minerals

Review
Thermochronology of Alkali Feldspar and Muscovite at
T > 150 ◦ C Using the 40Ar/39Ar Method: A Review
Richard A. Spikings 1, * and Daniil V. Popov 2

1 Department of Earth Sciences, University of Geneva, 1205 Geneva, Switzerland

2 School of Environment, Earth and Ecosystem Sciences, The Open University, Walton Hall,
Milton Keynes MK7 6AA, UK; [email protected]
* Correspondence: [email protected]

Abstract: The 40 Ar/39 Ar method applied to K-feldspars and muscovite has been often used to con-
struct continuous thermal history paths between ~150–600 ◦ C, which are usually applied to structural
and tectonic questions in many varied geological settings. However, other authors contest the use
of 40 Ar/39 Ar thermochronology because they argue that the assumptions are rarely valid. Here we
review and evaluate the key assumptions, which are that (i) 40 Ar is dominantly redistributed in
K-feldspars and muscovite by thermally-driven volume diffusion, and (ii) laboratory experiments
(high temperatures and short time scales) can accurately recover intrinsic diffusion parameters that
apply to geological settings (lower temperatures over longer time scales). Studies do not entirely
negate the application of diffusion theory to recover thermal histories, although they reveal the
paramount importance of first accounting for fluid interaction and secondary reaction products via
a detailed textural study of single crystals. Furthermore, an expanding database of experimental
evidence shows that laboratory step-heating can induce structural and textural changes, and thus



extreme caution must be made when extrapolating laboratory derived rate loss constants to the


geological past. We conclude with a set of recommendations that include minimum sample charac-
Citation: Spikings, R.A.; Popov, D.V.
terisation prior to degassing, an assessment of mineralogical transformations during degassing and
Thermochronology of Alkali Feldspar
the use of in situ dating.
and Muscovite at T > 150 ◦ C Using
the 40 Ar/39 Ar Method: A Review.
Keywords: 40 Ar/39 Ar; thermochronology; diffusion; K-feldspar; muscovite; in situ dating
Minerals 2021, 11, 1025. https://
doi.org/10.3390/min11091025

Academic Editor: Koen De Jong

1. Introduction
Received: 19 August 2021 Many geological processes alter the temperature of minerals, and hence an accurate,
Accepted: 17 September 2021 quantitative determination of that change can be used to study a wide range of phe-
Published: 21 September 2021 nomena, such as metamorphism, deformation, exhumation and burial. The recovery of
time(t)-Temperature(T) paths from isotopic data exploits the thermally driven diffusive
Publisher’s Note: MDPI stays neutral loss of isotopes that form by spontaneous radioactive decay, which leads to several key
with regard to jurisdictional claims in assumptions that form the basis of most thermochronological methods. Arguably the
published maps and institutional affil-
most important assumption is that thermally activated volume diffusion has been the
iations.
dominant influence on the redistribution and loss of daughter isotopes from minerals.
The diffusive process either results in the redistribution of isotopes towards a mineral or
subgrain boundary, or recrystallizes lattice defects (e.g., fission tracks). However, isolating
the effects of temperature on isotope mobility from other phenomena such as fluid induced
Copyright: © 2021 by the authors. mineral reactions and structural transformations (e.g., [1–3]) is challenging. The second
Licensee MDPI, Basel, Switzerland. key assumption is that laboratory diffusion experiments at high temperatures replicate the
This article is an open access article physical mechanisms that occur with natural rates of cooling and heating over geological
distributed under the terms and
timescales. Here we review published research on whether these assumptions hold for
conditions of the Creative Commons
the alkali feldspar and muscovite 40 Ar/39 Ar thermochronological methods, where some
Attribution (CC BY) license (https://
studies have suggested these can recover thermal histories at ~150–350 ◦ C (e.g., [4–6]) and
creativecommons.org/licenses/by/
~300–600 ◦ C [7–11], respectively. Many studies have questioned the applicability of these
4.0/).

Minerals 2021, 11, 1025. https://doi.org/10.3390/min11091025 https://www.mdpi.com/journal/minerals

Minerals 2021, 11, 1025 2 of 25

methods and argued that the migration of Ar isotopes in alkali feldspar and muscovite is
governed by different mechanisms in the laboratory and during the geological past, and
thus cannot be described using a single set of diffusion parameters [2,3,12–17]. Only a small
percentage of thermochronological studies have developed and applied thermochronome-
ters that can generate continuous t-T paths at T > 150 ◦ C, while the most frequently used
(fission track and (U-Th/He)) are sensitive to T < 150 ◦ C. Therefore, we aim to provide
ideas to stimulate further research into how to test the aforementioned key assumptions,
and perhaps identify intra-grain regions where natural argon diffusion profiles may have
been preserved and can be recovered intact.

2. Recovering Continuous Thermal History Information Using the 40 Ar/39 Ar Method

Some studies of Ar in K-feldspars and muscovite suggest that their Ar isotopic com-
positions can be exploited to recover accurate, continuous t-T paths at T ~150–350 ◦ C
(e.g., [4–6]) and ~300–600 ◦ C [7–11], respectively (Figure 1), in some cases. Following Fick’s
law of diffusion, thermochronological methods utilise a mathematical description that
relates properties of the host structure (activation energy of diffusion, Ea , and absolute
diffusivity, D0 ), cooling rate, the geometry and size of the diffusion domain(s) (i.e., length
scale(s) for diffusion) and t-T history with degree of daughter isotope loss (e.g., [4]). There-
fore, the application of thermochronology to any particular mineral and decay scheme is
completely dependent on whether or not the user (i) can demonstrate that the daughter
isotope has been lost by diffusion, both in the laboratory and in nature, (ii) can show that
laboratory (high-temperature) and natural (low-temperature) diffusion followed the same
Arrhenius relationship, (iii) has a knowledge of the intrinsic diffusion properties of the
mineral phase, and (iv) can determine how many length scales exist within a single or
bulk collection of crystals, and how these different length scales (domains) interact. The
user must also understand how the displacing daughter isotope is redistributed once it
reaches the host mineral surface. Is the mineral boundary open to the extent that it can
be accurately approximated to have a zero concentration of the diffusing isotope, or not
(e.g., [18–20])?
Two major approaches have been used to extract Ar isotope data for the purpose of
thermochronology. The first approach is step-heating analysis, where one or several grains
of either alkali feldspar or muscovite are degassed in a resistance furnace attached to a
thermocouple (larger volume fractions), or using an infra-red laser coupled to a pyrometer
(lower volume samples). Heating schedules are frequently cycled, such that individual or
sequences of heating steps are repeated with an overall increase in temperature. The two
distinct sources of information obtained from a step-heating experiment are the 40 Ar/39 Ar
age spectrum (Figure 1A,B), which is often used as a proxy for intra-grain distribution of
radiogenic Ar, and the Arrhenius plot (Figure 1C,D), which characterises the combined
effect of diffusion domain(s) properties on Ar release. A log(r/r0) plot shows the effective
diffusion length of domains that degas during a given heating step (Figure 1E,F; r0 is
considered to be the effective diffusion length during the first heating step), assuming that
the non-linearity in the Arrhenius plot is only a consequence of the presence of multiple
intra-grain diffusion domains. To extract t-T information from these data, the user must
(i) determine the number of diffusion domains and their respective diffusion properties (Ea
and D0 ), (ii) determine the relative sizes of the domains and their contribution to the volume
of gas released during each heating step, and (iii) invert or forward model the data to seek
plausible t-T paths (Figure 1G,H). This process is referred to as Multi-Diffusion Domain
(MDD) modelling, and the inversion theory was developed by Lovera et al. (1989) [4]
and Lovera and Richter (1991) [5], while several authors have written code to perform
this task (e.g., [21–23]). The second approach is to use in situ 40 Ar/39 Ar analysis, where
Ar isotopic compositions are measured in polished grains by ablation using a UV laser to
characterise intra-grain 40 Ar/39 Ar date variations (e.g., [6,16,24,25]). Potential t-T paths
can be generated by forward modelling using software such as Diffarg(P) and choosing
an appropriate set of diffusion parameters (Figure 2A; [8,26,27]). The semi-closed nature
 Minerals 2021, 11, 1025 3 of 26

Minerals 2021, 11, 1025 3 of 25

variations (e.g., [6,16,24,25]). Potential t-T paths can be generated by forward modelling
using software such as Diffarg(P) and choosing an appropriate set of diffusion parame-
ters (Figure 2A; [8,26,27]). The semi-closed nature of boundaries for Ar loss could be ac-
of boundaries
counted for byfor Ar loss could
changing be accounted
the boundary for byinchanging
conditions theorboundary
Diffarg(P), adoptingconditions
a more so-
in Diffarg(P), or adopting a more sophisticated approach, such as
phisticated approach, such as those used by Baxter (2003) [28] and Popov those used
andbySpikings
Baxter
(2003) [28] and Popov and Spikings (this volume) [20]. The potential presence of defects
(this volume) [20]. The potential presence of defects such as nanotunnels that may facili-
such as nanotunnels
tate diffusive Ar lossthat may facilitate
([29,30]) could bediffusive Ar for
accounted lossby
[29,30] could
applying a be accounted
model for by
of multi-path
applying a model of multi-path transport (e.g., [31]).
transport (e.g., [31]).

