Physics and Chemistry of the Earth 30 (2005) 1038–1046

www.elsevier.com/locate/pce

The use and usefulness of boron isotopes in natural

silicate–water systems
a,* b
Annette Deyhle , Achim J. Kopf
a
Scripps Institution of Oceanography, UCSD, 9500 Gilman Drive, La Jolla, CA 92093-0212, USA
b
Research Centre Ocean Margins, University Bremen, Klagenfurter Strasse, 28359 Bremen, Germany

Received 25 March 2004; received in revised form 13 April 2005; accepted 19 April 2005
Available online 8 August 2005

Abstract

Boron and its two stable isotopes 10B and 11B are considered powerful tracers in low temperature regimes like ocean waters and
subduction zones, while very little is known about the isotopic fractionation in high pressure–temperature (PT) regimes. However,
recent studies indicate that boron fractionation in silicate–water systems may follow a systematic relationship with temperature,
regardless of the geological regime. In this paper we review previous B isotope studies and test the empirical relationship proposed
by Williams et al. [Boron isotope geochemistry during diagenesis. Part I. Experimental determination of fractionation during illiti-
zation of smectite, Geochim. Cosmochim. Acta 65 (2001a) 1769–1782; Boron isotope geochemistry during diagenesis. Part II. Appli-
cations to organic sediments, Geochim. Cosmochim. Acta 65 (2001b) 1783–1794; Application of boron isotopes to the
understanding of fluid–rock interactions in a hydrothermally stimulated oil reservoir in the Alberta Basin, Canada, Geofluids 1
(2001c) 229–240] by comparing it with the wealth of earlier data from studies of different geological scenarios. Our main conclusion
is that, given the large variations of B isotope fractionation patterns in natural silicate–water systems, the majority of these systems
are not represented by the proposed relationship. Factors more complex than temperature alone appear to control B isotope geo-
chemistry, which include species of the silicate mineral, starting fluid, pH, geological setting, fluid/rock ratio (i.e. porosity), or time
for equilibration between the solid and fluid phase.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Boron; Stable isotopes; Clay minerals; B isotope fractionation; Water–silicate

1. Introduction mostly from the coordination change in B between the

Boron and B isotopes have been shown to represent a
powerful proxy in fluid–rock interaction processes in the
geochemically very reactive area of low temperature
alteration of geomaterials. This is mostly because of
the geochemical characteristics of B, i.e., its high solubil-
ity in aqueous fluids, its generally high volatility, and its
large isotopic variation in natural environments. The al-
most 100&-span of B fractionation in nature results
* 2002; Kopf and Deyhle, 2002), alteration of igneous
Corresponding author. Tel.: +1 858 822 4345; fax: +1 858 822
4945.
E-mail address: adeyhle@ucsd.edu (A. Deyhle).

trigonal B(OH)3 of dissolved to tetrahedral BðOHÞ4 ,
which substitutes for Al and Si in silicate minerals,
whereas 10B has a preference for tetrahedral bonds
(Kakihana and Kotaka, 1977; Palmer and Swihart,
1996; Palmer et al., 1987). In the field of interactive pro-
cesses between siliceous sediment/rock and aqueous
fluid in diagenetic regimes, B is one of the key tracers
in subduction zone processes (Spivack and Edmond,
1987; Bebout et al., 1993; You et al., 1993; Kopf et al.,
2000; Deyhle et al., 2001; Deyhle and Kopf, 2001,
rock (Smith et al., 1995; Benton et al., 2001), arc volca-
nism (e.g., Rosner et al., 2003; Ishikawa and Nakamura,

1474-7065/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pce.2005.04.003
 A. Deyhle, A.J. Kopf / Physics and Chemistry of the Earth 30 (2005) 1038–1046 1039

1994; Ishikawa and Tera, 1997; Smith et al., 1995; Ishik- 30

awa and Tera, 1999; Ishikawa et al., 2001), or diagenesis errors are size of symbols
(Williams et al., 2001c; Kopf and Deyhle, 2002; Kopf 20 2
1.6 I/S
x -2 n for
et al., 2003). Isotope ratios are mostly a function of tem- .09 atio

∆ mineral-water (‰)
3
10 y=1 t ion
perature, pH, water chemistry, and the silicate minerals f rac

1100 °C
yg en
involved, as well as of pressure (Palmer et al., 1992; Her- 0 Ox

350 °C
vig et al., 2002).

