Jamie E Elsila1, José C Aponte2, Donna G Blackmond3, Aaron S Burton4, Jason P Dworkin1, Daniel P Glavin1. 1. Solar System Exploration Division, NASA Goddard Space Flight Center , Greenbelt, Maryland 20771, United States. 2. Solar System Exploration Division, NASA Goddard Space Flight Center, Greenbelt, Maryland 20771, United States; Department of Chemistry, Catholic University, Washington, D.C. 20064, United States. 3. Department of Chemistry, The Scripps Research Institute , La Jolla, California 92037, United States. 4. Astromaterials Research and Exploration Science Division, NASA Johnson Space Center , Houston, Texas 77058, United States.
Abstract
The analysis of amino acids in meteorites dates back over 50 years; however, it is only in recent years that research has expanded beyond investigations of a narrow set of meteorite groups (exemplified by the Murchison meteorite) into meteorites of other types and classes. These new studies have shown a wide diversity in the abundance and distribution of amino acids across carbonaceous chondrite groups, highlighting the role of parent body processes and composition in the creation, preservation, or alteration of amino acids. Although most chiral amino acids are racemic in meteorites, the enantiomeric distribution of some amino acids, particularly of the nonprotein amino acid isovaline, has also been shown to vary both within certain meteorites and across carbonaceous meteorite groups. Large l-enantiomeric excesses of some extraterrestrial protein amino acids (up to ∼60%) have also been observed in rare cases and point to nonbiological enantiomeric enrichment processes prior to the emergence of life. In this Outlook, we review these recent meteoritic analyses, focusing on variations in abundance, structural distributions, and enantiomeric distributions of amino acids and discussing possible explanations for these observations and the potential for future work.
The analysis of amino acids in meteorites dates back over 50 years; however, it is only in recent years that research has expanded beyond investigations of a narrow set of meteorite groups (exemplified by the Murchison meteorite) into meteorites of other types and classes. These new studies have shown a wide diversity in the abundance and distribution of amino acids across carbonaceous chondrite groups, highlighting the role of parent body processes and composition in the creation, preservation, or alteration of amino acids. Although most chiral amino acids are racemic in meteorites, the enantiomeric distribution of some amino acids, particularly of the nonprotein amino acid isovaline, has also been shown to vary both within certain meteorites and across carbonaceous meteorite groups. Large l-enantiomeric excesses of some extraterrestrial protein amino acids (up to ∼60%) have also been observed in rare cases and point to nonbiological enantiomeric enrichment processes prior to the emergence of life. In this Outlook, we review these recent meteoritic analyses, focusing on variations in abundance, structural distributions, and enantiomeric distributions of amino acids and discussing possible explanations for these observations and the potential for future work.
Meteorites, the rocky
remnants of asteroids or comets that land on Earth, serve as historians
and messengers from the early Solar System. The organic contents of
meteorites reflect a long and potentially diverse history, beginning
with the formation of the Solar System in a molecular cloud in which
low temperature radiation-driven chemistry and isotopic fractionation
could occur in both the gas phase and in ices. Some of this molecular
cloud material was incorporated into growing planetesimals where additional
chemical reactions and processing took place. These planetesimals
include the asteroids and comets that are the parent bodies of meteorites.
Thus, meteoritic organic content reveals information not only about
early solar system chemistry but also about the histories of parent
bodies as recorded in the effects of physical and chemical processes
that occurred over the past 4.5 billion years. Meteorites are also
delivery vehicles, impacting the Earth with 40 million kg of cosmic
material each year,[1] with a much higher
flux earlier in the Earth’s history; this material may have
contributed to the inventory of organic compounds available for the
origin of life.Studies of the organic content of meteorites
date to 1834,[2] with compound-specific measurements
beginning in the 1960s.[3] Meteorite analyses
reveal a major organic component of insoluble macromolecular material,
as well as a complex and highly diverse suite of soluble organics,[4−6] including aliphatic and aromatic hydrocarbons,[7−12] carboxylic acids,[13−15] hydroxy acids,[16,17] polyols,[18] amino acids,[7,8,19−22] and more.[23−26] Of these, amino acids have been of particular interest
for several reasons. Amino acids are essential organic molecules as
the monomers of proteins and enzymes in all life on Earth, making
them targets for astrobiological studies. Analytical techniques exist
for isolation and analysis of amino acids. Many amino acids are chiral,
and the origin of homochirality of biological amino acids is a major
question in origin of life research. They are also a constrained yet
structurally diverse group of compounds. Figure illustrates the 23 isomers and enantiomers
of five-carbon aliphatic primary monoamino, monocarboxylic, non-heteroatom
(hereafter “simple”) amino acids, highlighting differences
in the position of the amine group relative to the acid group, as
well as the structure of the carbon backbone. The structural, isotopic,
and enantiomeric compositions of amino acids can be signatures of
their formation mechanisms and processing histories.[5,27,28]
Figure 1
Structure of amino acids can be classified
according to the position of the amine relative to the acid (e.g.,
if the amine is on the α, β, γ, or δ carbon)
and the structure of the aliphatic carbon backbone. For the five-carbon
aliphatic primary monoamino, monocarboxylic, non-heteroatom amino
acids shown here, there are 23 possible structural isomers and enantiomers.