Figure1.1.Multi-domain
Figure Multi-domaindiffusion
diffusionmodeling
modelingofofargon
argonisotope
isotopedata
dataacquired
acquiredfrom
fromalkali
alkalifeldspar
feldspar[22]
[22]
andmuscovite
and muscovite[32].
[32]. (A,B)
(A,B) The
The age
agespectrum
spectrum(distribution radiogenic4040Ar
(distributionofofradiogenic Ar relative
relativetotoreactor
reactor
produced ArKK),
produced3939Ar ), which
which isis interpreted
interpreted to
to be
be the
the function
function of
of the
the t-T
t-Thistory
historyof
ofthe
theanalysed
analysedgrain(s).
grain(s).
(C,D) The Arrhenius plot, which is a function of the heating schedule and the grain(s) structure. The
activation energy (268 kJ/mol) used to construct the Arrhenius plot for the muscovite is taken from
Minerals 2021, 11, 1025 4 of 26
25

(C,D) The Arrhenius plot, which is a function of the heating schedule and the grain(s) structure.
The activation energy (268kJ/mol) used to construct the Arrhenius plot for the muscovite is taken
hydrothermal
from diffusion
hydrothermal experiments
diffusion performed
experiments by Harrison
performed et al. (2009)
by Harrison [7].(2009)
et al. (E,F) The
[7].“log(r/ro)”
(E,F) The
plot [33], which
“log(r/ro)” measures
plot [33], which deviations from linearity
measures deviations frominlinearity
Arrhenian space, andspace,
in Arrhenian is a function
and is aof the
func-
tion of theof
structure structure of theand
the grain(s), grain(s),
their and their t-Tand
t-T history, history, and is independent
is independent of the heating
of the heating sched-
schedule, and
ule,
(G,H)and (G,H) modeled
modeled t-T solutions
t-T solutions that fit thethat fit the measured
measured data. The data. The inversion
inversion process process
assumesassumes
that Ar
that Ar is redistributed
is redistributed and lostandfromlost
thefrom the grains(s)
grains(s) by volumeby volume
diffusiondiffusion from non-interacting
from non-interacting domainsdo-of
mains of variable size, each of which is bounded by fast pathways to an infinite reservoir.
variable size, each of which is bounded by fast pathways to an infinite reservoir. Harrison and Lovera Harrison
and Lovera (2014) [32] report that the close correlation between the age and Log (r/ro) spectra
(2014) [32] report that the close correlation between the age and Log (r/ro) spectra (measured by the
(measured by the Cfg parameter where a value of 1 indicates perfect correlation) is evidence that
Cfg parameter where a value of 1 indicates perfect correlation) is evidence that volume diffusion in
volume diffusion in the laboratory mimics Ar loss in nature, and thus that the t-T models are ac-
the laboratory mimics Ar loss in nature, and thus that the t-T models are accurate.
curate.

Figure 2. (A) Composite in situ 40 Ar/39 Ar date profile obtained from depth profiles from [010] and [110] crystal faces of
Figure 2. (A)alkali
gem quality Composite in situ
feldspar
40Ar/39Ar date profile obtained from depth profiles from [010] and [110] crystal faces of
from Itrongay, Madagascar, with uncertainties of 1-sigma. Data were obtained by UV laser
gem quality alkali feldspar from Itrongay, Madagascar, with uncertainties of 1-sigma. Data were obtained by UV laser
ablation, and are from Flude et al. (2014) [6]. (B) Flude et al. (2014) [6] interpret the data to reflect diffusive 40 Ar loss40through
ablation, and are from Flude et al. (2014) [6]. (B) Flude et al. (2014) [6] interpret the data to reflect diffusive Ar loss
a single length scale with a distance of at least 1cm, and derive a possible t-T solution (in red) using diffusion parameters
through a single length scale with a distance of at least 1cm, and derive a possible t-T solution (in red) using diffusion
that were previously
parameters that wereobtained by Wartho
previously obtainedetby
al. Wartho
(1999) [34].
et al.Flude
(1999)et [34].
al. (2014)
Flude[6]
etsuggest the[6]
al. (2014) accuracy
suggestof their
the t-T solution
accuracy is
of their
supported
t-T solutionbyis similarities
supported bywith other t-T paths
similarities (shown)
with other t-T that
paths have been derived
(shown) that have forbeen
southern
derivedMadagascar using
for southern the U-Pb,
Madagascar
40 Ar/39 Ar and fission track methods.
using the U-Pb, 40Ar/39Ar and fission track methods.

2.1. Alkali
2.1. Alkali Feldspar
Feldspar
Many studies
Many studies have
have generated
generated continuous
continuous t-T t-T paths
paths by by applying
applying MDD
MDD modeling
modeling to to
40 Ar/39 Ar data acquired by step-heating of K-feldspars to investigate a wide range of
40Ar/ 39Ar data acquired by step-heating of K-feldspars to investigate a wide range of tec-

tectonic
tonic processes.
processes. These
These include
include mountain
mountain andandplateau
plateaubuilding
buildingprocesses
processes(e.g.,
(e.g., [35–38]),
[35–38]),
the post-orogenic histories of cratons (e.g., [39,40]), core complex formation
the post-orogenic histories of cratons (e.g., [39,40]), core complex formation (e.g., [41,42]) (e.g., [41,42])
and continental rifts (e.g., [43]). The use of step-heating 40 Ar/39 Ar analysis of K-feldspar
and continental rifts (e.g., [43]). The use of step-heating Ar/ Ar analysis of K-feldspar
40 39
for thermochronology
for thermochronologyisissupported supportedbybyLovera
Lovera et et
al. al.
(1996, 2002)
(1996, [44,45],
2002) whowho
[44,45], suggested
suggestedthat
correlation
that between
correlation betweeninflexions observed
inflexions in theinage
observed thespectra (which(which
age spectra they interpret to reflect
they interpret to
Ar accumulation and re-distribution in the geologic past) and the
reflect Ar accumulation and re-distribution in the geologic past) and the log (r/r0) log (r/r0) plots (which
plots
they interpret
(which to reflecttovariations
they interpret in sizes ofinactively
reflect variations sizes ofdegassing domains during
actively degassing domainslaboratory
during
laboratory analysis) is evidence that diffusion mechanisms and diffusion indomain
analysis) is evidence that diffusion mechanisms and diffusion domain boundaries nature
Minerals 2021, 11, 1025 5 of 25

are the same as those exploited during laboratory degassing. To quantify this, Lovera
et al. (2002) [45] defined a cross-correlation coefficient (Cfg ; Figure 1F), which showed a
high correlation in >70% of studied K-feldspars. This led them to conclude that MDD
modelling correctly simulates the natural diffusion history, and thus can be used to invert t-
T paths in most samples (e.g., [32]). Lovera et al. (1993) [46] performed a double-irradiation
experiment to test if hypothetical intra-grain diffusion domains remain stable over the
course of laboratory analysis, in which the same alkali feldspars underwent step-wise
heating at temperatures between 450–850 ◦ C, before and subsequent to a 2nd irradiation
step. Both step-heating experiments yielded almost identical Arrhenius plots between
450–850 ◦ C, which led them to conclude that departures from linearity in Arrhenian space
are not due to modifications of texture or structure, but are due to the exhaustion of Ar
from domains with variable length scales.
More recently, in situ 40 Ar/39 Ar dating has been applied to alkali feldspars to test the
assumption that Ar redistribution in this mineral can be dominated by volume diffusion.
Flude et al. (2014) [6] recovered 40 Ar/39 Ar date profiles over distances of ~1cm (UV
ablation) in single crystals of orthoclase (Itrongay, Madagascar). These variations were
attributed to volume diffusion through a single length scale (Figure 2A), partly because
they could be reproduced by forward modelling using diffusion parameters determined for
other crystals from the same locality [34] and the resulting t-T path is similar to the regional
thermal history constrained by other authors using the U-Pb, 40 Ar/39 Ar and fission track
methods (Figure 2B).

2.2. Muscovite
Some in situ 40 Ar/39 Ar dates in white micas have been reported as diffusion gradients
(e.g., [25,47,48]), and staircase-shaped 40 Ar/39 Ar age spectra obtained by step-heating
have been interpreted in some cases to reflect diffusive loss of Ar through the geologic
past [49,50]. Harrison et al. (2009) [7] performed hydrothermal diffusion experiments and
proposed that small flakes of muscovite can retain the Ar diffusion boundaries and length
scales that define their natural retentivity during in-vacuo step-heating (see also [45]), and
thus they can be used to reconstruct continuous t-T paths. The same authors report EA
and D0 diffusion data for muscovite, which have been used by subsequent workers to
derive thermal histories. Heizler and Harrison (2009) [51] expanded on that work and
report that diffusion domains within muscovite have length scales that vary between
≤125 and 1 micrometers, which provides clues about the nature of the domains, although
their identification remains elusive, if they exist. Forster et al. (2011) [52] corroborate
Harrison et al. (2009) [7] and report that laboratory furnace extraction of Ar from multi-
grain, detrital white mica (Indus Basin) reveals natural diffusional loss from two length
scales. Harrison and Lovera (2014) [32] applied MDD modelling to 40 Ar/39 Ar data from
muscovite from the Main Central Thrust (Figure 1), Himalayas, to generate t-T solutions
that are consistent with a large regional dataset, perhaps validating the use of muscovite as a
thermochronometer in their rocks, and the presence of multiple, intra-grain diffusion length
scales. Forster and Lister (2014) [9] claim that diffusion profiles can be extracted from multi-
grain, muscovite-phengite mixtures in high-pressure metamorphic rocks using in-vacuo
furnace heating. More recently, Uunk et al. (2018) [15] utilised the heterogeneity in total
fusion dates of single white mica crystals from retrogressed blueschists to identify some
hand specimens where the grains were semi-closed to Ar loss, and other hand specimens
that preserved diffusion profiles in white mica, thereby suggesting that diffusion profiles
can exist in certain circumstances. Long et al. (2018, Basin and Range) [10] and Gonzales
and Baldwin (2019, Baja California) [11] applied furnace step-heating and MDD modelling
to high-pressure phengite and muscovite, respectively, and derived continuous t-T histories.
Well-defined age gradients and highly correlated age spectra and log (r/r0) plots led these
authors to conclude that their t-T solutions are accurate.
Summarising, some studies have derived t-T solutions from suspected diffusion
profiles in muscovite by either (i) testing a restricted number of forward t-T models of bulk
Minerals 2021, 11, 1025 6 of 25

grains assuming a single length scale and using the MatLabTM code, Diffarg (e.g., [15]), or
(ii) inversion using MDD modelling (e.g., [7,10,11,32]). Only four studies have constrained
t-T solutions using inversion (i.e., testing 103 –104 potential t-T solutions), while permitting
the possible existence of more than one intra-grain diffusion length scale, thus emulating
some K-feldspar MDD studies. Similar to most thermochronological studies of alkali
feldspar, these four studies used Arrhenius relationships (i.e., younger dates from regions
with higher D/r2 ) and mathematical cross correlation (Cfg ; [45]) to test the assumptions
that Ar was lost in nature by thermally driven diffusion, and that laboratory degassing
revealed natural Ar diffusion kinetics, although these were not verified by petrographic or
in situ Ar isotopic analyses.