300 °C
Many studies have examined the nature of B ex- -10
Bor
change and fractionation in silicate–water systems, both on f
ract
-20 i ona
in the laboratory (e.g., Couch and Grim, 1968; You

et al., 1995; You and Gieskes, 2001; Williams et al.,
2001a) and in natural settings (e.g., Ishikawa and
Nakamura, 1993; Kopf and Deyhle, 2002; Deyhle and
Kopf, 2002; Kopf et al., 2003; Deyhle et al., 2003,
2004). Based on their own studies and work by Palmer
et al. (1987), Williams et al. (2001a,b,c) have proposed
a linear B isotope fractionation relationship, designed
to describe a temperature-dependent B fractionation in
natural silicate water systems, which can be applied
from low to high temperatures and to different silicate
minerals. The purpose of this manuscript is to review lit-
erature data from both the latter publications as well as
all other work available on fluids and silica-bearing sol-
ids. This will allow testing the suggested B fractionation
trend for silicate systems, and it will additionally demon-
strate the complexity of B-isotope fractionation in differ-
ent geological settings, and point to parameters other
than temperature that might control B fractionation.
2. Data compilation
2.1. Recent experimental data and postulated
relationship
In recent years, several papers (Williams et al., 2001a;
Hervig et al., 2002; Williams and Hervig, 2002) have at-
tempted to establish an universal relationship for the
fractionation behavior of B in silicate–water systems as
a function of temperature. From laboratory experiments
these authors established a systematic trend in B ex-
change between siliceous rocks and interstitial waters.
Williams et al. (2001a) carried out a series of long
term (120–150 days) autoclave reaction experiments of
a clay mineral–water slurry in an attempt to reach equi-
librium conditions. The temperature range was 300–
350 °C, and fluids were extracted under vacuum on an
extraction line. A total of 3 experiments gave two data
points for clay (at 300 °C and 350 °C, respectively; see
Fig. 1, central dots). The B isotopic composition of
the fluid was determined by a simple mass balance calcu-
lation using the B content and d 11Bclay-value of the solid
fraction (see Williams et al., 2001a, p. 1775). For details
we refer to Williams et al. (2001a,b,c) or Williams and
Hervig (2002). Hervig and Moore (2000) as well as Her-
vig et al. (2002) have reported results from high-T
25 °C
y=1 tion
0.12
x+
-30
2.44
-40
0 0.5 1 1.5 2 2.5 3 3.5 4
1000/T (K)
Fig. 1. Results from hydrothermal experiments as well as boron
isotope fractionation model by Williams et al. (2001a, their Fig. 13).
For comparison, the authors also showed oxygen isotope fractionation
from Yeh and Savin (1977). Data are shown as Dd11Bmudd11Bfluid
versus temperature (as 1000/TKelvin).
(1100 °C) melt experiments of mid-oceanic ridge basaltic
glasses at 100 MPa confining pressure. The experiments
were doped with B standard (NBS SRM 951) and ran
for 24 h. The fractionation between aqueous fluid and
basaltic melt, which is related to the coordination
change from trigonal in the fluid to tetrahedral sites in
the melt, resulted in a Dd11Bmud  d11Bfluid-value of
5& (see Fig. 1). In a later manuscript, Hervig et al.
(2002) have summarized experiments by other workers,
which cover a wider T-range from 550 °C to 1100 °C
(their Fig. 3). These data show different fractionation
trends, possibly because different mineral/rock systems
are presented in the same diagram (e.g., some silicates
like tourmaline do not plot anywhere near the linear
relationship). Only the 1100 °C melt-fluid fractionation
data were used for constructing the graph in Fig. 1,
whereas later data of melt experiments on rhyolites
and basalts by the same authors show considerable scat-
ter, (Hervig et al., 2002) which suggests that melt-fluid
systematics are also more complex and dependent on
other factors than temperature alone.
In addition to the data from autoclave clay testing
and melt experiments (see above), Williams et al.
(2001a,b,c) used a fourth data point from the literature
(at 25 °C from Palmer et al., 1987) and fitted a linear
graph through these data. This graph follows a linear
relationship: y = 10.12x + 2.44, where x = 1000/T
[K], as shown in Fig. 1. A different slope for the fraction-
ation curve (y = 12.2x + 5.66) was chosen by Hervig
et al. (2002), who did not extrapolate their data to the
low temperature endmember by Palmer et al. (1987).
Despite the fact that the two data points from the
three experiments by Williams et al. (2001a) lead to a
steeper gradient than the one published (see grey line in
Fig. 2; y = 21.42x + 21.37), and regardless of the fact
1040 A. Deyhle, A.J. Kopf / Physics and Chemistry of the Earth 30 (2005) 1038–1046

