations.

2O
An ultramicrotome thin-section, less than 200 nm thick, of the fourth IDP (L2009*F2), previously

examined using the Scanning Transmission X-Ray Microscope (STXM) at the NSLS, showed

absorptions near 2920 cm -1 and 2850 cm-1, the two strongest absorptions detected in the thicker

IDP samples, consistent with the C-H 2 features. This demonstrated that STXM and u-FTIR

measurements can be performed on the same IDP section, using the STXM to determine the bulk

carbon abundance, the spatial distribution of the carbon, and the abundance of graphitic carbon, and

using the u-FTIR to determine the types and relative abundances of the organic species present in

the section.

These results indicate that IDPs contain significant abundances of long chained aliphatic

hydrocarbons. Thus, IDPs could be an important resource for the development of life on Earth, other

planets such as Mars, and moons.

References: -

1. Anders, E., Nature 342:255-257 (1989).

2. Thomas, K.L. et al., Geochim. Cosmochim. Acta 57:1551-1566 (1993).

3. Clemett, S.J., et al., Science 262:721-724 (1993).

4. Swan, P., et al., Meteoritics 22:510-511 (1987).

5. Reffner, J., et aL, Synchrotron Radfation News 7:30-37 (1994).

ADDITIONAL EVIDENCE FOR POSSIBLE BIOGENIC ACTIVITY

IN THE MARTIAN METEORITE ALH84001

David S. McKay 1., Everett K. Gibson, Jr. 1, Kathie Thomas-Keptra 1,2,

and Christopher S. Romanek 3

1NASA Johnson Space Center; 2Lockheed-Martin Corp.; 3Univ. of Georgia

Martian meteorite ALH84001 has been shown to contain evidence of possible past biogenic activity

inside small carbonate aggregates or globules within the meteorite. The four lines of evidence

presented by McKay et al. /1/included the following: a) iron oxides and sulfides having textures

similar to terrestrial biominerals, b) carbonates formed at temperatures capable of supporting biogenic

activity, c) indigenous organic compounds in the form of PAHs associated with regions containing

carbonate globules, and d) morphologies of segmented, spherical and elongated features similar to

terrestrial micro-fossils and nanobacteria. None of these observations is in itself conclusive for the

existence of past life. Although there are alternative explanations for each of these phenomena taken

individually, when they are considered collectively, particularly in view of their close spatial association,

it was concluded/1/that they were evidence for primitive life on early Mars.

Since the report of McKay et al. /1/additional observations have been collected which support a

biologic origin for the globules including: i) carbon isotopic compositions (-55 to -65 %o), ii) biofilmlike textures, iii) chains of magnetite grains within carbonate globules similar to those produced by

magnetotactic bacteria, and iv) oxygen isotopic compositions within individual globules that are

indicative of low-temperature processes/2/.

Alternative hypotheses for the origins of the globules have been directed toward the nature of the

carbonate formation temperatures, magnetite morphologies and structures within the carbonates, the

sizes of nanostructures within carbonates rims, and potential terrestrial organic contaminants (i.e.

PAHs) introduced to the meteorite in Antarctica. The evidence, both pro and con, will be evaluated in

light of recent research efforts that have been conducted since the initial proposal regarding potential

biogenic activity in the martian meteorite ALH84001. After careful evaluation of the past and recent

information on ALH84001, we feel that our 1996 interpretation of possible biogenic activity within the

21
meteoritehasbeenstrengthen. All of the criticism offered to date may attack single points within our

model but they cannot account for the multitude of interesting phenomena within the sample.

References:

1. D.S. McKay et al., Science 273:924-930 (1996).

2. refs. within Lunar and Planetary Science-28th Abstracts (1997).

THE SEARCH FOR LIFE ON MARS

John F. Kerridge*

University of California, San Diego

A comprehensive understanding of the origin and nature of life will ultimately require knowledge

derived from non-terrestrial, as well as terrestrial, life. Although it is likely that life is widespread in the

universe, technical limitations currently restrict our search for extraterrestrial life to regions relatively

close to the Sun. Of the potential habitats presently known, none is more accessible than Mars. Also,

because environments on Earth and Mars were quite similar 3.5-4 Gyr ago, when life was emerging on

Earth, and because terrestrial life emerged very rapidly once conditions permitted, emergence of life

on Mars at that time seems quite plausible. Given that planet's presently hostile surface environment,

detection of any possible extant martian life represents a formidable technical challenge, but an active

search for evidence of an extinct biota is scientifically and technically feasible/1/. Furthermore, even if

life never began on Mars, any record of prebiotic chemical evolution preserved in martian rocks would

greatly enhance our understanding of such processe_ on Earth, where the record of that epoch has

been thoroughly destroyed.

The criteria to be satisfied for general acceptance of evidence of life, extant or extinct, on Mars will be

severe. The geochemical, mineralogical and morphological observations recently reported by McKay

et al./2/for the martian meteorite ALH84001 fail to meet those criteria. It is unlikely that study of any

known martian meteorites will improve upon this situation. A viable search for evidence of ancient life

on Mars will require a sequence of robotic-spacecraft missions, culminating in return of carefully

selected samples to Earth. By analogy with the record of early terrestrial life, those samples will be

aqueously deposited sedimentary rocks containing organic matter. Key to successful sample return

will be a series of precursor missions capable of, first identifying promising landing sites from orbit, and

second identifying promising rocks at such a site. Only modest enhancement of currently planned

orbital missions will be required, but considerable development of lander spacecraft will be needed,

particularly with regards to mobility on, and ascent capability from, the martian surface. A realistic time

frame for an exobiologically optimised Mars sample return mission is probably about 2009. Presently

unanticipated discoveries may permit an earlier mission, but otherwise an accelerated program would

be much less likely to succeed scientifically.

RQferences:

1. An Exobiological Strategy for Mars Exploration, NASA SP-530 (1995).

2. McKay D.S. et al., Science 273:924 (1996).

22
RADAR DETECTABILITY OF A SUBSURFACE OCEAN ON EUROPA

Christopher F. Chyba*

University of Arizona

The initial reconnaissance of the jovian system by the Voyager spacecraft and models of tidal heating

of natural satellites suggested the possibility of a liquid water ocean beneath the ice of Jupiter's moon

Europa. Recent high resolution imaging of Europa from the Galileo spacecraft is consistent with this

interpretation, and suggests that in some locations, liquid water may lie within a few kilometers of

Europa's surface. Since liquid water is essential for life as we know it, the possible existence of a

second liquid water ocean in the solar system is of great exobiological interest. In addition, a

subsurface Europan ocean may provide a model for the early Earth at the time of the terrestrial origin

of life. The search for and initial characterization of a Europan ocean, most likely via an orbiting

spacecraft, is now one of the highest priority objectives of solar system exploration.

An orbiting radar sounder may be able to detect directly the presence of a subsurface Europan ocean.

The radar detectability of the putative ocean depends on the transparency of the overlying ice, which

in turn will depend on the ice's purity and temperature gradient, as well as the radar wavelength. Here

we demonstrate that consideration of those factors plus available constraints on the properties of

Europan ice places a limit of about ten kilometers on the depth to which an ocean might be detectable

with an orbiting radar.

EARLY LIFE ENVIRONMENTS ON EARTH AND MARS (ELEEM)

G. Arrhenius I , S.J. Mojzsis 1,2*, T.M. Harrison 2, K.D. McKeegan 2, A.P. Nutman 3, C.R.L. Friend 4

1Scripps Institution of Oceanography, University of California, San Diego;

2WM Keck Foundation Center for Isotope Geochemistry, University of California, Los Angeles;

3Research School of Earth Sciences; Australian National University, Canberra, Australia;

4Oxford Brooks University, Headington, Oxford, UK

To evaluate model experiments seeking to reconstruct the sequence of events that led to the

synthesis of biomolecules and ultimately to the origin of life itself, it is necessary to examine the

geological record. This record in the oldest sediments on Earth is the only source of information

available about the physical chemical conditions (e.g. temperature, ocean pH, impacts, atmospheric

composition, life) present at the surface of the Earth at the time of the emergence of life before ca.

3900 Ma/1,2/.

Rocks of the Isua region in southern Greenland, are contained within extensive amphibolite to

granulite facies granitoid gneisses of early Archean (3600-3900 Ma) age. The identification of waterlain sediments such as banded iron-formation (BIF), metachert, and pillow lava basalts in these ancient

rocks attests to the presence of a developed marine sedimentary system by -3900 Ma/3/. Recent

carbon isotope studies on carbonaceous inclusions within apatite (basic calcium phosphate) grains

>from early Archean, Proterozoic and younger sediments up to presently forming marine deposits,

have demonstrated strongly negative (i.e. "isotopically light") isotope values of the carbon. Such

isotopically light carbonaceous matter is consistent with a bioorganic origin, and this finding has been

extended to the oldest known sediments which are >3850 Ma/3/. The 513C values measured on the

inclusions collected from the lsua supracrustal belt (ISB) of West Greenland (weighted mean: -30%0)

and a >3850 Ma BIF/3/from Akilia island (weighted mean: -37%0) deviate from the 513C values

reported previously in the majority of whole-rock reduced carbon >from the ISB.

23
Biopoesison Earth must have substantially pre-dated.this earliest appearance of life at -3900 Ma/2/.

The ancient surface of the planet Mars probably holds clues to the nature of the earliest environments

for the emergence of life. The search for the occurrence of phosphate minerals and possible

associations of isotopically fractionated carbon as applied to ancient terrestrial sediments, is part of the

exobiological search plan for Mars exploration and sample return, and for examination of the martian

meteorites/4/.

References:

1. Arrhenius, G., Sales, B., Mojzsis, S., and Lee, T. J. Theor. Biol. 187:503-522 (1997).

2. Mojzsis, S.J., Arrhenius, G., Harrison, T.M., McKeegan, K.D., Nutman, A.P., and Friend, C.R.L

Nature 384:55-59 (1996).

3. Nutman, A.P., Mojzsis, S.J., and Friend, C.R.L. Geochim. Cosmochim. Acta. 61:2475-2484

(1997).

4. Mojzsis, S.J., and Arrhenius, G. (1997) Phosphates on Mars: exobiological implications: Orig. Life

Evol. Biosph. 28 (in press, 1998).

Research supported by NASA NSCORT/Exobiology Grant #NAGW 2881.

IN VITRO EVOLUTION OF NOVEL RNA AND DNA ENZYMES

Gerald F. Joyce*, Martin. C. Wright, and Richard K. Bruick

Departments of Chemistry and Molecular Biology, The Scripps Research Institute

The principles of Darwinian evolution can be applied to a large, heterogeneous population of RNA or

DNA molecules to obtain particular molecules that have desired biochemical properties, including the

ability to catalyze a target chemical reaction. A population of variant molecules is subjected to repeated

rounds of selective amplification in the test tube. Only those individuals that perform a chosen catalytic

task are amplified so that, through successive rounds, the population adapts to the task at hand.

Recently we developed the ability to carry out the in vitro evolution of RNA-based catalytic function in

a continuous manner. The RNAs catalyze a ligation reaction that immediately makes them eligible for

amplification and the newly-produced RNAs are immediately eligible to catalyze another reaction. This

has enabled us to maintain laboratory "cultures" of evolving RNA enzymes, analogous to the way one

maintains cultures of bacteria. The RNAs are perpetuated by a simple serial transfer procedure,

amplifying indefinitely so long as an ongoing supply of substrate and other reaction materials is made

available. During one run of continuous in vitro evolution, the RNA enzymes were amplified by a factor

of 10298 over 52 hours. By the end of this process, new "generations" of progeny RNA molecules

were being produced approximately every 5 minutes.

We used stepwise in vitro evolution to develop a DNA enzyme that promotes the formation of a

peptide bond between an aminoacyl-oligonucleotide and a peptidyl-oligonucleotide, both bound via

their oligonucleotide components at adjacent positions along a complementary template. The

reaction format is analogous to that of the peptidyl transferase center of the ribosome, but the

chemistry is more akin to the biosynthesis of microbial peptides, involving attack of the c_-amine of an

amino acid on the carbonyl carbon of a thioester-linked peptide.

24

1|1-
CHEMISTRY OF THE BIOGENIC ELEMENTS IN DENSE INTERSTELLAR CLOUDS

AND RELATIONS TO THE SOLAR SYSTEM

W.M. Irvine and J.E. Dickens*

University of Massachusetts

The basic theme of this program is the study of molecular complexity and evolution in interstellar

clouds, and the relation of this chemistry to that in primitive solar system objects such as comets. This

research includes the identification of new molecular species in both environments and the probing of

chemical processes from accurate determination of molecular abundances. Such investigations

provide essential boundary conditions for the subsequent evolution of biogenic compounds in the

solar nebula and during planetary formation. The research emphasizes observations of the pure

rotational spectra of molecular species at submillimeter and millimeter wavelengths, which provide

powerful means of probing the physics and chemistry of the gas phase.

Recent research on dense interstellar clouds includes the identification of two new interstellar

molecules, ethylene oxide (c-C2H40) and the protonated formaldehyde ion (H2COH+), and a

comprehensive analysis of the interlinked chemistry and physics of two dark molecular clouds, TMC-1

and L134N. Ethylene oxide is only the third cyclic species unambiguously detected in the interstellar

medium. It is a higher energy isomer of the known interstellar species acetaldehyde (CH3CHO) and of

the as yet undetected molecule vinyl alcohol (CH2CHOH). The high abundance of c-C2H40 and

CH3CHO relative to gas phase chemical models suggests that their production involves grainmediated processes. For the dark cloud study emission from 34 transitions of 22 molecular species

and isotopomers was mapped in two clouds of similar physical but differing chemical properties. This

large data set allowed consistent determinations of temperature, density and chemical composition,

and the spatial gradients in these quantities.

The recent apparitions of Comets Hyakutake and Hale-Bopp provided a spectacular opportunity to

study cometary physics and chemistry, and possible links between interstellar and cometary material.

Important results include the first detection of cometary HNC (hydrogen isocyanide) and the first

detailed mapping of HCN and HCO + in cometary comae. The HNC/HCN abundance ratio is vastly

higher than that predicted by equilibrium chemistry, and is similar to values found in the interstellar

medium. The possibility that Cometary HNC includes preserved interstellar matter is being

investigated by analyzing the HNC/HCN ratio versus heliocentric distance.

Sample References:

1. Dickens, J.E. et al., "Hydrogenation of Interstellar Molecules: A Search for Methylene lmine

(CH2NH)," Ap. J. 479:307 (1997).

2. Dickens, J.E. et al., "Detection of Interstellar Ethylene Oxide," Ap. J. (in press 1997).

3. Irvine, W.M. et al., "Spectroscopic Evidence for Interstellar Ices in Comet Hyakutake," Nature

383:418 (1996).

4. Irvine, W.M. et al., "Interstellar and Cometary Ices: Molecular Emission from Comet Hale-Bopp," in

The Far Infrared and Submillimetre Universe, ESA SP-401 (in press 1997).

25
PHOTOCHEMICAL EVOLUTION OF THE BIOGENIC ELEMENTS

IN PRE-COMETARY/INTERSTELLAR ICE ANALOGS

L.J. Allamandola*

Astrochemistry Laboratory, NASA Ames Research Center

During the past two decades ground-, air-, and space-based infrared spectroscopic observations

combined with realistic laboratory simulations have revolutionized our understanding of interstellar ice

and dust, the raw materials from which planets, comets and stars are formed. Understanding the

chemical composition of this feedstock provides insight into the nature of the material brought into the

inner parts of the Solar System by comets and meteorites.

Most interstellar material is concentrated in large molecular clouds where simple molecules are formed

by dust grain and gas phase reactions. Gaseous species striking the cold (10° K) dust will stick,

forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV

photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically

fractionated species. Ice species identified in molecular clouds include H20, CH3OH, CO, CO2, and

H2 as well as nitriles and ketones or esters. During the past three years we have added several new

species to this list. This evidence, and the resulting photochemistry will be summarized, emphasizing

the potential prebiotic role of some of these species. The ready formation of complex organic species

from simple starting mixtures under interstellar conditions and the ice chemistry that ensues when

these ices are mildly warmed suggest that comets may have played an important role in the origin of

life.

IS MOTHER EARTH THE MOTHER OF LIFE?

THE SEARCH FOR ORGANIC MOLECULES INSIDE MINERALS AND ROCKS

Friedemann Freund* and Alka Gupta

SETI Institute and Department of Physics, San Jose State University

We explore the possibility that complex oxygenated organic molecules can be formed inside the hard,

dense matrix of magmatic minerals from dissolved H20 and CO2. The theoretical basis of our work is

well understood. When H20 and CO2 become incorporated as "impurities" in minerals crystallizing in

H20 and CO2-1aden environments, they undergo an internal redox conversion by which they split off

H2 and reduced C. Such H2 and C behave as "impurities" and segregate upon further cooling to

dislocations and other major defects. There, C-C and C-H bonds begin to form, building the

backbones of what will become organic molecules when the minerals are weathered.

To simulate weathering we start from upper mantle 10-20 mm large, gem-quality olivine single crystals.

We clean them with chloroform and then crush them to a medium fine powder which is then subjected

to a H20 Soxhlet extraction. The organics thus obtained are analyzed by GC-MS, using standard tertButyldimethylsilyl (t-BDMS) derivatization. One everlasting concern is contamination. We therefore

expanded our study to the vesicular basalt that had brought the olivine crystals from mantle depth

during a volcanic eruption. The rationale was that, if adventitious contamination occurred from

biogenic sources, the basalt would be much more receptive than the gem-quality olivine crystals. The

basalt was treated and extracted in exactly the same way.

While the basalt was essentially devoid of extractable organics, the olivine crystals yielded a rich

spectrum of compounds. This includes aliphatic monocarboxylic acids, H3C-(CH2)n-COOH with n

ranging from 6 to 10, and an N-bearing compound, C2H3NO2, most likely glycolamide. Other

compounds seen in the GC-MS data set still await identification. To our knowledge this is for the first

26

111-
time that fatty acids have been identified in extracts from olivine crystals from the upper mantle.

Glycolamide had been reported by George and Cronin (1994) from Murchison meteorite.

An extraneous source of the organics can be ruled out. We conducted full procedural blanks and

controls with the vesicular basalt from the same locality. Given the gem quality of the olivine crystals

plus the fact that the basalt yielded nil organics, we can dismiss the hypothesis by Tingle, Mathez, and

Hochella (1991) that the volcanic gases catalyzed organics by reacting with exposed surfaces and

micro-cracks which opened and closed during the eruption.

The chain molecules extracted from the olivine crystals suggest that the Cn backbones form by solute

C segregating into dislocations. These are 1-dimensional defects and act as trapping sites for

"impurities" in the mineral matrix. Minerals have an assortment of 1- or 2-dimensional defects. If they

all act as trapping sites for Cn backbones, the molecules to be released through weathering are

expected to belong to a select group of stereochemically restrained compounds. Massive weathering

of mafic/ultramafic rocks on the early Earth may have provided a source of such compounds - for the

benefit of our Life. On other planets with tectonics and surface water, similar weathering processes

are expected to provide similar organic compounds - for the benefit of their Life.

MOLECULAR MODELING

OF PROTOCELLULAR STRUCTURES AND FUNCTIONS

Andrew Pohorille*, Michael A. Wilson, Michael H. New, and Christopher Chipot

NASA Ames Research Center and University of California, San Francisco

Even the simplest protocell must have had the capability to catalyze the chemical reactions needed for

its survival and growth, capture and utilize energy, and communicate with its environment. These

functions must have been accomplished by simple molecules present in protobiotic milieu. One such

group of potential early catalysts and signaling molecules were peptides - likely precursors of enzymes

and receptors. Unfortunately, most short peptides are disordered in aqueous solution and, therefore,

do not appear suitable for performing cellular functions. However, many of these peptides,

depending on their sequence, can acquire a broad range of well defined secondary structures, such

as c_-helix and i3-strand, at water-membrane, water-oil or water-air interfaces. A crucial, common

characteristic of these interfaces is that a nonpolar phase is adjacent to water.

The organization of small peptides at aqueous interfaces, essential for catalytic activity and signaling,

was examined in large-scale molecular dynamics simulations of several peptides composed of two

amino acids, nonpolar leucine (L) and polar glutamine (Q). Based on results for the LQQLLQL

heptamer, designed to maximize interfacial stability of an (_-helix by exposing polar side chains to

water and nonpolar side chains to a nonpolar phase, it is proposed that, whenever possible, peptides

fold at interfaces through a series of amphiphilic intermediates. Once folded, the peptides form

structures that are suitable for polymerization and have potential for catalytic activity.

If peptides consist of nonpolar residues only, they insert into the nonpoiar phase. As demonstrated

by the example of the leucine undecamer, such peptides fold into an c_-helix as they partition into the

nonpolar medium. The folding proceeds through an intermediate, called 310-helix, which remains in

equilibrium with the (_-helix. Once in the nonpolar environment, the peptides can readily change their

orientation with respect to the interface from parallel to perpendicular, especially in response to local

electric fields. The ability of nonpolar peptides to modify both the structure and orientation with

changing external conditions may have provided a simple mechanism of transmitting signals from the

environment to the interior of a protocell.

27
Another protocellular function the mechanism of which has been studied using molecular modeling is

the activated formation of transmembrane proton gradient. This gradient could have driven chemical

synthesis in the protocetl. A simple, peptide-based model of a transmembrane proton pump consists

of a proton source and two acceptors. The directionality of the pump is ensured by a "gate-keeping"

mechanism involving a water molecule, conformational change of the primary acceptor or

tautomerization of a histidine. The pump can be formed by two transmembrane peptide helices but

not one helix.

STRUCTURE AND FUNCTION

OF ENCAPSULATED REPLICATING SYSTEMS

David W. Deamer*

Department of Chemistry and Biochemistry, University of California, Santa Cruz

The origin of cellular life necessarily involved the self-assembly of relatively simple organic molecules

into more complex membranous structures. Liposomes can be used to model this process,

particularly in the form of catalytic macromolecules encapsulated within lipid bilayer vesicles to produce

simple cellular structures. We have established two encapsulated polymerase systems that can

incorporate external substrates to synthesize nucleic acids in the internal volume. In the first, a lipid

with relatively short chains is used to prepare liposomes containing polynucleotide phosphorylase.

Under these conditions the enzyme is captured within the lipid vesicles, but the bilayer is sufficiently

permeable to allow a substrate like ADP to cross into the liposome, so that RNA is synthesized by the

polymerase (Chakrabarti et al. 1994).

We are now attempting to extend this result to a template-dependent process involving T7 RNA

polymerase. This enzyme synthesizes RNA using a DNA template and four nucleoside triphosphates

(NTPs). It should be possible to capture both the polymerase and a template in a liposome, supply

substrate and primer, and demonstrate the synthesis of RNA complementary to the template.

However, we found that considerably higher permeability of the lipid vesicles is required for the

reaction to proceed at useful rates. We are therefore exploring methods by which permanent pore-like

structures can be introduced into lipid bilayers. One such pore is produced by alpha hemolysin, a

bacterial toxin that self-assembles as heptamers in lipid bilayers to form a 2.2 nm transmembrane

channel (Song et al. 1996). We have found that the alpha hemolysin channel produces pores in lipid

bilayers that can accommodate high fluxes of ionic nucleotides. Surprisingly, single strands of RNA or

DNA up to 1000 nt in length can also pass through the channel (Kasianowicz et al. 1996). In

preliminary experiments we have had modest success in synthesizing RNA with encapsulated

polymerase, using the pore to transport NTP substrates at sufficient rates to support the polymerase

activity. This system represents a model for the first forms of cellular life, and its properties provide

information about the hurdles that were overcome by complex self-assembled molecular systems on

the evolutionary path to the first cells.

References:

1. Chakrabarti, A., R.R. Breaker, G.F. Joyce and D.W. Deamer, Production of RNA by a polymerase

protein encapsulated within phospholipid vesicles, J. MoL EvoL 39:555-559 (1994).

2. Kasianowicz, J., E. Brandin, D. Branton and D.W. Deamer, Characterization of individual

polynucleotide molecules using a membrane channel, Proc. Natl. Acad. ScL USA 93:13770-13773

(1996).

3. Song, Lo, M.R. Hobaugh, C. Shustak, S. Cheley, H. Bayley and J.E. Gouaux, Structure of

Staphylococcal a-hemolysin, a heptameric transmembrane pore, Science 274:1859-1866 (1996).

28
PHOTOSYNTHESIS AND IRON IN HIGH IRON MICROBIAL MATS

Beverly K. Pierson*

University of Puget Sound

Photosynthesis evolved early in the history of life on Earth and had major environmental impacts

locally and globally. Many different forms of photosynthesis exist on Earth today and the origin and

evolution of these forms is relevant to understanding some of the major events and environmental

impacts of photosynthesis on the history of life and the planet itself. The direct photo oxidation of iron

(photoferrotrophy) is one of the forms of photosynthesis that may have preceded the evolution of

oxygenic photosynthesis. Anoxygenic photoferrotrophs have recently been detected but their

relationship to the ancient emergence of oxygenic photosynthesis and their environmental impacts

are yet to be determined. Understanding the roles of photoferrotrophs and oxygenic phototrophs in

the oxidation of, precipitation of, and deposition of iron is important in interpreting the origin of

oxidized iron in the early history of Earth and possibly on Mars. We are studying a thermal iron spring in

Yellowstone National Park to determine the relationships of all of the phototrophs to the oxidized iron

accumulations and to seek additional types of photoferrotrophs. It may be possible to find a biological

signature in these iron deposits that could be preserved over geologic time.

Oxygenic cyanobacteria are abundant in the iron deposits at Chocolate Pots hot springs. The anoxic

source waters contain about 9 mg/L ferrous iron and 1.0 mg/L Mn. Four different communities are

present over a temperature range of 56 to 30° C. Dominant filamentous forms appear to have a role in

stabilizing the otherwise flocculant iron oxide/hydroxide precipitates. This stabilizing influence may

contribute to the building of the deposit. Microelectrode studies reveal that the oxygenic activity of

the cyanobacteria greatly increases the level of oxygen in the sediment/water interface to values as

high as 200% saturation. Their autotrophic activity raises the pH substantially from around 7 (in the

water) to over 9 during daylight in the top two mm of sediment. At night oxygen falls to below

saturation values at the interface and to zero within a mm of the sediment surface, pH values also fall at

night. The photosynthetic activity of two of the cyanobacterial communities is substantially increased

in the presence of 1.0 mM Fe(ll) although direct photoferrotrophy has not yet been demonstrated.

SPECIES COMPOSITION OF HOT SPRING CYANOBACTERIAL MATS

David M. Ward* and Thane Papke

Department of Microbiology, Montana State University

Modern microbial mats are studied as analogs of stromatolites, the predominant surviving fossils of

Precambrian microbial life. Mats which occur in hot springs are among the best-studied model

systems--understanding them gives insight as to the composition, structure and function of microbial

communities that might have once predominated Earth's biota, and consequently its

biogeochemistry. Limitations of traditional m!crobiological methods, such as microscopy and

cultivation, have impaired our ability to even understand which microbial populations comprise such

microbial communities. However, new molecular tools are enabling us to vastly improve our ability to

detect the native populations that inhabit these mats, and to understand their ecology and

evolutionary history. This knowledge is, in turn, helping us to better understand what procaryotic

species are, and the evolutionary processes that explain their biodiversity and ecological significance

within and among modem mat communities.

We have focused on cyanobacterial populations inhabiting the mat in Octopus Spring, Yellowstone

National Park. The simple morphology of the unicellular cyanobacteria (genus Synechococcus)

dominating this mat, combined with the overly selective pressure of culture methods, masks a

29
remarkable diversity of cyanobacterial populations which are defined by unique 16S rDNA gene

sequences. Because they exhibit unique ecological patterns of occurrence relative to environmental

gradients, these populations can be considered as unique species, provided that we abandon the

arbitrary concept of procaryotic species microbiologists usually use and replace it with the more

ecological view of species used by macrobiologists. The close genetic similarity among many of these

cyanobacterial species challenges us to consider whether 16S rDNA sequences are themselves too

conserved to detect individual species. We have begun to reveal genetic diversity within 16S rDNAdefined populations, by examining sequences in the intervening transcribed spacer region

separating 16S and 23S rDNA genes.

BIOGEOCHEMISTRY OF CARBON IN THE ANCIENT BIOSPHERE:

PERSPECTIVES FROM MODERN MICROBIAL COMMUNITIES AND

THE ANCIENT CARBON ISOTOPIC RECORD

David J. Des Marais .1 , A. Tharpe 1, and J. Thompson 2

1Ames Research Center; 2Eckerd College

The geologic record allows us to describe early habitable environments and to compare the timing of

environmental change and biological innovations. The 513C values of organics and carbonates reflect

the processing of C within organisms and ecosystems; and these 813C values can be retained in

ancient kerogens and carbonates. However, this 813C record is a product of the entire array of

processes and reservoirs that define the biogeochemical C cycle. Thus the fullest interpretation of the

513C record will be achieved only through a balanced approach to deciphering the history of the entire

C cycle.

Ecological processes affect organic 813C values of microbial mats. As the fraction of organic C

decomposed by sulfate reduction increased, relative to the rate of aerobic decomposition, secondary

production by aerobic sulfide oxidizing chemoautotrophs became a larger fraction of primary

production. Discrimination by sulfide-oxidizers was large, at times lowering mat 513C values by as

much as 8 per mil. This finding, which is analogous to a model proposed by J. Hayes for isotopic

discrimination within a methanogen/methanotroph cycle during the late Archean, indicates that

organic 513C values can be lowered substantially by secondary production in a microbial ecosystem.