2.3. Cross Correlation as a Means to Validate MDD Modelling

The use of 40 Ar/39 Ar data and the MDD approach to obtain t-T paths assumes that
volume diffusion was the dominant mechanism for the migration of Ar in alkali feldspar
and muscovite during their geologic histories and in the laboratory. A further assumption
is that Arrhenius relationships obtained at high temperatures and over short timescales in
the laboratory are representative of natural degassing at lower temperatures and longer
time scales. Some of the approaches to validate these assumptions are straightforward and
were cited above. These include, for example, comparisons of the recovered t-T paths with
a priori known thermal histories and comparisons of the observed spatial variations of
40 Ar/39 Ar dates with theoretical predictions (e.g., in situ dates becoming younger towards

an assumed crystal boundary). However, there is an additional less trivial aspect that is
specific for MDD modelling, which is discussed below.
When using the MDD approach, Ar diffusion parameters are determined for a specific
sample using an Arrhenius diagram that is constructed from data acquired by step-heating
analysis. It is assumed that any departure from linearity in this diagram is due to degassing
and mixing of Ar reservoirs from distinct intra-grain diffusion domains that remained
stable over geologic and laboratory timescales [4]. Smaller diffusion domains are expected
to exhaust early during the analysis, such that the effective radius of diffusion domains
that degas gradually increases with progressive heating, as illustrated by the log(r/r0) plot
(Figure 1E,F). These smaller domains are expected to have lower closure temperatures, such
that the average 40 Ar/39 Ar date of diffusion domains that degas increases with progressive
heating (Figure 1A,B). Thus, the topologies of both the log(r/r0) plot and the age spectrum
are expected to depend on the distribution of intra-grain diffusion domains. Lovera
et al. (2002) [45] developed the normalised cross-correlation coefficient Cfg to quantify the
degree of correlation between the log(r/r0) plot and the age spectrum, which is used to
validate the assumptions behind MDD theory. They used numerical modelling to show that
hypothetical, well-behaved alkali feldspar crystals that comply with all the assumptions
behind MDD theory yield highly correlated log (r/r0) plots and age spectra (Cfg > 0.95).
On the contrary, crystals whose diffusion domains were fragmented during their synthetic
geological past (which was done to simulate fluid-mediated alteration) frequently yielded
lower Cfg values (<<0.95), implying that the correlation between the log(r/r0) plots and the
age spectrum could be used to check the validity of t-T solutions. Lovera et al. (2002) [45]
used these same numerical experiments to argue that only volumetrically significant
alteration (>>6 vol%) can substantially reduce the accuracy of t-T paths obtained using the
MDD model (in alteration scenarios where Cfg > 0.95).

3. Arguments against the Reconstruction of Continuous t-T Paths Using the

40 Ar/39 Ar Method

The validity of the underlying assumptions and approaches described above to use
40 Ar/39 Ardata from K-feldspar and muscovite to recover t-T information has been chal-
lenged in several studies. It has been shown that diffusion profiles can be significantly
modified by (i) semi-closed system behaviour, and the introduction of extraneous Ar from
grain boundary fluids, which is common in high-pressure phengite (e.g., [18,53]; Figure 2),
Minerals 2021, 11, 1025 7 of 25

and (ii) fluid induced recrystallisation and low temperature alteration (e.g., [16,54–57]).
Furthermore, it was also suggested that mechanisms of Ar migration in laboratory diffusion
experiments and in nature are not the same, such that laboratory-derived kinetics of Ar
release cannot be used in thermochronological modelling (e.g., [14,58]). Finally, it has been
proposed that arguments used to validate the assumptions behind MDD modelling are not
valid [59]. Here we summarise key evidence and arguments that contest the application of
40 Ar/39 Ar data from K-feldspar and muscovite for thermochronology in its current form

(i.e., using both step-heating and in situ techniques).

3.1. The Effects of Fluid Interaction and Closed-System Behaviour

A fundamental observation in nature is that metasomatic fluids are more efficient
at mobilizing isotopes than temperature (e.g., [60–65]). Kinetic rate constants for fluid
mediated transport of solutes are orders of magnitude larger, with significantly smaller
activation energies than thermally driven diffusion (e.g., [66]). Consequently, many authors
conclude that Ar redistribution and loss from K-feldspar and white micas in nature is
controlled by sub-solidus transformations and/or fluid interaction (e.g., [2,3,12,14,30,54–
56,67–71]), and volume diffusion is subordinate.
The misidentification of even minor secondary replacement phases and their Ar iso-
tope reservoirs can lead to significant inaccuracies in t-T paths when using the MDD
approach. MDD analysis requires that the activation energy for Ar diffusion is determined,
enabling the log(r/r0) plot to be constructed and used to calculate the relative volumes of
the discrete domains. This is usually done using heating steps at low degassing tempera-
tures (Figure 1C–F), where gas may be predominately released from alteration phases that
are not representative of the primary mineral phase [14]. Consequently, the form of the
log(r/r0) plot is extremely sensitive to the presence of those alteration phases.
Argon isotope ratios in K-bearing secondary phases will also be influenced by thermal
diffusion, and thus they could be theoretically exploited to derive t-T solutions. Therefore,
the identification of secondary phases could provide more temporally resolved thermal
history information. However, we envisage extreme difficulty in exploiting these phases as
thermochronometers because the user must be able to determine their time of formation,
and the accuracy of the t-T paths will be subject to all of the phenomena that are discussed
here (Section 3).

3.1.1. Alkali Feldspar

The Chain of Ponds Pluton, USA, and the Aar Massif, Swiss Alps
The MDD model was developed via experiments using alkali feldspar extracted
from the Chain of Ponds Pluton, New England [4,5,46,72,73], and the realization that
separate samples apparently contained a distribution of domain sizes with respect to
thermally driven diffusion of 40 Ar. However, with the exception of Fitz Gerald and
Harrison (1993) [73], these early pioneering studies did not present a petrological study
of the alkali feldspar crystals, and assumed they were not affected by interaction with
fluids. However, mineralogical evidence indicates that fluid-induced recrystallisation and
alteration are common in alkali feldspar, including in samples used to develop the MDD
model [2,12,67,71,74–76].
Chafe et al. (2014) [71] sampled the Chain of Ponds Pluton at the same location where
Heizler et al. (1988) [72] took the samples that were first used to develop the MDD model.
Their petrographic characterisation of the alkali feldspar crystals (cathodoluminescence,
back-scatter electron imaging, and electron-probe microanalysis) showed that primary
magmatic alkali feldspars in hand-picked and un-hand-picked (i.e., not screened for vis-
ible alteration under a binocular microscope) aliquots had been affected by successive
generations of fluid infiltration (Figure 3A), causing adularisation and the introduction
of celsian-rich veins. Correlations between K, Ca and Cl that had been directly measured
and inferred from the Ar isotopic data showed that degassing of heterochemical phases
is responsible for deviations of Arrhenius trajectories from linearity (Figure 3B), as op-
 for visible alteration under a binocular microscope) aliquots had been affected by suc-
cessive generations of fluid infiltration (Figure 3A), causing adularisation and the intro-
duction of celsian-rich veins. Correlations between K, Ca and Cl that had been directly
measured and inferred from the Ar isotopic data showed that degassing of heterochem-
Minerals 2021, 11, 1025 8 of 25
ical phases is responsible for deviations of Arrhenius trajectories from linearity (Figure
3B), as opposed to a range in diffusion lengths in an inert, homogeneous medium with a
constant absolute diffusivity. Chafe et al. (2014) [71] conclude that alkali feldspar samples
posedbetogenerally
should a range insuspected
diffusion lengths in an multiple,
to contain inert, homogeneous mediumdiachronous
heterochemical, with a constant
genera-
absolute diffusivity. Chafe et al. (2014) [71] conclude that alkali feldspar samples should
tions and that the loss of argon is predominantly an effect of large-scale recrystallization
be generally suspected to contain multiple, heterochemical, diachronous generations and
in an
thatopen system,
the loss which
of argon can give riseantoeffect
is predominantly staircase-shaped age spectra (Figure
of large-scale recrystallization 3A). Sim-
in an open
ilarly, Villawhich
system, and Hanchar (2013)
can give rise [2] combined age
to staircase-shaped petrological characterization
spectra (Figure with
3A). Similarly, VillaSr, Pb
andandArHanchar
isotope analyses
(2013) [2] combined petrological characterization with Sr, Pb and Ar isotopeAlps,
to study alkali feldspar from the Aar metagranites, Central
Switzerland.
analyses to Comparisons of Pbfrom
study alkali feldspar andthe SrAar
isotopic compositions,
metagranites, and Switzerland.
Central Alps, Ca/K, Cl/K and
Comparisons
40Ar/ 39Ar dates led of Pb and Sr
them to isotopic
conclude compositions, and Ca/K, Cl/K
that staircase-shaped and 40 Ar/
age spectra 39 Ar dates
were a result of
led them to conclude that staircase-shaped age spectra were a result of
degassing primary and metasomatic feldspar, with little relation to volume diffusiondegassing primary
and metasomatic
through geological feldspar,
time. with little relation to volume diffusion through geological time.

FigureFigure
3. (A)3.Staircase-shaped
(A) Staircase-shaped ageage
spectrum
spectrum forforalkali
alkalifeldspar
feldspar extracted fromthe
extracted from theChain
Chain of of Ponds
Ponds Pluton
Pluton (New (New England,
England,
USA),USA),
highlighting the contribution
highlighting the contribution of gas
of gasderived
derivedfrom
fromalteration
alteration phases, adulariaand
phases, adularia and pristine
pristine magmatic
magmatic alkali
alkali feldspar.
feldspar.
The relative contributions suggest the staircase topology is a consequence of the co-existence
The relative contributions suggest the staircase topology is consequence of the co-existence of heterochemical phases of heterochemical phases
with different apparent ages (data and interpretation from [71]). (B) Arrhenius data corresponding
with different apparent ages (data and interpretation from [71]). (B) Arrhenius data corresponding to the age spectrum in to the age spectrum in
(A), which shows
(A), which that that
shows (i) variations from
(i) variations fromlinearity
linearityare
aredue
due to
to degassing
degassing ofofdifferent
different retrogressed
retrogressed phases
phases and and variations
variations in in
diffusivity (D; as
diffusivity (D;opposed
as opposed totosolely
solelybeing duetotovariations
being due variations in diffusion
in diffusion length
length scale), scale),
and (ii) and (ii) activation
activation energy determi-
energy determinations
nations derived
derived fromfrom regressing
regressing the low
the low temperature
temperature steps steps (determined
(determined from
from the the gradient)
gradient) relate torelate to alteration
alteration phases, andphases,
not and
not pristine,
pristine, magmatic feldspar. Colours relate to the same phases that are labelled in (A). Data and graphs are from Chafe et al.from
magmatic feldspar. Colours relate to the same phases that are labelled in (A). Data and graphs are
Chafe(2014)
et al. [71].
(2014) [71].
The The inferences
inferences about magmatic
about magmatic feldspar,
feldspar, adularia andadularia
alterationand alteration
phases phases
were made by were madeEPMA,
combining by combining
CL
EPMA, CL images and the argon
images and the argon isotope data. isotope data.