30 legend of Fig. 3 to which we refer for more information.

beginning
best fit through data by of tests In any case, the data compiled from the literature are
20 Williams et al. (2001a) I/S
y=21.41x + 21.37 nf
or similar to those from Williams et al. (2001a, Fig. 1) with
n atio 77)
tio 19
rac vin (
respect to the temperature range (i.e., approximately 10–
10 nf
x y ge d Sa 1000 °C), but they cover a larger variety of geological
n
∆ mineral-water (‰)

end of o ha
tests Ye settings. Furthermore, natural systems are open systems
0
prop
B5
and not closed as in the experimental setup. As a conse-
Willi osed D23
-10 ams fract
et a ionat D11
quence, more minerals and mineral assemblages are in-
l. (2 io
001 n tren volved, which are possibly the main reason for the
a,b, d
-20 c)
large scatter. It should also be noted that the natural
systems are assumed to allow the respective system more
-30
sand- time for equilibration between the fluid and solid phase
stone
-40 sand-
stone
(maybe excluding tectonically very active scenarios like
the Costa Rica forearc). Also, the corresponding fluid
mud-
-50 stone mud-
stone
and solid B signatures are not affected by possible arti-
facts in the fractionation pattern as a result of the
-60
0 0.5 1 1.5 2 2.5 3 3.5 4 artificial addition of B solutions (like ‘‘doping’’ the
1000/T (K) aliquot with boric acid standard NIST SRM 951 to
2000 ppm B, d11B = 0& solution, as in Hervig et al.
B isotope data Williams et al. (2001a) (2002), or a 10B spiked synthetic solution with a starting
B isotope data used by Williams et al. B ratio of 11B/10B = 0.038[d11B  990&], as in You
(2001a) to define fractionation trend
et al., 1995; You and Gieskes, 2001). Such B signatures,
O isotope data Williams et al. (2001a)
which are very dissimilar from any natural setting,
B isotope data Williams et al. (2001b)
might not be representative for a study that aims at sim-
PRE steam B isotope data Williams et al. (2001c) ulating natural processes (see discussion below). Also,
POST steam B isotope data Williams et al. (2001c) the spiked tests by You et al. (1995) and You and Gies-
B isotope data Williams et al. (2001d) * kes (2001) showed an opposite trend for d11B signatures
(fluids becoming more positive with increasing tempera-
Fig. 2. Results from hydrothermal experiments (Williams et al., ture) when compared with an unspiked test (fluids and
2001a), the proposed B fractionation relationship, and the oxygen
isotope fractionation graph proposed by Yeh and Savin (1977), as
solids becoming more negative with time and increase
shown in Fig. 1. We found it very informative to include the field data of T).
from the other studies by (some of) these authors (Williams et al., Furthermore, the temperature dependence of B isoto-
2001b,c,d) where reference is made to their fractionation model pic fractionation may be estimated only for a simplified
(Williams et al., 2001b, Fig. 1; 2001c, Fig. 2), as well as a best fit graph case where all monomeric units coexist without interac-
through the hydrothermal data (Williams et al., 2001a). All data shown
are from tables out of Williams et al. (2001a,b,c,d); some values were
tion (see Oi et al., 1989, where a simple approximation
averaged. has been used for polyborate ions).

