Acta Astronautica 94 (2014) 222–233

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Acta Astronautica
journal homepage: www.elsevier.com/locate/actaastro

In situ dating on Mars: A new approach to the K–Ar method

utilizing cosmogenic argon
William S. Cassata n
Lawrence Livermore National Laboratory, 7000 East Avenue, Livermore, CA 94550, USA

a r t i c l e in f o abstract

Article history: Cosmogenic argon isotopes are produced in feldspars via nuclear reactions between
Received 7 February 2013 cosmic rays and Ca and K atoms within the lattice. These cosmogenic isotopes can be used
Received in revised form as proxies for K and Ca, much like nuclear reactor-derived 39Ar and 37Ar are used as
23 July 2013
proxies for K and Ca, respectively, in 40Ar/39Ar geochronology. If Ca and K are uniformly
Accepted 28 July 2013
Available online 22 August 2013
distributed, then the ratio of radiogenic 40Ar (40Arn) to cosmogenic 38Ar or 36Ar (38Arcos or
36
Arcos) is proportional to the difference between the radioisotopic and exposure ages, as
Keywords: well as the K/Ca ratio of the degassing phase. Thus cosmogenic, radiogenic, and trapped
Mars Ar isotopes, all of which can be measured remotely and are stable over geologic time, are
Geochronology
sufficient to generate an isochron-like diagram from which the isotopic composition of the
Argon
trapped component may be inferred. Such data also provide a means to assess the extent
Cosmogenic
to which the system has remained closed with respect to 40Arn, thereby mitigating
otherwise unquantifiable uncertainties that complicate the conventional K–Ar dating
method.
& 2013 IAA. Published by Elsevier Ltd. All rights reserved.

1. Introduction may inform sample selection decisions (e.g., [25]). Regardless,

A longstanding objective of Mars research and stated goal
of the NASA Mars Exploration Research Program is to better
understand the geologic history of our planetary neighbor.
Although research on Martian meteorites provides vast
insights into Martian geology, petrology, and chronology, such
data lack geologic context. To better delineate the timescales
of climate change recorded by Mars' diverse terrains, deter-
mine the absolute ages of major events in Mars history, and
calibrate Martian cratering rates, data obtained in situ or from
returned samples are required (e.g., [10]). The engineering
challenges associated with a robotic launch from Mars render
in situ measurements more affordable and practical than a
sample return mission in the near future, albeit of consider-
ably lower precision and accuracy. If a sample return mission
comes to fruition in the future, then in situ measurements
n
Tel.: 925 423 2812.
E-mail address: cassata2@llnl.gov
technological advances in remote isotope analysis are poised
to improve our understanding of the geologic history of Mars,
and increased attention has turned to technique development
in recent years.
Efforts are underway to engineer hardware and establish
analytical protocols for in situ 87Rb–87Sr and 40K–40Ar radio-
isotopic dating. Approaches to Rb–Sr isotope measurements
have focused on laser desorption resonance ion resonance
mass spectrometry (e.g., [1]) and laser desorption plasma
ionization mass spectrometry (e.g., [10]). The strengths and
weaknesses of these methods are detailed in Coleman et al.
[10], Anderson et al. [1], and Conrad et al. [11]. Proposed
approaches to K–Ar measurements involve K elemental
analysis by laser-induced breakdown spectroscopy (LIBS;
e.g., [27,9,25]) or x-ray spectroscopy (e.g.. [28]) and Ar isotope
analysis by focal plane mass spectrometry (e.g., [17,10]),
quadrupole mass spectrometry (e.g., [22,9]), or magnetic
sector mass spectrometry [28]. Miniature quadrupole mass
spectrometers are capable of determining argon isotope ratios
and abundances at precisions of 1 and 10%, respectively [5],