Understanding the distribution of these species can help elucidate
the formation and processing histories of the meteorite in which they
are found. These five-carbon compounds are particularly useful, as
they provide a large suite of chemical isomers that can be individually
quantitated by current analytical methods.
Structure of amino acids can be classified
according to the position of the amine relative to the acid (e.g.,
if the amine is on the α, β, γ, or δ carbon)
and the structure of the aliphatic carbon backbone. For the five-carbon
aliphatic primary monoamino, monocarboxylic, non-heteroatom amino
acids shown here, there are 23 possible structural isomers and enantiomers.
Understanding the distribution of these species can help elucidate
the formation and processing histories of the meteorite in which they
are found. These five-carbon compounds are particularly useful, as
they provide a large suite of chemical isomers that can be individually
quantitated by current analytical methods.Meteorites are classified
according to their petrologic characteristics (e.g., texture, mineralogy),
whole-rock chemical composition, and oxygen-isotope composition.[29] One classification system yields 45 named groups
of meteorites,[29] ranging from metallic
meteorites composed almost entirely of iron and nickel metals from
protoplanetary cores to primitive stony meteorites that have never
been significantly heated; Figure gives a partial overview of the classification scheme.
There are also several meteorites that do not fit in the existing
groups.
Figure 2
This classification scheme divides into groups according to their
petrologic characteristics, and also assigns petrographic types (1–6)
representing their alteration history.[29] The abundance of the classes on Earth can be estimated by the percentage
of meteorites discovered immediately after they fall to Earth (falls).
To date, amino acids have been measured in representatives from all
groups shown in this figure except those shown in white.
This classification scheme divides into groups according to their
petrologic characteristics, and also assigns petrographic types (1–6)
representing their alteration history.[29] The abundance of the classes on Earth can be estimated by the percentage
of meteorites discovered immediately after they fall to Earth (falls).
To date, amino acids have been measured in representatives from all
groups shown in this figure except those shown in white.Most studies of meteoritic organics focus on what
are known as “carbonaceous chondrites”, the class of
primitive stony meteorites containing 2–5 wt % carbon.[30] Carbonaceous chondrites are divided into eight
groups, each of which appears to derive from a different parent body,
based on distinctive chemical and mineralogical compositions. These
meteorites are further assigned petrographic types, depending on the
type and extent of secondary processing they underwent in their parent
bodies. Secondary processing includes the effects of the physical
and chemical environment of the parent body, such as temperature (e.g.,
heating from radioactive species or from shock impacts)[31] and the amount of water present (caused by melting
of ice accumulated during parent body formation).[32] Petrographic types range from 1 to 6, with 3.0 indicating
minimal secondary processing, numbers less than 3.0 indicating increased
aqueous alteration, and types greater than 3.0 indicating increased
thermal metamorphism; this system does not describe meteorites with
both thermal and aqueous processing. As expected, both the composition
of a meteorite and the conditions it experienced in its parent body
have an observable effect on the amount and distribution of organic
molecules in that meteorite. This has been particularly well documented
for meteoritic amino acids.[20−22,33−50]Early studies of meteoritic organics focused primarily on
a few well-known, large meteorites. The year 1969 saw several important
events, including the first Apollo Moon landings and the fall of two
large carbonaceous chondrites: Murchison (CM2) and Allende (CV3).