that other field data gathered by the same authors do not

match the suggested fractionation trend (Williams et al., 3. Discussion
2001b,c,d), the authors postulate that the proposed B
fractionation trend represents a good geothermometer Our discussion will focus on the compatibility of the
for all natural silicate–water systems and that there is postulated B-fractionation trend by Williams et al.
no mineral specific fractionation of B isotopes. (2001a,b,c) of natural silicate–water systems with results
from available literature data from natural systems, as
2.2. Other global data on silicate–water systems given in Fig. 3. In the first part, we will try to illuminate
the problem with the proposed relationship by focusing
In order to test the geothermometer hypothesis as put on one group of silicate minerals, namely clay minerals
forward by Williams et al. (2001a,b,c) more completely, (and their transformation with PT). In the second part
we have compiled data from natural silicate water sys- of the discussion, we will discuss hypotheses that might
tems spanning the vast majority of geological scenarios. explain the mismatch of data from different natural sys-
Those data are summarized in Fig. 3. The different tems compiled from the literature and the proposed trend.
examples cover a range from low-T (<20 °C) marine sce-
narios such as the Mississippi delta or the Costa Rican 3.1. B fractionation in mineral-specific natural systems
Trench to volcanic (Mt. Etna, Sicily), hydrothermal
(Escanaba Trough) and magmatic systems (Mt. Shasta, From Fig. 3 it can be deduced that the linear
Cascades). A detailed list of references is given in the trend proposed by Williams et al. (2001a) is not readily
 A. Deyhle, A.J. Kopf / Physics and Chemistry of the Earth 30 (2005) 1038–1046 1041

Fig. 3. Data from B isotope studies of silicate rocks and accompanying fluids published previously; some data are averaged out the entire set of
results from the publication(s). Graph from B fractionation model by Williams et al. (2001a,b,c) is given for reference. Underlined references in the
legend have been cited in the manuscripts in question (Williams et al., 2001a,b,c). Note that all data presented were taken from field studies of
geosystems (silicates of subrecent to 3.8 Ga age, active as well as passive tectonic and hydrogeologic settings, various temperature regimes, etc.; see
references) with variable degrees of fluid–rock equilibration. Even if some of those systems are not fully equilibrated, it is surprising that the proposed
fractionation model fails to agree with any of them. See above references for more details.
1042 A. Deyhle, A.J. Kopf / Physics and Chemistry of the Earth 30 (2005) 1038–1046

applicable to all natural systems; instead it may only
represent a limited number of natural systems. However,
the distribution of the various silicate–water data pairs
in Fig. 3 is not random, but follows some systematic
trends. For instance, clay mineral-dominated systems
plot in the lower right corner of the diagram whereas
hydrothermally altered rocks plot in the central part,
and igneous rocks tend towards the left part of the dia-
gram (Fig. 3). An examination of each of the various
groups of silicate minerals or siliceous rocks would be
far beyond the scope of this short manuscript. We will
however illuminate our point of systematic trends by
focusing on some phyllosilicates.
Early work on shales established that reversible
adsorption of B at low temperatures occurs (e.g., Har-
der, 1961; Couch and Grim, 1968; Keren and Mezuman,
1981; Palmer et al., 1987). With increasing temperature
and stress (e.g., during burial or tectonic processes), bor-
on desorbs to enrich the fluid phase and is consequently
depleted in the clay (e.g., You et al., 1996). The ad-
sorbed species is predominantly the light isotope 10B,
so that fluids originating from clay-rich pore fluids ob-
tain lighter d11B values than seawater (e.g., Spivack
et al., 1987). In general, B gets enriched in fluids by pro-
cesses such as desorption from clay particles, mineral
dehydration reactions, increasing temperature (T), and
alteration of volcanic or igneous rocks (see Palmer and
Swihart, 1996, and references therein). Among others,
You et al. (1993, 1995), Deyhle et al. (2001), Deyhle
and Kopf, 2001 and Kopf et al. (2000) found that fluids
released in collision zones generally have elevated B con-
tents, and often show a bimodal d11B variation with
depth. Isotopes increase to compositions heavier than
seawater (up to >50&) at moderate depth (seawa-
ter = 39.5&; Spivack and Edmond, 1987), before
decreasing again to lower d11B values (25–30&) at great-
In a recent study, Kopf and Deyhle (2002) have
examined clay mineral-rich muds from mud volcanoes
all over the world. In mud domes, the fluid and mud
may be mobilized as deep as 10 km below the EarthÕs
surface, and is transported upwards due to its buoyancy
(Kopf, 2002). The muds and firm mudstones studied
consist predominantly of clay (>70 vol.%) and were
taken from the abyssal plain, an accretionary wedge,
its backstop, and from an onshore orogenic wedge of
collisional tectonic settings (Kopf and Deyhle, 2002).
As a result, the extruded material is expected to show
a prograde illitization of smectite with depth (i.e., tem-
perature). A plot of the difference between d11Bmud/mud-
11
stone and d Bfluid versus temperature has previously been
shown to be useful as a first-order estimate of a system-
atic diagenetic process (assuming equilibrium between
the solid and fluid phase; Williams et al., 2001a, see
Fig. 1). For the mud volcano samples, we find a good
correlation of the different areas with prograde illitiza-
tion due to inferred burial depth (Fig. 4) even though
it is not clear whether equilibrium between mud and
fluid has been reached since most of these are open sys-
tems. Interestingly, however, the comprehensive mud
volcano data resemble a trend established earlier from
d18O isotopes of smectite–illite clays (Yeh and Savin,
1977). This led Kopf and Deyhle (2002) to propose that
despite the fact that active flow may occur at some of the
mud domes sampled (e.g., on the Mediterranean Ridge;
see Corselli and Basso, 1996), re-equilibration between
30
I/S
20 for
tion )
tio
na 19
77
mineral-water (‰)