This secondary production can be sustained by oxidation either of organic C or sulfur substrates.

In Green Lake, NY, blooms of Synechococcus sp. dominate the precipitation of micritic carbonate

which exhibits 813C values as much as 4 per mil larger than the 513C of lake water dissolved inorganic

C (DIC). Micritic carbonate precipitates under highly alkaline conditions within and adjacent to

extracellular organic "S layers, where the 513C of DIC is elevated due to isotopic discrimination during

photosynthetic assimilation of C.

Post-depositional thermal alteration degrades kerogens, lowering elemental H/C and increasing 513C

in residual kerogen. A plot of H/C versus 513C for a large data set of Proterozoic kerogens can indicate

the magnitude of this 513C shift, if the time interval sampled witnessed no large long-term changes in

kerogen 513C values. Independent plots for mid-Proterozoic and Neoproterozoic kerogens both

indicated that 513C values were between 2 to 2.5 per mil more positive in kerogens with H/C values of

0.2, relative to kerogens with H/C of 0.8. Thus the thermal alteration of kerogen 5130 values has been

considerably lower than had been estimated previously.

3O
THE DISTRIBUTION OF PROTEROZOIC FOSSILS IN TIME AND SPACE

Andrew H. Knoll*

Harvard University

We know, and have known for decades, that Phanerozoic ecosystems were preceded by a long

interval of Precambrian evolution. The biology of Archean oceans remains poorly constrained, but in

recent years, taxonomic, paleoenvironmental, and stratigraphic patterns have emerged that enable us

to approach the Proterozoic fossil record in a predictive fashion that looks to generalizations about

early life.

Cyanobacteria are among the most morphologically diverse and developmentally complex of all

eubacteria, making them one bacterial clade for which morphology provides useful systematic

characters. Cyanobacteria were widely distributed in Proterozoic environments favoring fossil

preservation; fossil taxa show consistent patterns of paleoenvironmental distribution within a time

interval, as well as stratigraphic distributions that mirror those of sedimentary and geochemical indices

of Earth's environmental development. Even shallow branches of the cyanobacterial tree, including

the heterocyst-bearing Nostocales, are represented in fossil assemblages 2100 Ma or older,

indicating that much cyanobacterial diversification occurred during the Archean or earliest Proterozoic

Eon.

Eukaryotes are represented in Proterozoic rocks by both morphological and biomarker remains.

Although Simple microfossils and steranes of probable eukaryotic origin can be traced back to 1800

Ma and possibly as far as 2450 Ma, there is little evidence for pronounced algal diversification until

about 1200 Ma, when green, red, and chromophyte algae first appear in the record. Much of the

ordinal-level diversity architecture of the these algal groups was already in place by the time that

diverse Ediacaran fossils firstappear in the geological record.

THE BIOLOGICAL POTENTIAL OF MARS (AND MARS MISSIONS)

Bruce M. Jakosky*

Laboratory for Atmospheric and Space Physics, University of Colorado

Possible biological activity on Mars has been postulated on the basis of martian environmental

conditions meeting those necessary for an origin and continued existence of life. Based on the

terrestrial example, these conditions include: i) the existence of liquid water at the surface or in the

subsurface throughout geologic time, ii) the availability and accessibility of the biogenic elements, and

iii) a source of energy to drive the system out of chemical equilibrium, with the movement back toward

equilibrium providing energy for biota. Two aspects of this that have not been addressed in detail

include the availability of chemical energy to power life and the ability to find suitable locations on the

martian surface. Both of these are of significance in planning future missions to Mars that will search for

life.

Although it is difficult to estimate the total chemical energy available on Mars and the efficiency with

which it can be accessed, we can use simple scaling arguments to compare available energy with the

Earth. Assuming that early life got its energy from chemical energy obtained through hydrothermal

systems, the total amount of energy available is proportional to the total volume of volcanic materials.

Both instantaneously and integrated over time, Mars had about 1% the total volcanic eruption rate as

Earth. This means that the energy available on Mars in 4 billion years is equivalent to the energy

available on Earth in only 40 million years. If the propagation of life is energy limited, then Mars may

have contained no more life than was present on Earth after only 40 m.y. Of course, this comparison

31
assumes that all other factors don't matter; they do, although this calculations provides a basis for

quantitative comparison of martian and terrestrial life.

We can use Mars Pathfinder results to estimate the properties of sites that may contain fossil or extant

life. The Pathfinder site showed evidence at the surface for the same geological processes as have

acted at the larger scale seen from orbit. This is fundamentally different from the two Viking sites,

where there was no evidence at the ground for the same processes having acted, and the sites

appeared to consist only of rock, dust, crust, etc. This suggests that the geologically interesting sites

(not covered by dust) will show features resulting from the same processes that make them interesting

- for example, a volcanic site will look like a volcanic site from the surface. Unfortunately, this means

that rover traverses will be much more difficult than envisioned based only on the Viking data.

Traverses of several tens of kilometers may not be possible for some of the most interesting sites.

THE NASA SPECIALIZED CENTER OF RESEARCH AND TRAINING

(NSCORT) IN EXOBIOLOGY

Jeffrey L. Bada*, Stanley L. Miller, Gustaf Arrhenius, Russell F. Doolittle and Christopher Wills

University of Califomia, San Diego

Gerald Joyce

The Scripps Research Institute

Leslie Orgel

The Salk Institute for Biological Studies

The NSCORT/Exobiology program was initiated in January, 1992 and funded for five years. We

recently competed for a five year renewal, and this renewal was awarded effective April, 1997. The

NSCORT/Exobiology program has an annual budget of approximately $1,000,000, and in the five

year renewal the number of PIs has increased from five to six, and an Outreach Coordinator _li_ls) has

also been added.

The continued major function of the NSCORT is to train young scientists in the field of Exobiology.

Thus, the bulk of the $1,000,000 annual budget is used to support the research and training of

undergraduate, graduate and post-doctoral Fellows who are selected on a competitive basis. About

five Fellows at each level are supported each year. The goal of our training program is to produce the

next generation of young scientists needed to carry out cutting edge research in the areas relating to

the origin of life and exobiology.

The NSCORT/Exobiology research program addresses the central issue of the origin of life: the

nature of the first genetic material. The first appearance of a molecular system that could store

information and replicate Imperfectly marked the transition from the abiotic chemistry of the primitive

Earth to biochemical evolution. The projects of the various PIs constitute a concerted effort to

investigate all aspects of the chemistry that led to the origin and evolution of the first self-replicating

systems and how these systems eventually evolved into the biochemistry associated with modem day

organisms.

A vigorous Exobiology outreach program (annual budget = $25,000) involving the scientific

community, K-12 and college students and teachers and the general public is supported by the

NSCORT. An Internet site (address, http://www.chem.ucsd.edu/~nscort/NSCORT.html) describes

the NSCORT activities, research programs and Fellowship opportunities. The 1999 meeting of the

International Society for the Study of the Origin of Life (ISSOL) will be hosted by the NSCORT in La

Jolla.

32

[]1 I;
ENANTIOMERIC EXCESSES

IN THE AMINO ACIDS OF CARBONACEOUS CHONDRITES

John Cronin* and Sandra Pizzarello

Department of Chemistry and Biochemistry, Arizona State University

The organic matter of carbonaceous chondrites is representative of that fraction of the early Earth's

total organic matter delivered by the fall of such meteorites and perhaps interplanetary dust.

Consequently, it may provide insights to chemical evolution and the origin of life. Enantiomeric ratios

of chiral organic compounds in these meteorites have been of interest for many years because they

offer a way to assess terrestrial contamination. Furthermore, the finding of enantiomeric excesses (ee)

not related to contamination suggests that an asymmetric influence was manifest in chemical evolution

and may have played a role in the origin of the homochirality that characterizes terrestrial life.

Our recent finding /1/ of small L-ee in both of the two enantiomeric pairs of 2-amino-2,3-

dimethylpentanoic acid (DL-c_-methylisoleucine and DL-(_-methylalloisoleucine) and two other c_-

methyl amino acids, isovaline and c(-methylnorvaline, obtained from the Murchison meteorite has now

been confirmed in preparations of these amino acids from the Murray meteorite. As in Murchison, the

c_-hydrogen analogues of the latter amino acids, c_-amino-n-butyric acid and norvaline, were found to

be racemates. The L-excesses found for the enantiomeric pairs of 2-amino-2,3-dimethylpentanoic

acid from Murray were smaller than those found for their Murchison analogues. In addition, L-excesses

were observed in Murray for two other amino acids, _-methylvaline and (_-methylnorleucine.

We did not observe the substantial excess of L-alanine reported by others/2/in our fractionated

Murray extract. Without prior fractionation on a reverse-phase column, several other amino acids with

similar retention times are present in carbonaceous chondrite extracts and can interfere with

determination of the alanine enantiomer ratio.

Attempts to extend these observations to other classes of chiral organic compounds are underway,

but in some cases (amines, hydroxy acids) suitable analytical methods have proved difficult to

establish.

The hypothesis /3/, that enantiomeric excesses might originate from exposure of planetary or

interstellar organic matter to a flux of circularly polarized light (CPL) of a specific handedness produced

as synchrotron radiation by neutron stars, is an attractive explanation for the ee observed in meteorite

amino acids. This hypothesis predicts that the less abundant enantiomer in all cases (D) will

preferentially absorb CPL of a particular handedness. Stereospecific syntheses of the meteoritic

amino acids showing ee are being carried out with the intent of measuring their circular dichroism

spectra.

References:

1. Science 275:951 (1997).

2. Nature 348:47 (1990).

3. Nature 306:118 (1983).

33
MODIFICATION OF AMINO ACIDS

AT SHOCK PRESSURES OF 3.5 TO 32 GPa

Etta Peterson 1, Friedrich Horz2, George Cooper 3 and Sherwood Chang 1.

1Exobiology Branch, NASA Ames Research Center;

2Solar Systems Exploration Division, NASA-Johnson Space Center;

3SETt Institute

The majority of meteorites studied today are thought to originate in the asteroid belt. Impacts among

asteroidal objects generate heat and pressure that may have altered or destroyed pre-existing organic

matter in both targets and projectiles to a greater or lesser degree depending upon impact velocities.

Dynamical models of asteroid evolution suggest relative velocities quite low initially, but rising to a

maximum of about 5 km/s which corresponds to a shock pressure of -30 GPa. Very little is known

about the shock modification of organic matter relevant to this stage of the cosmic history of biogenic

elements and compounds or to impacts on early Earth. Our study describes the effects of impacts on

selected classes of organic compounds utilizing laboratory shock facilities. Amino acids were

subjected to shock impact over a pressure range of 3.5 to 32 GPa both within and without meteoritic

mineral matrices. The extent of amino acid destruction, racemization, and conversion to secondary

amino acids was examined. Abundances of parent compounds decreased by a factor of 103 over this

range. Racemization also occurred, but some residual optical activity remained in the amino acids

surviving shocks up to 32 GPa. Secondary amino acids formed in the high peak pressure range; those

identified were t3"alanine, glycine, alanine, y-aminobutyric acid, and 13-aminoisobutyric acid. At 30

GPa, the abundances of these daughter compounds exceeded those of the remaining initial amino

acids. As the concomitant effects of high mechanical stress and temperature accompanying shocks

cannot be separated in this work, their relative contribution to the observed transformations cannot be

estimated. Amino acid survival in shock experiments suggests that, after formation/emplacement of

amino acids in carbonaceous chondrite parent bodies, these objects never experienced impact

velocities >5 km/s, which suffices to generate 30 GPa for typical silicate/silicate impacts. Notably,

fragments of Canyon Diablo meteorite recovered from Meteor Crater, Arizona, are reported to have

suffered shocks of <13 GPa. Our results suggest that if the Canyon Diablo event was typical of

asteroidal impactors striking Earth at -14 km/s, some small fraction of the organic compounds

contained within such projectiles, even amino acids, would have survived intact.

AND

AN INVESTIGATION OF SUGARS

OTHER POSSIBLE FORMALDEHYDE PRODUCTS

IN THE MURCHISON METEORITE

George Cooper*

SETI Institute

Carbonaceous meteorites are of interest in the study of early solar system organic chemistry and the

origin of life. This is due to their pristine nature, age (~4.5 billions years), and abundance of organic

compounds. Because of the past and present delivery of meteoritic material to the Earth and other

solar system bodies, carbon and organic compounds were available for prebiotic chemistry. The

Murchison meteorite, the best characterized carbonaceous meteorite with respect to organic

chemistry, contains numerous compounds of potential prebiotic importance. These include amino

acids, amides, carboxylic acids, hydroxy acids, sulfonic acids, phosphonic acids, purines and

pyrimidines. Notably absent among the biologically important compounds reported in Murchison are

polyhydroxylated compounds, polyols, including sugars (polyhydroxy aldehydes or ketones). Ribose

and deoxyribose, which are five carbon sugars, are essential components of contemporary nucleic

34

1711 I"
acids, DNA and RNA. If polyhydroxylated compounds are shown to be indigenous to meteorites, this

would demonstrate that such compounds were abiotically synthesized at the beginning of the solar

system and therefore could have been part of the initial mixture of compounds available for the

origin/evolution of life on the early Earth. The objectives of this project are to determine the

abundance, structure, and origins of polyhydroxylated compounds in the Murchison meteorite. The

procedures used include gas chromatography-mass spectrometry and isotope-ratio mass

spectrometry.

One of the most generally agreed upon routes for the prebiotic synthesis of polyols is the "formose"

reaction. In this reaction, formaldehyde (CH20) in slightly basic aqueous solution reacts with itself to

gradually build a variety of hydroxylated compounds and sugars of increasing carbon number.

Because there was aqueous alteration on the Murchison parent body, and simple carbonyl

compounds are constituents of Murchison, this reaction would have been possible. Our preliminary

analysis of Murchison extracts suggests at least a partial product distribution of a formose-like reaction.

Thus far we have identified ethylene glycol, glycerol, dihydroxyacetone, glyceric acid, and other

possible polyols. Preliminary isotopic measurements of bulk samples also indicate that the majority of

Murchison polyols are indigenous to the meteorite. Isotopic measurements (D/H, 13C/12C, and

160/170/180) of individual compounds will help to determine their origins as well as if they are

indigenous.

CO-ORIGIN OF METABOLISM AND BIOPOLYMER SYNTHESIS

USING FORMOSE SUGAR SUBSTRATES

Arthur L. Weber*

SETI Institute

Modern life can be described as a complex chemical process (metabolism) that is catalytically

controlled by its products (proteins-nucleic acids) in a way that enhances the perpetuation of the

entire system. Consequently, the origin of life can be described as a continuous series of events in

which a prebiotic chemical process came increasingly under the control of its catalytic products. In our

search for this prebiotic process (earliest metabolism) that yielded catalytic take-over products (such as

polypeptides), we have investigated - (a) the thermodynamics of the reactions of carbon groups in

order to establish the general principles (a historical thermodynamic constraints) that govern modem

metabolism and chemical processes involved in its origin, and (b) the chemistry of laboratory models of

prebiotic processes that could have been involved in the origin of metabolism and biopolymer

synthesis. These studies of the chemical transformations of carbon point to sugars as the optimal

substrates for the co-origin of metabolism and biopolymer synthesis.

To better understand the energetics of prebiotic and biotic carbon chemistry, we examined the

relationship between redox disproportionation of carbon substrates and the free energy change of

biosynthetic and fermentative pathways. Redox disproportionation is defined as the transfer of

electrons between two carbon groups that results in an increase (by 4 oxidation number units per 2

electrons transferred) in the distance separating the two carbon groups on the oxidation number scale

of carbon. This study showed that in E. coil, redox disproportionation of sugar carbon accounted for

84% and 96% (and ATP only 6% and 1%) of the total energy amino acid and lipid biosynthesis,

respectively. Redox disproportionation of carbon, and not ATP, is the primary energy source driving

amino acid and lipid biosynthesis from glucose. Because disproportionation energy is determined by

the invariant half-cell reduction potentials of carbon groups, and since sugars have the highest energy

yield of multi-carbon substrates, sugars can be considered the universal optimal biosynthetic

substrate.

35
Sincethermodynamicnstabilityof sugarsalsomakesthemattractiveprebioticsubstrates,weare

currentlyinvestigatingtheprebioticsynthesisof"activated"aminoacidthioestersandpeptidesfrom

formaldehyde-derivedsugarsandammoniainthepresenceof thiolsundermildaqueousconditions.

We recentlydemonstratedthat alanineand homoserineare synthesizedfrom formaldehyde,

glycolaldehyde(substratesof theformoseautocatalyticycle)andammoniainthepresenceofthiol

catalysts.This'one-pot'thiol-dependent prebioticsynthesispresumablyyieldsaminoacidsviaamino

acidthioesterintermediatesthat canformpeptides.Thisprebioticsynthesis,whichmodelsboth

metabolism(glycolysis)andbiopolymersynthesis(proteinsynthesis)usesthesameredoxengine as

modern glycolysis and amino acid biosynthesis. We are also the examining possibility that this

chemical process generates autocatalytic products by using selection techniques to evolve the

system in a way that increases its production of autocatalytic products (rudimentary molecular

replicators).

THE ORIGIN AND EVOLUTION OF OXYGENIC PHOTOSYNTHESIS

Robert E. Blankenship*

Department of Chemistry and Biochemistry, Center for the Study of Early Events in Photosynthesis,

Arizona State University

Hyman Hartman

Institute for Advanced Studies in Biology

The advent of oxygen evolvlng photosynthesis is one of the central events in the development of life

on Earth. Prior to the evolutionary origin of this metabolic capability, the atmosphere of the early Earth

was largely anaerobic. The development of more advanced eukaryotic life forms did not take place

until the free oxygen level in the atmosphere rose to a sufficient level. While significant questions

remain over the timing of the beginning of oxygenic photosynthesis, no other process, either

biogenic or nonbiogenic, is capable of producing the large quantities of molecular oxygen that

demonstrably changed the course of life on Earth. Understanding the evolutionary origin of this

metabolic process is therefore of considerable importance.

The evolutionary developments that led to the ability of photosynthetic organisms to oxidize water to

molecular oxygen are discussed. Two major changes from a more primitive reaction center are

required, a charge accumulating system and a more oxidizing reaction center pigment. Intermediate

stages are proposed in which hydrogen peroxide was oxidized by the reaction center and an

intermediate pigment similar to chlorophyll dwas present.

HORIZONTAL GENE TRANSFER: PITFALLS AND PROMISES

J. Peter Gogarten*, Elena Hilario, and Lorraine Olendzenski

University of Connecticut

Phylogenetic reconstruction from protein or nucleic acid sequence families at best provides

information on the evolution of individual genes. In contrast to the assumed tree-like evolution of

genes, organismal evolution is characterized by the exchange of genetic information between

organisms and even by the fusion of formerly independent lines of descent. Horizontal gene transfer

often has been regarded as a last ditch attempt by systematists to reconcile controversial

phylogenies. While the recognition of horizontal transfer as a major factor in prokaryotic evolution

36

_!:]! I"
certainly complicates the interpretation of molecular phylogenies, it also allows synchronization of

different parts of the universal tree of life, and thus might provide the key to the detection of periods

of rapid substitutions.

Contradictions between molecular phylogenies can be either due to insufficient resolution and tree

building artifacts (the placement of the microsporidia either at the root of the eucaryal domain or with

the fungi probably falls into this category); unrecognized gene duplication events; or horizontal gene

transfer. In general, organismal evolution is clearly visible as the majority consensus of different

molecular phylogenies (e.g. ribosomal rRNAs, ATPase subunit, elongation factors, components of

signal recognition particles).

One noteworthy exception from using the majority consensus as backbone for the organismat

phylogeny are the Archaea. Although many characters clearly characterize the Archaea as a group

which is distinct from the Bacteria, recent genome analyses confirms earlier observations that the

majority of identifiable archaeal genes are very similar to their bacterial homologues. Not only are many

(most?) of the genes similar to the bacterial homologues, if gene families are analyzed in more detail,

the archaeal genes are found to group within the bacterial domain, and the different archaeal genes

do not even cluster together. Thus the majority consensus would dissolve both the Archaea and the

Bacteria into para- or polyphyletic groups. In contrast most genes involved in genome structure,

transcription, translation and chemiosmotic coupling clearly set the Archaea apart from the Bacteria. In

this case the backbone of our preliminary organismal phylogeny reflects those markers which are less

prone to horizontal gene transfer, and explains the many genes found in the Archaea which are

bacterial in character as the result of horizontal gene transfer. The fact that so many genes found in

the archaeal genomes are bacterial in character raises the question of how these genes were

transferred. Initially a single horizontal transfer event was considered; however, comparison of

individual gene families suggests at least several smaller transfer events.

GENES AND ENZYMES OF ANAEROBIC METABOLISM

IN SHEWANELLA PUTREFACIENS

Doug Lies*, Alexandre Tsapin, James Scott, and Ken Nealson

Center for Great Lakes Studies, University of Wisconsin

Shewane//a putrefaciens is a gram negative bacterium in the gamma group of the Proteobacteria. It is a

non-fermentative organism capable of utilizing molecular hydrogen as an energy source, and of

growth on a limited number of carbon sources, including formate, pyruvate and lactate. In contrast to

this limited array of energy sources, Shewanella utilizes an extensive array of electron acceptors for

metabolism, including oxygen (aerobic respiration), N (nitrate and nitrite), Mn (Mn(lll) and Mn(IV)

oxides), Fe (Fe(lll) oxides), S (elemental sulfur, thiosulfate, sulfite, tetrathionate, and

dimethylsulfoxide), trimethylamine oxide, fumarate, glycine, and others. Given this wide range of

electron potentials available, it was hypothesized that perhaps within this single organism could lie an

understanding of the evolution of anaerobic respiration. We have thus been on a program of cloning,

sequencing and comparing the various reductases and cytochromes used by Shewanella for its

diverse respiratory functions. We report here the purification and properties of several different

cytochromes of redox potentials ranging from -250 to +340 meV, and of several key proteins and/or

genes involved in the metabolism of manganese, iron, sulfur, nitrogen, and carbon compounds.

37
VIABLE BACTERIA IN SIBERIAN AND ANTARCTIC PERMAFROST

E.I. Friedmann 1., A.D. Gilichinsky 2, T. Shi I , G.S. Wilson 3, R.H. Reeves I , V.E. Ostroumov 2,

E.A. Vorobyova 4, V.S. Soina 4, V.A. Shcherbakova 2, T.A. Vishnivetskaya 2, J.P. Chanton I ,

R.O. Friedmann 5, C.P. McKay 6, and E.M. Rivkina 1,2

1Florida State University; 2Russian Academy of Science Pushchino, Russia;

3Ohio State University; 4Moscow State University; 5Florida A. & M. University;

6NASA Ames Research Center

Viable bacteria were isolated from permafrost core samples from northeast Siberia. The samples were

obtained from different depths, the deepest was 3 million years old. The average temperature of the

permafrost was -10 ° C. Twenty-nine bacterial isolates were characterized by 16S rDNA sequencing.

All strains grew well under anaerobic conditions. None of the strains was a true psychrophile.

Phylogenetic analysis revealed that the isolates fell into four categories: high-GC Gram positive

bacteria, _-proteobacteria, y-proteobacteria and Iow-GC Gram positive bacteria. Most low-GC Gram

positive bacteria came from 5000-8000 year old samples, and most of the other groups from 1.8 - 3.0

million year old samples.

In Antarctica, drillings were performed at three localities in the McMurdo Dry Valleys area. The oldest

sample was at least 2 million, possibly 15 million year old, permafrost temperatures were -18 ° C,

-21 o C, and -25 ° C to -27 ° C. Each core contained viable bacteria, including anaerobes, their number

varying up to 102-103 g-1 by plate counts and to 105 g-1 by fluorescence. Most samples contained

methane in quantities up to 670 mL kg -1 of biological origin (presumably by bacteria), shown by its

isotopic composition (813C = 54.8&). Enzyme (invertase) activity was present in most samples. The ice

content of all samples was unexpectedly high, at least 25% and up to 50%. Our findings revise ideas

about the "dry" Antarctic permafrost.

These results provide support to the idea that martian permafrost may contain ground ice and that

ancient permafrost on Mars may contain samples - possibly viable - of life forms from an earlier, wetter

period.

POLAR ANALOGS TO MARS

C.P. McKay*, D.T. Andersen, W.L. Davis, and E.I. Friedmann

NASA Ames Research Center; SETI Institute; Florida State University

Mars was probably quite cold even during its presumed warm and wet period. For this reason the

study of polar regions on Earth has been particularly fruitful as an analog for early Mars. The

observation that fluvial features on Mars were localized, possibly restricted to regions of geothermal

activity, and the difficulty of constructing self-consistent CO2 greenhouse models for Mars imply that

early Mars was quite cold and that fluvial features formed in association with a cold climate regime.

Polar regions provide important analogs to an early cold Mars in two ways. First, by elucidating the

physical process that allow liquid water to exist when the mean annual temperature is below freezing

and, secondly, by providing examples of the biological and fossil-forming processes operating in cold

climate regions. Liquid water can be maintained in permafrost by the insulating properties of an ice

cover or by geothermal activity, even when temperatures are below freezing.

38
THE END PERMIAN MASS EXTINCTION:

GEOCHRONOLOGY AND PATTERNS OF EXTINCTION

Douglas H. Erwin*

National Museum of Natural History, Washington, D.C.

Samuel A. Bowring, Mark Martin, Kathy Davidek

Massachusetts Institute of Technology

Jin Yugan

Nanjing Institute of Geology and Palaeontology

The mass extinction at the end of the Permian was the most extensive biotic crisis in the history of life,

but determining its cause has been hampered by a lack of high-precision ages. Authors have

proposed several patterns: two distinct extinction peaks; a long period of increased extinction

beginning in the late Middle Permian accelerating to a rapid pulse at the close of the Permian; or a very

rapid extinction just at the close of the Permian and perhaps extending into the earliest Triassic.

Discriminating between these extinction patterns, and between the plethora of proposed causes of

the extinction, including extraterrestrial impact, massive volcanism and rapid climate change, requires

high-resolution geochronologic age determinations and precise stratigraphic information on taxon

occurrences. Analysis of this event provides perhaps the best opportunity to identify the impact of

endogenous and exogenous events on the survivability of complex life.

Although the Permo-Triassic boundary in south China has been previously dated at 251.2 +3.4 Ma by

SHRIMP U-Pb zircon analysis, and 250.0 + 0.2 Ma by 40Ar/39Ar analysis, estimates of the duration of

the Wordian-Changxingian stages have varied from 10 to 21 my. There are fewer estimates of the

duration of the Changxingian Stage, but estimates of late Permian (Wuchaipingian plus Changxingian)

durations range from 5-16 my. The numerous Permo-Triassic (P-T) marine boundary sections in South

China provide critical data on the pattern of extinction, and are interbedded with abundant volcanic

ash beds, which now provide the first constraints on the duration of the extinction. Uranium-lead

zircon data from the Late Permian and Early Triassic rocks in South China essentially confirm (with a

precision of +500 ky) earlier estimates of the age of the Permo-Triassic boundary. Excellent

biostratigraphic control on additional ash beds indicate that the final, Changxingian Stage of the

Permian lasted about 1.5 million years. Samples from west Texas just below the Wordian/Capitanian

(mid-Permian) boundary indicate a duration of about 13 million years for the Capitanian through

Changxingian stages.

These results confirm that the final pulse of extinction occurred in less than 1 my, coincident with

pervasive geochemical changes at the close of the Permian. These ages also shed additional light on

rates of paleontological and geochemical change in the latest Permian, and allow critical tests of a

variety of extinction scenarios.

ORDOVICIAN BIODIVERSITY: GEOGRAPHY AND ENVIRONMENT

Arnold I. Miller*

University of Cincinnati

The Ordovician Period was among the most dynamic intervals in the history of life. During the period,

global biodiversity increased at unprecedented rates (the Ordovician Radiation), there was an

apparently protracted transition in dominance among major biotic elements, and the interval

culminated in a mass extinction that, on a percentage basis, may have been second in intensity only to

39
theLatePermian event. Despite the broad recognition of these attributes, which are readily apparent

in synoptic, global diversity compilations, there is still much to learn about the ways in which they

played out locally and regionally; their prominence at the global scale does not necessarily imply that

these transitions took place uniformly or randomly around the world. The central goal of my ongoing

research has been to investigate the possibility that this significant interval in the evolution and

proliferation of life was focused geographically or environmentally in settings with unique attributes.

More generally, this research addresses the extent to which the evolution and diversification of

advanced life, at scales ranging from local to global, has been mediated by physical processes and

events.

At the heart of this investigation is the compilation and analysis of a database that depicts occurrences

of Ordovician genera in strata worldwide. Because the database also contains a variety of subsidiary

data concerning the paleogeographic, paleoenvironmental, and geologic settings of each

occurrence, it permits investigation of myriad questions related to the general themes of the project.

Data compilation is ongoing, but the database is now sufficiently extensive to permit evaluation of

several questions related to Ordovician biodiversity. To date, my primary activities have included: 1)

the analysis of sampling effects on the raw, global diversity trajectory through the period, which

showed that the trajectory could not be accepted at face value and indicated that most of the global

diversity increase was concentrated in the first half of the period; 2) the demonstration of a geographic

linkage between the Ordovician Radiation and likely regions of tectonic activity; 3) the recognition that

diversification attributes differed strikingly from paleocontinent-to-paleocontinent, partly reflecting

their relative proximities to tectonic activity; 4) the discovery that Ordovician genera, on average,

expanded their geographic and environmental ranges significantly as they aged, which explains a

surprising difference between Ordovician diversity trajectories at different hierarchical levels; 5) a

preliminary confirmation of previous suggestions that the Late Ordovician mass extinction selectively

eliminated taxa with limited geographic ranges, which raises the possibility that this event was also

selective with respect to taxon age.