Megacrystic
Megacrystic Alkalifeldspar
Alkali feldsparfrom
from Itrongay,
Itrongay,Madagascar
Madagascar
Arguablythe
Arguably themost
most convincing
convincingevidence thatthat
evidence supports alkalialkali
supports feldspar thermochronol-
feldspar thermochro-
ogy using the 40 Ar/ 39 Ar method was presented in studies of alkali feldspar from Itrongay,
nology using the Ar/ Ar method was presented in studies of alkali feldspar from
40 39
Madagascar. Previous studies include Flude et al. (2014) [6], who reported a core to rim
Itrongay,
40 Ar/39 Madagascar. Previous studies include Flude et al. (2014) [6], who reported a
Ar date profile that was interpreted to result from diffusive loss of 40 Ar (Figure 2A),
coreandto the
rimwork
40Ar/39Ar date profile that was interpreted to result from diffusive loss of 40Ar
of Nägler and Villa (2000) [77], who reported 40 Ar/39 Ar and K-Ca dates
(Figure 2A), and the
and suggested theyounger
work of40 Ar/
Nägler
39 Arand
dateVilla
was a(2000) [77], who
consequence reported
of diffusive loss Ar/
40 39Ar and
of 40 Ar.
K-Ca dates and
However, suggested
these the younger
interpretations 40Ar/39Ar date was a consequence of diffusive loss
were recently questioned by Popov et al. (2020a) [16], who
utilised cathodoluminescence and back-scatter electron imaging of a transparent, cm-scale
crystal of Itrongay feldspar to reveal at least five distinct zones (Figure 4A–E; [16]) that
formed in five distinct episodes of growth from fluids with distinctly different compositions
(SiO2 rich, CO2 rich, and later H2 O rich). Each zone yields distinguishable weighted mean
40 Ar/39 Ar (in situ) dates that span between 477–176 Ma, while most dates are younger

than the K-Ca isochron date of 477 ± 2 Ma ([77]; Figure 4F–H). The spatial coincidence of
abrupt in situ 40 Ar/39 Ar dates and crystal zonation strongly suggests the dominant cause
 parent, cm-scale crystal of Itrongay feldspar to reveal at least five distinct zones (Figure
4A–E; [16]) that formed in five distinct episodes of growth from fluids with distinctly
different compositions (SiO2 rich, CO2 rich, and later H2O rich). Each zone yields distin-
guishable weighted mean 40Ar/39Ar (in situ) dates that span between 477–176 Ma, while
Minerals 2021, 11, 1025 most dates are younger than the K-Ca isochron date of 477 ± 2 Ma ([77]; Figure9 4F–H). of 25
The spatial coincidence of abrupt in situ Ar/ Ar dates and crystal zonation strongly
40 39

suggests the dominant cause of variation in dates was dissolution-precipitation reactions

that collectively
of variation span was
in dates tens dissolution-precipitation
to hundreds of millions reactions
of years. that
This collectively
is inconsistent spanwith
tensthe
conclusions of Flude et al. (2014) [6], who without petrographically
to hundreds of millions of years. This is inconsistent with the conclusions of Flude et al. analyzing their
feldspar crystal from Itrongay, interpreted their in situ date profiles to
(2014) [6], who without petrographically analyzing their feldspar crystal from Itrongay, be a consequence
ofinterpreted
volume diffusion through
their in situ a continuous
date profiles crystal structure
to be a consequence (Figure
of volume 2A), and
diffusion thus con-
through a
clude that Itrongay
continuous feldspar(Figure
crystal structure crystals2A),
acted
andasthus
grain-scale
concludediffusion domains.
that Itrongay feldspar Popov
crystalset al.
(2020a)
acted as[16] note that diffusion
grain-scale some in situ 40Ar/39Ar
domains. datesetof
Popov al.the inner [16]
(2020a) zonenote
(zonethat1 in Figure
some 4A,B)
in situ
40 Ar/39 Ar dates of the inner zone (zone 1 in Figure 4A,B) of their crystal increase towards
of their crystal increase towards its outer boundary. They hypothesise that 40Ar has dif-
its outer
fused intoboundary. They hypothesise
the boundaries that 40 Ar has
that form between the diffused
feldsparinto
hostthe boundaries
and inclusions, thatand
formthus
between the feldspar host and inclusions, and thus older in situ dates are
older in situ dates are a consequence of ablating regions with higher densities of inclu- a consequence of
ablating
sions, andregions
thus theywithdohigher densitiesrule
not entirely of inclusions,
out potentialand experimental
thus they do not entirelyfor
evidence rulevolume
out
potential experimental
diffusion on small scales. evidence for volume diffusion on small scales.

Figure
Figure4. Gem
4. Gem quality
qualityorthoclase
orthoclaseextracted from
extracted frompegmatites
pegmatites atat
the
thesite
site“Itrongay”,
“Itrongay”,southern
southernMadagascar,
Madagascar,collected
collectedby bythe
authors duringduring
the authors field work in 2016.
field work (A) Composite
in 2016. optical
(A) Composite cathodoluminescence
optical cathodoluminescence image
imageshowing
showing three
threedistinct
distinctzones
zones(la-
beled 1, 2 and
(labeled 1, 2 3).
and(B)
3). Back-scatter electron
(B) Back-scatter image
electron imagewhich
whichshows
showsthatthatzone
zone 22 can
can be dividedinto
be divided intotwo
twosub-zones
sub-zones (2a(2a
andand
2b),2b),
which
which are separated by a dark stripe. (C,D) cathodoluminescence and back-scatter electron images of the outer ~300 µm ofμm
are separated by a dark stripe. (C,D) cathodoluminescence and back-scatter electron images of the outer ~300
of the
the crystal, which show
crystal, which showthat
thatzone
zone33cancanbe
bedivided
dividedinto
into2 2sub-zones
sub-zones(3a, (3a, 3b).
3b). (E)(E) schematic
schematic sketch
sketch (not(not to scale)
to scale) showing
showing
thethe
relationships between all zones and their sub-zones. (F,G) In situ core-rim 40Ar/39Ar dates from our own in situ study
40 39
relationships between all zones and their sub-zones. (F,G) In situ core-rim Ar/ Ar dates from our own in situ
study [16], showing strip maps of back-scatter electron and cathodoluminescence images. Distinguishable variations in
40 Ar/39 Ar dates correspond with crystallographic zones, revealing periods of dissolution and diachroneity in crystallisation

(~477–176 Ma). (H) Probability density function of all in situ 40 Ar/39 Ar dates collected from 8 traverses into the same
crystal shown in (A). Detailed petrographic analyses of single crystals question previous interpretations that variations in in
situ 40 Ar/39 Ar dates are dominated by volume diffusion. Data and images are from [16].
Minerals 2021, 11, 1025 10 of 25

Klokken Syenite, Greenland

Alkali feldspars from the Klokken syenite (U-Pb baddeleyite age 1166 ± 4 Ma; [78])
have been central to the debate on the natural causes of the distribution of 40 Ar in alkali
feldspars. Parsons et al. (1988) [67] combined 40 Ar/39 Ar step-heating and transmission
electron microscopy to show that Ar leakage from some alkali feldspar from the Klokken
syenite was promoted by the formation of micropores (sub-µm channels) that give rise to
a turbid (translucent–opaque) appearance. This microporosity formed by the interaction
of deuteric fluids at ~500 ◦ C [76], which remove coherency strain and thus the volume
proportion of strain-controlled intergrowths, ultimately forming coarse patch perthites
composed of subgrains (e.g., coherent boundaries of perthitic lamellae; [79]). More recent
studies [76] showed that later microstructures formed and evolved in the Klokken feldspars
between ~450 and less than 90 ◦ C after the formation of the patch perthite, and describe
eight feldspar phases in single crystals. Scanning Electron Microscopy showed the youngest
and lowest temperature phase contains a K-feldspar end member, with microstructures
that are similar to those found in authigenic feldspars.
Parsons et al. (1988) [67] present a systematic relationship between 40 Ar/39 Ar total
fusion dates and feldspar texture. The least affected cryptoperthite yields 40 Ar/39 Ar dates
that are 20–60 Ma younger than their crystallisation age (Figure 5A), while the most turbid
feldspars (which host ≤4.5vol% micropores; [80]) yield 40 Ar/39 Ar step-dates as young as
~400 Ma with total fusion dates that are younger than 1 Ga (Figure 5B; [67,81,82]). Harrison
et al. (2010) [70] studied the same crystals that were analysed by Parsons et al. (1988; e.g.,
crystal 140025; Figure 5C) [67] using high spatial resolution 40 K-40 Ca dating by secondary
ion mass spectrometry. They observed that the 40 K-40 Ca system was variably disturbed to
yield apparent isochrons ranging from 718 to 2400 Ma and suggested that the disturbance
occurred at ≤718 Ma, and possibly as late as ~400 Ma. They concur that primary feldspar
from the Klokken Syenite has been modified by aqueous fluid mediated modification, and
characterisation of mineral textures is paramount before attempting to extract thermal
history information.
Clearly, turbid feldspar from Klokken has lost radiogenic 40 Ar through geologic time,
perhaps by the infiltration of fluids that utilise the micropermeability that micropores
can create (e.g., [79,80,82,83]), and also perhaps because the average interatomic bond
strengths are weakened by connected pores (e.g. [2]). Furthermore, the observation that the
crystals with the finest scale intergrowths are the most retentive to 40 Ar is counterintuitive
to the MDD model. Overall, these open the possibility that the non-deuterically altered
crypto-perthitic phases may have lost some 40 Ar by volume diffusion, and their 40 Ar/39 Ar
dates are consistent with being at T < 200 ◦ C since they formed ([82], Sanders, 2008).
However, younger 40 Ar/39 Ar and K/Ca dates from regions characterised by micropores
and subgrains suggests that fluid-induced replacement reactions can modify the argon
isotopic compositions of alkali feldspars at any time after they form [76,82].
Minerals 2021, 11, 1025 11 of 25
Minerals 2021, 11, 1025 11 of 26