0094-5765/$ - see front matter & 2013 IAA. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.actaastro.2013.07.040
 W.S. Cassata / Acta Astronautica 94 (2014) 222–233
and potassium abundance measurements by LIBS can be
determined with precisions of 0.5–5.5% [25]. Spiking samples
with 39Ar- and 41K-doped Li-rich flux material (e.g., [17]) may
considerably improve these uncertainty estimates.
It thus appears likely that achieving 10% precision on 40K/40Ar
will be possible, although the accuracy of ages inferred from
such measurements cannot be directly quantified as the K–Ar
method does not provide direct age determinations (it provides
“model ages”). Apparent ages inferred from 40K/40Ar are only as
accurate as underlying assumptions regarding the isotopic
composition of the trapped component and the extent to which
the system has remained closed with respect Ar (e.g., [26,4]). If
samples have experienced diffusive loss of Ar due to post-
crystallization reheating resulting from contact, burial, or post-
shock metamorphism, then the K–Ar method yields aberrantly
young ages. Conversely, if samples contain trapped atmospheric
or mantle-derived argon isotopes, then the K–Ar method yields
aberrantly old ages (unless accurate corrections for the trapped
component have been applied). The analysis of Martian meteor-
ites has shown that Martian rocks (1) exhibit significant inter-
sample variability in the isotopic composition of the trapped
component, (2) commonly contain multiple trapped compo-
nents located within different minerals phases (e.g., [7]), and (3)
rarely quantitatively retain radiogenic argon over geologic time.
Terrestrial rocks exhibit similar characteristics and inter-sample
variations, and without a means to constrain these variables a
K–Ar age is ambiguous, potentially misleading, and of question-
able utility. As a result, the traditional K–Ar method has been
rendered obsolete amongst geochronology labs around the
world. One cannot assign real uncertainties approaching the
analytical precision on isotope determinations unless the afore-
mentioned ambiguities can be addressed.
Fortunately, relative to terrestrial rocks, extraterrestrial
rocks often contain appreciable quantities of cosmogenic
argon isotopes. These cosmogenic isotopes provide a means
to circumvent the problems associated with assumptions that
are generally applied in K–Ar dating. In particular, incorporat-
ing cosmogenic isotopes into data reduction routines enables
one to estimate the isotopic composition of the trapped
component, recognize diffusive loss of argon, and identify
degassing mineral phases by their Ca/K ratios. In short,
cosmogenic Ar isotopes can be used as proxies for K and Ca,
thereby transforming the traditional K–Ar method into an
approach that is similar to 40Ar/39Ar dating. In this paper I
detail the isotope measurements, data reduction procedures,
and technical considerations relevant to this modified
approach to traditional K–Ar dating. I then apply the techni-
que to previously published isotope measurements on the
nakhlite MIL 03346 to demonstrate its efficacy.
2. Basic details of the modified approach to K–Ar dating
2.1. A single-phase system (e.g., feldspar or feldspathic glass)
The ubiquitous presence of non-radiogenic daughter
components in minerals commonly targeted for geochro-
nology has led to the widespread adoption of isochron
diagrams in geochronologic studies. These three-isotope
plots allow one to determine an age without making
assumptions about the isotopic composition of the
trapped component. Specifically, they exploit the linear
223
relationship that exists between the abundance of a radio-
genic daughter isotope (the y-axis numerator) and the
parent isotope to which it is related (the x-axis numerator)
when plotted relative to a non-radiogenic, stable isotope of
the same element (the x- and y-axis denominator) that is
present in fixed proportion to the initial (i.e., trapped/
extraneous) daughter isotope.
In 40Ar/39Ar dating experiments, samples are irradiated in a
nuclear reactor to generate 39Ar from K (39ArK) such that each
of the three aforementioned components (parent, daughter,
and stable reference) can be measured using a noble gas mass
spectrometer (i.e., 39ArK is used as a proxy for 40K). Following
irradiation, whole-rock fragments or individual crystals are
incrementally heated using a furnace or laser and the isotopic
composition of degassed argon is measured by mass spectro-
metry. The ratio of total 40Ar (40Artot) to 39ArK in a given
extraction generally varies over the course of an incremental
degassing experiment due to the differential release of the
trapped and radiogenic components. Such differential release
likely reflects the trapped component (40Artrap) residing in
defects, inclusions, and/or preferentially in near-surface
regions, and generates spread on a normal isochron diagram
(40Artot/36Artot vs. 39ArK/36Artot). The y-intercept defines the
isotopic composition of the trapped component and the slope
(40Arn/39ArK) is proportional to the age. Non-linearity in such
three-isotope space indicates that the system has not remained
closed with respect to 40Arn or that two or more isotopically
distinct trapped components exist.
Similar three-isotope plots (e.g., 38Artot/36Artot vs.
37
ArCa/36Artot) have been constructed to determine cosmo-
genic nuclide exposure ages (e.g., [19]). Like traditional
40
Ar/39Ar isochron diagrams, a reactor produced reference
isotope (in this case 37Ar that is generated from Ca; 37ArCa)
is used as a proxy for the parent/source component.
Incremental degassing leads to spread on the three-
isotope diagram, where the cosmogenic component
(38Arcos) is proportional to 37ArCa. The y-intercept defines
the isotopic composition of the trapped component and
the slope (38Arcos/37ArCa) is proportional to the exposure
age. This three-isotope plot is not, however, a true iso-
chron diagram, as 37ArCa is not a true proxy for the parent/
source component. Cosmic rays also interact with K, Fe, Ni,
Cr, Mn, and Ti nuclei to produce 38Arcos. Variations in the
concentration of these elements relative to Ca yield spatial
variations in 38Arcos/37ArCa. Thus chronological uniformity
(i.e., isochroneity) is not sufficient for linearity in three-
isotope space. Rather chronological and chemical unifor-
mity (i.e. isochroneity and isochemistry) are both requisite
conditions. As such, these diagrams are more accurately
termed isochemical isochrons, or “isochemochrons”.
Because the three-isotope plots described above utilize
isotopes that decay over timescales of months (37Ar) to years
(39Ar), they are not viable methods for in situ dating on Mars.
However, stable cosmogenic isotopes (e.g., 38Arcos or 36Arcos)
can be used as proxies for K and Ca, much like nuclear reactor-
derived 39Ar and 37Ar are used as proxies for K and Ca,
respectively, in 40Ar/39Ar dating. If Ca and K are uniformly
distributed, then the ratio of radiogenic 40Ar (40Arn) to 38Arcos
or 36Arcos is proportional to the ratio of the radioisotopic and
exposure ages, as well as the K/Ca ratio of the degassing
phase. Thus cosmogenic, radiogenic, and trapped Ar isotopes
224 W.S. Cassata / Acta Astronautica 94 (2014) 222–233

38
are sufficient to generate an isochemochron diagram Artot ¼ 38 Ar cos þ 38 Artrap ð2Þ
(e.g., 40Artot/36Artrap vs. 38Arcos/36Artrap or 40Artot/36Artrap vs.
36
Arcos/36Artrap; Fig. 1a). Like on a normal isochron diagram 36
Artot ¼ 36 Ar cos þ 36 Artrap ð3Þ
used in 40Ar/39Ar dating, the y-intercept defines the isotopic
38 36
composition of the trapped component. The slope is propor- Artot/ Artot of a given extraction defines the propor-
tional to the radioisotopic age, exposure age, and chemical tion of trapped and cosmogenic isotopes (assuming these
composition of the degassing phase (e.g., the plagioclase Ca/ are the only two components) according to the following
K ratio). equation:
To generate an isochemochron, samples must be incre- !
36 36 ð38 Ar=36 ArÞ cos ð38 Ar=36 ArÞtot
mentally degassed and 40Ar, 38Ar, and 36Ar isotopes must be Ar cos ¼ Artot 1 38 ð4Þ
ð Ar=36 ArÞ cos ð38 Ar=36 ArÞtrap
measured during each extraction. The following isotope
sources will be present (ignoring trivial abundances of 40Arcos): where (38Ar/36Ar)cos (the cosmogenic nuclide production
ratio) is 1.54 [30] and (38Ar/36Ar)trap (the isotopic composi-
40
Artot ¼ 40 Arn þ 40 Artrap ð1Þ tion of the Martian atmosphere) is 0.244 [2]. (40Ar/36Ar)trap is
Artot/36Artrap
40