WAS HIGH OBLIQUITY THE CAUSE OF

LOW-LATITUDE PRECAMBRIAN GLACIATION?

Darren M. Williams*, James F. Kasting, and Lawrence Frekes

Department of Geosciences, The Pennsylvania State University

Earth has experienced two episodes of apparent low-latitude glaciation in its history, with the first

occurring in the Huronian (-2.2 Ga) and the second in the Late Proterozoic (-750-550 Ma). This

suggests that either Earth was globally frozen over at those times or that Earth's obliquity was >54

degrees so that climatic zonation was reversed and the equator was the coldest part of the planet. The

main objection to the so-called "snow-ball Earth" scenario is that a global ice blanket would have likely

eliminated all photosynthetic life on the planet, contrary to the evidence of uninterrupted life in the

fossil record. Furthermore, the high albedo of the global ice cover and overlying CO2 and H20 clouds

may have prevented Earth from ever escaping its frozen state. To reconcile the geologic record with

the past and present evidence of life on the planet, we assume that Earth's obliquity was >54 ° for most

of its history, possibly as a result of the formation of the Moon. [The present inclination of the lunar

orbit is also better explained if Earth started out at high obliquity.] The obliquity is postulated to have

dropped rapidly during the last glacial period to its present value <25 ° by 430 Ma (in agreement with

the fossil and glacial record) as a consequence of climate friction.

Climate friction is a secular change in obliquity caused by large-scale changes to the planetary ice

cover and depth of oceans during an ice age. The displacement of water from the oceans to

continental glaciers changes the oblateness of Earth slightly, which affects both the rate of spin-axis

40
precessionandtheregularobliquityvariation.Thus,afteroneobliquitycycle(lasting41Kyrtoday,but

28 Kyr600Ma)the spinaxis is displacedslightlyfromits original starting point, and the obliquity

changes gradually over time. The rate of obliquity change depends mainly on the size of the

oblateness variations. Changes to Earth's oblateness and, hence, obliquity for the most recent

Quaternary ice ages are thought to have been negligible because of the small continental area

underlying the glaciers. However, changes to oblateness may have been over four times as large

during the Late Proterozoic when the bulk of Earth's continents are thought to have been clustered

around the South Pole and the surface area affected by ice loading and unloading was maximized.

The sign of the obliquity drift depends on the time lag between the obliquity/insolation oscillation and

the glacial oscillation. Under the assumption of maximum glacial coverage and a short (<1000 years)

glacial variation time lag, the secular change in obliquity is calculated to be -0.2°/Myr. This would allow

the obliquity to fall by as much as 30 ° in under 150 Myr, which would bring the obliquity from 55° down

to 25° in the time available. Thus, we are enabled a self-consistent, physically plausible explanation for

the low-latitude glacial climate of early Earth.

PALEOBIOLOGY OF THE TERMINAL PROTEROZOIC:

PRELUDE TO THE CAMBRIAN EXPLOSION

Bruce Runnegar*

University of California, Los Angeles

The Cambrian Explosion of complex life is the most obvious biological event in the history of the

Earth. Much of the research aimed at understanding this milestone in the evolution of life has focused

on the Cambrian fossil record, such as the famous Burgess Shale. However, many of the evolutionary

innovations were underway by before the beginning of the Cambrian. This research explores those

innovations in the superb terminal Proterozoic successions of Namibia, Nevada, Newfoundland and

South Australia.

Recent discoveries in Nevada and Namibia have taken core members of the Ediacara "fauna" to the

end of the Proterozoic, thus closing the stratigraphic gap (Kotlin interval) that had been assumed to

separate the Ediacaran biota from the Cambrian explosion. The times of origin of the Ediacaran

organisms and the animal phyla remain unknown but U-Pb ages on the ash bed that covered an

already diverse Ediacaran assemblage at Mistaken Point, Newfoundland, are approximately 20 million

years older than the base of the Cambrian. Molecular clocks indicate a significantly longer Precambrian

history for the Metazoa, but the oldest metazoan trace fossils are no older than ~550 million years.

Key questions concerning the nature of the Ediacaran organisms remain unresolved but there is

good morphologic and taphonomic evidence for the presence of several major clades (fronds,

petalonamans, trilobozoans, etc.), that are uncomfortably united in Seilacher's extinct kingdom, the

Vendobionta. Furthermore, old misconceptions are being discarded as we learn more about these

enigmatic organisms from recent discoveries in Namibia, Newfoundland, Nevada, and South Australia.

Few, if any, of the Ediacaran organisms belong to the crown groups of animal phyla, none were

cnidarian jellyfish, and some of the best known forms (Dickinsonia, Emietta, Phyllozoon, Pteridinium)

are difficult to place in any extant animal or plant group. However, even these "core vendobionts"

differ significantly from each other in the fundamental properties of construction, growth, mode of

preservation, and symmetry. Together with the associated carbonate skeletons and trace fossils, the

Ediacaran organisms provide a glimpse of biodiversity at the close of the Proterozoic. It is the

synchronous appearance of distantly related clades of megascopic organisms that points to the

poverty of intrinsic rather than extrinsic explanations for the nature of the Cambrian explosion of

multicellular life.

41
C02 GREENHOUSE IN THE EARLY MARTIAN ATMOSPHERE:

SO21NHIBITS CONDENSATION

Y.L. Yung*, H. Nair, and M.F. Gerstell

Division of Geological and Planetary Sciences, California Institute of Technology

Many investigators of the early martian climate have suggested that a dense carbon dioxide

atmosphere was present and warmed the surface above the melting point of water (e.g. Pollack et aL

1987). However, Kasting (1991) pointed out that previous thermal models of the primitive martian

atmosphere had not considered the condensation of CO2. When this effect was incorporated,

Kasting found that CO2 by itself is inadequate to warm the surface.

SO2 absorbs strongly in the near UV region of the solar spectrum. While a small amount of SO2 may

have a negligible effect by itself on the surface temperature, it may have significantly warmed the

middle atmosphere of early Mars, much as ozone warms the terrestrial stratosphere today. If this

region is kept warm enough to inhibit the condensation of CO2, then CO2 remains a viable

greenhouse gas. Our preliminary radiative modeling shows that the addition of 0.1 ppm of SO2 in a 2

bar CO2 atmosphere raises the temperature of the middle atmosphere by approximately 10 degrees,

so that the upper atmosphere in a 1D model remains above the condensation temperature of CO2, In

addition, this amount of SO2 in the atmosphere provides an effective UV shield for an hypothetical

biosphere on the martian surface.

DIFFUSION OF PHOTOCHEMICALLY PRODUCED HYDROGEN PEROXIDE

IN THE MARTIAN REGOLITH

Richard C. Quinn*

SETI Institute

Aaron P. Zent

NASA Ames Research Center

The initial biological examination of Mars by Viking failed to detect life; instead the Viking experiments

revealed that regolith material apparently contains chemical oxidants and is devoid of organic material

at the surface (e.g., Klein, 1979). Since reducing materials that are relict of prebiotic chemical

evolution are susceptible to chemical attack by such oxidants, their recovery is contingent upon

penetrating oxidized strata. Zent and McKay (1994) concluded that the most consistent explanation

for the Viking results calls on photochemically produced oxidants (odd-hydrogen and odd-oxygen

species), which originate in the atmosphere and diffuse into the regolJth. One study of the diffusion of

hydrogen peroxide into the regolith (Bullock, et al. 1993) has suggested that the depth of the

oxidized layer may be no more than several meters, although that modeling study was limited by the

lack of data on the lifetime of hydrogen peroxide against reaction in the regoiith, and it's adsorptive

behavior.

We report on experimentally determined rate constants and activation energies for the catalytic

destruction of hydrogen peroxide vapor by martian soil analogs. From these rate constants the lifetime

of hydrogen peroxide at Mars-like temperatures is calculated for each analog material. Fitting this new

data into the model of Bullock et al. (1993) yields estimates of the penetration depth of hydrogen

peroxide in the martian regolith. We find that for a basaltic analog material where the predominate iron

phases are ferrous the lifetime of hydrogen peroxide at 215 ° K is on the order of 105 seconds, which

corresponds to a penetration depth of 7 mm into the martian regolith. From the Viking GC-MS data we

know that the minimum depth of oxidized strata at the landing sites is approximately 10 cm. Therefore,

42

-_71 17
for a soil with an abundance of ferrous iron minerals, models of regolith mixing by wind or impact

cratering must be invoked if hydrogen peroxide is the oxidant responsible for the decomposition of

organic material. In the case of analog materials where the predominate iron phases are ferric, the

lifetime of peroxide is greater, however, regolith mixing, not diffusion, may still be the dominate

mechanism of oxidant transport in the martian regolith.

References:

1. Bullock, M., C.R. Stoker, C.P. McKay, and A.P. Zent, Icarus 107:142-154 (1993).

2. Klein, H.P., Rev. Geophys. and Space Phys. 1"7:655-1662 (1979).

3. Zent, A.P. and C.P. McKay, Icarus 108:146-157 (1994).

THE SUDBURY IMPACT EVENT: EFFECTS ON CARBONACEOUS MATTER

Ted Bunch* and David Des Marais

NASA Ames Research Center

Luann Becker

University of Hawaii

Wendy Wolbach

Illinois Wesleyan University

Jeffrey Bada and Danny Glavin

Scripps Institute of Oceanography, University of California, San Diego

The large (~200 km dia.), ancient (1.85 Gya) Sudbury Impact Crater contains exceptionally high

amounts of C in the Onaping Fm impact deposits (avg. 0.6 wt %) and in the overlying post impact,

water lain deposits of the Onwatin Fm (avg. 2.8%). Our primary objectives are: characterize

carbonaceous components and their distributions, identify their potential sources, contribute to

modeling P, T, t conditions in the impact plume and establish when life reappeared in the region.

Fullerenes (C60 and 070 ) have been found in the Onaping Fm/1/and are attributed to impact

formation, although a small number of these fullerenes contain trapped He with 3He/4He ratios of

interstellar signature/2/which implies extraterrestrial origin of some fullerenes and impact survival. We

have since found fullerenes of C numbers C74, C78, C84 and C100; the significance of these less

stable fullerenes is presently unclear. Raman spectroscopy shows that the bulk of the C is highly

disordered graphite (impact processed). Amino acids are terrestrial in origin and recent (<200 Kya).

Low concentrations of PAHs were found only in the Onwatin sediments. Soot (formed only by

combustion) has been found in a sample from the lower Onwatin. Our preliminary bulk (513C data

together with published bulk analyses/3,4/show a trend from very light carbon (-39 %0)in the melt

zone, through the Onaping (-32 to -27%0) to heavier carbon in the lower Onwatin (-25 to -21%0).

Although the Onaping data are consistent with biological activity, little supporting evidence has been

found. We suggest that the trend is the result of impact processing of carbonaceous matter (mostly

kerogen; avg. -29%0) that was present in the surface rocks before impact. In addition, contributions

may have come from the impactor and dissociation of C from carbonate by impact evaporation, in

contrast, the heavier C in the Onwatin sediments could be the result of sulfate reducing bacteria/4/.

Small carbonate platforms in the C-rich mudstones (slates) of the lower Onwatin may have formed via

hydrothermal venting from the deeply buried, hot impact zone. Some evidence of algal activity is also

present.

43
Soot(formedfromthe combustion of C during impact) may constrain the time of Onaping deposition

and the appearance of life (bacteria/algae) in that the fallout time of soot from the stratosphere is <2

years. If this is correct, then the Onaping formed within 2 years and fresh water or marine deposition

commenced together with possible incipient sulfate reduction, anoxygenic photosynthesis and

methanogenesis.

In contrast to being an entirely destructive event to life, the impact may have actually helped to rapidly

reestablish life in the region by furnishing nutrients and favorable environments.

Beferences:

1. Becker et al., Science 265:642 (1994).

2. Becker et al., Science 272:249 (1996).

3. Heymann and Dressier, Sudbury Conf. 97 (1997).

4. Whitehead et al., Chem. Geol. 86:49 (1990).

METEORITE IMPACT PRODUCTION OF VOLATILES AND THEIR BIOSPHERIC

EFFECTS AT THE CRETACEOUS/TERTIARY BOUNDARY

Kevin O. Pope*

Geo Eco Arc Research

Kevin H. Baines and Adriana C. Ocampo

Jet Propulsion Laboratory, California Institute of Technology

Impact cratering played a dominant role in the evolution of the terrestrial planets prior to 3.8 billion

years (Ga) ago. Life may have first appeared on Earth near the end of this heavy bombardment period,

but most evolution occurred since, during a period when large impacts were rare. Impacts were largely

ignored in the evolution of the Earth's biosphere until the discovery of meteoritic debris at the

Cretaceous/Tertiary (K/T) boundary (65 million years ago), which led to the proposal that a large impact

caused the mass extinction of life that marks this geological boundary. Analyses of global, synoptic

paleontological databases covering the last 500 million years have identified five such extinctions

events when a large percentage of Earth's species went extinct over a very brief period of time. These

crises mark major shifts in evolutionary trends and play a critical role in the evolutionary process. Large

impacts have been correlated with other extinction events and we now recognize that large impacts

played a major role in the evolution of life on Earth and perhaps on Mars.

The discovery that the Chicxulub crater in Mexico is the site of the K/T impact helped focus research

on the importance of target lithology, which at Chicxulub consisted of large amounts of water,

carbonate, and sulfate. Our comprehensive analysis of these target volatiles strongly supports the

hypothesis that impact-generated sulfate aerosols caused over a decade of global cooling, acid rain,

and disruption of ocean circulation, which contributed to the mass extinction at the K/T boundary. The

crater size, meteoritic content of the K/T boundary clay, and impact models indicate that the Chicxulub

crater was formed by a short period comet or an asteroid impact that released 1031 ergs of energy.

Impact models and experiments combined with estimates of volatiles in the projectile and target rocks

predict that over 200 gigatons (Gt) each of SO2 and water vapor, and over 500 Gt of CO2, were

globally distributed in the stratosphere by the impact. Modeling of the aerosol clouds demonstrates

that: 1) if the initial rapid pulse of sulfate aerosols was global, photosynthesis may have been shut

down for 6 months, and 2) that a second prolonged aerosol cloud, reduced solar transmission 80% by

the end of first year and remained 50% below normal for 9 years. As a result, global average surface

temperatures probably dropped between 5° and 31° K, suggesting that global near-freezing

conditions may have been reached. Impact- generated CO2 caused less than 1° K greenhouse

44
warmingandthereforewas insignificant compared to the sulfate cooling. The magnitude of sulfate

cooling depends largely upon the rate of ocean mixing as surface waters cool, sink, and are replaced

by upwelling of deep ocean water. This upwelling apparently drastically altered ocean stratification and

circulation, greatly prolonging the impact effects.

SHOCK SYNTHESIS OF ORGANICS IN COMETARY IMPACTS

C.P. McKay* and W.R. Borucki

NASA Ames Research Center

Recent paleontological evidence indicates that life was present on Earth as early as 3.9 Gyr ago. In this

case life arose on this planet during the late stages of accretion. It is likely that the main influx of volatile

material during this time was due to cometary infall. We use the known composition of Comet Halley to

model the probable composition of an atmosphere dominated by cometary volatiles. We also present

experimental results which show that shock processes in an atmosphere of cometary volatiles are

capable of producing organic compounds that could have been relevant to the emergence of life.

DEVELOPMENT OF A LASER RAMAN SPECTROMETER

FOR IN SITU EXOBIOLOGY EXPLORATION

Thomas J. Wdowiak,* David G. Agresti, Sergey B. Mirov, and Anatoly B. Kudryavtsev

University of Alabama at Birmingham

This is the third progress report, following those presented at the Conference on Early Mars (April 24-

27, 1997), and at the Laser Raman Workshop (June 6, 1997) and the PIDDP Meeting (June 10-11,

1997). Activities taking place since the last report include: a) demonstration of in situ wavelength

calibration of the spectrometer using Fraunhofer lines of the solar spectrum obtained from

atmospheric scattered sunlight; b) demonstration of the transmission of a laser Raman signal through

a polyimide coated optical fiber subjected to temperatures as low as 141 ° K (-132 ° C); and

c) determination of the spectral sensitivity of the Raman probe, fiber link, and spectrometer as a

system using a standard lamp. The first two items of course are important if a laser Raman

spectrometer is to be used on Mars, and the last item permits presentation of spectra on a normalized

scale. Now that a sensitivity calibration has been obtained, we have begun software development for

extraction of weak signals from "dark" samples and Raman peaks that are superimposed upon strong

photoluminescence or Rayleigh scattering backgrounds.

The work has utilized our Mark la device, which incorporated a room temperature CCD detector (the

Mark I version employed a diode array) and a "large" diode laser, which, along with a miniaturized

Raman probe, serves as a test bed. A new spectrometer incorporating a cooled CCD detector array

and packaged smaller than the %,ideo cassette size" Mark la/I system is under construction by our

industrial partner under a shared costs program. Also importantly, we have engaged with another

industrial partner to develop a 20 mW diode laser, suitable for Raman spectroscopy, that is in a

package having dimensions of 8.9 cm x 8.9 cm x 2.5 cm (the footprint of a 3.5 inch computer disk, but

1 inch thick). The combined Mark II laser Raman system, spectrometer, laser, and Raman probe

components are of a size (fit in a single hand) and mass suitable for deployment on spacecraft

contemplated for the beginning years of the next millennium (Mars Surveyor 2001 and beyond).

45
Finally,we are continuing our program to obtain laser Raman spectral signatures of interest to

planetary exploration and specifically exobiology. In September, 1997, samples of the Onaping

carbonaceous member of the Sudbury impact structure were obtained for use as analogs for what

might be associated with impact craters in the martian Highlands. Our laser Raman spectrometer

project has moved into the new 1000 square ft. Laboratory for Instrumentation for Space Exploration

(LISE).

NON-ENZYMATIC OLIGOMERIZATION OF MONONUCLEOTIDES

USING NON-STANDARD OLIGONUCLEOTIDE TEMPLATES

Christopher Switzer,* Thazha P. Prakash, Rajanikanth Bandaru,

Christopher Roberts, and John Chaput

University of California, Riverside

The origin of life on the Earth is likely to have begun with self-replicating polymers. Of all extant natural

molecules, RNA comes closest to exhibiting the requisite properties of the first self-replicating

polymer. The main reason for this consideration is its capability of serving both genotypic and

phenotypic roles. However, RNA is an imperfect candidate for the first genetic material in several

respects. The work to be presented focuses on the possibility of replication within four alternative

genetic systems: i) 2',5'-phosphodiester linked nucleic acids, ii) glycerol-nucleic acids, iii) iso-cytosine

and iso-guanine based nucleic acids, and iv) universal triplex forming nucleic acids. Results in all four

areas will be discussed, including the recent finding th._t 2',5'-linked RNA is a competent template for

the non-enzymatic synthesis of RNA.

TEMPLATE-DIRECTED SYNTHESIS OF DNA-PNA CHIMERAS

Leslie E. Orgel*

The Salk Institute for Biological Studies

Marcus Koppitz

Schering AG, Berlin, Germany

It is widely believed that the familiar RNA/DNA/protein world was preceded by an RNA world, that is a

world from which coded proteins were absent. However, the de novo origin of the RNA world is

problematical, since there are major obstacles to the prebiotic synthesis of nucleotides. Several

authors have proposed, therefore, that the RNA world was preceded by some other world controlled

by a genetic system simpler than RNA. This raises acutely the problem of information-conserving

transitions between genetic systems. Here we study one relevant pair of reciprocal transitions, from

peptide nucleic acids (PNAs) to nucleic acids and vice versa.

In earlier experiments we have shown that PNA templates will direct the synthesis of complementary

RNA products and vice versa. We have now completed a study of chimera formation, that is the

ligation of DNA and PNA on either a PNA or a DNA template. We find that chimera-function via a

phosphoramide bond is efficient when the ligation junction is isostructural with a DNA backbone, but

not otherwise. Ligation via a 3'-phosphoramidate bond is particularly rapid and efficient. Ligation via a

3'-phosphoramide bond is less efficient, owing to the low nucleophilicity of the 5'-OH group of DNA.

Replacement of the 5'-OH group by a 5'-NH2 group gives a substrate which ligates efficiently via a 5'-

amide bond.

46
TITAN HAZE: CYANOACETYLENE AND

CYANOACETYLENE-ACETYLENE PHOTOPOLYMERS

James P. Ferris*

Department of Chemistry, Rensselaer Polytechnic Institute

David Clarke

Department of Chemistry, Albany College of Pharmacy

The solar UV photolysis of the gases present in the atmosphere if Titan is believed to be the source of

the organic haze which obliterates the view of Titan's surface. The photochemical processes leading

to this haze provide a model for how complex molecules may have formed from simple ones in the

atmosphere of the primitive Earth. We have undertaken a study of the photolysis of cyanoacetylene

and cyanoacetylene-acetylene mixtures since these are two of the atmospheric compounds which

absorb solar UV strongly on Titan. Structural analysis of these polymers may contribute to our

understanding of the data returned from the Huygens probe of the Cassini mission that will pass

through the atmosphere of Titan.

Mechanistic studies established that the photodissociation of cyanoacetylene to a hydrogen atom

and the cyanoethyl radical proceeds with a quantum yield of 0.09. Previous studies established that

the photodissociation of cyanoacetylene into cyano- and ethynyl- radicals has a quantum yield of 0.05

so the formation of the excited state of cyanoacetylene must proceed with a quantum yield of 0.86.

Free radical addition and abstraction processes predominate in the subsequent reactions following

the photodissociation of cyanoacetylene present in the atmosphere of Titan.

Photolysis of acetylene in the presence of cyanoacetylene results in the polymerization of both

monomers. Quantum yield measurements established that cyanoacetylene is 2-5 times as reactive as

acetylene for polymer formation. The structure and morphological properties of polymers produced

photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been

examined in order to evaluate their possible contribution to the haze layers found on Titan. Infrared

analysis, elemental analysis and thermal methods (thermogravimetdc analysis, thermolysis, pyrolysis)

were used to examine structure of polycyanoacetylenes produced by irradiation of gas phase HC3 N at

185 and 254 nm by itself and in the presence of Titan's other atmospheric constituents (CH4, C2H6,

C2H 2 and CO). Of special significance is the copolymer of HC3 N and acetylene. Even though

acetylene was absorbing nearly all of the incident photons, the ratio of acetylene to HC3N found in the

resulting polymer was 2:1. Scanning electron microscopy (SEM) was used to visually examine the

polymer particles.

ABIOTIC ORGANIC SYNTHESIS

UNDER SIMULATED HYDROTHERMAL CONDITIONS

Bernd R.T. Simoneit*, T.M. McCollum, and G. Ritter

" Oregon State University, Corvallis

Ever since their discovery in the late 1970s, mid-ocean-ridge hydroth_:,-'mal systems have received a

great deal of attention as a possible site for the origin of life on Earth (and for potential origins of life on

Mars and elsewhere as well). Because no modern-day terrestrial hydrothermal systems are free from

the influence of organic compounds derived from biologic processes, confirmation of the potential for

organic synthesis in hydrothermal systems must come from laboratory experiments. Assessing the

potential for organic synthesis in prebiotic hydrothermal systems requires a better understanding of

47
reaction pathways and effects of the chemical and physical variables of the environment by carrying

out additional laboratory simulation experiments.

We report on research projects directed toward addressing these issues. Presently, our research

focuses on several areas: 1) understanding the factors (kinetic vs. thermodynamic) that control

reactions involving organic compounds in hydrothermal systems, 2) the formation of lipid compounds

during Fischer-Tropsch-type synthesis in an aqueous environment from formic or oxalic acids, 3) the

formation of organic compounds from decomposition of iron oxalate, and 4) the synthesis of amino

acids during the serpentinization of olivine. The hydrothermal Fischer-Tropsch-type synthesis has

been most successful, producing lipid compounds ranging from C2 to >C35 and consisting of

n-alkanes, alkenes, n-alkanoic acids, n_-alkanols and alkanones. The precursor carbon sources were

formic acid, which disproportionates to H2, CO2, and CO, and oxalic acid, which disproportionates to

H2 and CO2. Both yield essentially the same range of compounds.

HYDROTHERMAL ECOSYSTEMS IN A PLANETARY CONTEXT

Everett L. Shock* and William B. McKinnon

Dept. of Earth & Planetary Sciences and McDonnell Center for the Space Sciences

Washington University

Diverse lines of evidence converge on the hypothesis that life emerged on the Earth in water at

elevated temperatures like those encountered in hot springs and hydrothermal systems. The

phylogenetic tree constructed from small subunits of RNA indicates that the hyperthermophiles

populate the lowest branches. By inference, these organisms are closest (in an evolutionary sense) to

the common ancestor of the three domains of life. This fact has been used to argue that the common

ancestor was also a hyperthermophUe. This does not demand that high temperatures were required

for the emergence of the first living system, and researchers have argued that organisms in sea floor

hydrothermal systems may have been the only survivors of the last large impact during late-stage

accretion. However, the conditions of submarine hydrothermal systems are uniquely suited to the

synthesis and preservation of organic compounds. It follows that hydrothermal systems may be

similarly conducive to the emergence of living systems. As a consequence, hydrothermal systems are

often put forth as likely ecosystems throughout the solar system.

Our goal is to develop models to test whether likely geophysical, petrologic and geochemical

processes during the formation and early evolution of Earth, Mars, and Europa could have produced

hydrothermal systems capable of supporting life. The criteria adopted to indicate whether a system is

capable of supporting life include: 1) disequilibrium states derived from water/rock reactions and fluid

mixing that favor the synthesis of organic compounds from CO2, CO, or nebular condensates, and

2) additional redox disequilibria involving iron and sulfur minerals, and iron, sulfur and nitrogen

aqueous species that possess sufficient energy to drive metabolic processes. Our guide to likely

sources of chemical energy is provided by the overall metabolic processes of the deepest-branching

organisms of the terrestrial phylogenetic tree. These hyperthermophilic microbes pursue

lithoautotrophic lifestyles that are independent of light energy. Instead, consortia of microbes take

advantage of geologically-provided geochemical disequilibria. As a consequence, they provide

models of plausible subsurface ecosystems for other planets with liquid water and sources of heat.

However, there is considerably more to hydrothermal habitats than hot water and carbon, Fluid and

rock compositions have to be able to provide enough energy to drive metabolic processes, and

geophysical and petrologic processes have to be able to generate those fluid and rock compositions.

Outside of the Earth and Mars, the jovian moon Europa is emerging as a prime site of exobiological

interest, especially as evidence for an ocean underneath its icy surface continues to accumulate.

48
MeasurementsofEuropa'sgravitational momentstronglysuggesthatEuropahasdifferentiatedinto

astructurenotunlikethatoftheEarth:anironcore,rockmantle,andthick(-150km)surfacewater/ice

layer. Hydrotherma] systems are an inescapable consequence of volcanic activity in the presence of

liquid water, and would have been abundant during heating, differentiation and cooling phases of

Europa's evolution. After differentiation, rock compositions are likely to be basaltic in the parts of the

rock mantle that would be in close proximity to the ice layer. If so, hydrothermal systems would have

been hosted in basalt for the past -3.5 b.y., including systems that might accompany present-day

rock-mantleAce-layer boundary volcanism. Preliminary calculations reveal that such systems have a

high potential for synthesis of organic compounds from inorganic nitrogen and carbon compounds

likely to be in Europa's ice (and ocean).

ANOXIA AND EVOLUTIONARY PATTERNS IN THE SEA:

ONSHORE/OFFSHORE TRENDS AND RECENT RECRUITMENT

OF THE DEEP-SEA AND HYDROTHERMAL VENT FAUNAS

David K. Jacobs*

Department of Biology, University of California, Los Angeles

David R. Lindberg

Museum of Paleontology, University of California, Berkeley

The role of oxygen concentration as a controlling factor on the evolution of eukaryotes and

macrofauna has been a recurring theme in studies of Earth's Precambrian biota. More recently the role

of ocean-wide anoxic episodes in generating Phanerozoic extinction events, such as the PermoTriassic has received considerable attention. We argue that oxygen concentration has played a more

pervasive role in shaping the pattern of macro-evolution in Phanerozoic oceans. Over the last 15

years a striking pattern has been documented in the fossil record of benthic invertebrates. Higher taxa

(orders) tend to originate onshore, diversify offshore, and retreat into deep water environments.

Previous studies attribute this macro-evolutionary pattern to the role of disturbance in mediating biotic

interactions in the near shore environment, which in turn permitted evolution of novel forms accorded

ordinal rank. However, this onshore/offshore pattern of ordinal origination is not uniform over geologic

time. In the Post-Paleozoic, onshore origination of orders occurs preferentially in the early Mesozoic,

declines in the Late Cretaceous, and by the Tertiary bias in ordinal origination favors the offshore. We

argue that this temporal distribution results from changes in the frequency of anoxic/dysoxic

conditions in the offshore environment. Mesozoic marine rocks record anoxic/dysoxic events of

global and regional scale. These reduced oxygen conditions expand outwards from graben or other

basinal settings. Thus Mesozoic anoxia/dysoxia preferentially affects offshore settings. Many lower

Mesozoic offshore sections contain periodic dark (anoxia related) shales suggestive of Milankovitch

climatic forcing. Sediments indicative of low oxygen conditions are much less pervasive in the Tertiary.

This decline is consistent with the shift from a "greenhouse" world with warm polar regions and limited

thermal circulation of the deep ocean, to an "ice-house" world with more dynamic delivery of oxygen

to the deep ocean. Loss of an anoxia/dysoxia-related fauna, as well as an increase in burrowing,

document a biological response to more pervasively oxygenated conditions beginning in the Late

Cretaceous.