Figure 5.
Figure 5. (A)
(A) Step-heating
Step-heatingspectrum
spectrumfor foralkali
alkalifeldspar from
feldspar from sample
sample140025
140025 of the Klokken
of the Klokkenlayered series,
layered which
series, has con-
which has
siderable turbidity
considerable andand
turbidity coarse deuteric
coarse alteration,
deuteric alteration, 40Ar/
withwith 39Ar step
40 Ar/39 Ardates that are
step dates considerably
that younger
are considerably than the
younger zircon
than the
U-Pb baddeleyite
zircon age of the
U-Pb baddeleyite agesyenite [67]. (B)[67].
of the syenite Step-heating spectrum
(B) Step-heating for alkali
spectrum feldspar
for from sample
alkali feldspar from 140175
sampleof140175
the Klokken
of the
layered series,
Klokken layeredwhich
series,iswhich
a strain
is acontrolled microperthite
strain controlled that lacks
microperthite that turbidity, with with
lacks turbidity, a total fusion
a total age (1125
fusion ± 16±Ma)
age (1125 that
16 Ma)
suggests <5% of 40Ar 40has been lost [67]. (C) K-Ca data for alkali feldspar from sample 140025. The young isochron age
that suggests <5% of Ar has been lost [67]. (C) K-Ca data for alkali feldspar from sample 140025. The young isochron
relative to the U-Pb baddeleyite age was used by Harrison et al. (2010) [70] to conclude that the Klokken syenite was af-
age relative to the U-Pb baddeleyite age was used by Harrison et al. (2010) [70] to conclude that the Klokken syenite was
fected by aqueous fluid-mediated dissolution-reprecipitation, and the 40Ar/39Ar data are mainly not a consequence of
affected by aqueous fluid-mediated dissolution-reprecipitation, and the 40 Ar/39 Ar data are mainly not a consequence of
thermally driven Ar loss.
40

thermally driven 40 Ar loss.

Clearly, turbid feldspar from Klokken has lost radiogenic 40Ar through geologic
3.1.2.
time, Muscovite
perhaps by the infiltration of fluids that utilise the micropermeability that mi-
Several
cropores canstudies have[79,80,82,83]),
create (e.g., demonstratedand thatalso
fluid interaction
perhaps andthe
because retrogression can alter
average interatomic
Ar isotopic compositions in white mica by driving recrystallisation and
bond strengths are weakened by connected pores (e.g. [2]). Furthermore, the observation mica breakdown
(e.g., [1,3,53,54,69,84,85]),
that the crystals with the which occurintergrowths
finest scale at much faster rates
are the than
mostthermal
retentive isotopic
to 40Arresetting.
is coun-
Consequently, 40 Ar/39 Ar dates of white mica frequently do not reflect the cooling history
terintuitive to the MDD model. Overall, these open the possibility that the
expected from P-T-t
non-deuterically modelscrypto-perthitic
altered (via thermal diffusion),
phases mayand thus
havearelost
notsome
cooling ages.
40Ar byForward
volume
modelling
diffusion, and of Artheir
diffusion
40Ar/39in
Arhigh-pressure white micas
dates are consistent with wasbeingperformed
at T < 200 by°C Warren
since et al.
they
(2011; phengite in pelites of the Saih Hatah high-pressure terrane,
formed ([82], Sanders, 2008). However, younger Ar/ Ar and K/Ca dates from regions
40 39 Oman) [86] and McDon-
ald et al. (2016;by
characterised phengite and muscovite,
micropores Western
and subgrains Gneiss
suggests thatRegion, Norway) replacement
fluid-induced [3], assumingre- a
single diffusion length scale, to show that the distribution of in situ and
actions can modify the argon isotopic compositions of alkali feldspars at any time aftersingle crystal fusion
dates of high
they form pressure white micas are not compatible with natural diffusion being the
([76,82]).
dominant mechanism for the redistribution of Ar. Rather, these authors combined electron
Minerals 2021, 11, 1025 12 of 25

probe microanalyses of white micas with single grain and in situ 40 Ar/39 Ar analyses to
show that the 40 Ar/39 Ar dates were a result of chemical breakdown, partial melting and
fluid ingress (Figure 6A,B). Villa et al. (2019) [56] and Bulle et al. (2020) [57] degassed mag-
matic and hydrothermal muscovite from the Lardarello-Travale Geothermal Field, Italy, by
step-wise heating, and compared Ar isotopic data with K, Cl and Ca abundances obtained
by electron microprobe analyses, and in situ d18 O measurements to assess the significance
of 40 Ar/39 Ar dates. A Cl-poor, magmatic mica (2.7 Ma) and Cl-rich hydrothermal mica
(0.7 Ma) are inter-grown at the micron scale (Figure 6C), which gives rise to highly variable
40 Ar/39 Ar ages at km scales, showing that the Ar record in their muscovite samples is

dominantly a result of structure-controlled infiltration of meteoric water, and was not

caused by ambient temperature and diffusion. Finally, Mulch and Cosca (2004) [1] com-
bined in situ 40 Ar/39 Ar dating, δ18 O determinations and electron probe microanalysis with
detailed micro-structural studies to show that variations in 40 Ar/39 Ar dates in syntectonic
muscovite fish from the Porsgrunn-Kristiansand Shear Zone (southern Norway) reflect
recrystallisation during extensional deformation, and equilibration with meteoric fluids.
The most compositionally variable muscovites that consist of recrystallised subgrains yield
the largest dispersion in 40 Ar/39 Ar dates, which is not a function of thermally driven
diffusion (Figure 6D,E).
Heterogeneous distributions of Ar isotope reservoirs in phengite grains on the cm
to sub-mm scale can also be a consequence of grain boundary fluids, either by (i) the
introduction of Ar into the grains from Ar-rich fluids, where older 40 Ar is derived from
an earlier generation of K-bearing minerals (e.g., [18]), or by (ii) inefficient removal of Ar
due to restricted grain boundary fluid circulation (e.g., [53,87,88]). Semi-closed system
behaviour that retains inherited 40 Ar and reduces the efficiency of 40 Ar removal is contrary
to the assumption that 40 Ar diffuses from the grain (or sub-grain domain) to a fully open
system, and significantly complicates linking Ar concentrations to thermal histories. For
example, Di Vincenzo et al. (2004) [89] suggest that white micas of the Variscan basement
of Sardinia did not experience Ar loss during subsequent heating to >500 ◦ C due to the
presence of high Ar concentrations at their grain boundaries. Phengite from the Western
Gneiss Complex crystallised at <770 ◦ C, with peak metamorphism at 410–400 Ma [90], and
diffusion modelling with a fully open system suggests the single grain phengite dates
should be ~21–3 Ma younger than the time of crystallisation [53]. On the contrary, in situ
40 Ar/39 Ar dates vary between ~518–389 Ma, implying that grains with dates <400 Ma have

lost some Ar. However, Ar may have diffused into the older grains from either the grain
boundary fluid, adjacent grains, or have been incorporated as excess 40 Ar during crystalli-
sation (Figure 6A). The scattered dates reported by McDonald et al. (2018) [53] preclude
the construction of an inverse isochron, and thus cannot easily distinguish between these
possibilities. Importantly, semi-closed boundary behaviour does not preclude using the Ar
isotope data to obtain t-T paths, although it is included in this review because it signifi-
cantly complicates the process, and has not yet been accounted for in thermochronological
studies.

3.2. Laboratory Degassing and Changes in Diffusivity (D)

A key assumption when numerically simulating diffusion to obtain t-T solutions is
that the displacing isotopes utilise the same mineral pathways in the laboratory as they use
in nature, i.e., that grains or intra-grain diffusion domains in the material used to obtain
diffusion data remain stable over the course of laboratory experiments. In other words,
thermochronologists must be cautious when extrapolating laboratory derived diffusion
parameters obtained at high temperatures and short time scales to geologically relevant
conditions at lower temperatures and longer time scales. Do structural changes occur at
temperatures lower than laboratory degassing? Does the acquisition of 40 Ar/39 Ar data by
step-heating (i.e., MDD analysis) emulate the mechanisms that drove Ar loss during its
geologic past?
Minerals 2021, 11, 1025 13 of 25
Minerals 2021, 11, 1025 13 of 26

Figure 6.
Figure 6. (A)
(A) In
In situ
situ 4040Ar/
Ar/3939Ar
Ardates
datesin
inwhite
white mica
mica in
in medium
medium grained,
grained, unfoliated
unfoliated gneisses,
gneisses, Western Gneiss Complex,
Western Gneiss Complex,
Norway [3]. The white mica has been partially replaced at the rims by biotite-plagioclase symplectites.
Norway [3]. The white mica has been partially replaced at the rims by biotite-plagioclase symplectites. The dates reveal The dates reveal
patchy date distributions with no clear core-rim profiles, which would be predicted by volume diffusion with a fully
patchy date distributions with no clear core-rim profiles, which would be predicted by volume diffusion with a fully open
open boundary. Diffusion has not been the sole mechanism that redistributed Ar, despite cooling from temperatures
boundary. Diffusion has not been the sole mechanism that redistributed Ar, despite cooling from temperatures (~700 ◦ C)
(~700 °C) well above the closure temperature. Rather, Ar distribution was dominated by white mica breakdown to biotite
well above
(B), and thethe closure temperature.
introduction of extraneous Rather, Ar distribution
Ar from a semi-closed was dominated
grain boundary bynetwork.
white mica breakdown
G: Garnet, to biotite
Q: Quartz, WM: (B), and
White
the introduction of extraneous Ar from a semi-closed grain boundary network. G: Garnet, Q: Quartz,
Mica. Data and interpretation are from McDonald et al. (2016) [3]. (C) Microscale d O and chemical variability of mus-
18 WM: White Mica.
Data
coviteand interpretation
within monzogranite are from
from McDonald et al. (2016) [3].
the Larderello-Travale (C) Microscale
Geothermal d18 O and
Field (Italy), withchemical
a medium variability
grained,of muscovite
typical igne-
ous texture
within with primary
monzogranite from magmatic white mica Geothermal
the Larderello-Travale (mag) that isField
partially chloritised,
(Italy), hydrothermal
with a medium white mica
grained, typical (mag-hyd)
igneous texture
and late
with stagemagmatic
primary sericite (datawhiteand images
mica arethat
(mag) from [57]). (D)chloritised,
is partially Ti and Al compositions
hydrothermalofwhite
low-Al,
micafoliation parallel
(mag-hyd) and(grey) and
late stage
high-Al,(data
sericite foliation obliqueare
and images (white) muscovite
from [57]). (D) Ticrystals from the Porsgrunn-Kristiansand
and Al compositions Shear Zone,
of low-Al, foliation parallel (grey) southern
and high-Al,Norway [1].
foliation
The orange
oblique fieldmuscovite
(white) shows thecrystals
range of compositions
from obtained from composite
the Porsgrunn-Kristiansand muscovite
Shear Zone, fishNorway
southern (shown in [1].(E))
Thethat coverfield
orange the
entire compositional range, and also yield the largest range in in situ 40Ar/39Ar dates. Red rectangles show the region of in
shows the range of compositions obtained from composite muscovite fish (shown in (E)) that cover the entire compositional
situ ablations, and white and dark fields are the same as those shown in (D).
range, and also yield the largest range in in situ 40 Ar/39 Ar dates. Red rectangles show the region of in situ ablations, and
white and dark fields are the same as those shown in (D).
Minerals 2021, 11, 1025 14 of 25