Each fall was seen as a brilliant fireball accompanied by earth tremors
and a cloud of smoke, distributing >100 kg of fragments over a
wide radius. Analytical laboratories preparing for the study of Apollo
lunar samples eagerly investigated the organic contents of these two
meteorites. The Murchison meteorite and other CM2 chondrites, such
as the 12.6 kg Murray meteorite that fell in 1950,[51] dominated meteoritic amino acid analysis for decades, as
shown in the distribution of literature reports depicted in Figure .
Figure 3
An examination of published
literature reports of meteoritic amino acid analyses, shown as proportion
of total analyses by meteorite group (left) and proportion of CM analyses
of Murchison vs other CM meteorites (right), illustrates the domination
of Murchison and CM analyses until recent years. [Data taken from
SI Web of Science search through 2015 with the search terms TS = (meteorit*
or chondrite) and TS = (amino and acid) refined by document types
(article or letter). Only manuscripts including new amino acid data
were included.]
An examination of published
literature reports of meteoritic amino acid analyses, shown as proportion
of total analyses by meteorite group (left) and proportion of CM analyses
of Murchison vs other CM meteorites (right), illustrates the domination
of Murchison and CM analyses until recent years. [Data taken from
SI Web of Science search through 2015 with the search terms TS = (meteorit*
or chondrite) and TS = (amino and acid) refined by document types
(article or letter). Only manuscripts including new amino acid data
were included.]A shift in our understanding
of meteoritic amino acids has occurred recently, partly enabled by
an increasing supply of samples from carbonaceous chondrite groups
and types other than CM2. The bulk of these meteorites are from Antarctica,
where more than 22,000 meteorites have been collected to date on expeditions
by the Antarctic Search for Meteorites (ANSMET) program,[52] a joint operation between NASA, NSF, and the
Smithsonian Institution, with additional collection efforts by independent
European- and Japanese-led searches. Improvements in analytical instrumentation
have pushed detection limits ever lower and allowed for compound-specific
stable isotopic measurements,[53] as well
as analyses of very small samples of meteorites[54] and even milligram-sized Antarctic micrometeorites.[55]Recent amino acid results reveal differences
between meteorite classes that have implications for our understanding
of solar system and parent body chemistry, as well as for the contribution
of meteorites to the origin of life on Earth. This new information
on the diversity of meteoritic organic molecules highlights several
areas that are ripe for further investigation. Two topics of particular
interest are (1) understanding the signatures of formation mechanisms
and processing histories preserved in meteoritic amino acids and (2)
understanding the creation and amplification of observed amino acid
enantiomeric excesses and exploring the implications for the origin
of biological homochirality. Here, we discuss the current state and
future opportunities in these areas.
Amino Acid Distributions
Signatures
of Formation Mechanisms and Processing Histories
Extensive
investigations of Murchison over the past 45 years have shown it to
be particularly rich in soluble organic materials,[6] including part-per-million (ppm) levels of the most abundant
individual compounds among a suite of >70 named amino acids ranging
from two to ten carbons in length, and including eight proteinogenic
amino acids.[41,56] The amino acids in Murchison
are predominantly α-amino isomers, though appreciable levels
of other isomers are present. The large available sample mass of Murchison
and its relatively high abundances of amino acids have enabled its
study by many researchers. This led to an overrepresentation of Murchison
in meteorite literature (Figure ) and the development of a paradigm in which the distribution
of amino acids observed in Murchison was until recently considered
typical for all meteorites. Even today, Murchison is still often viewed
as the archetype to which other meteorites are compared.As Figure illustrates, however,
analyses of aqueous extracts of meteorites from different groups and
petrographic types reveal that the Murchison-like distribution of
amino acids, with ppm concentrations and mainly α-amino isomers,
appears to be limited to a narrow range of CM2, CR2, and CR3 chondrites.