38
Arcos/36Artrap 38
Arcos/36Artrap
Artot/36Artrap
40

38
Arcos/36Artrap 38
Arcos/36Artrap

Fig. 1. Hypothetical isochemochron diagrams. (a) Isochemochron diagram for a compositionally homogeneous, single-phase sample that has not
experienced diffusive loss (see Table 2 for a detailed calculation of each data point). Data lie on a straight line that represents mixing between a trapped
component with a 40Ar/36Ar value of 1425 (the y-intercept) and a radiogenic/cosmogenic component comprising 40Ar* and 38Arcos. The slope is
proportional to the radioisotopic age, exposure age, and chemical composition. (b) Isochemochron diagram for a compositionally homogeneous, single-
phase sample that has experienced diffusive loss. Extractions affected by diffusive loss of 40Ar* (i.e., having lower 40Ar*/38Arcos) yield curved arrays that lie
below an isochemochron defined by subsequent extractions that are unaffected by diffusive loss. (c) Isochemochron diagrams for a compositionally
heterogeneous, single-phase sample that has not experienced diffusive loss. Ca-enrichments at grain boundaries (i.e., more Ca-derived 38Arcos for given
amount of 40Ar*) yield curved arrays that lie above isochemochrons defined by subsequent extractions that sample compositionally homogeneous regions
of a grain. Conversely, K-enrichments at grain boundaries (i.e., a higher 40Ar*/38Arcos relative to subsequent extractions) yield curved arrays that lie above
the isochemochron. (d) Isochemochron diagram for a compositionally homogeneous, two-phase sample that has not experienced diffusive loss (see Table 2
for a detailed calculation of each data point). The more shallowly sloped array defined by the high temperature data reflects the lower K/Ca ratio of the
mafic minerals.
 W.S. Cassata / Acta Astronautica 94 (2014) 222–233 225

constrained by the y-intercept of an isochemochron diagram melt inclusions or as substituted cations in the mineral
and defines the proportion of trapped and radiogenic 40Ar in lattice. Thus mafic minerals are important contributors
a given extraction according to the following equation: to the total Ar budget in Martian meteorites and must be
! considered in whole-rock K–Ar dating experiments like
40
40 Ar
Ar n ¼ 40 Artot 40 Artrap ¼ 40 Artot 36 Artrap 36 ð5Þ those that may be conducted on Mars.
Ar trap Pyroxene, olivine, and Fe–Ti oxides degas at higher tem-
peratures than comparably sized feldspars and feldspathic
The ratio of the cumulative 40Arn released to the
40 glasses during laboratory degassing experiments [7,8,29,
K abundance determined using LIBS or x-ray spectro-
16,24]. Thus the release of argon from these phases can be
scopy can be used to calculate an age. Apparent ages
separated from that of feldspars and feldspathic glasses using a
inferred from such ratios are more accurate than those
sufficiently detailed incremental heating schedule. If the mafic
inferred from 40Artot/40K because they have been corrected
minerals are unaffected by diffusive loss (which is likely if
for the non-negligible trapped component.
feldspars retain 40Arn), then the high temperature data may
Like on conventional isochron diagrams used in 40Ar/39Ar
define an isochronous array with a distinct slope (Fig. 1d). The
dating, extractions affected by diffusive loss of 40Arn (i.e.,
production rates for cosmogenic 38Ar from K and Ca are one to
individual step ages that are not equivalent to the “plateau”
two orders of magnitude greater than those from Fe, Ti, Ni, Cr,
age) will not be concordant, but rather will yield curved arrays
and Mn. As such, compositional zoning with respect to the
that lie below an isochemochron defined by subsequent
latter elements is not expected to yield spurious or non-linear
extractions that are unaffected by diffusive loss (Fig. 1b). Unlike
isochron arrays. However, the heterogeneous release of Ca- and
on conventional isochron diagrams, extractions comprising gas
K-derived argon isotopes, either resulting from intra-grain
derived from regions of a crystal that are compositionally
compositional zoning or differential degassing (i.e., Ca in
heterogeneous with respect to Ca and K will also fail to yield
clinopyroxene and K in melt inclusions in olivine), may yield
linear arrays, as the ratio of 40Arn to 38Arcos is not constant. This
non-linear high-temperature arrays. Regardless, the high tem-
is true even if no diffusive loss of 40Arn has occurred (i.e., even if
perature data will always define a more shallowly sloped array
the ratio of 40Arn to K-derived 38Arcos is uniform). Grains having
that reflects the lower K/Ca ratio of the mafic minerals,
normal zoning (K-enrichment toward grain margins) yield
irrespective of the radioisotopic and exposure ages of the rock.
curved arrays with initial extractions that lie above an iso-
If the felsic and mafic components equilibrate with different
chemochron defined by subsequent extractions that sample gas
trapped components, a phenomenon that is not uncommon in
from compositionally homogeneous regions of a crystal
Martian meteorites (e.g., [7]), then distinct y-intercepts will be
(Fig. 1c). Grains having reverse zoning (Ca-enrichment toward
observed (Fig. 1d). These distinct values can be used to
grain margins) yield curved arrays with initial extractions that
determine 40Arn abundances from total 40Ar signals measured
lie below an isochemochron defined by subsequent extractions
in low and high temperature extractions (discussed in more
(Fig. 1c), much like extractions affected by diffusive loss of 40Arn
detail below).
(Fig. 1b). Thus an isochemochron will only be established if a
series of contiguous extractions are (1) unaffected by diffusive
2.3. Summary
loss of 40Arn and (2) derived from a crystal containing a
compositionally homogeneous zone with respect to Ca and
When a sample is incrementally degassed and 36Ar, 38Ar,
K1. Analysis of Martian meteorites and lunar rocks indicates
and 40Ar are measured, information about the isotopic compo-
that these criteria are generally satisfied (e.g., [7]). Even if they
sition of the trapped component(s) and chemical composition
are not, significantly more information about the system can be
of the carrier phases can be gleaned from a 40Artot/36Artrap vs.
gleaned than from a traditional K–Ar experiment. Moreover, in 38
Arcos/36Artrap isochemochron diagram. Samples that are com-
nominally Ca-free, K-rich rocks and minerals (e.g., jarosite),
38 positionally zoned with respect to Ca and K and/or have
Arcos is essentially a direct proxy for K (with minor contribu-
experienced diffusive loss of 40Arn may fail to define a linear
tions from e.g. Fe), comparable to 39ArK in the 40Ar/39Ar dating.
array, but will yield diagnostic patterns that reveal petrologic
and geochronologic information about the sample. Although
2.2. Multi-phase systems (felsic and mafic) considerable uncertainties may exist, such a data acquisition
and reduction routine represents a significant improvement
Thus far I have only discussed applications of the isoche- upon the traditional K–Ar method. The additional time and
mochron approach to dating a single phase like feldspar or energy devoted to an incremental degassing experiment pro-
feldspathic glass, the predominate hosts of 40Arn in Martian vides a means to assess the accuracy of results that might
meteorites. Volcanic rocks collected in situ will, in all likelihood, otherwise be ambiguous or inaccurate. In the following section
contain appreciable quantities of pyroxene, olivine, and Fe–Ti I will show that these data can further be used to approximate
oxides, all of which are sources of cosmogenic Ar isotopes the Ca/K ratio of the felsic and mafic phases and generate an
produced via nuclear reactions with Ca, Fe, Ti, Ni, Cr, and age spectrum analogous to that used in 40Ar/39Ar dating.
Mn. In addition to cosmogenic isotopes, it is not uncom-
mon for pyroxenes in Martian meteorites to host over 3. A hypothetical example calculation
25% of the total K, and therefore 40Arn, either in fluid and
It was noted above that the slope of an isochemochron
1
It is also possible that data obtained from a normally zoned sample
diagram is predominantly dependent on the K/Ca ratio of
that experienced diffusive loss fortuitously define a linear to curvilinear the degassing phase, exposure age, and radioisotopic age.
array with a positive y-intercept. It follows that the ratio of the slopes defined by the felsic
226 W.S. Cassata / Acta Astronautica 94 (2014) 222–233