To test this, Lovera et al. (1993) [46] conducted a double-irradiation experiment where
the same alkali feldspar fragments were step-heated to 850 ◦ C, before and after a second
irradiation. Sanders (2008) [82] compared step-heating 40 Ar/39 Ar data derived from several
aliquots of three alkali feldspar fractions, where some aliquots were partially outgassed
at different temperatures prior to irradiation. Both studies found only a minor effect of
laboratory heating on the properties and the size distribution of the hypothetical intragrain
diffusion domains over timescales relevant to conventional step-heating analysis. However,
it remains unclear as to which features separate these domains from each other and provide
fast diffusion pathways for the effective removal of Ar from their surfaces. On the contrary,
several experimental observations show that non-linearity in Arrhenius plots is either
due to fracturing or opening of fast diffusion pathways during sample preparation [91],
fast pathways for Ar loss that modify during progressive step-heating (e.g., [17,30]), or
modifications of intrinsic diffusion parameters by heating-induced structural transitions
(e.g., [14,58,92]). Regardless, it is critical to understand how the microtextural evolution
of minerals during laboratory step-heating affects 40 Ar/39 Ar data, and whether or not
laboratory data can be extrapolated to geological temperatures and timescales.

3.2.1. Alkali Feldspar

Ar diffusivity data from alkali feldspar frequently define non-linear arrays in Arrhe-
nius plots. This non-linearity lies at the base of MDD theory, where it is accounted for by the
presence of multiple intra-grain diffusion domains that remain stable through laboratory
heating to the initiation of melting. Indeed, any Arrhenius plot that can be represented as a
monotonic non-decreasing log(r/r0) is consistent with such an explanation. However, this
explanation is not unique, and many studies relate the non-linearity to modifications of
texture and structure during laboratory heating. Previous suggestions include homogeni-
sation of compositionally different domains within the analysed fragments along with
annealing or formation of crystal defects [12,30,93], fracturing of the analysed fragments
and the formation of Ar traps within them [17,91,94], structural transitions [71,92,93] and
changes in vacancy-specific diffusion mechanisms [34,55].
One group of suggestions about the causes of non-linearity in Arrhenius plots relates
it to the instability of boundaries that define apparent intra-grain diffusion domains during
diffusion experiments. Detailed mineralogical observations have shown that commonly
occurring alkali feldspar has a range of very complex textures on a micro- to nanoscale that
are modified due to laboratory heating. For example, approximately 70% (by volume) of
alkali feldspar megacrysts from Shap Granite are optically pristine, whereas the remaining
regions are turbid (e.g., [29–31]). The pristine regions are magmatic feldspar that exsolved
by Na-K interdiffusion to form coherent to semi-coherent Na-rich lamellae in a K-rich
matrix. They are transected by nanotunnels that formed by feldspar dissolution into fluids
along misfit dislocations at the boundaries of semi-coherent lamellae. The turbid regions
are feldspar that formed via fluid-induced dissolution-reprecipitation and include veins
of replacement Na-rich and K-rich sub-grains with incoherent boundaries. Most of these
textures are unstable during laboratory heating, as was first hypothesised by Parsons
et al. (1999) [12] and then experimentally documented by Fitz Gerald et al. (2006) [29],
Parsons et al. (2010) [30] and Popov et al. (2020b) [17]. During step-heating, exsolution
lamellae in Shap feldspar start to homogenise at ≥500 ◦ C, while complete homogenisation
can be achieved at ≥700 ◦ C and the process is complete in less than 1 hr at 1000 ◦ C.
Partial homogenisation also occurs between incoherent Na-rich and K-rich sub-grains in
replacive veins. Furthermore, upon heating to ≥500 ◦ C nanotunnels disappear or become
less obvious, exsolution lamellae get intersected by small cracks and arrays of planar
micropores form around them. Heating to >700 ◦ C leads to the formation of abundant
subspherical nanopores [30]. Finally, heating results in the development of interconnected
cracks, which form due to spatially uneven thermal expansion because of regions with
varied chemical composition and state of Si-Al order (Figure 7; [17]). Cracks were also
 Minerals 2021, 11, 1025 15 of 25

Minerals 2021, 11, 1025 16 of 26

reported in heated grains of alkali feldspar from the Chain of Ponds Pluton [73], the
Klokken intrusion [82], and the Benson Mines pegmatite [94].

FigureFigure
7. (A)7.Back-scatter electron
(A) Back-scatter electronimages
imagesof of uncoated (010)cleavage
uncoated (010) cleavage surfaces
surfaces of anof an alkali
alkali feldsparfeldspar
fragment fragment
taken from taken
the from
the Shap
Shap Granite, UK. The images were taken in the same region before step-heating (left), after a single 10 min heating step atheating
Granite, UK. The images were taken in the same region before step-heating (left), after a single 10 min
550◦ C°C
step at550 (middle)
(middle) andand
afterafter an additional
an additional eight heating
eight heating steps at◦ C600–825
steps at 600–825 °C (right).
(right). Blue Blue arrows
arrows show exsolution show exsolution
lamellae.
lamellae. Green
Green arrows
arrows highlight
highlight replacement
replacement perthite perthite veins
veins (dark (dark
regions areregions
Na-rich, are Na-rich,
brighter regionsbrighter regions
are K-rich). are arrows
Yellow K-rich). Yel-
low arrows show black
show cracks: cracks: blackindicates
outline outlinecracks
indicates cracks
that did that did with
not disappear not progressive
disappear heating,
with progressive
orange outlineheating, orange
indicates cracksoutline
indicates cracks that appeared after 1 heating step and became invisible after 9 heating steps. (B–D)
that appeared after 1 heating step and became invisible after 9 heating steps. (B–D) Arrhenius plots for the step/heating Arrhenius plots for
the step/heating
experiments with the corresponding repetitive heating schedules. The Arrhenius trajectory of smaller grains is consistentsmaller
experiments with the corresponding repetitive heating schedules. The Arrhenius trajectory of
grains with
is consistent
MDD theory, with MDD
while theory,
grains with while grains
half widths of with
0.5 mmhalf
andwidths of 0.5smaller
larger yield mm and larger
values 2 for
yield
for D/r smaller
highervalues for D/r2 for
temperature
higherheating
temperature heating
steps, which is steps, which to
contradictory is contradictory to MDD theory.
MDD theory. Non-linearity in theNon-linearity in the Arrhenius
Arrhenius trajectories was ascribedtrajectories
to the was
ascribed to the evolution
evolution ofduring
of fracturing fracturing during step-heating.
step-heating. All data
All data and images and images
are taken are taken
from Popov from Popov
et al. (2020b) [17]. et al. (2020b) [17].

Some authors have suggested that modifications to the texture of alkali feldspar
dynamically alter the boundaries of apparent intra-grain diffusion domains
([12,29,30,94]). However, until recently these suggestions were not supported by any
diffusivity data, which may have led other authors to conclude that changes in alkali
feldspar texture incurred during laboratory heating, such as fracturing, play no im-
Minerals 2021, 11, 1025 16 of 25

Some authors have suggested that modifications to the texture of alkali feldspar dy-
namically alter the boundaries of apparent intra-grain diffusion domains [12,29,30,94].
However, until recently these suggestions were not supported by any diffusivity data,
which may have led other authors to conclude that changes in alkali feldspar texture
incurred during laboratory heating, such as fracturing, play no important role in labora-
tory degassing [73,82]. However, Popov et al. (2020b) [17] reported Ar diffusivity data
showing that the effective diffusion length of alkali feldspar from Shap Granite decreased
during progressive step-heating by at least a factor of ~15 in grains that are larger than
~0.5 mm (assuming that Ea and D0 are unchanged; Figure 7C,D). They related this de-
crease to fracturing, which was shown to continue with increased heating using electron
microscopy observations (Figure 7A). The effective diffusion length appeared to increase
with progressive heating in smaller grains, such that their Arrhenius plots were consistent
with predictions of the MDD model (Figure 7B). This was interpreted by Popov et al.
(2020b) [17] to be due to the greater chance of cracks that form early in the step-heating
process intersecting the grain surface. Clearly, any attempt to reconcile curved Arrhenius
trajectories with the MDD model must first verify that the proposed intra-grain diffusion
domains remain stable during laboratory heating.
Another group of suggestions about the cause of non-linearity in Arrhenius plots
focuses on time and/or temperature dependent changes in parameters that characterise Ar
diffusion through the alkali feldspar structure (i.e., Ea and D0 ). Some authors speculate that
non-linearity may be caused by changes in vacancy-specific diffusion mechanisms [34,55,94].
Foland (1994) [94] also suggested that radiation damage can attenuate Ar diffusion and
its annealing during step-heating can complicate Ar release. While these ideas were not
developed further, evidence from diffusion studies in other materials [95–98] shows that
there is potential for such phenomena to occur in alkali feldspar. Cassata and Renne
(2013) [92] utilised molecular dynamics considerations to suggest that the downward
curvature of Arrhenius trajectories of sodic feldspars and potassic feldspars with exsolved
Na-rich lamellae is due to changes in the rate of thermal expansion during a transition from
triclinic to monoclinic symmetry. They supported this idea using step-heating experiments
with anorthoclase aliquots with different sizes from Easy Chair Crater, USA (and other
feldspars), which yielded non-linear Arrhenius arrays for Ar outgassing at temperatures
near the triclinic-monoclinic transition and linear Arrhenius arrays for Ne outgassing
at much lower temperatures. The claim was made that following MDD theory, these
arrays require that smaller grain fragments have smaller sized domains, which led those
authors to conclude that the non-linear Arrhenius trajectories must be caused by changes
in diffusivity. However, as pointed out by Lovera et al., (2015) [99], these arrays can
be explained within the framework of MDD theory if the largest domain is assumed to
occupy most of the analysed fragment (see also [17]). Finally, Kung and Villa (2021) [58]
observed that the rate of Ar release from a cleavage fragment of orthoclase from Itrongay,
Madagascar, varied during laboratory degassing at a constant temperature of 888 ± 2 ◦ C
(Figure 8A), which they correlated with heating-induced changes in vibrational modes
documented by Raman spectroscopy. However, most of the changes in vibrational modes
were instantaneous and reversible, and thus it is unclear how they can affect Ar diffusion.
Perhaps more importantly, Kung and Villa (2021) [58] observed an irreversible change
of colour, indicating that the inventory of structure defects had changed, and they also
report that the degassed fragment “crumbled into dozens of euhedral cleavage fragments”,
suggesting that many cracks had formed. The importance of the latter is corroborated
by the log(r/r0) plot (Figure 8B), which can be interpreted as showing a decrease of the
effective diffusion length until ~30% of 39 Ar was released.
 Minerals
Minerals 2021, 102511, 1025
11,2021, 17 of 25 18 of 26