Meteorites that experienced greater aqueous alteration without accompanying
high-temperature thermal alteration, such as the CI1, CM1, and CR1
chondrites, have lower abundances of amino acids and increased relative
amounts of simple β-, γ-, and δ-amino acid isomers.[20,41,47] Carbonaceous chondrites exposed
to aqueous alteration as well as higher temperatures up to 400–600
°C (e.g., certain thermally altered CI1 chondrites or the Sutter’s
Mill CM2 chondrite) contain even lower abundances of amino acids,[47,50,57] perhaps unsurprising given that
most amino acids start to thermally decompose above 150 °C in
the solid state.[58,59]
Figure 4
Average total amino acid abundances (top)
and structural distributions of amine position in C5 amino
acids (bottom) in carbonaceous chondrites vary greatly with class
and petrographic type. Structural distributions are shown as relative
abundances of isomers of C5 amino acids, normalized to
the total number of possible isomers (i.e., random selection of amine
position during formation should produce 25% each of α, β,
γ, and δ isomers in this plot). A “sweet spot”
of high abundance and high relative abundance of α-amino acid
isomers, such as those used in terrestrial biology, is observed in
the cool, moderately aqueously altered meteorites such as the Murchison
CM2. Data is taken from selected meteorites analyzed by the authors
using the same workup and analysis methods for all samples.[39,41,44,46−48,57]
Average total amino acid abundances (top)
and structural distributions of amine position in C5 amino
acids (bottom) in carbonaceous chondrites vary greatly with class
and petrographic type. Structural distributions are shown as relative
abundances of isomers of C5 amino acids, normalized to
the total number of possible isomers (i.e., random selection of amine
position during formation should produce 25% each of α, β,
γ, and δ isomers in this plot). A “sweet spot”
of high abundance and high relative abundance of α-amino acid
isomers, such as those used in terrestrial biology, is observed in
the cool, moderately aqueously altered meteorites such as the Murchison
CM2. Data is taken from selected meteorites analyzed by the authors
using the same workup and analysis methods for all samples.[39,41,44,46−48,57]CH3 chondrites, which contain ∼20% metal
by volume, have similar levels of amino acids to Murchison, but with
much higher relative abundances of β-, γ-, and δ-amino
acids.[46] CB chondrites, with 60–80%
metal by volume, have an order of magnitude lower amino acid abundance
than CH chondrites, and contain a higher fraction of straight-chained
amino acids with the amine group located on the carbon farthest from
the carboxylic acid (n-ω-amino acids).[46] Meteorites that experienced more parent body
heating, including the moderately heated CV3 and CO3 chondrites, as
well as the more extensively heated CK4–CK6 chondrites are
dominated by n-ω-amino acids, particularly
the δ-amino C5 isomer.[44,45,48] Certain other meteorites that experienced high temperatures,
such as intensely heated ureilites[44] and
the Martian meteorite Roberts Massif 04262,[60] also contain low levels of mostly n-ω-amino
acids, while other heated meteorites such as LL3 ordinary chondrites
have a different amino acid distribution.[45]It appears that abiotic amino acid formation chemistry, as
preserved by meteorites, is strongly dependent on the availability
of amino acid precursors, temperature and water activity, and the
mineralogical composition of the parent body. These factors influenced
the abundances as well as the structural, enantiomeric, and isotopic
composition of meteoritic amino acids. The ways in which these influences
operated, however, are only beginning to be elucidated.The
diversity observed in meteoritic amino acids suggests multiple formation
mechanisms in the early solar system and in parent bodies. In particular,
the abundance of α-amino acids in Murchison and other moderately
aqueously altered meteorites is consistent with Strecker-type syntheses
(Figure , bottom pathway).[61] Further support is also provided by the presence
and similar distribution of α-hydroxy acids in Murchison that
form by the parallel cyanohydrin reaction (Figure , top pathway) as well as analogous iminodicarboxylic
acids.[61,62] β-Amino acids cannot be produced through
the Strecker mechanism, but it has been postulated that they formed
through Michael addition of ammonia to α,β-unsaturated
nitriles.[25,63] Because Michael addition requires the presence
of liquid water, it has been seen as a plausible explanation for the
high levels of β-amino acids observed in some heavily aqueously
altered meteorites (e.g., Orgueil and Ivuna, CI1);[20] aqueous alteration and oxidation also lead to preferential
destruction of the more soluble and polar α-amino acids.[22] The origin of γ- and δ-amino acids
is less certain, but they could plausibly form from decarboxylation
or deamination of dicarboxylic ordiamino acids[53,64,65] and may also form via photochemically produced
radicals in pre-parent body environments, such as on the surfaces
of interstellar icy grains.[66−68] The dominant distribution of n-ω-amino acids in thermally altered meteorites may
be the result of so-called Fischer–Tropsch-type (FTT) reactions
occurring between trapped cooling gases and catalytic mineral surfaces.[44,69−71]
Figure 5
Strecker-cyanohydrin synthesis can produce either α-hydroxy
acids (top pathway) or α-amino acids (bottom pathway), depending
on the availability of ammonia.