and mafic phases is proportional to the ratio of the
individual K/Ca ratios, as the radioisotopic and exposure
ages a priori do not vary between mineral phases of a
given rock (at least when mineral phases yield linear
arrays that are unaffected by diffusive loss). In this section
I will show that the ratio of the slopes, when coupled with
compositional data obtained by LIBS or x-ray spectroscopy,
can be used to iteratively solve for the abundances of K
and Ca in the felsic and mafic phases. These results
constrain the relationship between 38Arcos and K in each
phase, which can in turn be used to generate apparent age
spectra from incremental release data, much like 40Ar/39Ar
age spectra are based on the relationship between
39
Ar and K.
For the purposes of this discussion, consider a hypothe-
tical igneous rock (composition given in Table 1) in which
plagioclase (Ca/K ¼10) is the only felsic phase and pyrox-
ene (Ca/K ¼300) is the only mafic phase. Let us assume
that the rock crystallized at 1300 Ma and has been
exposed to cosmic rays at the Martian surface for
100 Ma. To a good approximation, we can assume that
Fe, Ti, Ni, Cr, and Mn are sited within the pyroxene. Thus
the following sources of 38Arcos will be present in our
hypothetical rock:
38
Ar cos ¼ 38 ArCaplag þ 38 ArKplag þ ArCapyx
þ 38 ArKpyx þ 38 ArFe;Cr;Mn;Ti;Nipyx ð6Þ

Table 1
Model parameters for hypothetical mafic rock.

Parameter Parameter value Unit

Radioisotopic age 1300 Ma

Exposure age 100 Ma
Cosmogenic 38Ar/36Ar ratio 1.54 atoms/atoms
Atmospheric 38Ar/36Ar ratio 0.244 atoms/atoms

Whole rock information

Plagioclase concentration 20 weight-%

Pyroxene concentration 80 weight-%
K concentration 0.1 weight-%
Ca concentration 10 weight-%
Fe concentration 18.35 weight-%
38
ArK abundance 1.30E-13 mol
38
ArCa abundance 7.98E-12 mol
38
ArFe abundance 8.02E-13 mol

Plagioclase information

Trapped 40Ar/36Ar ratio 1425 atoms/atoms

Ca/K ratio 10 atoms/atoms
Fraction of total K 0.7
38
Arcos production rate 3.33E-14 mol/g/Ma
38
Arcos abundance 6.67E-13 mol
40
Arn abundance 2.26E-10 mol

Pyroxene information

Trapped 40Ar/36Ar ratio 28 atoms/atoms

Ca/K ratio 300 atoms/atoms
Ca:Mg:Fe ratio 0.7:0.3:1.0
Fraction of total K 0.3
38
Arcos production rate 1.03E-13 mol/g/Ma
38
Arcos abundance 8.25E-12 mol
40
Arn abundance 9.69E-11 mol

Model results

True Ω 30.0
F (fraction of total 38Arcos in plagioclase) 0.075
Ω1 28.9
Plagioclase 40Arn/38Arcos ratio 339 atoms/atoms
Pyroxene 40Arn/38Arcos ratio 11.7 atoms/atoms
Ω2 26.0
Plagioclase 40Arn/38Arcos ratio 339 atoms/atoms
Pyroxene 40Arn/38Arcos ratio 13 atoms/atoms
Inferred plagioclase Ca/K ratio 10.4 atoms/atoms
Inferred pyroxene Ca/K ratio 276 atoms/atoms
Ω3 29.8
Plagioclase 40Arn/38Arcos ratio 390 atoms/atoms
Pyroxene 40Arn/38Arcos ratio 13.1 atoms/atoms
Inferred plagioclase Ca/K ratio 9.98 atoms/atoms
Inferred pyroxene Ca/K ratio 300 atoms/atoms
Inferred age 1286 Ma
 W.S. Cassata / Acta Astronautica 94 (2014) 222–233 227