Pervasive anoxia has additional implications for the evolution of the deep-sea fauna. Major events

such as that at the Cenomanian/Turonian boundary, must have disrupted much, if not all, of the deep

sea habitat for normal marine as well as vent related benthose. Thus the deep sea can not have been

continuously and widely inhabited without disruption. The deep sea faunas must have experienced a

biogeographically complex history in the Mesozoic involving retreat to more appropriately oxygenated

regions, most likely in shallow water. Vent organisms of all stripes also require oxygen. Even

49
chemosyntheticbacteriarequireredoxgradients.Thustheoriesof theventoriginof lifemustalso

accommodate the changing topology of interaction between redox gradients in the sea and

hydrothermal activity.

M(SSSBAUER SIGNATURES THAT MAY BE USEFUL IN IDENTIFYING

RESIDUES OF ANCIENT MARTIAN HYDROTHERMAL SYSTEMS

Thomas J. Wdowiak*, David G. Agresti, Manson L. Wade, Lawrence P. Armendarez

University of Alabama at Birmingham

Jack D. Farmer

NASA Ames Research Center

Iron-rich thermal springs may have been present on early Mars and served as environments suitable

for possible ancient martian life. The residues left by such structures, if they existed in the past, would

be amenable to spectroscopic investigation. A MSssbauer spectrometer, which focuses on ironcontaining materials, is likely to be employed as an in situ instrument during a future mission to Mars.

Therefore, we have been investigating the nature of information M6ssbauer spectroscopy can

provide about such hydrothermal deposits and whether spectral signatures exist that would be

characteristic of them or of any biomarkers they might contain.

Among our first results in this effort was the identification of nanophase iron oxides in hydrothermal

deposits collected at Manitou Springs, CO, and at Chocolate Pots, Yellowstone National Park. Such

fine-grained material is a characteristic of subaerial hydrothermal sediments and would serve as a

potential fossilizing medium. Recently, we have investigated a suite of samples collected from several

locations, and at several depths up to -1 cm, along the outflow channel of a large vent mound at

Chocolate Pots.

Most samples show the spectral signatures of siderite, Fe2+CO3, and nontronite,

(CaNa)o.66Fe3+4Si7.34AIo.66020(OH)4nH20, a member of the smectite group of clays. Goethite,

FeOOH, and hematite, Fe203, have also been observed. The presence of siderite and nontronite in

all samples (except those very near the vent or the surface, which are amorphous) has been

confirmed by XRD and is consistent with major element analysis.

A localized deposit of nanophase material on Mars would suggest an ancient hydrothermal spring. To

identify such material, the acquisition of MSssbauer spectra at different temperatures (diumal variation)

would likely be necessary. On the other hand, an association of siderite and nontronite, for example in

the interior of a martian rock, could be identified by M6ssbauer spectroscopy with a single

measurement. Such a finding would be consistent with a hydrothermal origin and thus suggest a site

of potential exobiological interest. The presence of all three signatures would be even more

definitive.

5O
EXPLORATION OF MONO LAKE USING TROV:

APPLICATION OF TELEPRESENCE TECHNOLOGY

TO EXOBIOLOGY STUDIES

C.R. Stoker*

NASA Ames Research Center

The search for a fossil record of life on Mars is a key goal of the Mars Surveyor program. Two key

environments where life on Mars may have occurred include hypersaline lakes and hydrothermal

springs. The study of modem analogs of these environments provides important information leading

to an understanding of the martian environment and helps develop the context for searching for a

fossil record.

This paper describes a field experiment to explore Mono Lake using the Telepresence Controlled

Remotely Operated Vehicle (TROV). The goal of the experiment was to study mineralization

processes associated with thermal and non-thermal spring inflow into Mono Lake, a hypersaline,

alkaline lake in eastern California located in a volcanically active area. The high pH and high salinity

make the lake a very hostile environment for diving. Tufa towers, large spires formed by the

precipitation of calcium carbonate around cold springs on the lake floor, protrude above lake level

along the lake's western shore. In addition, non-mineralizing tliermal springs observed along the

eastern shore of Paoha Island were traced into shallow offshore areas using the TROV. Objectives

included obtaining video records of the study area, sampling water column properties, obtaining and

analyzing water samples, and obtaining sediments and mineral precipitates (primarily carbonates)

associated with sub-aqueous spring outflows on the floor of the Lake.

The instrument complement on TROV included: a matched pair of stereo video cameras on a rapid

pan and tilt platform, a single fixed downward pointing camera. Additional capabilities included high

resolution 750 KHz pencil beam sonar imaging and 1 MHz scanning sonar, instruments for measuring

water column properties (C,T,D, pH), a water sampling system which pulled water into syringes, and a

three function manipulator arm used to collect mineral samples and place them in a rock box carried by

the TROV. TROV was navigated using a Dive Tracker acoustic navigation system. All data were

continuously recorded throughout the experiment. TROV was deployed from the deck of a boat

anchored above the field site. Control and data recording equipment was located on the boat. The

location of the boat was continuously recorded using a differential GPS system.

Results of the experiment along with implications for applying these techniques to the study of

subaqueous hydrothermal systems will be discussed.

RECOGNIZING BIOGENIC SIGNATURES

NEAR LIFE'S UPPER TEMPERATURE LIMIT:

THE ROLE OF HYPERTHERMOPHILIC BIOFILMS

IN SPICULAR GEYSERITE MORPHOGENESIS

Sherry L. Cady.1 , David J. Des Marais2, Jack D. Farmer 2, Malcolm R. Walter 3

Carrine E. Blank 4, and Norman R. Pace 4

1SETI Institute/NASA Ames Research Center, 2NASA Ames Research Center

3Macquarie University, Australia, 4University of California, Berkeley

Hydrothermal systems were likely to have been widespread on early Mars at a time when life had

already established itself on Earth. Molecular phylogenetic studies of extant life suggest that the

earliest ecosystems on our planet were inhabited by hyperthermophiles, microorganisms that define

life's upper temperature limit. Whether life originated in such ecosystems or whether

51
hyperthermophileswere the only microbes to survive the early bombardment period remains

debatable. In any case, the potential for life to exist above 113° C requires a re-evaluation of the

contributions of hyperthermophiles to the formation of hydrothermal mineral deposits.

To maximize NASA's ability to recognize and assess hyperthermophilic biogenic signatures (i.e.

stromatolites, microfossils, chemofossils) in the rock record, we are investigating how these

signatures are preserved in modem ecosystems. Our current efforts have focused on characterizing

the biodiversity of extant hyperthermophilic communities in near-boiling subaerial thermal springs, and

on identifying how hyperthermophiles influence the structuring of the mineral deposits that

precipitate in their presence. This work will provide a framework within which the biogenicity of ancient

homologue deposits can be assessed, and will serve as a basis for evaluating the biogenicity of

siliceous epithermal (shallow subsurface) hydrothermal deposits, a potentially important

paleobiological repository that has yet to be characterized systematically.

We have found that the presence of hyperthermophilic biofilms influences the microstructural

development of high-temperature siliceous geyserites. Geyserites had previously been considered

abiogenic structures. We have also found that the heterogeneous distribution of biogenic laminations

controls the morphogenesis of larger scale structures, such as laminated conical-shaped spicules,

that are recognizable in fossilized material. Our findings demonstrate the potential for macro-scale

features of ancient siliceous hydrothermal deposits that formed near life's upper temperature limit to

record some aspects of the history of hyperthermophiles. Molecular phylogenetic analysis of these

geyserites has revealed that subaerial and subaqueous microenvironments of a spring host distinct

communities that can be correlated with different geyserite morphotypes. In addition, a unique, novel

lineage of Bacteria was identified in subaqueous geyserite sediments by C. Blank. The branch point

of this organism lies closer to the root of the phylogenetic 'universal tree of life' than any other

divergence identified to date. Further study of such organisms will elucidate the nature of early life on

Earth, and improve our understanding of how early life diverged into the three super-kingdoms

Archaea, Bacteria, and Eucarya..

FOSSILIZATION PROCESSES IN THERMAL SPRINGS: COMPARATIVE STUDIES

OF MODERN AND ANCIENT SILICEOUS SPRING SYSTEMS

Jack Farmer 1., Brad Bebout 1, Linda Jahnke 1, David DesMarais 1, and Malcolm Walter 2

1NASA Ames Research Center; 2Macquarie University, Sydney, Australia

Present evidence for the origin of life suggests that it developed quickly, sometime between 3.8 and

4.4 Ga. The higher heat flow, widespread volcanism, and likelihood of giant impacts during the early

Archean supports the view that hydrothermal systems were probably widespread over the Earth

during the time the biosphere emerged. In addition, RNA-based molecular phylogenies suggest that

the last common ancestor of life was an extreme thermophile. Because hydrothermal environments

have been shown to be thermodynamically favorable places for the synthesis of prebiotic organic

chemicals, we must entertain the possibility that many of the earliest organisms not only lived at higher

temperatures, but that life may have actually originated there.

From a paleontological standpoint, hydrothermal systems are important targets for studies of early

biosphere evolution because they are usually rapidly mineralizing environments where many

microorganisms are entombed by precipitating minerals and fossilized. Around vents and along spring

outflows, microbiological information is captured within deposits in a variety of ways, including cellular

fossils, biofabrics and biosedimentary structures (e.g. stromatolites). The rapid changes in

temperature and pH observed along thermal spring outflows, and the corresponding changes in the

microbiotas occupying these environments, make thermal springs excellent natural laboratories for

52
studying the processes of stromatolite morphogenesis and microbial fossilization over a broad range

of conditions.

Petrographic thin section studies of Yellowstone sinters indicate that organically preserved

microfossils are rare, being restricted to lower temperature microfacies. For the cyanobacterial mat

systems of siliceous springs, the dominant mode of preservation is by surface encrustation of

individual cells and filaments, followed by the rapid degradation of organic materials to produce

external molds. Although rare, cyanobacterial sheaths are occasionally preserved by permineralization

at temperatures below -35 ° C. This indicates that even though organic matter is rapidly entombed by

precipitating minerals, at higher temperatures it is quickly destroyed prior to the in-filling (cementation)

of typically porous sinter frameworks during early diagenesis. In fact, the only organic materials

observed in thin sections of higher temperature microfacies are plant fragments (lignin).

Comparative studies of Devonian-aged (350 Ma) sinters from the Drummond Basin (NE Queensland,

Australia) revealed trends in preservation that are consistent with observations of modern thermal

spring systems in Yellowstone. Oxygen isotope data obtained from the Drummond sinters over the

entire paleotemperature shows a "shot-gun" pattern, indicating that primary temperature signatures

were not preserved during diagenesis. The Drummond sinters also show very low total organic carbon

abundances, consistent with our thin section observations of Yellowstone sinters. As with the modern

sinters, the most commonly preserved organic materials in the Drummond sinters were fragments of

multicellular plants. These materials tend to be more abundant at the lower temperature end of the

system where higher plants are more abundant. This accounts for the slight rise in TOC values

observed for low temperature microfacies. Furthermore, the carbon isotope values for the Drummond

sinters show little variation over the entire paleotemperature range. The average value (-26 per mil) is

what would be expected from plant materials, again consistent with the thin section observations

noted above.

THE IKIRYU SINTER

(500,000-300,000 YRS.), KYUSHU, JAPAN

Donald R. Lowe*

Department of Geological and Environmental Sciences, Stanford University

Eiji Izawa

Department of Mining, Faculty of Engineering, Kyushu University, Japan

Siliceous deposits, including hot-spring sinter and subaqueous sedimentary rocks, contain much of

the early terrestrial record of life and are likely to be targets in the exploration for life on Mars. The goal

of the present project is to develop criteria for distinguishing between biological and abiological

features in modern and ancient siliceous hot-spring deposits that will aid in recognizing biological

remains in and the influence of organisms on similar deposits in the early terrestrial geologic record

and on Mars.

The Ikiryu sinter is a siliceous hot-spring deposit near Kuju Volcano, central Kyushu, Japan. It crops

out discontinuously for about 800 meters between an underlying 500,000-year-old rhyolitic

sequence and an overlying 300,000-year-old andesitic breccia and includes two members: (1) a lower

colored member up to 5 m thick composed of dense, recrystallized, largely structureless chert

containing an abundance of iron and other impurities; and (2) an upper member, 4.0 to 4.5 m thick,

that consists of white siliceous sinter showing well preserved primary features. These include layers of

conical stromatolites and silicified filaments representing the filamentous cyanobacterium Phorrnidi_m

deposited in quiescent pools at temperatures of 30-60 ° C.; layers of silicified horizontal streamers and

53
silicifiedflatsheet-likematswithunderlyingcavities,representingtrappedoxygenbubbles,deposited

bythe bacteriaPhormidium and Mastiaocladus in rapidly flowing water at 30-60 ° C.; and layers of

vertical silicified bacterial filaments representing the filamentous cyanobacterium Calothrix deposited

in terraced pools below 30 ° C. No actual preserved primary organic matter, including bacterial

filaments, have yet been recognized. No sinter facies were identified representing water

temperatures above 60 ° C, although in modern systems the temperature range from 60-73° C is

seldom represented by significant silica deposits. The succession of layers suggests that initial hightemperature (>30 ° C) outflow reaching the area represented by the present outcrops was followed by

gradual cooling and sinter deposition at temperatures below 30 ° C. Lateral temperature relationships

provide a means of locating the vent, which appears to have been removed by erosion.

The contrasts between the lower, dense, poorly-structured and upper, porous, well-structured sinter

members reflect the cessation of hydrothermal activity and burial of the upper sinter member before it

could be completely recrystallized and cemented by its own hydrothermal waters.

IN

PRESERVATION OF HALOARCHAEA

AND THEIR MACROMOLECULAR CONSTITUENTS

BRINE INCLUSIONS FROM BEDDED SALT DEPOSITS

J.K. Fredrickson 1., T.C. Onstott 2, T.J. Bailey 1, and D.P. Chandler 1

1Environmental Microbiology Group, Pacific Northwest National Laboratory;

2Dept. of Geology and Geophysical Sciences, Princeton University

Although results from the Viking mission appear to preclude the presence of life forms on the surface

of modern Mars, the presence of life on a wetter and warmer, early Mars, cannot be precluded. The

culturing of viable microorganisms (Bacillus) from insects trapped in 40 m.y. old amber suggests that

some microorganisms have an extreme capacity for su_ivinggeological time periods in isolation and in

a physiologically inactive state. Reports of haloarchaea cultured from salt deposits as old as 200 m.y.

have been attributed to the preservation of organisms entombed in brine inclusions within salt

crystals. Direct proof of this, however, is lacking. Hypersaline lakes may have existed on early Mars. If

so, evaporite minerals containing froze n brine inclusions may0ccur on the surface or near subsurface

of Mars today. Direct evidence for the long term preservation of viable bacteria or DNA within brine

inclusions will have an immediate impact upon the search for life on Mars, the evolution of life on Earth

and on the procedures for analyzing samples from future Mars sample return missions. The overall

goal of this research is to establish the survival potential of haloarchaea or their DNA in brine inclusions

by analyzing bedded halite samples that vary in geological age.

Recently-deposited salt from Laguna Grande de la Sal in New Mexico was collected in order to assess

and develop methods of analysis. These samples contained viable haloarchaea. PCR amplification of

DNA extracted directly from four-year-old (modern) Laguna Grande de la Sal salt revealed the

presence of archaea 16S rDNA. Cloned genes were sequenced, phylogenetically analyzed, and

determined to be closely related to members of the genus, Haloferax, within the haloarchaea. In

contrast, no halophilic archaea were cultured from 200 m.y. polyhalite from the Salado Formation in

New Mexico. In addition, archaea 16S rDNA was not detected by PCR amplification of salt extracts.

These results could be interpreted as consistent with theoretical expectations on the survival of

bacteria trapped in brine inclusions. The results do not, however, provide an accurate assessment of

the survival time for haloarchaea or how their macromolecular constituents survive in liquid, brine

inclusions.

54
Thefocusof the currentresearchis to investigatethe potentialfor preservationof haloarchaea

trappedwithin brineinclusions.A combinationof microbiological,molecular,and geochemical

approachesarebeingusedto establishthechronologicalageat whichinclusionsformedandthe

presenceof viable(culturable)halophilesand/orintactmacromolecules. Forthisresearch,wehave

selecteda sequenceofbeddedsaltdepositsinDeathValley,Californiawhichrangeinagefrom0to

200kyr.

EXPOSURE OF OSMOPHILIC MICROBES

TO THE SPACE ENVIRONMENT ON BIOPAN:

UV-RADIATION, THE EFFECT OF ANHYDROBIOSIS

AND PROTECTION MECHANISMS

R.L. Mancinelli* and M.R. White

SETI Institute

The environment in which an organism lives plays a critical role in its evolution. This study prov!des a

better understanding of how organisms may have developed survival strategies to protect them from a

significant detrimental environmental parameter, that is, the UV-radiation flux at the early Earth's

surface during life's origin and early evolution (e.g., evolving UV absorbing pigments, or adapting to

life in a protective salt crystal, which involves understanding the physiology of halophily and

osmophily). It is even more relevant to the potential for the evolution of life on early Mars which also

had a high UV flux during its early history when life would have arose; the relevance continues to

when Mars became cold and desiccated leaving organisms that could survive in evaporites as a

possible last vestige for life. This last statement becomes more important in the realization that salts in

the form of duricrusts may be abundant on Mars. By extension this also has relevance to Mars

Exobiology site selection in the search for evidence of a possible past martian biota if evaporitic

material served as the last vestige for a possible martian biota. Lastly, This research provides new data

useful for the technical and programmatic decisions that must be made regarding planetary protection

requirements for future missions, especially those to Mars.

The objective of is this study is to determine the survivability of osmophilic microorganisms in space,

as well as examine the DNA breakage in osmophilic cells exposed to solar UV-radiation plus vacuum

and to vacuum only. The BIOPAN facility is used to accomplish the objective of the study. BIOPAN (a

pan shaped biological facility developed to fly in Earth orbit on recoverable satellites) was developed

by the Europan Space Agency (ESA) to conduct experiments leading to a better understanding of

the responses of microbes to space vacuum and solar UV-radiation. The organisms used in this study

were an unidentified species of Synechococcus (N&geli) that inhabits the evaporitic gypsum-halite

crusts that form along the marine inter-tidal, and an unidentified species of the extremely halophilic

genus Haloarcula (designated as isolate G) isolated from a evaporitic NaCI crystal. Because these

organisms are desiccation resistant and gypsum-halite as well as NaCI attenuate UV-radiation, we

hypothesized that these organisms would survive in the space environment, better than most others.

The organisms were exposed to the space environment for 2 weeks while in Earth orbit aboard the

BIOPAN facility. Ground controls time course studies were tested in a space simulation facility. All

samples were compared to unexposed samples. Survivability was determined by plate counts and the

most probable number technique. DNA breakage was determined by labeling breaks in the DNA with

32p followed by translation. Results indicate that the osmophilic microbes survived the 2 week

exposure. The major cause of cell death was DNA damage. The number of strand breaks in the DNA

from vacuum UV exposed cells was greater than the vacuum only exposed cells. Based on these data

we have hypothesized that these organisms survive due to their pigments, salt environment and

desiccation resistance.

55
THE ORIGINS OF THE TRANSLATION MACHINERY

Deana C. Larkin, Susan A. Martinis, and George E. Fox*

Department of Biochemical and Biophysical Sciences, University of Houston

Detailed comparisons of recently completed microbial genome sequences reveals that the

components of the translation machinery are extremely conserved and in many cases distributed

throughout the Archaea, the Bacteria and the Eukaryota. This strongly supports the notion that

translation originated well before the last common ancestor that is defined by 16S rRNA sequence

comparisons and therefore is an extremely ancient process. The prebiotic synthesis of peptide bonds

on the early Earth may have occurred in a number of ways in the absence of ribosomes. What is

unique about translation is the fact that it allows a template directed synthesis of defined sequence

peptides and thereby makes the existence of a complete genetic apparatus advantageous. The

essence of this modern translation system in turn is that the key component, the transfer RNA (tRNA)

can simultaneously interface the RNA world via the codon/anticodon interaction with the peptide

world via the fact that the distal portion of the tRNA is aminoacylated. Although modern ribosomes are

very complex in terms of size and number of components, a key issue for exobiology is how RNA

molecules carrying amino acids came to participate in peptide synthesis. Perhaps the most obvious

scenario is that a simplified tRNA molecule which could have existed in even a limited scope RNA

world would be capable of carrying amino acids and participate in peptide bond synthesis in the

absence of ribosomes. It has already been shown that small RNAs of this type can be aminoacylated.

Our immediate goal is to extend this result by demonstrating that once charged such RNAs can also

participate in peptide bond formation. As a first step in obtaining this objective we have verified several

earlier results which suggested, but did not convincingly establish, that charged tRNAs can in fact

participate in peptide bond formation in the absence of ribosomes. Experiments utilizing charged

leucine tRNA will be described. The results show that in fact dipeptide synthesis is obtainable in two

ways. In the first, the leucine tRNA is incubated with the leucyl tRNA synthetase for periods of time

significantly beyond those required for aminoacylation and dipeptide bond formation is shown to

occur. One might thus envision translation as arising from primitive synthetases which can both charge

an RNA and catalyze peptide bond formation once the RNA is charged. Regardless of the significance

of this result, proper controls must be used to show that peptide bond formation in the absence of

enzymes is not due to extended exposure of aminoacylated RNA to the synthetase. We have most

recently shown that charged tRNAs can participate in dipeptide formation in the absence of both

synthetase and ribosomes. In order to accomplish this a dipeptide Ala-His is used as a catalyst/cofactor. The use of similar catalyst/co-factors such as His-Ala and His alone do not facilitate significant

peptide bond formation. Studies of the effect of pH have provided some insight to the nature of the

reaction.

THE CASE AGAINST COMETARY ORIGIN OF THE OCEANS

Kevin Zahnle*

NASA Ames Research Center

Atmospheres are found enveloping those planets and satellites best able to hold them. Apparently,

the existence of an atmosphere depends as much on escape as it does on supply. A consequence of

this view is that volatile supplies were probably much greater than the atmospheres that remain. The

likeliest candidates are sources associated with the major events of planetary accretion itself, such as

volatile-rich planetesimals or direct gravitational capture of nebular gases. Late-accreting volatile-rich

veneers, either asteroids or comets, seem attractive but present quantitative difficulties. Comets in

particular appear to be quantitatively inadequate. Only one comet in three million hits Earth. For Earth

to accrete an ocean of water through comets, some 3000 Earth masses of comets must have been

56

-3 I1
scattered to the Oort Cloud or beyond. This is excessive. This difficulty applies to Uranus-Neptune

planetesimals as well as to a putative massive early Kuiper Belt. Objects falling from a much

augmented ancient asteroid belt remain a viable option, but timing is an issue: can the depopulation of

a massive asteroid belt be delayed long enough that it makes sense to talk of asteroids as a late

veneer? Another appealing candidate population of volatile-rich objects for the inner solar system are

scattered planetesimals associated with the accretion of Jupiter, for two reasons: (i) before there was

Jupiter, there was no object in the solar system capable of expelling comets efficiently; (ii) the crosssection of the inner solar system to stray objects was greater when there were many planetesimals.

ORGANICS IN SPACE: FROM STARDUST TO PLANETESIMALS

Yvonne Pendleton*

NASA Ames Research Center

An ongoing observational research effort to investigate the nature of organic solid-state materials in

space has resulted in the discovery of remarkably similar absorption features, attributed to aliphatic

hydrocarbons, among interstellar dust clouds in our own galaxy, dust embedded distant galaxies, and

the Murchison meteorite. Comparisons between the infrared observations and laboratory processed

organic residues suggests that energetic processing of simple ices (such as H20, CO, CH3OH, NH3,

and/or N2) results in materials similar to those seen in space. Observations at other near-infrared

wavelengths have revealed absorption features from some nitrogen-bearing species, and similar

comparisons are underway between interstellar dust and laboratory residues in order to learn about

the production pathways and the identity of these organic solids. Primitive solar system bodies, such

as Kuiper Belt comets, have also been observed spectroscopically, and their relationship to

interstellar precursor materials is intriguing. Latest results from these efforts will be presented.

References:

1. Pendleton, Y., Tielens, A.G.G.M., and Tokunaga, A., Astrophysical Journal (submitted 1998).

2. Pendleton, Y., "Detection of organics in space," Origin and EvoL of the Biosphere 27:53 (1997).

3. Brown, R.H, Cruikshank, D., Pendleton, Y., and Veeder, G., Science (submitted 1998).

4. Pendleton, Y., in New Extragalactic Perspectives in the New South Africa, ed. D. Block, and J.M.

Greenberg, Kluwer, Dordrecht (1996).

5. Pendleton, Y. and Chiar, J., 1997, in From Stardust to Planetesimals, ed. Y.J. Pendleton, Y. and

A.G.G.M. Tielens, ASP San Francisco Conference Proceedings, paper 122 (1997).

6. Pendleton, Y., et al., Astrophysical Jouma1437:683 (1994).

INTERSTELLAR PRECURSORS OF METEORITIC ORGANIC MOLECULES

S.B. Charnley*

Astronomy Department, University of California, Berkeley

The early Earth may have obtained most its volatile material from the arrival of meteorites and comets at

its surface. Some of this matter was accumulated in the form surviving organic compounds.

Determining the most likely distribution of meteoritic and cometary organic molecules that could seed

primitive planets is a major research goal for Exobiology since it sets the initial conditions for, at least

part of, their phase of prebiotic chemical evolution. Sun-like stars form by the gravitational collapse of

dust and molecular cloud gas, leading to the formation of a protostar surrounded by an accretion disk

57
fromwhichplanets,comets,asteroidsandotherdebriseventuallyform.Thesedarkcloudsarethusa

pivotalphaseinthegalacticevolution of the biogenic elements in that the chemical processing that

occurs in them provides the raw organic material for meteoritic and cometary processing. A coherent

theoretical picture of the development of organic complexity from interstellar biogenic material to the

beginning of prebiotic evolution, based upon observations and measurements of the chemical

composition of primitive Solar System organics, and of dense molecular clouds, is being developed.

In this theory, the organic molecules observed in dense molecular clouds are either the direct

products of grain surface reactions or derive from secondary gas phase reactions amongst surface

products. A study has been completed of the deuterium fractionation ratios expected from grain

surface reactions involving atom additions. It was found that the observed gas phase interstellar D/H

ratios in CH2DOH and CH3OD are lower than expected solely from formation on grains and that

chemical reactions must also be forming CH3OD in the gas. Recently, a significant step towards

calculating the molecular evolution of grain mantles in a correct, self-consistent, manner has been

made. The need to correctly account for the stochastic nature oft gas-grain interaction in molecular

clouds is leading to a new way of performing astrochemical calculations. The general surface reaction

scheme, based on the principle of organic radical stability, has been extended to consider oxidation

and nitrogen atom additions to carbon chain radicals. It was found that the organic ring molecule

ethylene oxide, recently-discovered in the interstellar medium, arises naturally from this extended

scheme.

WHAT BIOPOLYMERS ARE EXPECTED

IN EXTRATERRESTRIAL ENVIRONMENTS

Steven A. Benner*

Department of Chemistry, University of Florida, Gainesville

To extrapolate from biochemical structures found in terrestrial life to those that might be found

extraterrestrially, one must identify structures in contemporary terrestrial biochemistry that are unique

chemical solutions to challenges faced by the general living system. Research on terrestrial nucleic

acids shows some structural features that are likely to be universal, and others that are not. The design

of probes for planetary missions to detect extraterrestrial life is discussed.

TOWARD RNA - THE MINERAL INDUCED PHOSPHORYLATION OF

GLYCOLALDEHYDE

G. Arrhenius 1, R. Krishnamurthy 2., and S. Pitsch 3

1Scripps institution of Oceanography, University of California, San Diego;

2Skaggs institute for Chemical Biology, Scripps Research Institute;

3ETH, Zentrum, Laboratorium for Organische Chemie, Z0rich, Switzerland

Conceptual studies of molecular evolution have recently focused on an initial role of RNA or similar

precursor molecules, mainly due to the catalytic properties of RNA. The application of geochemical

and geophysical constraints further strengthen this concept. One factor is the relative ease with which

parent molecules of sugars, such as formaldehyde and glycolaldehyde, are formed in experimental

model atmospheres that, at least partly, satisfy geophysically and geochemically imposed constraints

58
andthusarebasedonthe recognitionof carbondioxideandnitrogenas likelymajorcomponents

/11/.

Another factor, contributing to the geochemical consideration of the RNA world concept is the charge

imparted by the phosphate ion. This excess negative charge makes it possible to achieve high,

reactive concentration on surface active minerals starting from extensive dilution in the hydrosphere

/1-3/. Finally, single aldehyde phosphates are found, upon sorption in bilaterally surface active

minerals to readily aldomerJze to form sugar phosphates/4/. Testifying to its importance in biopoesJs,

phosphate is found intimately associated with the earliest traces of life on Earth/9/.

The major objection against nucleosides and nucleotides as prebiological molecules has in the past

been the apparent lack of a process that, from a wide variety of aldehydes and aldehyde derivatives,

could preferentially give rise to a single, ultimately functional species. This particular objection was

overcome in principle with the demonstration of mineral-induced selective formation of the hexose2,4,6-triphosphate diastereoisomer altrose from glycolaldehyde phosphate, in high yield, from

aqueous solution at pH 9/4/and also the production at near-neutral pH of pentosephosphates (-41%

ribosephosphate) from glyceraldehyde-2-phosphate and glycolaldehyde phosphate/12/.