Strecker-cyanohydrin synthesis can produce either α-hydroxy
acids (top pathway) or α-amino acids (bottom pathway), depending
on the availability of ammonia.Although several formation mechanisms have been suggested
for meteoritic amino acids, laboratory studies in this area have focused
primarily on the mechanisms most relevant to the more heavily studied
aqueously altered meteorites, such as Strecker-type syntheses leading
to α-amino acids. Future work is needed to assess the formation
potential of other mechanisms, such as the FTT reactions, as well
as the effects of alteration conditions on amino acid preservation
and formation. Production of amino acids in laboratory analogue reactions
and measurement of structural distributions and isotopic fractionation
to compare with meteoritic data would help constrain chemical environments
in the early solar system and in parent bodies.Studying the
meteoritic abundances and distributions of compounds related to amino
acids may also provide insight into the formation of soluble meteoritic
organics. Such compounds include hydroxy acids, carboxylic acids,
and amines. Like amino acids, these compounds have the advantage that
they are soluble, extractable, and stable under conditions necessary
for analysis. These compounds’ aliphatic moieties may originate
from precursors common to amino acids as well, via ion/radical or
photochemical reactions in the gas phase or on icy grain surfaces
in interstellar or protostellar nebulae, and subsequent modification
during and after accretion of the meteorite parent body.[25,72] Hydroxy acids may be the most closely related compounds to amino
acids in the carbonaceous chondrites, as Strecker-type synthesis would
produce both α-hydroxy and α-amino acids, with the relative
abundance of each depending on the ratio of available H2O to NH3 (Figure ). Thus, the hydroxy to amino acid ratio in a meteorite may
provide information on parent body conditions.[61] This ratio has been studied in only a few exclusively CM
and CR meteorites, with results suggesting some common precursors
and a dependence on the concentration of parent body ammonia in determining
the relative abundance of amino and hydroxy acids.[16,17] Future comparisons of the molecular distributions of these compounds
across more meteorites may constrain the contribution of parent body
Strecker-type syntheses versus other synthetic routes.Carboxylic
acids and amines can interconvert to amino acids through the addition
or loss of CO2 or NH3 (Figure ). They may also share common precursors
with amino acids, such as aldehydes, ketones, and nitriles. Abundances
of these compounds vary, with carboxylic acids among the most abundant
soluble compounds in CM2 chondrites, but present in only low concentrations
in CR2 meteorites.[15,38,73] Similarly, amines are more abundant than amino acids in CM2 chondrites,
but less abundant in CR2 meteorites.[38,40] The molecular
distributions of all of these compounds in CM2 and CR2 chondrites
follow similar trends, decreasing in concentration with increasing
molecular weight.[15,74,75] Additionally, amines and amino acids both favor structures with
the amino group on secondary carbons relative to other structural
isomers.[74,75] These similarities between carboxylic acids,
amines, and amino acids suggest that meteoritic aliphatic organics
may have been synthesized (or destroyed) through similar processes
that yielded a full suite of structural isomers; future studies of
these compounds across additional carbonaceous chondrite groups and
types will aid in understanding these formation processes.
Figure 6
Amino acids may interconvert with carboxylic
acids through loss or addition of NH3, and with amines through loss or addition of CO2, shown here with the amino acid isovaline and its analogous carboxylic acid (2-methylbutyric acid) and amine (sec-butylamine).
Amino acids may interconvert with carboxylic
acids through loss or addition of NH3, and with amines through loss or addition of CO2, shown here with the amino acid isovaline and its analogous carboxylic acid (2-methylbutyric acid) and amine (sec-butylamine).The variety and complexity
of meteoritic organics is becoming clearer as more meteorites are
studied. In addition to further studies of meteorites, sample return
missions to comets and asteroids will be of critical value. Missions
such as NASA’s OSIRIS-REx[76] and
JAXA’s Hayabusa2[77] will provide
samples from primitive bodies with greater contextual information
than typically studied meteorites.[76] Careful
contamination control will result in minimal contamination, and the
analysis and archiving of spacecraft components and witness materials
will provide unprecedented knowledge of any terrestrial contributions
to these samples.