Table 2 shows the 40Ar, 38Ar, and 36Ar isotopic data that
would obtained from a 10-step incremental degassing experi-
ment, assuming the release of argon follows plagioclase and
pyroxene diffusion kinetics reported in Cassata et al. [6,8]. The
relative abundance of trapped atmospheric argon to radiogenic
and cosmogenic argon in a given extraction was arbitrarily
varied between 0 and 0.5 to generate spread on the isoche-
mochron diagram (Fig. 2a). To constrain the relationship
between 38Arcos and K in plagioclase and pyroxene, we must
determine the fraction of total 38Arcos that is sited in each
phase. Such information can be deduced from a plot of
40 n 38
Ar / Arcos as a function of the cumulative fraction of 38Arcos
released, where plagioclase and pyroxene have distinct ratios
that reflect their compositions (Fig. 2c). The fraction of total
38
Arcos that is sited within plagioclase (F) is given by the
x-axis value (in this case x¼7.5) corresponding to the marked
decrease in 40Arn/38Arcos. A detailed incremental heating
schedule better isolates the diffusive loss of gases from
individual mineral phases, and therefore affords more precise
constraints the relative distribution of 38Arcos. Having con-
strained F, Eq. (6) can then be sub-divided into the following:
ArCaplag þ 38 ArKplag ¼ 38 Ar cos n F
ArCapyx þ 38 ArKpyx þ 38 ArFe;Cr;Mn;Ti;Nipyx ¼ 38 Ar cos n ð1FÞ ð8Þ
The relative production rates for 38Arcos from K, Ca, Fe,
Ti, Ni, Cr, and Mn are given by the following equation [13]:
PR ¼ 8:08½Ca þ12:9½K þ0:44½Fe þ Ni þ 1:70½Tiþ Cr þMn;
ð9Þ
where PR is in units of 10 –13
mol/Ma and elemental
concentrations are in weight-%. Thus 38ArCa, 38ArK, and
38
ArFe,Cr,Mn,Ti,Ni can be extracted from Eq. (9) using the
whole rock composition determined by LIBS or x-ray
spectroscopy. K and Ca account for 495% of the total
38
Arcos budget in nominally basaltic rocks, with Fe
accounting for 490% of the remaining 38Arcos. As such,
K, Ca, and Fe concentration measurements are adequate to
characterize the system, and for the remainder of
this discussion 38ArFe,Cr,Mn,Ti,Ni will be approximated
by 38ArFe. The total 38Arcos budget can thus be further
source-attributed according to the following equations:
38
ArCa ¼ 38 ArCaplag þ 38 ArCapyx
 
8:08½Ca
¼ 38 Ar cos ð10Þ
ð7Þ 8:08½Ca þ 12:9½K þ 0:44½Fe

Table 2
Incremental degassing data for hypothetical mafic rock.

Temp. Time Fractional 40

Artrap 40
Arn 40
Artrap 38
Arcos 38
Artrap 36
Arcos 36
Artrap 40
Artot 38
Artot 36
Artot
(1C) (s) Loss (%) (mol) (mol) (mol) (mol) (mol) (mol) (mol) (mol) (mol)

Plagioclase
400 600 0.002 0.5 4.52E-13 4.52E-13 1.33E-15 7.75E-17 8.66E-16 3.17E-16 9.05E-13 1.41E-15 1.18E-15
500 600 0.015 0.45 2.94E-12 2.41E-12 8.67E-15 4.12E-16 5.63E-15 1.69E-15 5.35E-12 9.08E-15 7.32E-15
600 600 0.069 0.4 1.21E-11 8.10E-12 3.58E-14 1.39E-15 2.33E-14 5.68E-15 2.02E-11 3.72E-14 2.89E-14
700 600 0.225 0.35 3.52E-11 1.90E-11 1.04E-13 3.25E-15 6.75E-14 1.33E-14 5.42E-11 1.07E-13 8.08E-14
800 600 0.545 0.3 7.24E-11 3.10E-11 2.13E-13 5.31E-15 1.39E-13 2.18E-14 1.03E-10 2.19E-13 1.60E-13
900 600 0.920 0.25 8.49E-11 2.83E-11 2.50E-13 4.84E-15 1.62E-13 1.99E-14 1.13E-10 2.55E-13 1.82E-13
1000 600 1.000 0.2 1.81E-11 4.53E-12 5.35E-14 7.77E-16 3.47E-14 3.18E-15 2.27E-11 5.43E-14 3.79E-14
1200 600 1.000 0.15 2.26E-14 3.99E-15 6.67E-17 6.83E-19 4.33E-17 2.80E-18 2.66E-14 6.74E-17 4.61E-17
1400 600
Fusion

Pyroxene
400 600
500 600
600 600
700 600
800 600
900 600
1000 600 0.000 0.5 9.69E-15 9.69E-15 8.25E-16 8.45E-17 5.36E-16 3.46E-16 1.94E-14 9.10E-16 8.82E-16
1200 600 0.002 0.45 1.45E-13 1.19E-13 1.24E-14 1.04E-15 8.04E-15 4.25E-15 2.64E-13 1.34E-14 1.23E-14
1400 600 0.011 0.4 8.82E-13 5.88E-13 7.51E-14 5.12E-15 4.88E-14 2.10E-14 1.47E-12 8.02E-14 6.98E-14
Fusion 1.000 0.35 9.59E-11 5.16E-11 8.17E-12 4.50E-13 5.30E-12 1.84E-12 1.48E-10 8.62E-12 7.15E-12

Whole rock
400 600 4.52E-13 4.52E-13 1.33E-15 7.75E-17 8.66E-16 3.17E-16 9.05E-13 1.41E-15 1.18E-15
500 600 2.94E-12 2.41E-12 8.67E-15 4.12E-16 5.63E-15 1.69E-15 5.35E-12 9.08E-15 7.32E-15
600 600 1.21E-11 8.10E-12 3.58E-14 1.39E-15 2.33E-14 5.68E-15 2.02E-11 3.72E-14 2.89E-14
700 600 3.52E-11 1.90E-11 1.04E-13 3.25E-15 6.75E-14 1.33E-14 5.42E-11 1.07E-13 8.08E-14
800 600 7.24E-11 3.10E-11 2.13E-13 5.31E-15 1.39E-13 2.18E-14 1.03E-10 2.19E-13 1.60E-13
900 600 8.49E-11 2.83E-11 2.50E-13 4.84E-15 1.62E-13 1.99E-14 1.13E-10 2.55E-13 1.82E-13
1000 600 1.81E-11 4.54E-12 5.43E-14 8.61E-16 3.53E-14 3.53E-15 2.27E-11 5.52E-14 3.88E-14
1200 600 1.68E-13 1.23E-13 1.24E-14 1.04E-15 8.08E-15 4.25E-15 2.91E-13 1.35E-14 1.23E-14
1400 600 8.82E-13 5.88E-13 7.51E-14 5.12E-15 4.88E-14 2.10E-14 1.47E-12 8.02E-14 6.98E-14
Fusion 9.59E-11 5.16E-11 8.17E-12 4.50E-13 5.30E-12 1.84E-12 1.48E-10 8.62E-12 7.15E-12