Important remaining problems concern the initial phosphorylation of the simple aldehydes involved

/7,8/and the formation /5,6/and attachment of nucleobases to the sugars. The phosphorylation

problem has now been approached by a process that involves reactants that are produced in

geochemically plausible, simulated primordial environments, and brought to reactive concentration by

sorption in surface active minerals /1,2,10/. This process of spontaneous, mineral assisted

phosphorylation of glycolaldehyde is the main subject of the present report.

References:

1. Arrhenius, G., Gedulin, B., and Mojzsis, S., Phosphate in models for chemical evolution, Chem.

Evolution and Origin of Life, C. Ponnamperuma andJ. Chela-Flores, Eds. A. Deepak Publ., Hampton,

VA, pp. 25-50 (1993).

2. Gedulin, B. and Arrhenius, G., Sources and geochemical evolution of RNA precursor moleculesthe role of phosphate, Early Life on Earth, Nobel Symposium 84 S. Bengtson, Eds., Columbia Univ.

Press, New York, pp. 91-110 (1994).

3. Mojzsis, S., Nutman, A.P., and Arrhenius, G., Evidence for a marine sedimentary system at >3.87

Ga in southern West Greenland EOS, Trans. Am. Geophys. Union 75:690 (1994).

4. Pitsch, S., Eschenmoser, A., Gedulin, B., Hui, S., and Arrhenius, G., Mineral induced formation of

sugar phosphates Orig. Life Evol. Biosphere 25:294-334 (1995).

5. Braterman, P.S., Arrhenius, G., Hui, S., and Paplawsky, W., Preferential uptake of ammonium ions

by zinc ferrocyanide Orig. of Life EvoL Biosphere 25:531-538 (1995).

6. Arrhenius, G., Baldridge, K.K., Richards-Gross, S., and Siegel, J., Glycolonitrile oligomerization:

structure of oxazolines, potential heterocycles on early Earth J. Org. Chem. 62:5522-5525 (1996).

7. Arrhenius, G., Sales, B., Mojzsis, S., and Lee, T., Entropy and charge in molecular evolution - the

case of phosphate J. Theor. BioL 187:503-522 (1996).

8. Dickens, J., Irvine, W.M., Ohishi, M., Arrhenius, G., Pitsch, S., Bauder, A., MOiler, F., and

Eschenmoser, A., A search for oxirane carbonitrile; a potential source for primitive aldehyde

phosphates Origins Life EvoL Biosphere 26:97-110 (1996).

9. Mojzsis, S.J., Arrhenius, G., McKeegan, K.D., Harrison, T.M., Nutman, A.P., and Friend, C.R.L.,

Evidence for life on Earth before 3800 million years ago Nature 384:55-59 (1996).

10. Kolb, V., Zhang, S., Xu, Y., and Arrhenius, G., Mineral-induced phosphorylation of glycolate ion - a

metaphor in chemical evolution Orig. Life Evol. Biosphere 27 (in press 1997).

11. Arrhenius, G., Carbon dioxide warming of the early Earth Ambio26:12-16 (1997).

12. Krishnamurthy, R., S. Pitsch, and G. Arrhenius, Mineral induced synthesis of ribose phosphates

Orig. Life Evol. Biosphere 26:240-241 (1996).

59
MARS SAMPLE RETURN QUARANTINE PROTOCOL WORKSHOP

Donald L. DeVincenzi*

NASA Ames Research Center

With the possibility of a Mars Sample Return Mission launch as early as 2005, there is renewed interest

in, and a sense of urgency about, the requirements for Planetary Protection that might be imposed on

such a mission. In Spring 1997, the Space Studies Board issued a report dealing with Mars Sample

Return issues. One of the recommendations of this study was that samples returned from Mars should

be contained and treated as though potentially hazardous until proven otherwise. This issue was

examined further in a Quarantine Protocol Workshop held at NASA's Ames Research Center, June 4-

6, 1997.

The objectives of the workshop were: 1) Given procedures employed during the lunar program,

develop up-to-date containment procedures, a methodology to detect biological materials, and a

methodology to determine if Mars samples are hazardous; and 2) For each set of procedures, identify

research and technology needs to specify more detailed procedures. The containment sub-group

considered technology requirements to prevent escape of potentially hazardous materials in the Mars

sample and evaluated currently available technology and procedures for facility testing and personnel

training. The life detection sub-group considered techniques available for detection of biological

entities and/or organics in returned samples and examined test priorities and sequences. The hazard

determination sub-group focused on methods to determine pathogenicity of Mars samples and

evaluated other issues including shortcomings of this approach and criteria or conditions for

distribution of the sample.

PLANETARY PROTECTION AND MARS SAMPLE RETURN:

FROM NOW THROUGH LAUNCH AND BEYOND

Margaret S. Race*

SETI Institute

The public's current fascination with space exploration and its concerns about environment, health

and safety all but ensure that plans for returning samples from Mars and handling them on Earth will

generate considerable attention. The future success of a 2005 Mars sample return mission will require

consideration of not only the scientific and technical aspects of the mission but also the public and

legal contexts in which mission plans will be scrutinized. To be responsive to legal requirements and

legitimate public concerns, planetary protection must be integrated early into all phases of the mission

design. In addition, NASA must keep other government agencies and the public informed throughout

the decision making and review process and ensure that quarantine, handling and testing protocols

for martian samples on Earth will be stringently followed.

With legal and public contexts in mind, recent research has focused on several important aspects of

mission planning in order to anticipate and perhaps minimize future external impediments. Among the

areas that have received special attention recently are: 1) consideration of the environmental impact

statement and supplemental launch approval process, both of which will require extensive

documentation and public review; 2) identification of legal ambiguities and scientific uncertainties that

could complicate mission review and approval; 3) developing a systematic, updated testing protocol to

determine whether returned martian materials are biohazardous; and 4) studying public risk

perceptions and responses to preliminary sample return plans. Information from these areas will be

helpful in fulfilling legally required steps in the launch approval process for a sample return mission.

6O

l-I I_
Moreover, the information will help in anticipating problems areas and legitimate public questions, as

well as prepare for legal challenges to sample return plans should they arise.

THE ABUNDANCE OF 13C IN MARINE ORGANIC MATTER

AND ISOTOPIC FRACTIONATION

IN THE GLOBAL BIOGEOCHEMICAL CYCLE OF CARBON

DURING THE PAST 800 MA

John M. Hayes .1, Harald Strauss 2, and A.J. Kaufman 3

1Woods Hole Oceanographic Institution; 2Institute for Geology, Ruhr-University Bochum, Germany;

3Department of Geology, University of Maryland, College Park

For the late Proterozoic and earliest Cambrian, the new records of 135org and of the fractionation of

13C associated with fixation of CO2 by phytoplankton, estimated from 13_org and 136carbonate' are

based on results compiled from the literature and on new analyses and stratigraphic correlations

developed by Grotzinger, Hoffman, Kaufman, and Knoll at MIT and Harvard. For the Paleozoic and

most of the Mesozoic, the records are based on results compiled from the literature and on new

analyses of carefully selected carbonates by Veizer and coworkers at Bochum and Ottawa. For the

Cretaceous and Cenozoic, the record of 13_org is based on a new compilation of data from the Initial

Reports of the various international programs in ocean drilling, with attention to revisions of

stratigraphic assignments. For this same interval of time, the record of 135carbonate is based on

Shackleton's analyses of total sedimentary carbonate.

Although the records of both 13,5organd 135carbonate are quite intricately structured, a picture of

remarkable simplicity emerges when they are viewed in the context of recent studies of marine

phytoplankton (particularly by Bidigare, Laws, Popp, and coworkers at Hawaii). For most of the past

800 Ma, fractionation of 13C has not differed significantly from the maximum set by the physiology and

enzymology of marine algae. However, between 550 and 520 Ma (according to a time scale which

places the end of the second Varangian Ice Age at 575 Ma and the boundary between the NemakitDaldyn and the Tommotian at 534 Ma) the fractionation declined from the maximum by about five per

mil. A second decline has long been recognized in the Neogene. The new record shows that it

begins abruptly about 29 Ma ago (mid-Oligocene) and that its magnitude increases almost linearly with

time, maximizing presently at eight per mil. These declines are probably due to some combination of

increased rates of planktonic growth (due to invigoration of oceanic circulation and consequent

fertilization of surface waters) and decreases in the abundance of carbon dioxide in the ocean and

atmosphere. For the more recent episode, the range of possible variations would include, for

example, either constant rates of growth and a 3.6-fold decline in PCO2 or a trebling in growth and a

2.5-fold decrease in PCO2.

61
MOLECULAR BIOMARKERS FOR CYANOBACTERIA

Linda L. Jahnke*

NASA Ames Research Center

Roger E. Summons

Australian Geological Survey Organization

Harold P. Klein

SETI Institute

The evolution of oxygenic photosynthesis within the cyanobacterial lineage was one of the most

important event in Earth's history. Cyanobacteria diversified and evolved to dominate the early

biosphere as witnessed by microfossil assemblages. A crucial means to understand these ancient

ecosystems are the modern microbial mats that survive today in many and diverse environments. By

studying representative mat organisms in pure culture, insights into the dynamics of mat community

structure can be gained. Studies of hydrocarbons extracted from ancient sediments can provide firm

connections to modern biology by linking diagnostic molecular fossils, i.e. biomarkers, to specific

groups of source organic In addition, understanding the function and influence of environmental

factors on the synthesis of such biomarker molecules within the source organism can extend our

knowledge of this ancient organic carbon record. To this end we are presently studying a group

specific lipid biomarker for the cyanobacteria, mid-chain, methyl branched alkanes.

A variety of branched alkanes have been isolated from modern cyanobacterial mats. These generally

consist of a C16 to C19 hydrocarbon chain with a single methyl group (MMA) at the 6-, 7-, or 8- position

(e.g. 7-methylheptadecane). In some instances dimethylalkanes (DMA) with similar chain lengths and

methyl positions have also been identified. The presence of MMA in cyanobacterial cultures has been

well documented, however, we have only recently identified a C19 DMA with methyl groups at 7,11- or

7,10- in a UTEX culture of Phormidium luridum. Quite remarkably, we found that P. luridum DMA were

only synthesized when the culture was grown with low dissolved inorganic carbon (DIC). Cells grown

with atmospheric levels of CO2 (0.4 mM) contain DMA while cells grown with 1% CO2 (18 mM) have

mostly n-C17. The Phormidium genus comprise fine, filamentous cyanobacteria which dominate mat

formation in the mid-temperature zone (below 55 ° C to -30 ° C) in Yellowstone National Park.

Phormidium isolated from these mats also synthesize DMA, however, the DIC level does not in itself

appear to be a controlling factor in DMA expression in these isolates. In the PhotTnidium mats found at

Fountain Paint Pots in YNP, only low levels of DMA are detected in mats submerged in the high DIC

waters (6 mM) of these siliceous hot springs, however, dramatically higher levels of DMA were

detected in a closely adjacent, sub-aerially exposed mat analog. The subaerial mat now exposed to

atmospheric CO2 levels was also at a much lower temperature as witnessed by increased levels of

polyunsaturated fatty acids. These results suggest that DMA synthesis is controlled by a variety of

environmental factors affecting membrane function and point to the potential for pure culture studies

to provide insights for interpretation of the molecular fossil record.

THE MARTIAN CARBON CYCLE AND IMPLICATIONS FOR

THE 813C VALUE OF THE ATMOSPHERE

David Kass* and Yuk Yung

Division of Geological and Planetary Sciences, California Institute of Technology

In between measurements of the martian atmosphere, precise laboratory measurements on the SNC

meteorites, thought to come from Mars, and the possibility of a direct sample return mission, we are

62

I- ]! i-
getting data on the carbon isotopic system for Mars. The question then becomes, what do these

measurements mean? In order to understand the results, it is necessary to consider what happens to

carbon on Mars.

Unlike on the Earth, carbon does not cycle through the martian environment. Instead, primordial

carbon is out-gassed from the mantle into the atmosphere. While it may condense onto the polar caps

or in a regolith reservoir, it remains in the atmosphere-cap-regolith reservoir until it is lost. Carbon may

either be lost from the planet by sputtering and other exospheric processes, or it may be converted

into carbonate. On the Earth, carbonate is eventually subducted back into the mantle and then

released again during out-gassing. On Mars, there appears to be little, if any, recycling of carbonate (or

other crustal material). This effectively makes carbonate a permanent sink for carbon on Mars. It is also

why all the out-gassed carbon is primordial instead of mostly recycled as on Earth. If there was life on

Mars, it probably never proliferated like on Earth and never represented the carbon reservoir that is

seen on Earth. Thus overall, primordial carbon out-gasses from the mantle into the atmosphere and is

then either lost into the atmosphere or permanently sequestered in carbonate.

While the carbon system on Mars is, in many ways, much simpler than on the Earth, it is also

significantly different. This means that our intuition for the behavior of the 613C isotopic system cannot

be applied to Mars. On the Earth, the ocean acts as a large buffer reservoir for carbon. This, coupled

with the continual cycling of carbonate and extremely slow escape processes, means that the 513C

value for the Earth generally remains close to a fixed value that does not change with time. On Mars,

where this is not the case, the (313C value of the atmospheric reservoir can change with time. Using

measurements of the SNC Meteorites, we can make reasonable assumptions for the (513Cof the outgassed source carbon. Then by examining the loss processes, we can create a model of the (313C

behavior of the atmosphere over the history of Mars. Using constraints on the current atmosphere

from measurements as well as laboratory and numerical experiments on the various loss processes,

we find that the martian atmosphere started out quite light and has progressively gotten heavier as the

atmosphere evolved.

Our modeling implies that when measuring 613C values for Mars, it is critical to know, not only where

the carbon is, but also when it was stored. This is especially true for sinks that acquired their carbon

from the atmosphere-cap-regolith system. For example, carbonate from two different rocks formed at

different times, but by the same process in similar environments may have significantly different 613C

values that only reflect their different formation ages. This effect will be especially important when

trying to distinguish biotic and abiotic carbonate since the two may have similar 813C values because

the carbon came from different reservoirs or because they formed at different epochs.

DETECTION, FORMATION, AND EVOLUTION

OF COMPLEX HYDROCARBONS IN PROTOSTELLAR CORES

Thangasamy Velusamy*, William D. Langer, and Steven Levin

Jet Propulsion Laboratory, California Institute of Technology

The complex chemical ingredients brought to the early solar system may play an important role in the

chemical reservoir of the dust and small bodies that form the planets, and in objects such as comets,

which continue to supply material to the planets throughout their lives. To understand the initial

chemical environment it is especially important to detect and determine the types and abundances of

complex hydrocarbons produced during protostar and protostellar disk evolution. We have begun a

systematic program to search for complex hydrocarbons and prebiotic molecules in protostellar cores

using the radio emission at centimeter wavelengths characteristic of heavy molecules in a low

temperature environment. These hydrocarbons and nitriles have a direct bearing on the issues within

63
exobiologyandtheorigin of life. We report on our progress to date, including the first detections of

the longest cumulene carbene and linear carbon chain radicals.

The cumulene carbenes, acetylenic chains, and linear carbon chain radicals are important

components of hydrocarbon chemistry in low mass protostellar cores. Their detection and

characterization is important for determining the hydrocarbon chemistry. We made the first

astronomical detection of the long chain cumulene carbene, H2C6, in a protostellar core from

observations of two of its rotational transitions (Langer et al. 1997) in TMC1 and here we also report

the detection of the carbon chain radical C8H. We also observed the shorter cumulene carbene

chains H2C 3 (propadienyldene) and H2C4 (buttatrienylidene) and several other complex molecules,

including HC9N, HCTN, C5H, C7H, and c-C3H2, to shed light on the hydrocarbon chemistry. We

compare the observed abundance ratios with to chemical models appropriate to the protostellar core.

All these observations were made with NASA's Deep Space Network (DSN) 70 meter antenna at

Goldstone, CA. The cumulene carbenes are distributed similarly to those of other complex carbon

compounds, such as HC2n+IN and CnH, but differently from the cyclopropenylidene ring c-C3H2. We

compare the observed ratios to gas phase chemical models appropriate to cores. The fractional

abundance of H2C6 relative to H2 is about 3 x 10-11 and that of H2C4 about 8 x 10-10. The H2C6

abundance is in reasonable agreement with gas phase chemical models for early evolutionary stages

while the H2C4 is more abundant than predicted.

This research was conducted at the Jet Propulsion Laboratory, California Institute of Technology,

under support from the National Aeronautics and Space Administration.

References:

1. Langer, W.D., Velusamy, T., Kuiper, T.B.H., Peng, R., McCarthy, M.C., Travers, M.J., 2. Kovdcs, A.,

Gottleib, C.A., and Thaddeus, P., Ap J. Letters 480:L63-66 (1997).

ANALYSIS OF THE CARBONACEOUS COMPONENT

OF COMET HALLEY DUST

Marina N. Fomenkova*

Center for Astrophysics and Space Sciences, University of California San Diego

Sherwood Chang

NASA Ames Research Center

Comets consist of frozen water, organic and inorganic compounds, and they may have contributed to

an early inventory of prebiotic compounds on the primitive Earth and to the reservoir of liquid water on

our planet Comets probably had dual influences on the origin and evolution of life, on one hand, they

provided a source of precursors for biochemical while on the other hand their impacts caused severe

environmental perturbation. Hence, characterizing the nature and flux of cometary organic material is

an integral aspect for understanding life's origins and evolution.

In this work we discuss the compositional groupings obtained by cluster analysis of the carbonaceous

component of comet Halley dust. A few basic types of compounds are identified, and we hypothesize

that they are essential 'building blocks' which in various combinations give rise to the variety of

compositional types observed in cometary dust.

64

3_i1'
Mass-spectra of about 5000 individual submicron cometary grains were obtained during fly-by

missions to comet P/Halley in 1986 [1]. It has been established that cometary dust is extremely rich in

organics (-50% by mass). CHON grains, dominated by C alone or in combination with H, O, N. were

studied by cluster analysis which revealed more than 30 distinguishable types of grains [2]. We

applied the same procedures of cluster analysis to study the composition of the organic component of

Mixed particles which are assemblages of organic and inorganic components. These particles

represent about 50% of the population of comet Halley dust grains.

In most cases, the carbonaceous component of Mixed particles can be characterized as a

multicomponent mixture of carbon phases and organic compounds. Some compositionally simple

types identified by cluster analysis are the same as previously found in CHON grains: elemental

carbon ([C]-group), hydrocarbons ([H,C]-group), polymers of carbon suboxide and of

cyanopolyynes. The proportions of all these species are similar in CHON and in Mixed grains.

In addition, polymers of formaldehyde, of hydrogen cyanide and various unsaturated nitriles appear to

be present in Mixed particles. Note that the relative abundance of N is higher in Mixed particles than in

the previously analyzed CHON group. Some H-containing species observed may form from carbon

suboxide and/or cyanopolyynes polymers by hydrogenation on grains in the interstellar medium [3].

Finally, some simple ices are observed in individual grains and mixed with organic compounds. These

icy grains may survive at the distance of -10-15 thousand km from the nucleus if they were initially

emitted as relatively large particles (> 10 Am) [4].

We conclude that the chemical make-up and the overall variety of dust grain types are consistent with

the interstellar grain model [5].

References:

1. Kissel, J. et al., Nature 321:280-282 (1986).

2. Fomenkova, M. et al., GCA 58:4503-4512 (1994).

3. Charnley, S., in Astronom. & Biochem. Origins & the Search for Life in the Universe, C. Cosmovici

et al. Eds, pp. 89-96, Editrice Compositori (1997).

4. Lichtenegger, H. and N. Komle, Icarus 90:319-325 (1991).

5. Greenberg, J.M., in Comets, L. Wilkening, Eds., pp. 131-163, Univ. of Arizona Press (1982).

THE STRUCTURE OF EXTRATERRESTRIAL WATER ICE

David Blake 1., Peter Jenniskens 2, and Lance Delzeit 1

1NASA Ames Research Center; 2SETI Institute

Vapor-deposited amorphous water ice plays an important role in the natural history of the biogenic

elements. Such ice is observed spectroscopically as a frost on interstellar dust in dense molecular

clouds, and constitutes the bulk of matter in comets. The initial association of the biogenic elements

occurs within the icy mantles of grains in cold molecular clouds, and it is here that the first organic

compounds are formed. Ultimately, these materials were trapped within icy planetesimals, and were

most likely transported to the early Earth within comets or cometary dust.

Nearly all of the properties of extraterrestrial ices (chemical reaction rates, volatile retention and

release, vaporization behavior, thermal conductivity, infrared spectral characteristics and the like) are a

direct consequence of ice structure. However, the characterization of astrophysical ices and their

laboratory analogs has typically utilized indirect measurements which yield phenomenological

interpretations.

65
When water ice is vapor-deposited at 14° K and warmed until it volatilizes in moderate vacuum, the ice

undergoes a series of amorphous to amorphous and amorphous to crystalline structural transitions

which we have characterized by diffraction methods. These structural transitions correlate with and

underlie many phenomena observed in laboratory infrared and gas release experiments.

The elucidation of the dynamic structural changes which occur in vapor-deposited water ice as a

function of time, temperature and radiation history allows for the more complete interpretation of

remote observations of astrophysical ices and their laboratory analogs.

References:

1. Jenniskens, P. and D.F. Blake, "Structural transitions in amorphous water ice and astrophysical

implications," Science 265:753-756 (1994).

2. Jenniskens, P., D.F. Blake, M. Wilson, and A. Pohorille, "High density amorphous ice, the frost on

interstellar grains," Astrophysica/Jouma/455:389-401 (1995).

3. Wilson, M.A., A. Pohorille, P. Jenniskens and D.F. Blake, "Probing the structure of cometary ice,"

Odgins of Life and Evolution of the Biosphere 25:3-19 (1995).

4. Jenniskens, P. and D.F. Blake, "Crystallization of amorphous water ice in the solar system."

Astrophysica/Jouma/, 473(2.1):1104-1113 (1996).

5. Jenniskens, P. and D.F. Blake, "A mechanism for forming deep cracks in comets," Planet. Space

Sci 44(00) (1996).

6. Jenniskens, P. D.F. Blake, and A. Kouchi. "Amorphous water ice, a solar system material." in:

proceedings of "Solar Systems Ices," Toulouse, Mar 27-30, B. Schmitt and C. De Bergh, Eds, (1995).

7. Jenniskens, P., S.F. Banham, D.F. Blake, and M.R.S. McCoustra. "Liquid water in the domain of

cubic crystalline ice Ic." J. Chem. Phys. 107(4):1232-1241 (1997).

THE MECHANISM OF AMINE-CATALYZED HYDROLYSIS OF RNA

David A. Usher* and John R. Townsend

Department of Chemistry, Cornell University

Nucleophilic attack on the phosphorus atom of a phosphate diester by a hydroxyl group is central to

the cleavage and ligation reactions that are carried out by ribozymes. This reaction occurs also in the

base or RNase-catalyzed hydrolysis of RNA, and may have been involved in the de novo formation of

RNA in prebiotic times.

This reaction is known to be catalyzed by amines, particularly alkanediamines, yet the mechanism of

this catalysis has been a subject of controversy in recent years. We have investigated the imidazolecatalyzed hydrolysis of an analog of RNA, the dinucleoside monophosphate 3',3'-UpU. This

dinucleotide is particularly interesting as a model for ribozyme action, for the leaving group is the

2',3'-diol of a nucleoside, just as it is in many ribozyme-catalyzed transesterifications. This is a better

leaving group than the 5'-OH of a normal 3',5'-dinucleotide, and so the reaction of our model

compound takes place about twenty times faster than for the normal dinucleotide.

We have studied the general species-catalyzed cleavage of 3',3'-UpU in imidazole buffers under

carefully controlled conditions, and find that if the polarity of the solvent is held constant as the

concentration of buffer is varied, the cleavage reaction shows simple general base catalysis. This is in

contrast to the anomalous behavior reported earlier for 3',5'-UpU by Breslow and co-workers, on which

they based a series of mechanistic suggestions. Some of their curved plots appear to be artifacts of

their experimental method.

66

111
However, in spite of the mechanism of amine-catalyzed cleavage now appearing to be simple generalbase catalysis, earlier work from our laboratory suggests that the actual mechanism of amine-catalyzed

hydroxyl attack on a phosphate diester involves the kinetically equivalent protonated amine plus the

deprotonated hydroxyl group. These results are guiding our search for amine catalysts that can

improve the yield of RNA oligomers in the de novo formation of RNA from nucleoside 2',3'-cyclic

phosphates under simulated prebiotic conditions.

INORGANIC SOLIDS AND THE ORIGINS OF LIFE

Paul S. Braterman*, Kevin Shannon, and Joseph Boclair

University of North Texas

Inorganic solids would have provided opportunities for adsorption and concentration, ordering,

catalysis and photochemistry not available to materials in solution, and we are exploring some of these

possibilities. We have concentrated so far on layered double hydroxides (LDH's), of general type

M(II)I-xM(III)x(OH)2Yx which are naturally occurring ion exchangers and base catalysts, and on the

solid state photochemical reduction of carbonate by iron(ll).

Layered double hydroxides containing 10 atom % M(II) as iron(ll) and incorporating 13C-labeled

carbonate, when subjected to UV light, turn darker but generate only traces of formaldehyde

(detected by GC-MS as its 2,4-dinitrophenylhydrazone). Iron(ll) carbonate itself, under the same

conditions, is converted to carbonate green rust [iron(ll) iron(Ill) hydroxide carbonate, itself a member

of the LDH family], but again the production of formaldehyde is negligible. Manganese(ll), chosen

because it could in principle act as the source of two electrons per ion, was without effect either on its

own or in the presence of iron(ll). We intend, however, to search for other products from these

reactions.

Layered double hydroxides readily adsorb ferrocyanide (which we regard as a possible prebiotic

species under closed basin conditions) from solution. At high pH, carbonate displaces ferrocyanide

from the bulk (but not from the surface) of the LDH particles. In addition, ferrocyanide readily forms

insoluble products with magnesium, which can incorporate Group 1 cations, with a possible

preference for ammonium. We have evidence that the reaction between ammonium magnesium

ferrocyanide and formaldehyde gives rise to a wide range of products, and intend to explore the

nature of these, the lower concentration limits for their formation, and which components of the

system are necessary for these reactions to take place.

THE CHEMISTRY, MINERALOGY, AND SPECTROSCOPY

OF THE BIOGENIC ELEMENTS IN MARS SOIL ANALOGS

James Orenberg*, Amos Banin, and Ted Roush

San Francisco State University

Susan White

NASA Ames Research Center

Characterization of the surface of Mars is part of an international effort to determine "whether life ever

began on Mars, and if so, in what form". A crucial and key step in the establishment of the early history

of abiotic evolution on Mars is the measurement of the concentrations and understanding of the

67
geologicalcyclesofthesix major biogenic elements, hydrogen, carbon, nitrogen, oxygen, sulfur, and

phosphorus on the surface of Mars. Laboratory studies to evaluate the reactivity and mineralogy of the

biogenic elements in a model Mars soil matrix are being conducted. Experimental and theoretical

approaches are being used to study the spectral fingerprints of the biogenic element minerals in order

to constrain their detectability limits for remote sensing observations. Studies are focusing on the

effects of the biogenic elements on the reactivity (surface acidity and redox potentials) of Mars soil

analogs and on simulations of the Viking Biology experiments. The broad objectives of these

experiments are to constrain the mineralogy of the biogenic elements in model Mars soil matrices, to

suggest scenarios for their distribution and transformations in the martian environment, and to support

interpretation of remote sensing and Mars surface probing data obtained from orbiters and landers.

Reflectance spectroscopic evaluation of mixtures of the biogenic elements in a Mars soit matrix has

been initiated using both physically prepared mixtures and those prepared by acid weathering

procedures in the laboratory. For the physical mixtures, initial interpretation of the visual and nearinfrared wavelength region (0.25-2.5 mm) spectra indicates a subtle increase of the overall reflectance

at the highest concentrations of sulfate and in a mixture of all salts. In the far-infrared region (2.5-25

ram), distinctive spectral features are visually observed for carbonate and sulfate salts at all

concentrations, but no distinctive spectral features are seen for the nitrate or phosphate. Additional

spectral analyses are planned in the far-infrared to investigate whether subtle spectral features will

help identify the presence of the nitrates and phosphates.

Mars soil analogs were prepared by acidolytic weathering of a partly palagonitized volcanic tephra by

adding varying inputs of sulfuric, nitric and hydrochloric acids, at levels of addition covering the range

from zero to the corresponding biogenic element concentration found (or estimated) in Mars soil and

beyond. These acidified Mars soil analogs were characterized by a titration-extraction procedure which

measures solid-surface and solution acidity and by X-ray diffractometry. The results show that volcanic

palagonitized tephra, "artificially-weathered" by addition of various acids, is stabilized at pH levels

buffered by the AI and Fe hydrolysis products. Titration curves show that the total final acidity is

practically equal to the added acidity, the majority being present as hydrolytic species of AI, Fe and Mg

released from the tephra minerals.

EARLY EVOLUTION OF LIFE IN NON-MARINE ENVIRONMENTS

L. Paul Knauth*

Arizona State University

The Earth today contains about 1.3 x1022 g of NaCI stored as subsurface salt deposits in sedimentary

basins and probably an even greater amount in continental brines and ground waters. If all this salt

were returned to the ocean the salinity would rise by at least 60%. Assuming that CI was outgassed

with water, the early oceans may have been this saline until significant halite was removed by evaporite

deposition in sedimentary basins on continental platforms. Ideas vary regarding when such platforms

became established and when huge accumulations of salt were finally sequestered, but it may not

have happened until sometime in the Proterozoic. Until oceanic salinity was drawn down, early

evolution of life may have been especially active in the lower salinity, non-marine waters in lakes,

rivers, and soils. These environments sit high on continents and their deposits are preferentially

eroded away relative to marine deposits. However, some non-marine deposits have been preserved,

and many contain horizons conducive to the preservation of microfossils. The purpose of this project

is to identify silica and carbonate that formed in early sub-aerial and other non-marine environments

and explore further the newly emerging fossil record of life on land in the Precambrian.