Enantiomeric Excesses
Formation, Amplification,
and Potential Relevance to Origin of Homochirality
Meteoritic
amino acid studies also focus on enantiomeric compositions, which
are important in elucidating a contribution to the origin of biological
homochirality, as well as judging the level of terrestrial contamination.
The near homochirality observed in biological molecules—l-amino acids and d-sugars—is crucial for molecular
recognition, enzyme function, information storage, and structure,
and is thought to be a property of the origin or early evolution of
life.[78] With a few rare exceptions, only l-amino acids are found in biology, while all abiotic syntheses
of amino acids result in equal mixtures of l- and d-amino acids unless forces that induce chiral excesses are included.
Since there appear to be no biochemical reasons to favor l-amino acids over d-amino acids in enzymes,[79] and early prebiotic chemistry experiments produced only
racemic amino acid mixtures, some have argued that the selection of l-amino acid homochirality by life on Earth was random.[80] The origin of homochirality from presumably
racemic mixtures in a prebiotic world is a major unsolved question
and an area of intense research. The problem contains two parts: (1)
establishing an initial imbalance in the two enantiomers; and (2)
amplifying that imbalance over time.An extraterrestrial origin
for an initial imbalance between l- and d-amino
acids has been proposed based on meteoritic analyses that reveal nonracemic
abundances of certain amino acids. In particular, as shown in Figure , l-enantiomeric
excesses (lee) of up to 21% have been reported
for isovaline, a terrestrially rare, nonproteinogenic amino acid,
across a wide range of carbonaceous meteorites.[35,39,41,46,81−84]lee of other α-methyl amino
acids have been reported, as have lee of isoleucine
and dee of its diastereomer allo-isoleucine.[35,85,86] Analyses of pieces of the Tagish Lake (C2ungrouped) meteorite
showed large lee of ∼99, 80, 45, and 55%,
respectively, for the protein amino acids threonine, serine, aspartic
acid, and glutamic acid,[83] and a racemic
composition for the common protein amino acid alanine, suggesting
minimal terrestrial biological contamination. Enriched 13C contents of alanine and aspartic acid indicated an abiotic, extraterrrestrial
origin of these compounds, suggesting that the other amino acids (present
at levels below limits of detection for isotopic analysis) may be
indigenous to the meteorite as well. These are the largest presumed
extraterrestrial enantiomeric excesses for proteinogenic amino acids
reported from a meteorite. The racemization half-lives for these amino
acids are long compared to the time period of aqueous alteration on
the parent body, and it is expected that an l-excess could
persist over the 4.5 billion-year lifetime of a meteorite.[87]
Figure 7
l-Enantiomeric excesses of the amino acid isovaline
of 0 to 20.5 ± 7.1% have been measured in carbonaceous chondrites.
All data shown here was generated by the authors using the same workup
and analysis methods.[39,41,46,47,82,83]
l-Enantiomeric excesses of the amino acid isovaline
of 0 to 20.5 ± 7.1% have been measured in carbonaceous chondrites.
All data shown here was generated by the authors using the same workup
and analysis methods.[39,41,46,47,82,83]It has been suggested that lee measured in meteorites
are the result of asymmetric photolytic decomposition of the amino
acids or their precursors by polarized radiation in the presolar cloud[88] or the effects of spin-polarized secondary electrons.[89] Laboratory experiments have shown that chiral
amino acid symmetry breaking and enantiomeric enrichment of up to
a few percent can be produced by exposure to ultraviolet circularly
polarized light (UV CPL).[90−94] However, polarized light cannot be the sole source of the large
enantiomeric enrichments observed, since these enrichments would require
photodestruction of ≫99% of the starting materials, requiring
impossibly high initial concentrations.[90] Photosynthetic routes by UV CPL[92] minimize
the destruction argument, but large lee in presolar
ices should manifest in lee across meteorite classes.