Fractional loss data represent the fraction of uniformly distributed 40Ar*, 38Arcos, and 36Arcos released in a given extraction.
Plagioclase fractional loss data were calculated using diffusion parameters reported in Cassata et al. [6].
Pyroxene fractional loss data were calculated using diffusion parameters reported in Cassata et al. [8].
228 W.S. Cassata / Acta Astronautica 94 (2014) 222–233

Artot/36Artrap
40

38
Arcos/36Artrap 38
Arcos/36Artrap

Fig. 2. Hypothetical isochemochron diagrams for a compositionally homogeneous, two-phase sample that has (a) not experienced diffusive loss (see
Table 2 for a detailed calculation of each data point) and (b) has experienced 10% loss of 40Ar*. (c) Plot of 40Ar*/38Arcos as a function of the cumulative
fraction of 38Arcos released for the hypothetical sample shown in (a). The fraction (F) of total 38Arcos that is sited within plagioclase is given by the marked
decrease in 40Ar*/38Arcos at x¼ 0.075. (d) Plot of 40Ar*/38Arcos as a function of the cumulative fraction of 40Ar* released for the hypothetical sample shown in
(b). Because this sample experienced diffusive loss, it fails to yield a well-defined plateau. (e) Apparent age spectrum for the hypothetical sample shown in
(a) and (c). (f) Apparent age spectrum for the hypothetical sample shown in (b) and (d).

38
ArK ¼ 38 ArKplag þ 38 ArKpyx 38
ArFe;Cr;Mn;Ti;Ni  38 ArFe  38 ArFepyx
   
12:9½K 0:44½Fe
¼ 38 Ar cos ð11Þ  38 Ar cos ð12Þ
8:08½Ca þ 12:9½K þ 0:44½Fe 8:08½Ca þ 12:9½K þ 0:44½Fe
 W.S. Cassata / Acta Astronautica 94 (2014) 222–233 229

Eqs. (10)–(12) cannot be directly solved using compositional
data obtained by LIBS or x-ray spectroscopy without knowledge
of the K/Ca ratio of either plagioclase or pyroxene. However, the
ratio of 40Arn/38Arcos in plagioclase to that in pyroxene (defined
here as Ω1) is proportional to the ratio of the individual K/Ca
ratios (defined here as Ω), and through an iterative process
it is possible to solve for the absolute K/Ca ratios of the phases.
In our working example, the plagioclase and pyroxene
40
Arn/38Arcos values (Fig. 2c; Table 1) are 339 and 11.7,
respectively, which yields Ω1 ¼28.9 (Table 1). Although in
this instance Ω1 only underestimates the true ratio of the
individual Ca/K ratios (Ω¼30; Table 1) by o5%, contribu-
tions to the 38Arcos signal from elements other than Ca (e.g.,
K and Fe) can result in more significant discrepancies
between Ω1 and Ω in rocks of different chemical composi-
tions (i.e., more K-rich rocks), and additional steps must be
taken to maximize accuracy.
To improve the correspondence between Ω1 and Ω we
can correct individual step 38Arcos measurements for
contributions from Fe. As noted above, to a good approx-
imation Fe is sited within pyroxene, and thus Fe-
corrections are not required for low temperature (i.e.,
plagioclase) 38Arcos measurements. If we assume that Fe
is uniformly distributed relative to Ca and K in pyroxene,
the 38Arcos abundance in a given extraction (38Aricos) can be
corrected using to the following equation:
 
38 0:44½Fe 1
Aricos no Fe ¼ 38 Aricos 1
8:08½Ca þ12:9½K þ0:44½Fe 1F
ð13Þ
The resulting Fe-corrected 40Arn/38Arcos values for plagio-
clase (unchanged) and pyroxene are 339 and 13.0, respectively
(Table 1). The ratio of the Fe-corrected 40Arn/38Arcos ratios
(defined here as Ω2) is 26.1. Provided that the low temperature
phase (i.e., plagioclase) has a lower Ca/K ratio than the high
temperature phase (i.e., pyroxene), as is true of all Martian
meteorites identified to date, Ω2 will always underestimate Ω.
We can now preliminarily attribute the total 38Arcos budget to

Table 3
Sample parameters and calculation results for MIL 03346.

Parameter Parameter value Unit

a
Radioisotopic age 13397 89 Ma
Total 38Arcosa 9.62E-16 mol

Whole rock information

Ca concentrationb 10.3 weight-%

Fe concentrationb 14.8 weight-%
K concentrationc 0.135 weight-%
Massd  1.12 mg

Mesostasis glass informationa

Trapped 40Ar/36Ar ratio 1425 7 230 atoms/atoms

Ca/K ratio  2.2 atoms/atoms

Pyroxene informationa

Trapped 40Ar/36Ar ratio 28 78 atoms/atoms

Ca/K ratio 47000 atoms/atoms

Calculation results

Mesostasis glass trapped 40Ar/36Ar ratio 7007 270 atoms/atoms

Pyroxene trapped 40Ar/36Ar ratio 25 725 atoms/atoms
F (fraction of total 38Arcos in mesostasis) 0.045
True Ω 43200
Ω1 17787 111
Mesostasis 40Arn/38Arcos ratio 157007 780 atoms/atoms
Pyroxene 40Arn/38Arcos ratio 8.81 7 0.33 atoms/atoms
Ω2 1688 7 106
Mesostasis 40Arn/38Arcos ratio 157007 780 atoms/atoms
Pyroxene 40Arn/38Arcos ratio 9.29 7 0.35 atoms/atoms
Inferred mesostasis Ca/K ratio 1.42 atoms/atoms
Inferred pyroxene Ca/K ratio 2479 atoms/atoms
Ω3 35777 224
Mesostasis 40Arn/38Arcos ratio 332007 1660 atoms/atoms
Pyroxene 40Arn/38Arcos ratio 9.29 7 0.35 atoms/atoms
Inferred mesostasis Ca/K ratio 1.38 atoms/atoms
Inferred pyroxene Ca/K ratio 4989 atoms/atoms
Fraction of total K in mesostasis 0.985
Fraction of total K in pyroxene 0.015
Mesostasis 38Arcos/gram-K 1194 mol/g-K
Mesostasis plateau age 13417 52 Ma

a
Cassata et al. [7].
b
Day et al. [12].
c 39
K concentration based on the total release of ArK.
d 37
Mass calculated based on the total release of ArCa and Ca concentration of Day et al. [12].
230 W.S. Cassata / Acta Astronautica 94 (2014) 222–233