68
Chert-bearingcarbonatestratathatundergointenseweatheringyielda distinctivepaleokarstdeposit

composedof insolublechert,clay,andsecondarylow 180carbonateandsilicathataredeposited

from meteoricwatersduringthe event. 13C-depleted CO2 is injected into the ground waters by

vegetated surfaces and gets incorporated into the secondary carbonate, thereby providing an

isotopic signature of sub-aerial organisms. Microfossils of probable cyanobacteria have been found in

the associated secondary silica in paleokarsts as old as 1200 m.y. 13C depletions are comparable to

modern karsts suggesting a very significant subaerial biomass at that time. More complicated

pseudofossils in this silica are currently being evaluated for possible biogenicity and even older

horizons will be examined.

Quartz-filled amygdules and veins in silicic volcanic deposits are normally assumed to be of

hydrothermal origin. However, recent oxygen and hydrogen isotope analyses show that much of this

silica actually formed at surficial temperatures as weathering products of the silica-rich volcanic glasses.

Modern examples near the surface are often little biospheres containing cyanobacteda and other

microorganisms. The preservation of such organisms in this type of silica is currently being examined

and ancient examples are a new target material for exploring the fossil record of life on land in the

Precambrian and possibly on Mars. Calcite alteration veins in terrestrial basalts are being similarly

examined and may provide easily accessible target material for future sample returns from Mars.

THE DIVERSITY OF THE OUTER PLANETARY SYSTEM

H. Levison* and J. Lissauer

A set of plausible outer planetary systems were constructed using direct numerical integrations.

Included in these simulations were the effects of the solar nebula. This included the accretion of

nebular gas in order to form Jupiter-like planets. It was found that some sort of dissipation was required

for time scales longer than 10 million years in order to construct systems like ours. The number of

planets can vary from one to seven. Systems with a large number of planets never contain large,

Jupiter-like planets, but instead are made up of Uranus-like planets. Stable planetary systems can

include planets in mean motion resonances with one another. Perhaps most surprisingly, it is possible

to construct stable systems in which that planetary orbits can undergo large, semi-periodic changes.

FORMATION OF THE ASTEROID BELT

1George W. Wetherill*, 1Stephen Kortenkamp, and 2John E. Chambers

1DTM, Carnegie Institution of Washington; 2Armagh Observatory

Little attention has been given to the formation and early history of asteroid belts, despite their

importance. Asteroids are the source of almost all meteorites, including the primitive carbonaceous

meteorites that carry a record of prebiotic chemistry in the early Solar System. Devastating impacts of

asteroids, and their probably much larger counterparts in the early Solar System were a major factor in

shaping the course of the earliest evolution of life on Earth, and probably in other planetary systems

as well. Collision debris in the much more populated early asteroid belt will spiral into the terrestrial

planet region by gas drag and make a significant contribution of otherwise rare crustal and upper

mantle elements to the Earth's surface.

A central problem in asteroid belt formation is understanding why there is a region in our Solar System

that is depleted in mass by a factor of several thousand, as compared with the terrestrial and giant

planet regions. To approach this problem, models of the formation of bodies interior to giant planets in

69
planetarysystemshavebeendevelopedusingthesametechniquesusedto studyterrestrialplanet

formation:

(1) Treatmentof planetesimals as analogues of molecules in gas dynamic transport theory,

(2) ~104 body Monte Carlo evolution of growth evolution of ~ 1024 g bodies,

(3) Numerical integration of - 40 larger bodies for times up to > 108 years.

Assuming an approximately smooth decrease in nebular surface density, the earlier stages of growth

lead to an asteroid belt population of -25 bodies as large as Mars or more between Earth and Jupiter

within a few million years. Numerical integration shows that, in about half the cases, mutual

perturbations, together with resonant long range forces due to the giant planets removes all these

large bodies from the asteroidal region on a -108 yr time scale. Otherwise one or more of these small

planets remain between the terrestrial and giant planets. Remnant bodies analogous to Mars are also

found. The present asteroids are then the products of collisions between the larger bodies, as well as

those of the associated retinue of smaller bodies. The present -5 km/sec relative velocities of the

asteroids, their number, position, degree of mixing and size distribution are shown to be consistent

with their being consequences of these events.

The above models make the conventional assumption that gas giants postdate the formation of the

Mars-sized asteroidal bodies. Recently, A. Boss has proposed that solar system and extrasolar gas

giants can form from gravitational instabilities in the disk during the final stages of formation of the

central star. We have investigated the effect of this process on the formation of Earth-like bodies and

asteroids interior to the gas giants. Preliminary results suggest this process could preclude formation

of such bodies, despite the tendency of similar phasing of gas giant perturbations to limit the relative

velocity between growing planetesimals.

THE ROUTE FROM INTERSTELLAR TO PROTOSTELLAR ABUNDANCES:

EVIDENCE OF VARIABILITY IN THE INTERSTELLAR MEDIUM

P. Wannier*, P. Schloerb, and G. Moriarty-Schieven

Jet Propulsion Laboratory

We have tested the often-made assumption that there is a steady evolution of nuclear abundances in

the Galaxy, which results in a balanced enrichment of the elements considered essential for the

evolution of life. Our test consists of making observations, on the scale of a solar mass, which might

indicate whether or not the abundances of the nuclides in the interstellar medium are uniform. A

finding of non-uniformity would imply that stellar systems with abundances much like the present-day

solar system, could have existed already in early Galactic history, nearly 5 billion years before the

creation of the Sun.

The particular nuclear abundance ratio chosen for study is 17-O/18-O: The most precisely determined

extra-solar abundance ratio, and one which is known to be evolved by means of production in red

giant stars. There is also significant evidence for local enrichment, based on the presence of enriched

grains in meteorites, showing anomalous abundances of the oxygen isotopes (Clayton et al., 1977;

Huss et al., 1994)

We have completed a study of Rho Oph, a nearby, molecular cloud complex, using the isotope pair

most favorable for accurate studies: 17-O/18-O. We have tentatively concluded that there are,

indeed, measurable variations in abundances on solar-mass scales. Our present goal is to confirm this

finding, and to extend the result to an examination of the nearest known interstellar molecular cloud:

7O

!! I1
L1457. The observations were carried out at the Five College Radio Observatory (FCRAO) with their

array receiver.

SPECTROSCOPIC STUDIES OF PRE-BIOTIC CARBON CHEMISTRY

Geoffrey A. Blake*

Division of Geological & Planetary Sciences, California Institute of Technology

Research in the Blake group supported by the Exobiology program seeks to understand the

evolution of molecular complexity in pre-biological environments. The major tool used is

spectroscopy, and the program has observational, laboratory, and theoretical components. In our

observational work, we combine high resolution (sub)millimeter-wave and IR images from the

OVRO/Hat Creek Arrays and Keck telescope with high dynamic range spectra from the !SO satellite to

constrain, for the first time, the overall chemical budgets of the biogenic elements during the star

formation process. We also have an active observational program characterizing the composition and

thermal properties of comets (Hyakutake, Hale-Bopp) and Kuiper Belt Objects.

Imaging with the Millimeter Arrays is designed to probe, at the highest possible angular resolution, the

critical coupling of gas phase and grain mantle chemistry in the prebiotic evolution of protoplanetary

nebulae. We stress that such aperture synthesis data at "long wavelengths" (compared to optical and

near-IR studies which suffer greatly from extinction) is the only general probe of gas-phase chemistry

in material that must become part of the young star and any attendant planetary system. In our work to

date, it is clear that certain species are excellent probes of the structure of out-flowing gas, but that the

unambiguous detection of in-falling and rotating gas - material which is dynamically bound to the

young star - is difficult even at high angular resolution.

Comets are among the most primitive bodies left over from the planetesimal building stage of the solar

nebula, and so their physical and chemical composition provides an important link between nebular

and "interstellar" processes. At OVRO, local oscillator settings were optimized to allow access to

transitions of HCN, HC3N, CH3CN, HNCO, CS, SO, SO2, OCS, H2S, HDO, CO, H2CO, CH3OH, and

HCOOH. Comet Hale-Bopp was detected in each of these molecules during the spring of 1997, and

was sufficiently large that millimeter-wave thermal emission from the nucleus itself was detected. This

unique data set is the first to image many of these molecules at spatial resolutions characteristic of

optical astronomy with the tremendous spectral resolution of radio techniques.

Our laboratory work, performed with mid-infrared tunable diode laser, VUV --_ mid-IR pulsed field

ionization (PFI), and far-IR photomixer/supersonic jet spectrometers that were constructed, in part,

with Exobiology support, concentrates on acquiring spectra that will shed new light on the

extraordinarily complex prebiotic chemistry of carbon as reflected in interstellar and primitive solar

system materials. There are two major targets of emphasis. The first includes small, reactive

intermediates such as the vinyl radical, benzyne diradical, and carbenes which are thought to be key

components in the synthesis of larger "molecular grains" such as PAHs or carbonaceous grains. The

second is the examination of such molecular grains themselves, particularly long chain polyacetylene

or cyanopolyacetylene species along with refractory species such as carbide clusters.

71
THEORETICAL STUDIES OF THE EXTRATERRESTRIAL CHEMISTRY

OF BIOGENIC ELEMENTS AND COMPOUNDS

David E. Woon*

Molecular Research Institute

Gas-grain reactions are thought to play an important role in the formation of molecular species in

interstellar and circumstellar clouds. These include known species with important exobiological

implications such as alcohols, ketones, aldehydes, and carboxylic acids, as well as candidate species

including small amino acids such as glycine. Grain surfaces may influence reactions in different ways:

as reaction sites for catalyzing the formation of species that possess high gas-phase barriers or as

sinks for excess reaction energy in association reactions without barriers. Grain surfaces also provide

nucleation centers for macroscopic accretion and the consequential depletion of elements from the

gas phase. The goal of this work is develop new theoretical models for elucidating the mechanisms of

important gas-grain reactions that incorporate as much information as possible from accurate quantum

chemical calculations.

One of the reactions of greatest interest is the hydrogenation of CO to form the formyl radical HCO, a

critical early step in the formation of many larger organic species. The H + CO _ HCO reaction

possesses a very high barrier in the gas phase, but several experimental studies have provided

evidence that the process is greatly enhanced on icy surfaces comprised of water or other molecules.

We are using correlated ab initio molecular orbital methods to investigate the microscopic mechanism

by which water modifies the reaction. We are doing this by first considering small clusters, particularly

H + CO --_ HCO with one and two water molecules present. Our calculations indicate that water has

a negligible impact on the energetics of the reaction, the barrier remaining very high. However, even

one water fundamentally alters the form of the potential energy surface (as depicted below) by

providing a substrate to which hydrogen can adhere and repeatedly attempt to tunnel through the

barrier.

H+CO

Gas Phase Complexed with One Water

TS TS...H20

H+CO+H20 / .

H+CO...H20

k HCO

HCO+H20

/

HCO...H20

REDUCED NITROGEN ON THE EARLY EARTH

David P. Summers and Narcinda Lerner*

SETI Institute and NASA Ames Research Center

With current geochemical evidence pointing to a non-reducing atmosphere, the formation of reduced

nitrogen on the early Earth, or other planets with a carbon dioxide/nitrogen atmosphere, is

problematic. One source of reduced nitrogen starts with the fixation, by shock heating, of nitrogen to

72

-I[-]i I"
NO followed by photochemical conversion of the NO into nitrite. The nitrite can then be reduced to

ammonia by ferrous iron (Reaction 1).*

6 Fe+2 + 7 H+ + NO2"---) 6 Fe(lll) + 2 H20 + NH 3 (1)

It has been suggested that the reaction of ammonia with nitrite (Reaction 2)

NO2- + NH3 + H+ --) N2 + 2 H20 (2)

prevents reaction 1 from being a significant source of ammonia on the early Earth. However, whether

this is true depends on how the kinetics of reaction 2 compare with other sources and sinks for both

ammonia and nitrite. Any evaluation of the importance of various sources and sinks of nitrite and

ammonia, and of whether ammonia is likely to be present in significant amounts, requires an analysis of

all the kinetic processes affecting these species.

One potential source of amino acids under non-reducing conditions is via the Strecker synthesis,

equation 3, utilizing the ammonia produced above.

H2CO + HCN + NH3 --) CH(NH3)(CO2H ) (3)

However, several question arise. Is ammonia, from the reduction of nitrite by iron(ll), compatible with

the Strecker synthesis? Will complexation of the cyanide to the iron deactivate one or the other (or

both)? Will both of the reactions proceed under the same conditions? Conversely, could a

Fe(CN)n+(2-n) type species provide some catalytic effect, either for the reduction of nitrite/nitrate or

for the formation of amino acids?

The analysis of sources and sinks of nitrite and ammonia found that, under most environmental

conditions, the primary sink for nitrite is reduction to ammonia. The reaction between ammonia and

nitrite is not an Important sink for either nitrite or ammonia. Destruction at hydrothermal vents is

important at acidic pHs and at low ferrous iron concentrations. Photochemical destruction, even in a

worst case scenario, is unimportant under many conditions but could be important under acidic, low

iron concentration, or low temperature conditions. The primary sink for ammonia is photochemical

destruction in the atmosphere. Under acidic conditions, more of the ammonia is tied up as ammonium

(reducing its vapor pressure) and hydrothermal destruction becomes more important.

The studies on the interactions of reactions 1 & 3 found that; A cyanide/iron ratio of 2:1 or less doesn't

prevent the formation of ammonia by the iron(ll) reduction of nitrite. However, a cyanide/iron ratio of

4:1 or greater, no ammonia is formed across all pHs. At lower pHs nitrite is reduced to other products.

The Strecker synthesis does not appear to be hampered by the presence of iron. The Strecker

synthesis and the iron (11)reduction of nitrite to ammonia can be combined to form amino acids from

nitrite, iron(ll), cyanide, and formaldehyde.

PREFERENCE FOR INTERNUCLEOTIDE LINKAGES

AS A FUNCTION OF THE NUMBER OF CONSTITUENTS IN A MIXTURE

Anastassia Kanavarioti*

Department of Chemistry and Biochemistry, University OfCalifornia, Santa Cruz

Phosphoimidazolide activated ribomononucleotides (*pN, see structure) are useful substrates for the

non-enzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous

73
solutionsof*pN(0.01M)typicallyyieldonlysmall amounts of dimers and traces of oligomers; most of

*pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN

reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the

percent yield of the condensation products increases and the yield of the hydrolysis product

correspondingly decreases with *pN concentration (Kanavarioti, 1997).

Here we report product distributions in reactions with one, two or three reactive components at the

same total nucleotide concentration. *pN used as substrates were the nucleoside 5' phosphate 2-

methylimidazolides, 2-MelmpN with N = cytidine (C), uridine (U) or guanosine (G). Reactions were

conducted as self-condensations, i.e. one nucleotide only; with two components in the three binary

U,C-, U,G- and C,G-mixtures and with three components in the ternary U,C,G-mixture. The products

are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3',5'-Iinked-dimers, cyclic dimers and a small percentage of

longer oligomers. The surprising finding was that, under identical conditions, including the same total

monomer concentration, the product distribution differs substantially from one reaction to another,

most likely due to changing intermolecular interactions depending on the constituents. Even more

unexpected was the observed trend according to which reactions of the U,C,G-mixture produce the

highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and

the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the

apDroxim_tely two-fol_ increase of the Dercent yield of interrlucle0tide-linked dimers is not due to a

concentration effect or a catalyst, but it is due to the increased complexity of the system from a single

to two and three components. These observations, perhaps, provide an example of how increased

complexity in relatively simple chemical systems leads to organization of the material and

consequently to chemical evolution.

O

II

HO OH

R=H, CH 3

N = Uracil, Cytosine,

Adenine or Guanine

References:

1. Joyce, G.F. and L.E. Orgel, in The RNA World, R.F. Gesteland and J.F. Atkins, Eds., Cold Spring

Harbor Lab. Press, Cold Spring Harbor, pp 1-25 (1993).

2. Kanavarioti, A., Origins Life Evol Biosph 24:479-495 (1994).

3. Kanavarioti, A., Origins Life Evol Biosph 27:357-376 (1997).

INTERACTIONS OF CARBON COMPOUNDS AND PHOSPHATE WITH PYRITE IN

AQUEOUS SOLUTIONS

Martin Schoonen* and Joakim Bebie

Department of Geosciences, State University of New York at Stony Brook

Pyrite plays a central role in the chemo-lithotrophic model championed by Wachtershauser/1/. The

pyrrhotite-hydrogen sulfide/pyrite (FeS-H2S/FeS2) redox couple is assumed to have reduced CO2 or

CO to simple organic compounds. Once formed, these simple C-compounds as well as phosphate are

thought to sorb onto the pyrite surface and undergo reactions leading to more complex molecules.

Experimental work shows that the FeS-H2S/FeS2 redox can reduce CO/2/and CS2 (or COS)/3/, but

74

!I I I "
there is no evidence for direct reduction of CO2/4/. Sorption of simple C-compounds and phosphate

onto pyrite is based on the notion that the pyrite has a positive surface charge and will accumulate

anionic species due to electrostatic attraction. Our research is directed to: (a) evaluate the energetics

and kinetics of the reduction of inorganic C1 compounds with the FeS-H2S/FeS2 couple as reductant

and (b) to determine the effectiveness of pyrite as a scavenger of C-compounds and phosphate.

Thermodynamic calculations were carried out to evaluate the energetics of CO2 reduction via a

sequence of reactions limited to a transfer of two electrons per step. The calculations were conducted

for a temperature range of 0 to 300 ° C (P = 300 bar). The results show that the reducing power of the

FeS-H2S/FeS2 couple drops with increasing temperature. Furthermore the first step, reduction of

CO2 to HCOOH, is energetically unfavorable. A Frontier Orbital Theory (FOT) analysis shows that the

Lowest Unoccupied Molecular Orbital of CO2 is at an energy level that would require electrons

donated from H2S to the FeS to gain energy. This energy barrier prevents facile CO2 reduction. FOT

analysis provides also insight into the facile reduction of CS2 and CO. FOT analysis may be useful as a

guide for future experimental work.

The surface chemistry of pyrite is complex. The surface charge of pyrite is negative in the absence of

added iron between pH 2 and 11, but becomes positive in the presence of dissolved ferrous iron

between pH 2-5 and above pH 8. Hence, the iron content of the Hadean ocean may play a pivotal role

in controlling sorption of C-compounds. The interactions of C-compounds with pyrite depends on

there functionality. Phosphate and phosphorylated compounds are strongly retained on pyrite, while

acetate, alanine, and glycine show little interaction. It is noteworthy that phosphate sorption onto

pyrite requires that anionic phosphate species overcome electrostatic repulsion as they approach the

pyrite surface. This indicates that the phosphate species form a chemical bond with the pyrite surface.

References:

1. Wachtershauser, G., Microbio/ogicaf Review 52:452-484 (1988).

2. Huber, C. and Wachtershauser, G., Science 276:245-247 (1997).

3. Heinen, W. and Lauwers, A. M., Origins of Life and Evolution of the Biosphere 26:131-150 (1996).

4. Keefe, A.D., Miller, S.L., McDonald, G., and Bada, J., Proceedings of the National Academy of

Science 92:11904-11906 (1995).

THE MEENTHEENA CARBONATE, ANCIENT LAKES, FACIES,

AND EXOBIOLOGY

Stanley M. Awramik*

University of California, Santa Barbara

H. Paul Buchheim

Loma Linda University

The Meentheena Carbonate Member of the Tumbiana Formation (Fortescue Group; Late Archean)

with its abundant and diverse stromatolites and rare microfossils represents an important unit with

significant exobiological implications for understanding ancient life in lakes. The Meentheena was

deposited some 2715 Ma ago within an intracratonic basin, either as one large lake over 350 km

across or ina series of smaller lakes.

A complex picture develops as one analyzes data obtained from a detailed study of the Meentheena.

A lithofacies association with repetitive cycles was identified for the unit: from base to top - oolite-flatpebble conglomerate, rippled oolite, parallel-laminated oolite/grainstone, and shale. Stromatolites

75
increaseinabundanceupwardinthecarbonate part of the lithofacies association and occur in several

sedimentary units. Some individual carbonate units and cycles of the lithofacies association could be

correlated over 16 km locally, and at least 190 km regionally. Lateral facies changes occur over short

distances; however, significant changes occur within a few km where the entire carbonate portion is

nearly replaced by shale and rippled tufaceous siltstone and sandstone. Two key stromatolites

provide marker beds permitting local and regional correlation. One, laterally-linked, low profile domes,

permits regional correlation over 190 km. The other, dense clusters of Alcheringa narrina, permits local

correlation over 16 km. The lithofacies association is interpreted as a transgressive lacustrine

sequence with upward decreasing energy and increasing depth. The basal oolite-flat-pebble

conglomerate represents a high energy shallow-water, near shore facies. Increasing depth and lower

energy levels resulted in deposition of wave-rippled oolite. The parallel-laminated oolite/grainstone

facies (with larger stromatolites) was deposited in deeper water as transgression continued. Finally,

deposition of shale dominated the system as depths increased. Dynamic fluctuations in lake depth

resulted in incompleteness of lithofacies associations. Similar lithofacies, cycles, and associations are

found in the Eocene Green River Formation, a model system for large ancient lakes.

The Meentheena and its stromatolites indicate that during the late Archean microbial life thrived in

lakes and, that despite higher atmospheric pCO2 levels, carbonates preserving aspects of this fossil

record can be widespread. It is our suggestion that the search for evidence for ancient life on Mars,

include lacustrine deposits with repeated sequences that might represent fluctuating water depths.

MARS STUDIES

H.P. Klein*

SETI Institute

This work began as an outgrowth of participation on the Russian Mars '96 mission, and was initially

directed toward two aspects of that mission: involvement in the Mars Oxidant experiment (MOx),

which was chosen to be flown on the small lander, and involvement in establishing geological criteria

of exobiological relevance for detailed study by the orbiter.

For the first of these objectives, I played a role on the science definition team, paying particular

attention to the selection of organic coatings for the MOx. For the second, in collaboration with Ron

Greeley of Arizona State University, and Drs. Dave DesMarais and Jack Farmer of NASA Ames, I

helped to assemble a list of about twenty sites on Mars for critical study by the orbiter.

With the loss of the Mars '96 mission in November 1996, further participation in that mission was

precluded. However, collaboration with Greeley has continued and was extended to include

characterization of the Ma'Adim Vallis-Gusev Crater region and of the Ares Vallis region, which was to

become the landing site for the Pathfinder spacecraft. Currently, good progress is being made in

analyzing the flooding events feeding into the Pathfinder region, and detailed mapping of the Gusev

Crater area is continuing, in addition, further analysis of the Viking orbiter data will continue, with the

objective of finding additional sites for exobiological study on Mars' surface.

76

_]-I I _
ABSTRACTS

of

POSTER PRESENTATIONS

(Shown in alphabetical order by the first author's name)

IGNEOUS ROCKS THAT SPARKLE, CRACKLE AND GLOW

Oxidizing Radicals Activated by Low Velocity Impacts

Jerome G. Borucki*, Steven J. Butow, Marshall Lis6, and Friedemann Freund

NASA Ames Research Center; SETI Institute;

Department of Physics, San Jose State University

Water dissolves in minerals that make up most common igneous and highly metamorphic. However,

the complexity of the dissolution mechanism has only recently been more fully understood. When

H20 becomes incorporated in nominally anhydrous minerals, it forms at first X-OH (with X = Si4+, AI3+

etc.), but X-OH pairs subsequently undergo an internal redox reaction into peroxy links, x/OOkx, plus

H2 These peroxy links are interesting entities: Physically, they are self-trapped pairs of positive hole

charge carriers; Chemically, they are two O- radicals held together by a short but labile O--O- bond.

The O--O- bond can be thermally broken, leading to highly mobile positive hole charge carriers.

Fracture experiments demonstrate that the shock arising from brittle fracture is enough to also cause

the O--O- bond to come apart. We set up low velocity (100 m/sec) impact experiments and found that

they produce positive hole charge carriers that propagate through our 3/4" diameter, 3" long rock core

targets at 330 m/sec. The charge carriers generate positive surface potentials in the range of +0.5 V to

+1.0 V, draw currents as high as 0.4 mA, emit electromagnetic radiation in the 1 to 40 KHz

The insets show the core with detector lay-out

.......... ....................... i ............

.-.-.-,.-.-.- (a) ....

Ch. 2: Front end ring capacitor, 200 mV/div;

Ch. 3: Back end plate capacitor, 20 mV/div;

Ch. 4: Front end light emission, 200 mV/div;

The impactor hits from the left at 100 m/sec

l 'Impact : (b) ....

[..... [ 500mY "'_/\_ : " Ch. 1

!i L'ght i Ch4

Ch.1-3: Three collector electrodes.

Ch 4: Light

79
rangeandalsoemitlight.Thelightiscausedbyplasmadischargesthatoccuralongthesurfaceand

alongtherimof our rock cores.

This work is relevant to Exobiology. When rocks are stressed during tectonic events leading to microfracture or shocked during earthquakes, positive holes will be generated. Those coming to the

surface of the rocks will act as highly oxidizing O- radicals, capable of "burning" H2 to H20 and

organics to CO2. They may have forced early Life to develop enzymatic defense mechanisms.

FAMILY CALONYMPHIDAE:

TERMITE PROTISTS RELEVANT TO EARLY EUKARYOTIC EVOLUTION

Michael Dolan and Lynn Margulis

Graduate Program in Organismic and Evolutionary Biology

University of Massachusetts, Amherst

Trichomonads are anaerobic, amitochondriate protists that comprise one of the earliest lineages of

eukaryotes. The trichomonad family Calonymphidae, found only as symbionts of termites, displays an

evolutionary sequence that can provide insight into the origin and evolution of mitosis while serving as

ideal organisms in the search for kinetosome DNA. This family has evolved from ancestral

karyomastigont-containing cells (Coronympha, Metacoronympha, Stephanonympha) in which the

nucleus reproduces as a unit with the mastigont structures (kinetosomes and undulipodia) to the

partial separation of nucleus from kinetosomes (Calonympha) to the complete removal of nucleus from

kinetosomes (Snyderella). Calonympha and Snyderella are ideal organisms for the search for

kinetosome DNA in that they lack mitochondria, and have cortical kinetosomes separated from nuclei,

which can function as internal controls for the presence of DNA.

An 8 minute video showing each of the genera in this family will be presented by Lynn Rothschild*.

HYDROTHERMAL PROSPECTING ON MARS

Jack D. Farmer*

NASA Ames Research Center

On Earth, the surface expression of hydrothermal activity varies greatly in relationship to such things

as the tectonic setting, geothermal gradient, geohydrology and secular variations in climate. Our

knowledge of the geological expression and spatial localization of hydrothermal systems and their

historical importance in the thermal history of Mars is presently poorly constrained and must await a

more detailed understanding of martian surface geology and its evolution. Nevertheless,

hydrothermal processes have been suggested to explain a number of recent observations for Mars,

including hydrous mineral assemblages and D/H ratios of water extracted from SNC meteorites, as a

mechanism for the removal of CO2 from the martian atmosphere and its sequestering in the crust as

carbonates, and the origin of nontronite clays in martian dust and iron oxide-rich spectral units on the

floors of some chasmata. Numerous examples have been noted of martian channels formed by

discharges of subsurface water, and hydrothermal processes are a suggested mechanism for aquifer

recharge needed to sustain long term erosion by sapping channels.

8O

I • I(
Simple channel systems associated with potential heat sources, such as impact craters or shallow

igneous intrusives and volcanic constructs, provide the present focus in targeting sites for

hydrothermal prospecting during upcoming mission opportunities. Most of the work to date has been

based on visible imaging obtained by Viking. But reliable site evaluations also require information

about surface composition. A preferred method is high spatial resolution, mid- or near-IR

spectroscopy, tools of choice for mineralogical mapping on Earth. Comparative studies of Mars

imaging data and hydrothermal systems on Earth have focused our site selection efforts on a number

of high priority geotectonic terranes that appear to offer the best targets for ancient hydrothermal

systems on Mars. These include the following: impact structures, rifted basins, areas flanking volcanic

constructs and shallow intrusives, caldera floor deposits, and features formed by volcano-ground ice

interactions in sub-glacial and periglacial environments. Site lists organized around these terrane

types will provide targets for orbital imaging during the MGS '96 mission and beyond. The new orbital

data will provide a basis for refining site selection priorities for landed missions in 2001 and 2003, as

well as a sample return mission in 2005.

ORGANIC CARBON ASSOCIATED WITH CARBONATE IN ALH84001

G.J. Flynn*

SUNY-Plattsburgh

L.P. Keller and M.A. Miller

MVA Inc.

McKay et al. /1/ suggest the ALH84001 meteorite contains evidence suggesting ancient biological

activity on Mars. One line of evidence is the concentration of polycyclic aromatic hydrocarbons

(PAHs), frequently produced by the decay of living material, occurring in close proximity to magnetite

and sulfide similar in size and shape to those produced by terrestrial bacteria/1/.