The racemic isovaline in CR2 and CR3[39] and
large lee in CR1[41] meteorites
render imbalances induced by UV CPL insufficient to explain the observed
enantiomeric excesses. Furthermore, molecular distributions and stable
isotope ratios suggest that the α-amino acids in Murchison and
other CM2 meteorites were likely produced during aqueous alteration
in their parent body,[16,28] when they would have been shielded
from circularly polarized radiation. Therefore, additional amplification
mechanisms have been proposed to explain the large l-isovaline
excesses.[95−99]Probing how amplification of an initial enantiomeric excess
in amino acids can occur is a topic of much research in biogenesis.[100] Theoretical work from the mid-20th century
proposed the purely chemical mechanism of autocatalytic reactions,[101] but the only experimental corroboration of
this concept involves chemistry that has no prebiotic relevance.[96,97] Other proposals involving physical phase behavior or the combination
of physical and chemical processes may help to explain the observed
extraterrestrial l-enantiomeric excesses of isovaline and aspartic acid
and suspected l-excesses of glutamic acid and threonine. Unlike
alanine, these amino acids can crystallize as enantiopure solids (conglomerates),
forming separate crystals containing only d or l molecules.[102] A proposed mechanism for
the emergence of homochirality from conglomerates supports the idea
that amplification of a slight initial l-excess of these
amino acid conglomerate crystals could have occurred during repeated
periods of aqueous alteration on the Tagish Lake meteorite parent
body.[83,103,104] Observations
of larger l-isovaline excesses in the aqueously altered CI1,
CM1, CM2, and CR1 meteorites compared to the less altered CR2 and
CR3 meteorites[39] also suggest that aqueous
alteration aided the amplification of l-isovaline excesses
on meteorite parent bodies. Large isovaline lee (∼5 to 21%) have also been observed in whole-rock extracts
of several metal rich CB and CH3 carbonaceous chondrites.[46] Although it is unclear if high metal content
can contribute to the amplification of enantiomeric excesses in these
meteorites, the CB and CH chondrites analyzed all contain a mix of
both heavily hydrated and anhydrous material, suggesting that an aqueous
alteration phase occurred in an asteroidal setting prior to incorporation
into the CB and CH parent bodies.[105]Studies of species related to amino acids may also aid in understanding
the origin of enantiomeric excesses, although there are few reported
studies of the enantiomeric composition of these meteoritic compounds.
Enantiomeric excesses ranging from 3 to 12% for l-lactic
acid have been reported in extracts of Murchison and two CR2 chondrites,
with isotopic evidence suggesting that this was not terrestrial contamination.[17] However, these results are complicated by sample
losses during workup, which caused measurable isotopic and, potentially,
enantiomeric fractionation. Future studies of hydroxy acids in a broader
range of meteorites are needed to determine if enantiomeric excesses
of hydroxy acids correlate with amino acid excesses. Some measurements
of carboxylic acids and amines have also been reported, with emphasis
on structural analogues of isovaline (2-methylbutyric acid and sec-butylamine; Figure ). Isovaline, 2-methylbutyric acid, and sec-butylamine contain analogous chiral centers; however, although isovaline
has been found to contain an lee, only racemic
compositions of 2-methylbutyric acid and sec-butylamine
have been reported in Murchison, Orgueil, and various Antarctic carbonaceous
chondrites.[74,75,106,107] Recent anisotropy studies show
that UV CPL can induce enantiomeric excesses in amino acids, but not
in amines and carboxylic acids,[108,109] perhaps explaining
these observations. The contrast between the observed lee of isovaline and the racemic nature of its analogous acid
and amine suggest that either (1) an initial imbalance was induced
in the amino acid enantiomers but not the carboxylic acid or amine;
(2) degradation of a chiral amino acid led to loss of stereochemistry
at the chiral carbon; (3) racemization occurred in the carboxylic
acids and amines at a faster rate than in the amino acids, although
the lower acidity of the α-hydrogen in these compounds argues
against this possibility;[110−113] or (4) physical properties of amino acids
(e.g., higher polarity) led to the amplification of a small imbalance
through aqueous processes inside carbonaceous chondrites.[107] Further studies of these aliphatic compounds
from other meteorites may provide additional information on the origins
of enantiomeric excesses in amino acids.The detection of nonracemic
amino acids in meteorites suggests that meteoritic delivery to planetary
surfaces could have contributed to the origin of homochirality in
life on Earth. The observation that only l-excesses have
been found in amino acids containing a single asymmetric carbon in
carbonaceous chondrites could indicate that the origin of life on
Earth, and possibly elsewhere in our solar system, was biased toward l-amino acid homochirality prior to the stratification of the
solar nebula. Although amino acid homochirality is an important signature
of biological processes in the search for evidence of life, the detection
of indigenous l-amino acid excesses in some meteorites indicates
that nonbiological processes can lead to significant enantioenrichment
for some amino acids, potentially complicating the use of this biosignature
for life detection missions and the search for a second genesis.