Artot/36Artrap
40

38
Arcos/36Artrap

Fig. 3. (a) Isochemochron diagram for a whole-rock analysis of Martian meteorite MIL 03346 (argon isotope measurements from Cassata et al. [7]). Partially
transparent symbols indicate extractions comprising gas derived from both felsic and mafic phases. (b) Apparent age spectrum (see text for calculation
details). Filled symbols indicate data that were included in the plateau age calculation. Open symbols to the left of the plateau are affected by diffusive loss
of 40Ar*. Open symbols to the right of the plateau comprise gas derived from both felsic and mafic phases, which cannot be accurately corrected for trapped
40
Ar*. (c) Plot of 40Ar*/38Arcos as a function of the cumulative fraction of 38Arcos released (log scale). The fraction (F) of total 38Arcos that is sited within the
mesostasis glass is given by the marked decrease in 40Ar*/38Arcos at x  0.035 (mid-point of decline; see inset). This panel highlights the high-temperature
(mafic) 40Ar*/38Arcos value. (d) Plot of 40Ar*/38Arcos as a function of the cumulative fraction of 40Ar* released (log scale). This panel highlights the low-
temperature (K-rich, felsic) 40Ar*/38Arcos value.

individual elements within each mineral phase beginning with corrected according to the following equation:
38
ArCaplag by solving the following equation: !
! 38 i 38 i 8:08
38 38 38 Ar cos no K;Fe ¼ Ar cos no Fe ½K
ð16Þ
ArCaplag Artot Ωð1FÞ ArFe Ω 8:08 þ12:9½Ca
38
A rtot ¼ 1 þ 38 Ω 38
F ArCatot 38 ArCa
plag
ArCatot 38 ArCa plag