We employed the Scanning Transmission X-Ray Microscope at the National Synchrotron Light Source

(NSLS) at Brookhaven National Laboratory to determine the bonding state(s) and the spatial

distribution of the carbon in ultramicrotome thin-sections of carbonates and the rims on these

carbonates from ALH84001 /2/. Both the carbonate and the rim sections contained carbon-rich

regions (other than carbonate), but each gave a different C-XANES spectrum, suggesting the carbonbearing compound was different in the rim and the carbonate/2/. We then examined the same

sections using a Spectra-Tech micro-Fourier Transform Infrared (u-FTIR) spectrometer, on an infrared

beamline at the NSLS, to identify the carbon compounds.

The u-FTIR spectra of the rim samples showed a broad absorption near 1000 cm-1, characteristic of

silicate glass, and two weaker features at 2918 cm-1 and 2850 cm-1. These two features are

consistent in position and relative depths with the symmetric and asymmetric stretching vibrations of

the C-H2 in aliphatic hydrocarbons. The u-FTIR spectrum of the carbonate globule showed a narrow

absorption at -1500 cm-1 , characteristic of carbonate, and a weaker absorption at 2964 cm-1. Two

even weaker features appear at 2920 cm -1 and 2850 cm-1. The feature at 2960 cm-1 is characteristic

of the C-H3 asymmetrical stretching vibration. Although a weaker C-H3 symmetrical stretching vibration

generally occurs near 2870 cm-1, this feature is absent in the carbonate globule spectrum, and is

suppressed in certain compounds containing C-H3 groups. One particularly good spectrum of the

carbonate globule sample appears to show a weak, broad absorption over the range 2990 cm-1 and

3060 cm -1. If real, this feature could indicate the detection of C-H stretching vibrations of a mixture of

PAHs, which would have an absorption near 3030 cm-1 .

81
These preliminary results confirm that high concentrations of organic carbon are associated with

carbonate globules and rims in ALH84001, and further confirm the STXM observation that the rim and

the carbonate globule contain different types of carbon. The results seem to rule out the simplest

form of organic contamination of ALH84001, simple evaporation of an organic-rich fluid, which would

be expected to leave the same residue in both the carbonate globules and the adjacent rim material.

References:

1. McKay, D.S., et al. Science 273:924-927 (1996).

2. Flynn, G.J., et al., Meteoritics 32:A46-A47 (1997).

THE EFFECTS OF AMONG SITE RATE VARIATION ON

PHYLOGENETIC RECONSTRUCTION FROM AMINO ACID SEQUENCES

J. Peter Gogarten*

University of Connecticut

Olga Zhaxybayeva

Kazakh State National University (Planetary Biology Institute fellow)

Systematic artifacts have long been recognized as important complications in phylogenetic

reconstruction. The most serious of these is long branch attraction. Two scenarios can yield long

branches: (A) some sequences evolve faster due to higher substitution rates; or (B) the long

branches can be due to the absence of side branches in some lineages.

Protein sequences are useful for comparisons between distantly related sequences because their 20

letter alphabet in conjunction with substitution bias facilitates the alignment of divergent sequences.

Sequence alignment is further aided by highly conserved residues that remain unchanged even

between distantly related proteins. In case of nucleotide sequences simulations have been

performed to estimate the effect of among site rate variation (ASRV) on phylogenetic inference;

however, at present the effect of ASRV on long branch attraction on protein based phylogenies has

not been explored.

Using computer simulation to generate sequence data for protein families, we studied the influence of

among site rate variation on the performance of phylogenetic reconstruction. The algorithm used for

simulation incorporates both among site rate variation and substitution bias. Among site rate variation

was simulated using discrete approximations to continuous Gamma distributions with different shape

parameters. In the chosen parameter range the simulation was shown to be consistent with maximum

likelihood estimation of the shape parameter. The simulation utilized different tree topologies to

explore the effect of long branch attraction with data that incorporated substitution bias and different

degrees of among site rate variation. While all methods tested showed errors due to long branch

attraction under extreme conditions, maximum likelihood was by far the most successful in accurately

resolving deep phylogenies.

Using protein parsimony long branch attraction already became a problem with modest differences in

rate (ratio 1:3) and sequences that were about 50% identical, whereas maximum likelihood methods

still performed well with realistic values of among site rate variation and branch lengths ratios of 1:12

(sequences less than 30% identical).

In the absence of fast evolving lineages (i.e., long branches were due to the absence of side

branches only) all tested algorithms performed well even when sequences were below 20% identity,

82

-'I-11 I
and even when the alignment step was part of the reconstruction process. In contrast to findings

obtained with nucleotide sequences, ASRV was found to facilitate phylogenetic reconstruction,

especially if the alignment step is included.

ABUNDANT VIRUSES IN ANTARCTIC LAKES

Ray Kepner* and Bob Wharton

Desert Research Institute

Curtis Suttle

University of British Columbia

Perennially ice-covered Antarctic lakes exemplify microbially-dominated ecosystems existing at the

extremes of conditions found on our planet. Viruses are the simplest, and conceivably most ancient,

particles possessing the fundamental properties of living systems and may have been the original

and/or only 'predators' near the dawn of life. It is now widely accepted that viruses are ubiquitous and

abundant components of many extant aquatic ecosystems, where they are involved in gene transfer

and may account for a significant fraction of microbial mortality. Current research is directed towards

improving our understanding of forces operating on microbial evolution in early-Earth environments

through the study of analogous systems.

In four of the lakes found in the McMurdo Dry Valleys, southern Victoria Land, Antarctica (i.e., Lakes

Hoare, Fryxell, Bonney ,and Joyce), planktonic, extracellular virus-like particles (VLPs) are plentiful. In

two of these lakes, large, possibly novel icosahedral forms have been observed by transmission

electron microscopy (TEM), and these viruses are morphologically similar to double-stranded DNA

(dsDNA) viruses that are known to infect algae and protozoa but which have not been fully

characterized. In one lake thus far examined, viruses also appear to have potentially high production

potential. We summarize data on water column VLP distributions in four lakes collected during the

1995/96 and 1996/97 austral summer field seasons. Based on our data, we suggest that virallymediated mortality may be a major biotic factor regulating the abundance of many of the microbes in

these extreme environments. In addition, Antarctic lakes may constitute a large reservoir for

undiscovered viruses possessing novel characteristics.

EFFECT OF LEAVING GROUP ON THE DIMERIZATION OF

PHOSPHOIMIDAZOLIDE-ACTIVATED NUCLEOTIDES

Lynn F. Lee* and Anastassia Kanavarioti

Department of Chemistry and Biochemistry

University of California, Santa Cruz

The discovery that RNA displays catalytic properties in conjunction with information transfer abilities

has accelerated interest in RNA's role in the origins of life. For the RNA world hypothesis to be

plausible, it is important to establish a mechanism for the non-enzymatic oligonucleotide synthesis.

Before oligomerization can occur in any proposed mechanism, the initial steps must include the

dimerization of monomers, and it is within this area that this study focuses upon. The broad goal of this

project is to elucidate the factors that influence the dimerization process, thus presenting possible

conditions where a substantial production of the intemucleotide-linked dimers is viable.

83
Activatedribomononucleotides(seestructure)arebuildingblocksin non-enzymaticpolynucleotide

synthesis.In aqueoussolutions,thesesubstratesdecomposeto a varietyof products,including

nucleotide5'-monophosphate(5'NMP)by cleavageof P-Nbondandintemucleotide-linkeddimers

(pNpN)byreactionof theribosehydroxylof onemoleculewiththeP-Nbondof another.Imidazoleand2-methylimidazole-activated nucleotideswereinvestigated,andtheeffectsof theseactivating

groupsontheproductdistributionisthefocusof thisreport.Notonlydoestheleavinggrouphavea

dramaticeffectonthe relativeproductdistributionsof 5'NMPandpNpN,butit alsoinfluencesthe

dimerdistributionofpNpNandpyrophosphate-linkedN5'ppN.Moresurprisingly,thepNpNdimersare

significantlyenhancedat the expenseof N5'ppNwith 2-methylimidazolewhen comparedto

imidazole.

/=_ OII

HO OH

R=H, CH 3

N = Uracil, Cytosine,

Adenine or Guanine

HORIZONTAL GENE TRANSFER OF ARCHAEAL GENES

INTO THE DEINOCOCCACEAE

Ryan Murphy, Lorraine Olendzenski, Scott MacNamara, and J.Peter Gogarten*

University of Connecticut

Members of the deep branching bacterial lineage Deinococcaceae (e.g. Thermus and Deinococcus)

are classified as Bacteria based on cell wall and lipid composition, and ribosomal RNA sequence. In

contrast, molecular phylogenetic analysis clearly shows that the catalytic and non-catalytic ATPase

subunits found in Thermus thermophilus and Deinococcus radiodurans are archaeal or vacuolar type

(AN-ATPases). The best explanation for the presence of the AN-type ATPase operon in Thermus

and Deinococcus is horizontal gene transfer from the archaeal/eukaryotic lineage into the base of this

bacterial lineage. Evidence which supports the transfer of other archaeal/eukaryotic genes into this

lineage include:

• A Thermus prolyl tRNA synthetase fragment, first detected and isolated from a genomic

library using a probe made against Thermoplasma acidophilum DNA, shows closest

similarity to eukaryotic and archaeal homologues by BLASTX search.

• Both the Thermus prolyl tRNA synthetase fragment and its full length Deinococcus

homologue (obtained from the TIGR database) group among archaeal and eukaryotic

homologues with distance and quartet puzzling maximum likelihood methods.

• The next gene downstream from the A-ATPase operon of Sulofolobus sulfotaricus is

prolyl tRNA synthetase (pers. comm., M. Ragan, D. Fague, Marine Resources Center,

Halifax, NS)

• Although the data set is very complicated and suggests instances of paralogy, gene

conversion and mis-assignment of function, malate dehydrogenase from Thermus and

Deinococcus groups with other eukaryotic cytoplasmic MDH homologues rather than with

the majority of bacterial sequences

Our findings indicate that these genes were horizontally transferred early in the evolution of the

Deinococcaceae. The donating organism groups close to the root of the archaeal/eucaryal domains.

84
The transferredgenescannotbe characterizedby similarfunction,but their proximityin the

Sulfolobus genome suggests that these genes might have been neighbors also in the genome of

the donating organism.

CHICXULUB IMPACT EJECTA IN BELIZE:

INSIGHTS INTO THE ROLE OF ATMOSPHERES AND VOLATILES

IN LARGE IMPACTS

Adriana C. Ocampo*

Jet Propulsion Laboratory, California Institute of Technology

Kevin O. Pope

Geo Eco Arc Research

Alfred G. Fischer

Department of Earth Sciences, University of Southern California

John R. Marshall

SETI Institute

The mass extinction event at the Cretaceous/Tertiary boundary has been linked to the release of

volatiles by the Chicxulub impact into the carbonate platform of northern Yucatan, Mexico. Chicxulub

ejecta deposits in Belize provide the closest exposures of ejecta to the crater and the only known

exposures of proximal ejecta deposited in a terrestrial environment. A quarry on Albion Island in

northern Belize exposes ejecta deposits that are composed of a basal, -1-m-thick clay and dolomite

Spheroid Bed overlain by a -15-m-thick coarse Diamictite Bed. Many and perhaps most of the clay

spheroids are altered glass. Many dolomite spheroids have concentric layers and angular cores and

are probably of accretionary lapilli origin. A slight iridium concentration (111-152 parts/trillion) was

detected in the base of the Spheroid Bed. The Diamictite Bed contains -10% altered glass, rare

shocked quartz, 3-8 m diameter boulders, and striated and polished cobbles, one with a penetrating

rock chip that plastically deformed the cobble. Chicxulub ejecta is exposed in several roadside

quarries in the Cayo District of central Belize. Here, the upper surface of the Late Cretaceous

carbonate platform is a highly irregular and extensively recrystallized horizon possibly representing

deep karst weathering. Approximately 30 m of diamictite overlies this horizon with a texture similar to

the Diamictite Bed at the Albion quarry, but with a more diverse lithology. In three locations the Cayo

diamictites contain red clay layers with abundant polished and striated limestone pebbles and cobbles

called Pook's Pebbles, several of which have penetrating rock chips and ablated surfaces.

We interpret the Albion Spheroid Bed as a deposit from the impact vapor plume that entrained fine

debris from the ejecta curtain, but may also contain carbonate vapor condensates. The Albion and

Cayo diamictites are the result of a turbulent flow induced by the interaction between the ejecta

curtain and the atmosphere. The polished, striated, and ablated Pook's Pebbles are interpreted as

high altitude ballistic ejecta that were partially melted upon reentry through the atmosphere. The

Belize deposits provide valuable information on vapor plume dynamics and ejecta-atmosphere

interactions that can be used to constrain impact models. They are also important for interpreting

ejecta on other planets, especially the fluidized ejecta blankets on Mars, which may be a good

analogue for the Belize ejecta deposits.

85
THE PHYLOGENETIC POSITION OF THE MICROSPORIDIA:

DEATH OF AN EARLY BRANCHING LINEAGE?

Lorraine Olendzenski, Elena Hilario, and J.Peter Gogarten*

University of Connecticut

Phylogenetic analyses based on small subunit (SSU) ribosomal RNA sequences consistently group

certain unicellular amitochondriate eukaryotes at the base of the eukaryotic lineage. These include

the diplomonads, microsporidia and trichomonads and these organisms are believed to represent

extant relatives of the oldest eukaryotes. The exact branching order of these lineages, however, is

not consistent in all analyses and changes depend on which types of analyses are run and which

organisms are included. Recently, the phylogenetic position of microsporidia has been called into

question. Although SSU rRNA analyses suggest that these organisms are perhaps the most basal

eukaryotic lineage, recent evidence, including phylogenetic analyses of _-tubulin sequences, heat

shock proteins, RNA polymerases and reassessment of their meiotic life cycle, suggests that

microsporidia may be most closely related to the fungi (for a recent summary see M. Mueller, "What are

the Microsporidia?"Parasitologv Today, in press, Oct. 1997).

Using vacuolar and archaeal type ATPase catalytic subunits we show that for this molecular marker the

placement of the microsporidia at the bottom of the eukaryotic domain is not based on strong

phylogenetic evidence. In agreement with SSU rRNA data distance analysis places Nosema on a long

branch toward the base of the eukaryotic lineage, although the diplomonacl Giardia remains the

deepest eukaryotic branch. The deep branching is supported through bootstrap analyses; however,

comparative analysis of altemative tree topologies employing maximum likelihood ratio tests indicates

that the deep placement of the Microsporidia might be an artifact due to long branch attraction and

peculiar substitution patterns in this lineage. Note that the same type of test provides strong support

for the earlier branching of Giardia. In contrast, using maximum likelihood ratio testing on SSU rRNA

phylogenies the placement of the microsporidia in the eukaryotic crown group together with fungi is

significantly less likely than the deeper branching of the microsporidia. However, when the placement

of the branch leading to the microsporidia is varied, the placement with the fungi corresponds to a

local maximum of likelihood, suggesting that SSU rRNA and the different protein based phylogenies

reflect the same evolutionary history. The contradiction between the different molecular phylogenies

apparently is not due to a horizontal gene transfer of some protein encoding genes from higher

eukaryotes into the microsporidia.

METABOLIC ACTIVITY OF MICROORGANISMS IN PERMAFROST

E.M. Rivkina 1,2, E.I. Friedmann 1., C.P. McKay 3, and A.D. Gilichinsky 2

1Florida State University; 2Russian Academy of Science Pushchino, Russia;

3NASA Ames Research Center

The presence of significant numbers of bacteria in 3-5 million year old permafrost in North Polar

regions and, according to recent findings, in Antarctica poses the question whether these organisms

are in a state of "anabiosis" or are metabolically active. Although several reports of such activity at

subzero temperatures exists in literature, quantitative studies have been lacking. The temperature of

permafrost in N.E. Siberia is around -10 ° C while in the Antarctic McMurdo Dry Valleys region it varies

between -18 ° C and -27 ° C.

We measured the incorporation of 14C labeled acetate into lipids by bacteria in N.E. Siberian

permafrost during an incub,ation period of 18 months at temperatures between +5 and -20 ° C. In

thawed samples (+5 and 0° C) the labeled acetate was exhausted after 200-300 days. In frozen soil,

86

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incorporation started after an over-one-month to six-months lag phase, increased until 200-300 days

and appeared to stabilize (became non-measurable by our methods) after about 300 days. After 18

months of incubation the incorporation of 14C into lipids represented 1245, 472 and 50 cpm for

samples at -1.5, -5.0, and -10 ° C and very low but measurable counts, several cpm over the zero

point, at -15.0 and -20.0 ° C.

We conclude that metabolic activity in permafrost is possible until at least -20 ° C. After freezing, such

activity stabilizes at a level which is very low, yet sufficient to ensure repair of cell damage due to

radiation and racemization.

SINGLE

WHAT ARE THE CARRIERS OF THE UIRS?

PHOTON INFRARED EMISSION SPECTROSCOPY

(SPIRES) OF UV-EXCITED PAHS

D.R. Wagner, D.J. Cook, and R.J. Saykally*

College of Chemistry, University of California at Berkeley

Identification of the carriers of the UIR bands remains a central problem in astrophysics. The currently

available data generally support the "PAH Model" for UIR production, although identification of any

specific carrier molecules has not been accomplished.

We have developed a new experiment for addressing this problem. Simultaneous desorption and

excitation of PAH molecules in a cryogenic vacuum chamber is followed by time resolved detection of

the dispersed infrared fluorescence. The very weak transient signals are detected by a novel liquid

helium cooled spectrometer featuring a single photon counting BIB array.

The entire UIR spectral region (3-15 _m) was monitored for a variety of small to medium sized PAHs

(naphthalene, phenanthrene, pyrene, perylene, coronene) as well as heterosubstituted/functionalized PAHs (2-methyl-naphthalene, 2-methyl-phenanthrene, phenanthridine,

dibenzofuran). While a general resemblance to the UIR bands was noted, major discrepancies in

wavelength and relative intensities of the observed bands indicate that none of these PAHs are major

carriers of the UIRs.

Further experiments are in progress to test PAH ions as possible UIR carriers.

References:

1. S. Schlemmer, D.J. Cook, J.A. Harrison, B. Wurfel, W. Chapman, and R.J. Saykally Science

265:1686-1689 (1994).

2. D.J. Cook, S. Schiemmer, N. Balucani, D. R. Wagner, B. Steiner, and R.J. Saykally Nature 380:227

(1996).

3. D.J. Cook and R.J. Saykally, Astrophys. J. (accepted 1997).

4. D.J. Cook, S. Schlemmer, N. Bulacani, D.R. Wagner, J.A. Harrison, B. Steiner, and R.J. Saykally J.

Phys. Chem. A (submitted 1997).

87
STABLE CARBON ISOTOPE COMPOSITION

OF CYANOBACTERIAL AND CHLOROFLEXUS BIOMARKERS

IN HOT SPRING MATS CONSTRUCTED BY

OXYGENIC AND/OR ANOXYGENIC PHOTOTROPHS

David M. Ward*

Department of Microbiology, Montana State University

Marcel van der Meer and Jan de Leeuw

Netherlands Institute of Sea Research

Modern microbial mats are studied as analogs of stromatolites, the predominant surviving fossils of

Precambrian microbial life. Mats which occur in hot springs are among the best-studied model

systems--understanding them gives insight as to the composition, structure and function of microbial

communities that might have once predominated Earth's biota, and consequently its

biogeochemistry. Most modern mats, including those in hot spring, are constructed by cyanobacteria,

which are thought to cross-feed photosynthate to co-occurring green non-sulfur bacteria resembling

Chloroflexus. However, some geothermal mats are constructed solely by Chloroflexus in the absence

of cyanobacteria. These are of particular evolutionary interest as Chloroflexus, being more primordial

than cyanobacteria, might have constructed the earliest stromatolites. This would have direct

implications on whether the occurrence of stromatolites indicates the availability of biogenic oxygen

on Earth, since green non-sulfur bacteria do not produce oxygen during photosynthesis.

We hypothesized that the stable carbon isotope signatures of Chloroflexus biomarkers should be

different when it is growing alone (i.e., photoautotrophically using its unique CO2 fixation pathway) as

compared to when it is cross-fed by cyanobacteria (i.e., photoheterotrophically; assuming that "you

are what you eat," its isotopic signature should be controlled by the cyanobacterial Calvin Cycle).

Isotope ratio monitoring-gas chromatography was used to compare the isotopic compositions of lipid

biomarkers in Chloroflexus mats and cyanobacterial mats. Chloroflexus mats are found in sulfidic

carbonate-rich springs in the Mammoth Terraces Group, Yellowstone National Park; cyanobacterial

mats occur downstream in the same springs. Chloroflexus biomarkers in the Chloroflexus mats were

isotopically heavier than were cyanobacterial biomarkers in the cyanobacterial mats, consistent with

the predominance of different autotrophic pathways. Chloroflexus biomarkers in the cyanobacterial

mats were isotopically lighter than in the Chloroflexus mats, but were still substantially heavier than

expected if Chloroflexus were predominantly cross-fed photosynthate from cyanobacteria. We infer

that Chloroflexus is growing mixotrophically in these cyanobacterial mats, with photoautotrophy

possibly supported by small amounts of primary sulfide remaining above the mat, or by biogenic

sulfide produced within the mats.

MARTIAN PALEOLAKE SEDIMENTS AND TERRESTRIAL ANALOGS:

EXTANT AND EXTINCT ICE-COVERED LAKES

Robert A. Wharton Jr.* and Peter T. Doran

Desert Research Institute

Images of purported fluvial systems on Mars suggest that there must have existed downstream

locations where water pooled (e.g. Valles Marineris, Margarifter Sinus, Ma'Adim Vallis/Gusev Crater

system), and the sediment load deposited (i.e. lakes). As the martian climate cooled, ice-covered

lakes probably persisted as viable liquid water habitats for a long period of time. For this reason,

perennially ice-covered lakes found in the polar regions are considered excellent analogs of potential

past martian environments. Our research has focused on defining these extreme terrestrial habitats,

88

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and the deposits they leave behind so that future Mars missions will be better able to make inference

from lacustrine deposits discovered.

In the McMurdo Dry Valleys of East Antarctica we are presently concentrating on the controls of

isotopic signatures left in the lake and deltaic sediments of the perennially ice-covered lakes. This

research has led to the discovery of a paleoproductivity signal in the sediments. Organic mats in highly

productive (shallow) areas exhibit decreased fractionation of carbon isotopes due to a diffusion

limitation. Deep water sediments exhibit a more standard RUBISCO fractionation. This relationship

breaks down in regions of stream inflow where environmental variability appears to be enforcing some

influence on fractionation. Our upcoming field season will focus on this phenomenon so that deltaic

sediments can better be used to elucidate paleoenvironmental information.

In order to define the succession of perennially ice-covered lakes we have investigated lakes in the

high Arctic that occasionally retain their ice cover through the summer, and have located an Antarcticlike perennially ice covered lake in the Canadian high Arctic. Future investigation of this lake will tell us

about how standard the Antarctic perennially ice-covered lake communities are, at least on this planet.

We have also initiated investigations of a new lake environment in the Antarctic. Lake Vida is one of

the largest lakes in the dry valleys, yet was previously thought to be frozen solid. Our recent field

investigations revealed this lake to have an -19 m ice cover over a hypersaline water body of

undetermined depth. Ice cores retrieved contain microbial mat throughout, and once thawed,

heterotrophic and autotrophic microbes are metabolically active. Samples of the sub-ice brine have

not yet been obtained. Further investigation of this lake type will define a new extreme environment,

and answer questions about the fate of a lake community upon cold termination of the lake.

THE OXIDATIVE STRATIGRAPHY OF THE MARTIAN REGOLITH

Aaron Zent*

NASA Ames Research Center

We explore the role of impact cratering on the redistribution of oxidized materials on the martian

surface. Although oxidation probably results from diffusion of photochemcally-produced odd-H and O

species, a diffusion/reaction model cannot predict the oxidative stratigraphy of Mars because the

stratigraphic column itself is not stable. Both impact cratering and aeolian redistribution stir the

regolith, burying oxidized surfaces and exposing reduced material to the atmosphere. Recovery of

reducing materials from below the oxidized zone of the martian regolith is contingent upon

understanding the chemical process responsible for the oxidation and the physical processes that stir

the regolith.

The cratering/oxidation model assumes that the regolith is completely oxidized through depth Ze,

below which it retains its reducing nature. The model uses the actual cratering size-frequency

distribution to calculate regolith gardening.

The probability of being missed by an impact is the ratio of the total area to the area of the crater, and

the probability of being missed by n impact craters of the same size is (ratio) n. The probability of being

struck at least once is then 1 - (ratio) n. The probability of being buried by ejecta is estimated by a similar

ratio of areas. The relative areas excavated and buried are tracked continuously, and the relative

abundance of oxidized material is tracked with depth. At small sizes, the number of impacts can be

extremely high, and the probability of a random point being affected by n impacts approaches 1.

89
We havemeasured the lifetime of H20 2 on basaltic material at 215 ° K, and found it to be - 105

seconds; the corresponding extinction depth, Ze is 7 ram. The oxidation profile of the regolith is

shown in Figure 1, assuming that only the upper 7 mm of the regolith are actively oxidized, but that a

cratering flux representative of the heaviest Noachian cratering has stirred the regolith. Because

roughly the upper 100 m has been excavated and buried many times, all material has visited the upper

7 mm and been oxidized. Return of reducing materials requires penetration to depths of 200 m. In

Figure 2, the cratering record of the Chryse region is used. Cratering is ineffective in mixing the

regolith after the end of heavy bombardment. The onset of oxidizing atmospheric conditions needs to

be determined to establish the oxidized depth of the martian regolith.

Fig. 1

0.8 tO

o.s

x

O

o o.4

w 0.2 O

Degree of Oxidation

.................. 1 ...................... i _ ! =-. '...................... '...................... ',;3;-

i]iiiil]i]i]]il]iiiiiii,, ,, ,

* Ititi ................ i........................ _........... ._'_-"c_'_'-

IIIIIi J _.i=°._'_m

 l HIr; ........... i.....................i..........

;=....................... •...... :......................... _........................ . ......................

_....................... _':..... =!':..................... hL/LLI _] J l[_i[$i ....................... "=ii ...................... '

0 100 200 I00 400 500

Depth (m)

Fig. 2 Degree of Oxidation

..............................................b-L_-

C - 8.86x10 _

_'_' ............................................................... i............... "_'_ _tse"-E_ase.--

ilt i i Ejecta FulI._ Oxidized

....•t .....,...-.,-..--.i...,.,......,...--.,.....J...:.=-::; ............ !..................... ;..:-- ...............

0 2 4 6 8 10

Depth (m)

¢: 0.8

0

c_

"O

"R o.s

o

_ 0.4

o

C3 0.2

9O

! BIT
ATTENDEES

Sara Acevedo

MS 245-1

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-4223

FAX# 650-604-6779

SACEVEDO @MAIL.ARC.NASA.GOV

Emma Bakes

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0787

FAX# 650-604-6779

bakes @dusty.arc, nasa.gov

Joel Achenbach

The Washington Post

1150 15th St. NW

Washington, D.C. 20071

TEL# 202-994-1589

ach enbachj @washpost.com

Louis Allamandola

MS 245-6

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6501

FAX# 650-604-6779

allamando/a @SSA 1.ARC.NASA.GOV

Gustaf Arrhenius

Scripps Institution of Oceanography

University of California

at San Diego

La Jolla CA 92093-0220

TEL# 619-534-2961

FAX# 619-534-0784 or 4-2961

ARRHENIUS@ UCSD.EDU

Stanley Awramik

Department of Geological Sciences

University of California

Santa Barbara CA 93106

TEL# 805-893-3830

FAX# 805-893-2314

awramik@ magic.geol.ucsb.edu

Jeff Bada

Scripps Institution of Oceanography

University of California

at San Diego

La Jolla CA 92093-0212

TEL# 619-534-4258

FAX# 619-534-0784

JBADA@ UCSD.EDU

Brad Bebout

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-3227

FAX# 650-604-1088

bbebout @mail.arc.nasa.gov

Robbins Bell

MS245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0788

Steven Benner

Department of Chemistry

University of Florida

PO Box 117200

Gainesville FL 32611-7200

TEL# 352-392-7773

benner@chem.ufl.edu

Max Bernstein

MS 245-6

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-4811

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maxb @SSA1 .ARC;NASA.GOV

Janice Bishop

MS 239-4

NASA Ames Research Center

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TEL# 650-604-0297

FAX# 650-604-1088

jbishop @mail.arc.nasa.gov

91
DavidBlake

MS 239-4

NASA Ames Research Center

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TEL# 650-604-4816

FAX# 650-604-1088

DBLAKE @maiI.ARC.NASA.GOV

Geoffrey Blake

Division of Geological

and Planetary Sciences

California Institute of Technology

Pasadena CA 91125

TEL# 626-395-6296

FAX# 626-585-1917

gab@gps.caltech.edu

Ben Bova

207 Sedgwick Road

West Hartford CT 06107

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Boval @aol.com

Paul Braterman

University of North Texas

College of Arts and Sciences

Dept. of Chemistry

P.O. Box 5068

Denton TX 76203-0068

TEL# 940-565-2357

FAX# 940-565-4824

psb@ unt.edu

Carrine Blank

Dept. of Molecular and Cellular Biology

Pace Lab

281 Koshland Hall

University of California, Berkeley

Berkeley CA 94706

TEL# 510-643-2034

FAX# 510-642-4995

cblan k@natu re.berkeley.ed u

Jennifer Blank

Department of Geology and Geophysics

301 McCone Hall

University of California

Berkeley CA 94720-4767

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jenblank@ popd.ix.netcom.com

Robert Blankenship

Department of Chemistry

Arizona State University

Tempe AZ 85287-1604

TEL# 602-965-1439

FAX# 602-965-2747

Blankenship@ASU.EDU

Jerome Borucki

MS 239-12

NASA Ames Research Center

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Geoffrey Briggs

MS 245-1

NASA Ames Research Center

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gbriggs @mail.arc.nasa.gov

Theodore Bunch

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5909

FAX# 650-604-6779

tbunch @mail.arc.nasa.gov

Steve Butow

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035

TEL# 650-604-3278

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sbutow @mail.arc.nasa.gov

Nathalie Cabrol

MS 245-3

NASA Ames Research Center

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ncabrol@mail.arc.nasa.gov

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Sherry Cady

MS 239--4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-3826

FAX# 650-604-1088

scady@ mail.arc.nasa.gov

Christopher Chyba

Department of Planetary Sciences

University of Arizona

Tucson AZ 85721-0092

TEL# 520-621-6362

FAX# 520-621-4933

chyba@lpl.arizona.edu

Lawrence Caroff

MS 239-23

NASA Ames Research Center

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TEL# 650-604-1545

Icaroff @mail.arc.nasa.gov

Sherwood Chang

MS 239-4

NASA Ames Research Center

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SCHANG @maiI.ARC.NASA.GOV

Steven Charnley

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Jean Chiar

MS 245-3

NASA Ames Research Center

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chiar @dusty.arc.nasa.gov

Glennda Chui

San Jose Mercury News

750 Ridder Park Drive

San Jose CA 95190

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gchui @sjme rcury.com

George Cooper

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5968

FAX# 650-604-1088

gcooper@ mail.arc.nasa.gov

John Cronin

Dept. of Chemistry and Biochemistry

Arizona State University

Tempe AZ 85287-1604

TEL# 602-965-3728

FAX# 602-965-2747

CRONIN @ASUCHM.LA.ASU.EDU

Ken Cullings

San Francisco State University

1600 Holloway Avenue

San Francisco CA 94132

cullings @sfsu.edu

Leonard David

Space Data Resources & Information

P.O. Box 23883

Washington DC 20026-3883

TEL# 202-546-0363

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Idavid @delphi.corn

Wanda Davis

MS 245-3

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93
DavidDeamer

Dept. of Chemistry and Biochemistry

34-145

University of California

Santa Cruz CA 95064

TEL# 408-459-5158

FAX# 408-459-5158

DEAMER@ HYDROGEN.UCSC.EDU

David Des Marais

MS 239-4

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DDESMARAIS @maiI.ARC.NASA.GOV

Donald DeVincenzi

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Steven Dick

US Naval Observatory

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Washington DC 20392

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James Dickens

Univ. of Massachusettes

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619 E GRC/N Pleasant & Gov.