Conclusions
The
study of meteoritic organics has entered a new era with the increased
availability of meteorites probing a range of solar system milieus.
Highly sensitive and selective laboratory instruments capable of characterizing
organics present at low abundances and in small samples maximize the
information obtained. Knowledge of the diversity of abundances and
structural and enantiomeric distributions in meteorites has expanded
as larger data sets have been acquired. Observed heterogeneity in
amino acids in meteorites from the same carbonaceous chondrite group,
even of the same alteration type, provides evidence that minor changes
in reaction conditions can significantly affect the composition and
abundances of the resulting amino acids, a conclusion that surely
applies to amino acid synthesis on the early Earth as well. Future
work combining meteorite analyses with laboratory experiments, as
well as samples returned by missions to solar system bodies, will
aid in better understanding the formation and alteration of meteoritic
organics and their potential contributions to the origin of life on
Earth or elsewhere.
Authors: Christopher D K Herd; Alexandra Blinova; Danielle N Simkus; Yongsong Huang; Rafael Tarozo; Conel M O'D Alexander; Frank Gyngard; Larry R Nittler; George D Cody; Marilyn L Fogel; Yoko Kebukawa; A L David Kilcoyne; Robert W Hilts; Greg F Slater; Daniel P Glavin; Jason P Dworkin; Michael P Callahan; Jamie E Elsila; Bradley T De Gregorio; Rhonda M Stroud Journal: Science Date: 2011-06-10 Impact factor: 47.728
Authors: Michael P Callahan; Mildred G Martin; Aaron S Burton; Daniel P Glavin; Jason P Dworkin Journal: J Chromatogr A Date: 2014-01-18 Impact factor: 4.759
Authors: K Kvenvolden; J Lawless; K Pering; E Peterson; J Flores; C Ponnamperuma; I R Kaplan; C Moore Journal: Nature Date: 1970-12-05 Impact factor: 49.962
Authors: Uwe J Meierhenrich; Guillermo M Muñoz Caro; Jan Hendrik Bredehöft; Elmar K Jessberger; Wolfram H-P Thiemann Journal: Proc Natl Acad Sci U S A Date: 2004-06-11 Impact factor: 11.205
Authors: José C Aponte; Hannah K Woodward; Neyda M Abreu; Jamie E Elsila; Jason P Dworkin Journal: Meteorit Planet Sci Date: 2018-11-12 Impact factor: 2.487
Authors: Fabio Pietrucci; José C Aponte; Richard Starr; Andrea Pérez-Villa; Jamie E Elsila; Jason P Dworkin; A Marco Saitta Journal: ACS Earth Space Chem Date: 2018-06-21 Impact factor: 3.475
Authors: José C Aponte; Neyda M Abreu; Daniel P Glavin; Jason P Dworkin; Jamie E Elsila Journal: Meteorit Planet Sci Date: 2017-10-13 Impact factor: 2.487
Authors: Edward W Schwieterman; Nancy Y Kiang; Mary N Parenteau; Chester E Harman; Shiladitya DasSarma; Theresa M Fisher; Giada N Arney; Hilairy E Hartnett; Christopher T Reinhard; Stephanie L Olson; Victoria S Meadows; Charles S Cockell; Sara I Walker; John Lee Grenfell; Siddharth Hegde; Sarah Rugheimer; Renyu Hu; Timothy W Lyons Journal: Astrobiology Date: 2018-05-04 Impact factor: 4.335
Authors: José C Aponte; Jamie E Elsila; Daniel P Glavin; Stefanie N Milam; Steven B Charnley; Jason P Dworkin Journal: ACS Earth Space Chem Date: 2017-02-15 Impact factor: 3.475
Authors: Jon M Friedrich; Hannah L McLain; Jason P Dworkin; Daniel P Glavin; W Henry Towbin; Morgan Hill; Denton S Ebel Journal: Meteorit Planet Sci Date: 2018 Impact factor: 2.487