ð14Þ The K,Fe-corrected 40Arn/38Arcos values for plagioclase

where Ω2 is substituted for Ω. Substituting the results of
Eq. (14) into Eqs. (10)–(12) completes the preliminary
elemental source attribution (Table 1), and initial esti-
mates of the plagioclase and pyroxene Ca/K ratios are
extracted from the following equation:
38  
½Ca ArCaplag 12:9
¼ ð15Þ
½K 38
ArKplag 8:08
The estimated plagioclase and pyroxene Ca/K ratios
(Table 1) of 10.4 and 276, respectively, are accurate to 4
and 8%. To improve the correspondence between Ω2 and Ω
we must correct individual step 38Arcos measurements for
contributions from K. If we assume that K is uniformly
distributed relative to Ca, 38 Aricos no Fe values can be
and pyroxene (Table 1) are 390 and 13.1, respectively. The
ratio of the K,Fe-corrected 40Arn/38Arcos ratios (defined
here as Ω3) is 29.8, which is indistinguishable at 1% from
true the Ω of 30. A second iteration through the elemental
source attribution (Eqs. (10)–(12)) and K-correction (Eq.
(16)) yields Ω3 ¼30.0 and plagioclase and pyroxene Ca/K
ratios of 300 and 10, respectively (the true values). Thus
two iterations are sufficient to complete a source attribu-
tion that is accurate to better than 1% (excluding real
analytical uncertainties). We can then solve for the con-
centration of K in each phase according to the following
equation:
!
38
ArKX
½KX ¼ ½K 38
ð17Þ
ArK
 W.S. Cassata / Acta Astronautica 94 (2014) 222–233
Having solved for the abundance of K that is in
plagioclase and pyroxene, and therefore the relationship
between 38Arcos and K in each phase, one can convert the
40
Arn/38Arcos ratio evolution diagram into an age spectrum
(Fig. 2e). Discordant low-temperature data or spurious
high-temperature data that depart from the “plateau”
age can be disregarded in calculating an age (Fig. 2f). To
improve accuracy it is essential that adequate thermal
separation of phases be achieved with the thermal degas-
sing schedule. The more detailed the schedule, the more
likely that a series of consecutive steps of the low
temperature phase will be chemically homogeneous, free
of diffusive loss, and uncontaminated by gas from higher
temperature phases.
4. Feasibility
An important consideration in assessing the feasibility of
the approach described herein is the minimum exposure
duration required to generate a measurable signal of 38Arcos.
Assuming a near-surface 38Arcos production rate of
1.25  1010 atoms/g/Ma (e.g., [18]), vacuum pyrolysis capa-
city of  1 g [14], and quadrupole mass spectrometer detec-
tion limit of  109 atoms (e.g., [28]), exposure durations of
100 ka are required to generate measurable signals of
38
Arcos. To achieve 10% precision on 10 or more successive
extractions, exposure durations of 410 Ma would be
required, with longer durations necessary for more deeply
buried rocks. This minimum required radiation dose is
probably substantially exceeded by outcropping bedrock, as
erosion rates are sufficiently slow (e.g., 0.03–10 mm/Ma;
[15]) such that mass loss is generally not a concern. Similarly,
regolith boulders are likely to have received sufficient radia-
tion doses if their exposure durations are comparable to
those of typical lunar regolith rocks (e.g., 10–300 Ma).
A second consideration in assessing the feasibility of K–Ar
dating is the power required to degas basaltic rocks by
pyrolysis. According to the Stefan–Boltzmann law, the radia-
tive output from 1 g of basalt with a density of
3 g/cm3, emissivity of 0.7, and spherical geometry is 72.3 W
when heated to 1400 1C. Maintaining a sample
at this temperature would thus require more than 57%
of the available power produced by the radioisotope thermo-
electric generator aboard Curiosity (125 W at the beginning
of the mission; [20]), assuming perfect energy conversion.
Given such constraints, quantitative extraction of argon
might be challenging, although more power may be available
on future rover missions, particularly if needed for key
experiments. While the requirement of completely degassing
Ar is also an issue for traditional K–Ar dating, the approach
described herein certainly consumes more power.
A final consideration is the uncertainty introduced into
age determination by ambiguities regarding the K-spallation
38
Ar/36Ar ratio and atmospheric 38Ar/36Ar ratio on Mars. In
the case of SNC meteorites, Ca/K ratios in felsic phases vary
between 1 and 4100 (e.g., [7]). Cosmogenic 38Ar/36Ar
ratios observed in lunar basalts that have protracted expo-
sure durations (4100 Ma) and similar compositional varia-
tions lie within  5–10% of 1.5 (e.g., [24,23]). Thus typical
variations in potassium concentration do not appear to have
significant effects on the cosmogenic 38Ar/36Ar ratio in lunar
231
rocks. Likewise, estimates of the Martian atmospheric
38
Ar/36Ar ratio are reasonably constrained between 0.182
and 0.256 (see review by [3]). Thus while assumptions
regarding the isotopic composition of atmospheric and
cosmogenic argon introduce uncertainty into age determina-
tions, it is not likely to exceed  10%. Moreover, measure-
ments of the isotopic composition of atmospheric argon
obtained from the Mars Science Laboratory mission may
significantly reduce this uncertainty.
5. A case study
In this section I work through an example calculation
using previously published data on the relatively un-
shocked [21] Martian meteorite MIL 03346, an igneous
rock that may be a reasonable analog for those on the
surface of Mars. Sample parameters and calculation results
are given in Table 3 and complete argon isotope data can
be found in Table S1. By inspection of the isochemochron
diagram shown in Fig. 3 it is apparent that at least two
distinct mineral phases are present. A linear regression to
the low temperature data (derived from mesostasis glass)
yields a (40Ar/36Ar)trap value of 700 7270, which is distin-
guishable from the previously identified trapped ratio
(1425 7230; [7]) at 1s. The difference arises primarily
due to diffusive 40Arn loss in initial extractions, which
skews the isochemochron toward lower y-intercept values.
The higher temperature data associated with the release of
Ar from pyroxenes and other mafic phases form a sub-
horizontal array with no clearly defined y-intercept. Such a
non-linear array likely reflects compositional heterogene-
ity with respect to Ca and K and or differential degassing
of mafic phases. Regardless, it is safe to assume
that (40Ar/36Ar)trap is less than 54.2711.3, the minimum
40
Artot/36Aratm value defined by the high-temperature
extractions (otherwise the inferred age would be nega-
tive). Thus adopting a value of 25725, which encom-
passes all the possible values between zero and the
aforementioned datum, is a conservative approach.
Figs. 3c and d illustrate the ratio of 40Arn/38Arcos as a
function of the cumulative fraction of 38Arcos and 40Arn
released, respectively. Total 40Ar signals in plagioclase and
pyroxene extractions were corrected using (40Ar/36Ar)trap
values of 7007270 and 25725, respectively. The marked
decrease in 40Arn/38Arcos at F¼0.035 (Fig. 3c inset) reflects the
transition from felsic to mafic derived argon isotopes. The
40 n 38
Ar / Arcos values of the felsic and mafic phases define an Ω1
value of 17787111 (Table 3), which significantly underesti-
mates the true Ω of 43000 (Table 3). The Fe-corrected
40 n 38
Ar / Arcos values define an Ω2 of 16887106 (Table 3). A
preliminary source attribution using Eq. (14) and Eqs. (10)–(12)
yields felsic and mafic Ca/K ratios of 1.42 and 2479, respectively
(Table 3). The resulting K,Fe-corrected 40Arn/38Arcos values
define an Ω3 of 35777224 and felsic and mafic Ca/K ratios
of 1.38 and 4989 (Table 3). After solving for the abundance of K
that is in mesostasis glass and pyroxene using Eq. (17), we can
convert the 40Arn/38Arcos ratio evolution diagram into an age
spectrum (Fig. 3) using the measured 40Arn/38Arcos value and
calculated 38Arcos/40K. The mesostasis glass defines an apparent
plateau age of 1341752 Ma, which is indistinguishable from
the previously determined 40Ar/39Ar age of 133978 Ma
232 W.S. Cassata / Acta Astronautica 94 (2014) 222–233
(Fig. 3). For comparison, the inferred K–Ar age based on the
total release of 40Ar and 39ArK [7] is 1468 Ma. Thus in this
instance the effect of not correcting for trapped 40Ar is only
partially offset by the effect of not correcting for diffusive loss
of 40Arn, resulting in an age that is 10% too old. While such an
age may be acceptably accurate in hindsight, one has no
means to evaluate these considerations when using the
traditional K–Ar method, and rocks on the Martian surface
may not be so well behaved. Clearly the isochemochron
approach is preferable as one may directly assess the isotopic
composition of the trapped component and the extent to
which the system has remained closed.
6. Conclusions
Application of the conventional K–Ar dating method to
extraterrestrial materials yields ambiguous and often inac-
curate results. Regardless of the achievable precision on
in situ isotopic and elemental abundance ratios, the validity
of fundamental assumptions regarding the isotopic composi-
tion of the trapped component and the extent to which the
system remains closed with respect to 40Arn cannot be
directly assessed. These assumptions, which may bias results
toward anomalously old or young ages, introduce uncon-
strained uncertainty into age estimates. Such shortcomings
of the traditional K–Ar method can, at least in part, be
overcome by incorporating cosmogenic argon isotopes that
serve as proxies for Ca and K into data reduction routines.
This modified approach to K–Ar dating enables one to
estimate the isotopic composition of the trapped component,
recognize diffusive loss of argon, and identify degassing
mineral phases by their Ca/K ratios. As such, it may be
possible to achieve accuracies on in situ K–Ar age determina-
tions that approach the analytical uncertainties on isotopic
and elemental abundance ratios. It is imperative to adopt
such an approach if efforts to determine in situ K–Ar ages
that are accurate to 10–20% are to be realized.
Acknowledgments
This work was performed under the auspices of the U.S.
Department of Energy by Lawrence Livermore National
Laboratory under Contract DE-AC52-07NA27344.
Appendix A. Supplementry material
Supplementary data associated with this article can be
found in the online version at http://dx.doi.org/10.1016/j.
actaastro.2013.07.040.
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