Figure 8.Figure Data from

Data8.from Kung Kung
andand Villa
Villa (2021) [58]
(2021) [58] obtained
obtained byby
in-vacuo degassing
in-vacuo of alkali
degassing offeldspar from Itrongay,
alkali feldspar fromMadagascar.
Itrongay, Mada-
The experiment included 3 heating phases where the 1st and 2nd phases were heated at 888 ◦ C, while the 3rd phase was rd
gascar. The experiment included 3 heating phases where the 1 and 2 phases were heated at 888 °C, while the 3 phase
st nd

step-heated between1024 1024°C ◦ C and 1449 ◦ C. The analysed fragment was removed from the spectrometer between each
was step-heated between and 1449 °C. The analysed fragment was removed from the spectrometer between each
39 Ar degassing rates during the first 2 phases of heating compared to a theoretical curve for a single
heating heating
phase. phase.
(A) 39Ar(A)degassing rates during the first 2 phases of heating compared to a theoretical curve for a single
domain domain with constant
with constant diffusivity
diffusivity (see(see [58],
[58], forfor details).The
details). The departure
departure ofofthe experimental
the experimental fromfrom
the theoretical curve was
the theoretical curve was
interpreted to reflect changes in diffusivity through time. (B) log(r/r0) plot for all 3 heating phases
interpreted to reflect changes in diffusivity through time. (B) log(r/r0) plot for all 3 heating phases assuming an activation assuming an activation
energy ofenergy
241.9ofkJ/mol
241.9 kJ/mol
(derived(derived
fromfromthethe slope
slope definedby
defined by heating
heating steps
steps7676
andand77).77).
TheThe
topology of the of
topology log(r/r0) plot for plot for
the log(r/r0)
the first 2 phases of heating does not depend on the activation energy because the heating
the first 2 phases of heating does not depend on the activation energy because the heating temperature remained con- temperature remained constant.
Abrupt changes in log(r/r0) coincide with reloading of the analysed fragment into the spectrometer and thus may represent
stant. Abrupt changes in log(r/r0) coincide with reloading of the analysed fragment into the spectrometer and thus may
an analytical artifact. We have attempted to correct for these artifacts (grey line) by (i) arbitrarily shifting the plot segment of
represent an analytical artifact. We have attempted to correct for these artifacts (grey line) by (i) arbitrarily shifting the
the 1st phase of heating by −0.3 log units (to avoid overlap with the original data, rendering it easier to see), and (ii) shifting
plot segment of the 1st phase of heating by −0.3 log units (to avoid overlap with the original data, rendering it easier to
the plot segments of the 2nd and 3rd phases of heating such that the second heating step in each of them yields the same
see), and (ii) shifting the plot segments of the 2nd and 3rd phases of heating such that the second heating step in each of
log(r/r0) value as the final heating step in the preceding phase of heating. Note that the effective diffusion length decreases
them yields the same log(r/r0) value as the final heating step in the preceding phase of heating. Note that the effective
until ~30% of 39 Ar has been released, after which it increases. This trend in log(r/r0) is visible in the log(r/r0) plot with and
diffusion length decreases until ~30% of 39Ar has been released, after which it increases. This trend in log(r/r0) is visible in
without artefacts, and is consistent with observation that the heated fragment crumbled into dozens of euhedral cleavage
the log(r/r0) plot with and without artefacts, and is consistent with observation that the heated fragment crumbled into
fragments after the 2nd phase of heating [58].
dozens of euhedral cleavage fragments after the 2nd phase of heating [58].
Summarising, many authors argued that heating-induced structural modifications
3.2.2.affect
Muscovite
the diffusion of Ar in alkali feldspar during laboratory experiments. While un-
ambiguous evidence to support these claims is currently lacking, existing data warrant
Unlike alkali feldspar, muscovite micas are hydrous, and it has been known for
more careful consideration of whether Ar diffusivity data obtained in the laboratory at
some timetemperatures
higher that dehydration reactions during
can be extrapolated to lowerstep-wise
temperatures degassing
to model Ar of diffusion
Ar can causeover micas
that geological
have an timescales.
a priori known zoned
The latter intra-grain
is important for bothArstep-heating
distribution andtoinyield plateaus on age
situ approaches
40 Ar/39 Ar thermochronology because both approaches use laboratory derived diffusion
spectra ([100]). This is generally unsurprising because degassing hydrous muscovite in
to
vacuo parameters.
proceeds by structural modifications during dehydroxylation that start at ~650–
780 3.2.2.
°C ([101–103]).
Muscovite Dehydroxylated muscovite has cell parameters that are larger than
hydratedUnlikemuscovite [104], and thus it seems possible that diffusivities also vary with
alkali feldspar, muscovite micas are hydrous, and it has been known for some
structural expansion (e.g., see [92]).
time that dehydration reactions during step-wise degassing of Ar can cause micas that have
anCélèrier
a priori (2007) [105] and
known zoned Harrison
intra-grain et al. (2009)
Ar distribution [7] examined
to yield plateaus onthe
ageAr loss [100].
spectra characteris-
tics in muscovite during hydrothermal heating experiments, and conclude thatbyvacuum
This is generally unsurprising because degassing hydrous muscovite in vacuo proceeds
structural
degassing of modifications during dehydroxylation
both hydrothermally treated, and in that start at
vacuo ~650–780 ◦ C [101–103].
step-heating of muscoviteDe- can be
hydroxylated muscovite has cell parameters that are larger than hydrated muscovite [104],
described by a diffusion model with multiple diffusion length scales, and thus that de-
and thus it seems possible that diffusivities also vary with structural expansion (e.g.,
hydroxylated
see [92]). muscovite preserves Ar/ Ar gradients that can be subsequently used to
40 39

obtain thermal
Célèrierhistory solutions
(2007) [105] using the
and Harrison et al.MDD
(2009)approach.
[7] examinedSince then,
the Ar losssome
40Ar/39Ar age
characteris-
gradients in age spectra
tics in muscovite duringhave been interpreted
hydrothermal as diffusionand
heating experiments, gradients,
concludeand
thathave
vacuum been used
degassing of both hydrothermally treated, and in vacuo step-heating
to estimate the diffusivities of discrete domains with the general assumption that onlyof muscovite can
primary igneous phases were degassing and that these remained stable throughout the
degassing experiment (e.g., [10,11,106]). In response, Villa (2021) [107] recently
re-examined the data of Célèrier (2007) [105] in detail, and based on the study of Hess et
al. (1987) [108] suggest that a more highly resolved analysis of the muscovites using TEM
Minerals 2021, 11, 1025 18 of 25

be described by a diffusion model with multiple diffusion length scales, and thus that
dehydroxylated muscovite preserves 40 Ar/39 Ar gradients that can be subsequently used
to obtain thermal history solutions using the MDD approach. Since then, some 40 Ar/39 Ar
age gradients in age spectra have been interpreted as diffusion gradients, and have been
used to estimate the diffusivities of discrete domains with the general assumption that
only primary igneous phases were degassing and that these remained stable through-
out the degassing experiment (e.g., [10,11,106]). In response, Villa (2021) [107] recently
re-examined the data of Célèrier (2007) [105] in detail, and based on the study of Hess
et al. (1987) [108] suggest that a more highly resolved analysis of the muscovites using
TEM would probably reveal reaction products, which are the cause of staircase-shaped age
spectra. This would be consistent with the observation by Harrison et al. (2009) [7] who
report fine, euhedral neoformed grains that crystallised during hydrothermal heating. Villa
(2021) [107] concludes that the range of variations in Ca/K ratios in muscovite can only
be accounted for by open system reactions (and possibly the neoformed grains observed
by Harrison et al., 2009; [7]) during the hydrothermal degassing experiments, and volume
diffusion has not dominated Ar loss.

3.3. Relevance of Cross-Correlation of log(r/r0) Plots with Age Spectra

Lovera et al. (2002) [45] used numerical modelling of fluid-mediated recrystallisation
to show that log(r/r0) plots and age spectra are expected to be highly correlated if Ar
loss during laboratory heating occurred along the same boundaries and via the same
mechanism as in the geologic past. According to them, the frequent observation of high
correlations (>70% of samples in their database) simultaneously validates the assumption
that natural 40 Ar loss was dominated by volume diffusion and that sample-specific Ar
diffusivity data acquired by step-heating can be used to obtain accurate t-T paths by
inversion modelling. However, fluid-mediated recrystallisation of alkali feldspar simulated
by Lovera et al. (2002) [45] only caused fragmentation of intra-grain diffusion domains,
leaving volume diffusion as the sole mechanism for 40 Ar displacement. A more realistic
approach to simulating the effects of fluid interaction was taken by Popov and Spikings
(2020; Figure 9) [59], where 40 Ar is completely removed from the affected zones at the time
of fluid interaction, mimicking the consequence of fluid-induced dissolution-reprecipitation
(e.g., [55,71,109]). They showed that the age spectrum and log(r/r0) plots can also be
highly correlated when fluid flow affects Ar loss through geological time, and dry volume
diffusion drives degassing in the laboratory. This correlation exists because fluid-mediated
alteration can also lead larger domains to have generally older apparent 40 Ar/39 Ar dates,
which is a prediction of MDD theory. Furthermore, the same simulations also showed that
volumetrically low degrees of recrystallisation and alteration (e.g., ~3%) can significantly
reduce the accuracy of t-T solutions constructed using MDD theory. Therefore, high Cfg
values alone cannot be used to validate the assumptions behind MDD theory and the
accuracy of its predicted thermal histories.
 have generally older apparent Ar/ Ar dates, which is a prediction of MDD theory
Furthermore, the same simulations also showed that volumetrically low degrees of
recrystallisation and alteration (e.g., ~3%) can significantly reduce the accuracy of t-T
solutions constructed using MDD theory. Therefore, high Cfg values alone cannot be
Minerals 2021, 11, 1025
used to validate the assumptions behind MDD theory and the accuracy of 19 itsof predicted
25

thermal histories.