Amherst MA 01003

TEL# 413-545-0789

FAX# 413-545-4223

dickens @swas.phast.umass.edu

Michael Dolan

Planetary Biology Internship

Biology Program

University of Massachusetts

Amherst MA 01003-5810

TEL# 413-545-3244

FAX# 413-545-3243

pbi @bio.umass.edu

F. Ronald Dutcher

SPACELINE

Department of Physiology

USUHS

4301 Jones Bridge Road

Bethesda MD 20814

TEL# 301-295-2708

FAX# 301-295-5271

fdutcher@ mx3.usuhs.mil

Jason Dworkin

MS 245-6

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dworkin @ssal .arc.nasa.gov

Douglas Erwin

Smithsonian Institute

Dept. of Paleobiology, MRC-121

Washington DC 20560

TEL# 202-357-2053

FAX# 202-707-8476

erwin, doug @nmnh.si.edu

Jack Farmer

MS 239-4

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James Ferris

Department of Chemistry

Rensselaer Polytechnic Institute

110 8th Street

Troy NY 12180-3590

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FERRIJ@RPI.EDU

Timothy Ferris

KCTS

1815 Grant St.

Berkeley CA 94703

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George Flynn

Plattsburgh State Univ. of New York

Department of Physics

Plattsburgh NY 12901

TEL# 518-564-3163

FAX# 518-564-3152

flynngj @splava.cc.plattsburgh.edu

Everett Gibson, Jr.

SN4 Planetary Sciences Branch

NASA Johnson Space Center

Houston TX 77058

TEL# 281-483-6224

FAX# 281-483-5347

EGIBSON @EMS.JSC.NASA.GOV

Marina Fomenkova

Center Astrophysics and Space Sciences

University of California

at San Diego

La Jolla CA 92093-0111

TEL# 619-534-6163

FAX# 619-534-7051

mfomenkova @ucsd.edu

J. Peter Gogarten

Department of Molecular and Cell Biology

University of Connecticut

75 North Eagleville Road

Storrs CT 06269-3044

TEL# 860-486-4061

FAX# 860-486-1784

GOGARTEN @UCONNVM.UCONN.EDU

George Fox

3802 Holder Forest Drive

Houston TX 77088

TEL# 713-743-8363

FAX# 713-743-8351

FOX@UH.EDU

James Fredrickson

MS K4-06

Pacific NW National Laboratory

Batelle Memorial Institute

P.O. Box 999

Richland WA 99352-0999

TEL# 509-375-3908

FAX# 509-375-6666

jim.fredrickson @pnl.gov

Edmond Grin

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0312

FAX# 650-604-6779

egrin @mail.arc.nasa.gov

Valeriy Grushin

Center for Astrophysics & Space Sciences,

University of California

at San Diego

La Jolla CA 92093-0111

TEL# 619-534-6163

FAX# 619-534-7051

mfomenkova @UCSD.edu

0424

Friedemann Freund

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5183

FAX# 650-604-1088

ffreund @mail.arc.nasa.gov

Virginia Gulick

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0781

FAX# 650-604-6779

vgu[ick@ mail.arc.nasa.gov

E. Imre Friedmann

Department of Biological Sciences

B-142

Florida State University

Tallahassee FL 32306-2043

TEL# 850-644-5438

FAX# 850-644-9829

FRIEDM@BIO.FSU.EDU

Alka Gupta

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-3206

FAX# 650-604-1088

agupta@mail.arc.nasa.gov

95
HymanHartman

Inst for Advanced Studies in Biology

880 Spruce Street

Berkeley CA 94707

TEL# 510-525-3354

FAX# 510-525-3466

HARTMAN @NATURE.BERKELEY.EDU

Prof. John Hayes

MS 8

NOSAMS Facility

Woods Hole Oceanographic Institute

Woods Hole MA 02543-1539

TEL# 508-289-2585

FAX# 508-457-2183

jhayes@whoi.edu

Heinrich Holland

Dept of Earth and Planetary Science

20 Oxford Street

Harvard University

Cambridge MA 02138

FAX# 617-495-8839

Richard Hoover

Building 4481

NASA Marshall Space Center

Alabama 35812

TEL# 205-544-7617

Rollin Hu

The Stanford Daily

Storke Publications Building

Stanford CA 94305-2240

William Irvlne

Department of Radio Astronomy

619 Lederie GRC

University of Massachusetts

Amherst MA 01003

TEL# 413-545-0733

FAX# 413-545-4223

IRVlNE@ FCRAOI.PHAST.UMASS.EDU

David Jacobs

Dept. of Biology

University of California

at Los Angeles

Los Angeles CA 90095-1606

TEL# 310-206-7885

FAX# 310-206-3987

djacobs @UCLA.edu

96

Linda Jahnke

MS 239--4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-3221

FAX# 650-604-1088

Ijahnke@mail.arc.nasa.gov

Bruce Jakosky

LASP Campus Box 392

University of Colorado

Boulder CO 80309-0392

TEL# 303-492-8004

FAX# 303-492-6946

jakosky @argyre.colorado.edu

Gerald Joyce

Dept. of Molecular Biology

Scripps Research Institute

10550 North Torrey Pines Road

La Jolla CA 92037

TEL# 619-784-9844

FAX# 619-784-2943

GJOYCE@SCRiPPS.EDU

Anastassia Kanavarioti

Dept. of Chemistry and Biochemistry

University of California

Santa Cruz CA 95064

TEL# 408-459-2978

FAX# 408-459-2935

TESSI @HYDROGEN.UCSC.EDU

David Kass

150-21

California Institute of Technology

Pasadena CA 91125

TEL# 626-395-6960

FAX# 626-585-1917

dkass @gps.caltech .edu

Ray Kepner

Biological Sciences Center

Desert Research Institute

P.O. Box 60220

Reno NV 89506

TEL# 702-673-7419

FAX# 702-673-7397

kepner@ maxey.dri.edu

-l: | I"
John Kerridge

Department of Chemistry (0317)

University of California

at San Diego

La Jolla CA 92093

TEL# 619-534-0443

FAX# 619-534-7441

JKERRIDG@ UCSD.EDU

Bishun Khare

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-2465

FAX# 650-604-1088

bkhare @mail.arc.nasa.gov

Harold Klein

SETI Institute

2035 Landings Drive

Mountain View CA 94043

TEL# 650-856-2349

FAX# 650-961-7099

hpklein @seti.org

Paul Knauth

Dept. of Geolgy

Box 871404

Arizona State University

Tempe AZ 85287-1404

TEL# 602-9_5-2867

FAX# 602-9{ _5-8102

Knauth @asu.edu

Andrew Knoll

Botanical Museum

Harvard University

26 Oxford Street

Cambridge MA 02138

TEL# 617-495-9306

FAX# 617-495-5667

AKNOLL@ OEB.HARVARD.EDU

Connie Kral

Department of Biological Sciences

SCEN-629

University of Arkansas

Fayetteville AR 72701

TEL# 501-575-6338

FAX# 501-575-4010

TKRAL@ UAFSYSB.UARK.EDU

Timothy Kral

Department of Biological Sciences

SCEN-629

University of Arkansas

Fayetteville AR 72701

TEL# 501-575-6338

FAX# 501-575-4010

TKRAL@ UAFSYSB.UARK.EDU

Ram Krishnamurthy

Scripps Research Institute

10550 N. Torrey Pines Road MB16

La Jolla CA 92037

TEL# 619-784-8520

FAX# 619-784-9573

rkrishna @scripps.edu

Ragnhild Landheim

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0774

FAX# 650-604-6779

LANDHEIM @GAL.ARC.NASA.GOV

William Langer

MS 169-506

Jet Propulsion Laboratory

4800 Oak Grove Drive

Pasadena CA 91109

TEL# 818-354-5823

FAX# 818-354-8895

langer@ nimba.jpl.nasa.gov

Lynn Lee

Dept. of Chemistry & Biochemistry

University of California, Santa Cruz

533 Palm St.

Santa Cruz CA 95060

TEL# 408-460-9232

FAX# 408-459-2935

Iflee@cats.ucsc.edu

Louis Lerman

University of California, Berkeley

Berkeley CA 94720

97
NarcindaLemer

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6941

FAX# 650-604-1088

nlemer @mail.arc.nasa.gov

Jason Lohn

MS 269-1

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5138

FAX# 650-604-3594

jlohn @ptolemy.arc.nasa.gov

Steven Levin

MS 169-5O6

Jet Propulsion Lab

4800 Oak Grove Drive

Pasadena CA 91109

TEL# 818-354-1917

steve @beta.jpl.nasa.gov

Hal Levison

Geo, Astro, & Planetary Sciences

Southwest Research Institute

1050 Walnut Street

Suite 429

Boulder CO 80302

TEL# 303-546-0290

FAX# 303-546-9687

hal@gort.space.swri.edu

Shoudan Liang

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6631

FAX# 650-604-1088

sliang @mail.arc.nasa.gov

Doug Lies

Center for Great Lakes Studies

University of Wisconsin at Milwaukee

600 E Greenfield Avenue

Milwaukee Wl 53204

TEL# 414-382-1712

FAX# 414-382-1705

lies@ CSD4.CSD.UWM.EDU

Marshall Lis_

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035

TEL# 650-604-5000

FAX# 650-604-1088

Donald Lowe

Department of Geological

and Environmental Sciences

Stanford University

Stanford CA 94305

TEL# 650-725-3040

FAX# 650-725-0979

Iowe @pangea.stanford.edu

Claudine Madras

1556 California Street

San Francisco CA 94122

TEL# 415-681-0322

FAX# 415-263-4020

cmadra @sapient.com

Rocco Mancinelli

MS 239-12

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6165

FAX# 650-604-1088

RMANCINELLI@ maiI.ARC.NASA.GOV

John Marshall

MS 239-12

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-4983

FAX# 650-604-0092

jmarshall @mail.arc.nasa.gov

Harry McDonald

MS 200-1

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5111

hmcdonald @mail.arc.nasa.gov

98
ChristopherMcKay

MS245-3

NASAAmesResearchCenter

MoffettField CA 94035-1000

TEL# 650-604-6864

FAX# 650-604-6779

MCKAY@GAL.SPAN.NASA.GOV

DavidMcKay

MailCodeSN4

NASAJohnsonSpaceCenter

HoustonTX 77058

TEL# 281-483-5048

FAX# 281-244-8892

DMCKAY@ems.jsc.nasa.gov

JamesMcKinley

PacificNorthwestNationalLab

MSINK3-61

P.O.Box999

RichlandWA 99352

TEL# 509-375-6841

FAX# 509-375-6954

jp_mckinley@pnl.gov

Rev.ErnanMcMullin

1814OakParkDrive

SouthBend IN 46617

TEL# 219-233-4332

FAX#219-631-4268

JayMelosh

LunarandPlanetaryLaboratory

UniversityofArizona

TucsonAZ 85721

TEL# 520-621-2806

FAX# 520-621-4933

jmelosh@Ipl.arizona.edu

MichaelMeyer

AstrobiologyDisciplineScientist

CodeSR

SolarSystemExplorationDivision

NASAHeadquarters

WashingtonDC20546

TEL# 202-358-0307

FAX# 202-358-3097

mmeyer@ mail.hq.nasa.gov

Kaleb Michaud

Stanford University

Stanford CA 94305

kaleb @stanford.edu

Arnold Miller

Department of Geology

University of Cincinatti

Cincinatti OH 45221

TEL# 513-556-4022

FAX# 513-556-6931

ARNOLD. MILLER @UC. EDU

Stanley Miller

Department of Chemistry 0506

University of California

at San Diego

9500 Gilman Drive

La Jolla CA 92093

TEL# 619,534-3365

FAX# 619-534-6128

SMILLER @UCSD.EDU

Stephen Mojzsis

Mail Code 0220

Scripps Institution of Oceanography

University of California

at San Diego

La Jolla CA 92093-0220

TEL# 619-534-2961

FAX# 619-534-2961

smojzsis @ucsd.edu

David Morrison

MS 200-7

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5094

FAX# 650-604-1165

dmorrison @mail.arc.nasa.gov

Stephen Most

KCTS

1815 Grant St.

Berkeley CA 94703

TEL# 510-841-4582

FAX# 510-486-2115

smost @earthlink.net

99
MichaelNew

MS239-4

NASAAmesResearchCenter

MoffettField CA 94035-1000

TEL# 650-604-4762

FAX# 650-604-1088

mnew@maiI.ARC.NASA.GOV

DavidPerlman

San Francisco Chronicle

901 Mission Street

San Francisco CA 94119

TEL# 415-777-1111

FAX# 415-896-1107

perlmand @sfgate.com

Adriana Ocampo

MS 183-601

Jet Propulsion Laboratory

4800 Oak Grove Drive

Pasadena CA 91109

TEL# 818-393-1080

FAX# 818-393-4530

aocampo @jpluvs.jpl.nasa.gov

James Orenberg

Department of Chemistry

San Francisco State University

1600 Holloway Avenue

San Francisco CA 94132

TEL# 415-338-1292

FAX# 415-338-2384

ORENBERG @SFSU.EDU

Leslie Orgel

Chemical Evolution Laboratory

Salk Institute for Biological Studies

PO Box 85800

La Jolla CA 92186-5800

TEL# 619-453-4100 x1321

FAX# 619-558-7359

orgel@salk.edu

Karen Patrias

National Library of Medicine

8600 Rockville Pike

Bethesda MD 20894

TEL# 301-435-4887

FAX# 301-402-1384

pat rias @him .nih.gov

Yvonne Pendleton

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-4391

FAX# 650-604-6779

pendleton @gal.arc.nasa.gov

Beverly Pierson

Biology Department

University of Puget Sound

Tacoma WA 98416

TEL# 253-756-3353

FAX# 253-756-3352

bpierson @ups.edu

Andrew Pohorille

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5759

FAX# 650-604-1088

pohorill @raphael.arc.nasa.gov

Kevin Pope

GEO ECO ARC Research

2222 Foothill Boulevard

Suite E-272

La Canada CA 91011

TEL# 818-240-6365

FAX# 818-240-6365

kpope @primenet.com

Janet Powers

SPACELINE

USUHS

7514 Wisconsin Ave., Suite 500

Bethesda MD 20814

TEL# 301-295-2706

FAX# 301-295-5271

jpowers@ mx3.usuhs.mil

Lee Prufert-Bebout

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6052

FAX# 650-604-1088

Ibebout @mail.arc.nasa.gov

100

T| I _
Richard Quinn

MS 239-14

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6501

FAX# 650-604-1088

rquinn@maiI.ARC.NASA.GOV

James Schilling

MS 245-1

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-2796

FAX# 650-604-6779

jschilling @mail.arc.nasa.gov

Margaret Race

30 Windsong Way

Lafayette CA 94549

TEL# 510-947-1272

FAX# 510-947-3992

mracemom @aol.com

Alexander Rich

Department of Biology, Rm. 68-233

Massachusetts Inst. of Technology

Cambridge MA 02139

TEL# 617-253-4715

FAX# 617-253-8699

cbeckman @mit.edu

John Rummel

Marine Biological Laboratory

7 MBL Street

Woods Hole MA 02543

TEL# 508-289-7218

FAX# 508-457-1924

JRUMMEL@ HOH.MBL.EDU

Bruce Runnegar

Dept. of Earth and Space Sciences

405 Hilgard Ave.

University of California, Los Angeles

Los Angeles CA 90095-1567

TEL# 310-206-1738

FAX# 310-825-0097

runnegar@ ucla.edu

Richard Saykally

Department of Chemistry

University of California

Berkeley CA 94720

TEL# 510-642-8269

FAX# 510-642-8369

RJS @HYDROGEN.CCHEM.BERKELEY.EDU

Martin Schoonen

Dept. of Earth and Space Sciences

State University of New York -

Stoney Brook

Stoney Brook NY 11794-2100

TEL# 516-632-8007

FAX# 516-632-8240

mschoonen @notes.cc.sunysb.edu

Mitchell Schulte

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0527

FAX# 650-604-1088

msch uIte@mail. arc. nasa. gov

Karl Schweighofer

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5000

karl @templar, arc.n asa.gov

Everett Shock

Department of Earth

and Planetary Sciences

Washington University

One Brookings Drive

St Louis MO 63130

TEL# 314-935-4258

FAX# 314-935-7361

SHOCK @ZONVARK.WUSTL.EDU

Bernd Simoneit

College of Oceanic & Atm Sciences

Oregon State University

Oceanography Admin. Bldg. 104

Corvallis OR 97331-5503

TEL# 541-737-2155

FAX# 541-737-2064

simoneit@oce.orst.edu

101
KellySnook

MS245-3

NASAAmesResearchCenter

MoffettField CA 94035-1000

TEL# 650-604-3524

FAX# 650-604-6779

ksnook@mail.arc.nasa.gov

GeraldSoften

Director of University Programs

NASA Goddard Space Flight Center

Code 160

Greenbelt MD 20771

TEL# 301-286-9690

FAX# 301-286-1610

GSOFFEN @MAIL.GSFC.NASA.GOV

Mitchell Sogin

Water Street

Marine Biological Lab

Woods Hole MA 02543

TEL# 508-548-7393

Sogin @evoll .mbl.edu

Dimitris Stassinopoulos

MS 269-1

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6381

FAX# 650-604-3594

stassi @ptolemy.arc.n asa.gov

Brad Stone

Department of Chemistry

San Jose State University

San Jose CA 95192-0101

TEL# 408-924-4938

stone @sjsuvml

Christopher Switzer

Chemistry Department

University of California, Riverside

Riverside CA 92521

TEL# 909-787-7266

FAX# 909-787-4713

switzer@ citrus.ucr.edu

David Usher

Department of Chemistry

Cornell University

Ithaca NY 14853

TEL# 607-255-7063

FAX# 607-255-4137

DAU1 @CORNELL.EDU

Thangasamy Velusamy

MS 169-506

Jet Propulsion Laboratory

4800 Oak Grove Drive

Pasadena CA 91109

TEL# 818-354-6112

FAX# 818-354-8895

velu @rams.jpl.nasa.gov

Todd Stevens

Pacific Northwest Laboratory

P.O. Box 999

Mail Stop P7-54

Richland WA 99352

TEL# 509-373-0891

to_stevens @pnl.gov

Carol Stoker

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6490

FAX# 650-604-6779

cstoker@ mail.arc.nasa.gov

James Walker

Space Physics Research Lab

University of Michigan

2455 Hayward

Ann Arbor MI 48109

TEL# 313-763-6217

FAX# 313-764-5137

jcgwalker@ umich.edu

Peter Wannier

MS 169-506

Jet Propulsion Laboratory

4800 Oak Grove Drive

Pasadena CA 91109

TEL# 818-354-3347

FAX# 818-354-8895

peter @wannier.jpl.nasa.gov

102

-3-]I I-
David Ward

Department of Microbiology

Montana State University

Bozeman MT 59717

TEL# 406-994-3401

FAX# 406-994-4926

umbdw@ gemini.oscs.montana.edu

Robert Wharton

Desert Research Institute

PO Box 60220

Reno NV 89506

TEL# 702-673-7469

FAX# 702-673-7421

wharton @maxey.dri.edu

Thomas Wdowiak

Physics Department

University of Alabama, Birmingham

Birmingham AL 35294-1170

TEL# 205-934-8036

FAX# 205-934-8042

wdowiak@ phy.uab.edu

Ms Lisa White

MS 239-12

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-6530

FAX# 650-604-0092

Iwhite@mail.arc.nasa.gov

Arthur Weber

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-3225

FAX# 650-604-1088

AWEBER @mail.ARC. NASA.GOV

Darren Williams

525 Davey Lab

Penn State University

University Park PA 16802

TEL# 814-863-7947

FAX# 814-863-3399

dwilliams @astro.psu.edu

Esther Weber

MS 239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-3226

FAX# 650-604-1088

EWEBER @maiI.ARC.NASA.GOV

Michael Wilson

MS239-4

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5496

FAX# 650-604-1088

mwilson @mail.arc.nasa.gov

Sarah West

MS245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-4882

FAX# 650-604-0000

swest @misty.arc.nasa.gov

Carl Woese

Department of Microbiology

University of Illinois

Urbana IL 61801

TEL# 217-333-2938

FAX# 217-244-6697

carl @phylo.life.uiuc.edu

George Wetherill

Department of Terrestrial Magnetism

Carnegie Institution of Washington

5241 Broad Branch Road NW

Washington DC 20015

TEL# 202-686-4375

FAX# 202-364-8726

wetherill@ eros.ciw.edu

David Woon

Molecular Research Institute

845 Page Mill Road

Palo Alto CA 94304

TEL# 650-424-9924

FAX# 650-424-9501

woon @hecla.molres.org

I03
Yuk Yung

Division of Geological

and Planetary Sciences

California Institute of Technology

Pasadena CA 91125

TEL# 626-395-6940

FAX# 626-585-1917

yly @mercu 1.gps .caltech.edu

Kevin Zahnle

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-0840

FAX# 650-604-6779

kevin @boombox.arc.nasa.gov

Aaron Zent

MS 245-3

NASA Ames Research Center

Moffett Field CA 94035-1000

TEL# 650-604-5517

FAX# 650-604-6779

zent @mawrth.arc.nasa.gov

104

-I 1 I_
Form Approved

REPORT DOCUMENTATION PAGE DUBNo.ozo4.o 88

Publicreportingburden for this collectionof informationis estimated to average 1 hourper response,includingthe time forreviewing Instructions,searching existingdata Bournes,

gathering and maintaining the data needed and completingand reviewingthe collectionof information. Send commentsregarding this burdenestimate or any other aspect of tl-,;s

collection of information,includingsuggestions forreducingthis burden,to Washington HeadquartersServices. Directoratefor nformatonOperations and Reports, 1215 Jefferson

Davis Highway, Suite 1204, Arlington,VA 22202-4302, and to the Office of Management and Budget, PapenNorkReductionProject (0704-0188), Washington, DC 20503.

1. AGENCY USE ONLY (Leave blank) 2. REPORT DATE | 3. REPORT TYPE AND DATES COVERED

September 1998 I Conference Publication

4. TITLE AND SUBTITLE 5. FUNDING NUMBERS

Sixth Symposium on Chemical Evolution and the Origin and Evolution

of Life

6. AUTHOR(S)

Sara Acevedo, Donald L. DeVincenzi, and Sherwood Chang,

Editors

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESStES)

Ames Research Center SETI Institute

Moffett Field, CA Mt. View, CA

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration

Washington, DC 20546-0001

RTOP 344-38

8. PERFORMING ORGANIZATION

REPORT NUMBER

A9812411

10. SPO NSORING/MONITORING

AGENCY REPORT NUMBER

NASA CP- 1998-10156

11. SUPPLEMENTARY NOTES

Point of Contact: Sara Acevedo, Ames Research Center, MS 245-l, Moffett Field, CA 94035-1000

(650) 604-4223

12a. DISTRIBUTION/AVAILABILITY STATEMENT

Unclassified-Unlimited

Subject Category - 55

Available from the NASA Center for AeroSpace Information,

800 FJkrid_e Landin_ Road t Linthicum Heights r MD 21090} _301 / 621-0390.

13. ABSTRACT (Maximum 200 words)

12b. DISTRIBUTION CODE

Distribution: Standard

The 6th Symposium on Chemical Evolution and the Origin and Evolution of Life was convened at NASA Ames

Research Center, November 17-20, 1997. This Symposium is convened every three years under the auspices of

NASA's Exobiology Program Office. All Principal Investigators funded by this Program present their most recent

research accomplishments at the Symposium. Scientific papers were presented in the following areas: cosmic

evolution of the biogenic elements, prebiotic evolution (both planetary and chemical), evolution of early organisms and evolution of organisms in extreme environments, solar system exploration, and star and planet formation. The Symposium was attended by over 200 scientists form NASA centers and Universities nationwide.

14. SUBJECT TERMS

Exobiology, Biological evolution, Chemical evolution, Planetary evolution,

Solar System exploration, Planetary atmospheres

17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATION

OF REPORT OF THIS PAGE

Unclassified Unclassified

NSN 7540-01-280-5500

19. SECURITY CLASSIFICATION

OF ABSTRACT

lB. NUMBER OF PAGES

122

16. PRICE CODE

A06

20. LIMITATION OF ABSTRACT

Standard Form 298 (Rev. 2-89)

Prescribed by ANSI Std. Z3ao18

298-102
INDEX OF SPEAKERS

Allarnandola .............................................. 26

Awramik .................................................... 75

Bada ........................................................ 32

Benner ..................................................... 58

Blake, D .................................................... 65

Blake, G.................................................... 71

Blankenship ............................................. 36

Borucki ..................................................... 79

Braterman ................................................. 67

Bunch ...................................................... 43

Cady ........................................................ 51

Chang ...................................................... 34

Chamley ................................................... 57

Chyba ...................................................... 23

Cooper ..................................................... 34

Cronin ...................................................... 33

Deamer .................................................... 28

Des Marais ................................................ 30

DeVincenzi ............................................... 60

Dickens .................................................... 25

Erwin ........................................................ 39

Farmer ................................................ 52, 80

Ferris ........................................................ 47

Flynn ....................... .i ......................... 20, 81

Fomenkova .............................................. 64

Fox .......................................................... 56

Fredrickson .,. ........................................... 54

Freund ..................................................... 26

Friedmann .......................................... 38, 86

Gogarten ................................. 36, 82, 84, 86

Hayes ....................................................... 61

Jacobs ........ ,..... ....................................... 49

Jahnke ..................................................... 62

Jakosky .................................................... 31

Joyce ....................................................... 24

Kanavarioti ................................................ 73

Kass ......................................................... 62

Kepner ..................................................... 83

Kerridge ................................................... 22

Klein ........................................................ 76

Knauth ..................................................... 68

Knoll ........................................................ 31

Krishnamurthy .......................................... 58

Lee .......................................................... 83

Lerner ...................................................... 72

Levison .................................................... 69

Lies .......................................................... 37

Lowe ........................................................ 53

Mancinelli ................................................. 55

McKay, C.P ......................................... 38, 45

McKay, D.S ............................................... 21

Miller ........................................................ 39

Mojzsis ..................................................... 23

Ocampo ................................................... 85

Orenberg ................................................. 67

Orgel ........................................................ 46

Pendleton ................................................ 57

Pierson .................................................... 29

Pohorille ................................................... 27

Pope ........................................................ 44

Quinn ....................................................... 42

Race ........................................................ 60

Rothschild ................................................ 80

Runnegar ................................................. 41

Saykally .............................................. 19, 87

Schoonen ................................................ 74

Shock ...................................................... 48

Simoneit ................................................... 47

Stoker ...................................................... 51

Switzer ..................................................... 46

Usher ....................................................... 66

Velusamy ................................................. 63

Wannier .................................................... 70

Ward .................................................. 29, 88

Wdowiak ....................................... 19, 45, 50

Weber ...................................................... 35

Wetherill ................................................... 69

Wharton ................................................... 88

Williams .................................................... 40

Woon ....................................................... 72

Yung ........................................................ 42

Zahnle ...................................................... 56

Zent ......................................................... 89

105

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