Figure 9.Figure
Forward modelling
9. Forward of Popov
modelling of PopovandandSpikings
Spikings (2020) [59]toto
(2020) [59] test
test thethe ability
ability of theofCfg
theparameter
Cfg parameter (Lovera
(Lovera et ettoal., 2002)
al., 2002)
to compare laboratory
compare laboratoryand
andnatural
natural Ar degassing
Ar degassing mechanisms,
mechanisms, andthe
and thus thus the validity
validity of MDDtoinversion
of MDD inversion to generate
generate accurate t-T accu-
rate t-T histories.
histories. AllAll simulations
simulations assumeassume that laboratory
that laboratory degassing
degassing occurs occurs
by volume by volume
diffusion, and onlydiffusion,
the mode ofand onlyArthe
natural lossmode of
natural Ar loss is modified.
is modified. (A–D)
(A–D) no fluid no fluid
interaction interaction
during during natural
natural degassing; degassing;
(E–H) fluid (E–H)
interaction fluid
driving interaction driving dissolu-
dissolution-precipitation
tion-precipitation
and Ar loss.and Ar loss.
Figures show Figures show forward
forward modelled modelled
t-T paths t-T paths
and aqueous historyand aqueous
(B,F), resultanthistory (B,F),
age spectra resultant
(C,G) age spectra
and best-fit
(C,G) andt-T best-fit
solutionst-T solutions
generated bygenerated by inversion
inversion using using MDD
MDD modelling (D,H).modelling
In scenario (D,H).
with noIn scenario
fluid withano
interaction fluidwith
crystal interaction
3 non-interacting spherical domains with radii of 150, 50 and 16 microns occurring in proportions
a crystal with 3 non-interacting spherical domains with radii of 150, 50 and 16 microns occurring in proportions 1:5:150 1:5:150 have only lost
40 Ar by 40
have only lost volume
Ar by diffusion. The best fitThe
volume diffusion. t-T path
bestobtained by MDD
fit t-T path inversion
obtained yields ainversion
by MDD high degree of correlation
yields (crystal of
a high degree #1;correla-
Cfg = 0.96) between the age spectrum and the log(r/ro) plot (not shown), and the modelled t-T path obtained by MDD
inversion (D) closely matches the original t-T path (B). Similarly, we forward modelled a t-T path (F) with accompanying
fluid assisted dissolution-precipitation that reset specific volumes of the three modelled domains at specific times (crystal
#2). The best fit t-T path obtained by MDD inversion yields a Cfg of 0.94, although the t-T solution (H) does not accurately
recreate the original t-T model (F). MDD theory would utilise the high degree of correlation to interpret the t-T paths
obtained by MDD inversion in both cases, as accurate. Details are provided in Popov and Spikings (2020) [59].

4. Recommendations
Displacement of isotopes by volume diffusion always occurs, although it is unlikely
to displace isotopes at rates that dominate over the effects of fluid-induced modifications.
Potassium-rich alkali feldspars from magmatic rocks are normally a combination of semi-
coherent perthite with one or more replacement phases, and thus it is likely that multiple
phases of replacement are commonplace in plutonic feldspars [75,76]. Therefore, while
studies of alkali feldspar from the Chain of Ponds Pluton, Aar Massif, Klokken Syenite
and Itrongay may not entirely negate the application of diffusion theory to recover t-T
paths, they reveal the paramount importance of combining a detailed textural study of
single crystals with 40 Ar/39 Ar data before doing so. A similar conclusion can be made
regarding white micas, where a combination of petrology and in situ 40 Ar/39 Ar dates of
white mica from high pressure terranes in Oman, the Western Gneiss region and Porsgrunn-
Kristiansand Shear Zone in Norway, and the Lardarello-Travale Geothermal Field in Italy
clearly reveal the absolute necessity of first accounting for fluid interaction and secondary
reaction products before seeking diffusion profiles and extracting t-T information. In addi-
tion, an expanding database of experimental evidence shows that laboratory step-heating
at elevated temperatures (e.g., ~400–1100 ◦ C) can induce structural and textural changes
such as symmetry transitions, dehydroxylation, and creation and annealing of crystal
structure defects and cracking, and thus extreme caution must be made when extrapolating
laboratory derived rate loss constants (D/r2 ) to the geologic past. However, some publica-
tions that have combined in situ 40 Ar/39 Ar dates with petrological information could not
Minerals 2021, 11, 1025 20 of 25

rule out the possibility of the presence of diffusion profiles on small scales. Thus, it may be
possible to use such data to find crystals of alkali feldspar and white mica that are suitable
for thermochronology, and below we provide some recommendations that will assist in the
recovery of potential t-T paths.
(1) Even carefully selected grains of alkali feldspar and muscovite from common
magmatic and metamorphic rocks are likely to represent polycrystalline materials featuring
multiple generations of a single or several minerals. Therefore, it is of paramount impor-
tance to characterise such grains prior to isotopic analysis to identify the likely causes of
disturbances in 40 Ar/39 Ar systematics. At bare minimum, thermochronological interpreta-
tions of 40 Ar/39 Ar data should be supported by cathodoluminescence and/or high-contrast
back scattered electron images. Chemical and isotope composition can provide further
evidence for the presence of recrystallised regions as well as their origin. Of particular
importance are Ca, K and Cl, as they partially convert to Ar isotopes during neutron
irradiation and provide information on the sources of the analysed gas. Attention should
be paid even to volumetrically minor secondary alteration. For example, the study of [59]
Popov and Spikings (2020) showed that only 3–6 vol% of reprecipitated K-rich feldspar
can significantly change t-T paths obtained by the MDD approach. 40 Ar/39 Ar dates of
Muscovite are frequently older than from K-feldspar in the same rock sample (e.g., [39]),
which is predicted by thermal-diffusion, although this does not negate the possibility that
fluid interaction has modified the Ar isotopic composition.
(2) In vacuo step-heating for the purposes of thermochronology should only be per-
formed on grains where any intra-grain diffusion domains are shown to be stable and
any non-linearity in Arrhenius relationships for Ar diffusivity through an uninterrupted
structure is known and can be accounted for. The applicability of extrapolation of exper-
imentally determined diffusion parameters to geological temperatures and time scales
should be carefully assessed. In vacuo step-heating degassing experiments can be affected
by phenomena such as heating-induced fracturing, symmetry changes, the appearance
and disappearance of various structure defects, and dehydroxylation. Hydrothermal de-
gassing experiments can be influenced by mineral reactions whereby the rate constants of
degassing compound several displacement mechanisms, and include Ar loss via mineral
reactions as well as diffusive loss. Therefore, detailed observations are required to assess
the degree of mineral transformation when extracting parameters for Ar diffusion from
both types of experimental data (step-heating and in situ ablation). Cross correlation of
age spectra and log(r/r0) plots should not be used to compare laboratory and natural
degassing pathways because high-degrees of cross-correlation can also be achieved when
these are not equivalent.
(3) In situ analyses are extremely powerful because they can directly associate 40 Ar/39 Ar
dates with textural and compositional information, and thus can be used to seek what
may at least be suspect diffusion profiles from what is shown to be regions that formed at
the same time and have equivalent intrinsic diffusion properties. Such regions in alkali
feldspars may include regions that are distal from any later veins, or regions within homo-
geneous cores of gem-like megacrystic feldspars (e.g., Itrongay feldspar). However, the
extraction of thermal history information from such profiles is dependent on knowledge
of the intrinsic diffusion properties (see recommendation ii), which cannot be obtained
from in situ data without an apriori knowledge of the thermal history. Furthermore, as
with the step-heating approach, the in situ technique also requires an understanding of
the boundary condition, where the concentration of Ar isotopes may only be semi-closed
(see Popov and Spikings, this issue). Numerous in situ dates are required from any given
monomineralic phase to attempt to recover the composition of the non-radiogenic isotope
reservoir(s).
(4) Overall, the 40 Ar/39 Ar technique has tremendous potential to reveal information
about fluid flow, deformation, the timing of sub-solidus transformations and thermal
histories. It is likely that in most cases 40 Ar/39 Ar dates neither record end-member fluid
events nor thermal diffusion profiles, and are instead mixed dates. However, extracting
Minerals 2021, 11, 1025 21 of 25

the thermal-diffusion component requires careful petrographic analyses with elemental

and isotopic characterisation, which are the primary tools to deduce the origins of the Ar
isotope reservoirs. Arguably, with the exception of 40 Ar/39 Ar geochronology of sanidine
from volcanic rocks, 40 Ar/39 Ar data are better used to estimate the timing of fluid flow and
deformation events (i.e., the age of neo-formed grains).

Author Contributions: Conceptualization: R.A.S., investigation, R.A.S. and D.V.P.; data curation,
R.A.S. and D.V.P.; writing—original draft preparation, R.A.S. and D.V.P.; writing—review and editing,
R.A.S., funding acquisition, R.A.S. and D.V.P. Both authors have read and agreed to the published
version of the manuscript.
Funding: This review benefited from funding from the Swiss National Science Foundation grants
200021_160052, awarded to R.A.S., and an Early Postdoctoral Mobility fellowship P2GEP2_191478,
awarded to D.V.P.
Data Availability Statement: This is a review, and therefore all data can be found indexed from the
original sources in the citations that are provided.
Acknowledgments: The manuscript benefited from discussions with members of the Isotope Geo-
chemistry group at the University of Geneva.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study, in the collection, analyses, or interpretation of data, in the writing of the manuscript, or
in the decision to publish the results.

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1. Mulch, A.; Cosca, M.A. Recrystallization or Cooling Ages: In Situ UV-Laser 40 Ar/39 Ar Geochronology of Muscovite in Mylonitic
Rocks. J. Geol. Soc. 2004, 161, 573–582. [CrossRef]
2. Villa, I.M.; Hanchar, J.M. K-Feldspar Hygrochronology. Geochim. Cosmochim. Acta 2013, 101, 24–33. [CrossRef]
3. McDonald, C.S.; Warren, C.J.; Mark, D.F.; Halton, A.M.; Kelley, S.P.; Sherlock, S.C. Argon Redistribution during a Metamorphic
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