f rac v in,
er depth. Alteration of igneous rocks usually leads to 10
yg
en
nd
Sa
Ox ha
d11B lighter than seawater, with a less profound enrich- mY
e
ment in B content of the fluid (Palmer, 1991). 0 (fro oe
s
an
volc
One aspect which complicates the behavior of B in ud
-10 nm Barbados
clays is the transformation of smectite to illite when tem- I/ Si
n for
perature and stress increase (e.g., Colten-Bradley, 1987). tio Pakistan
-20 na Malaysia
ctio Mediterranean
Hydrothermal experiments have demonstrated that fra Makran
ron Ridge
some of the B in the pore fluid can be incorporated into -30 Bo
Caucasus
the illite mineral lattice (substituting Si and Al; e.g., Wil- Western Alps
-40
liams et al., 2001a), but may also be re-adsorbed if con- 0 0.5 1 1.5 2 2.5 3 3.5 4
fining pressures are sufficiently low. These laboratory 1000/T (K)
results suggest that in a natural scenarios, both muds
Fig. 4. Data from selected clay mineral–water systems from mud
and fluids may have high B concentrations. As a result volcanoes all over the world. Boron isotope ratios of different mud
of illitization (i.e., greater mobilization depth of the volcano provinces (as Dd11Bmudd11Bfluid) are plotted versus temper-
mud), the B content in the mud is expected to increase, ature (as 1000/TKelvin), where the temperatures are estimated from the
while d11B of the mud decreases (Williams et al., 2001a). average depth of the mud and fluid in each area using the regional
geothermal gradient and average d11B data from Kopf and Deyhle
This is in general agreement with earlier work by You
(2002). For reference, we show d18O isotope data of smectite-illite clays
et al. (1996, where an illite-rich sediment from the Nan- from Yeh and Savin (1977). Note that the dashed line through the mud
kai accretionary prism was used) and Deyhle et al. volcano data is not a calculated best fit, but the projected relationship
(2004, where mature claystones were considered). from the oxygen isotopes during illitization.
 A. Deyhle, A.J. Kopf / Physics and Chemistry of the Earth 30 (2005) 1038–1046
mud and fluid may have occurred in the majority of the
features. The overall agreement of the data supports
the hypothesis that B geochemistry can be used to trace
the depth of mud volcano roots (i.e., faults) as a func-
tion of temperature (i.e., geothermal gradient), at least
when a single group of minerals (or a process, like the
progressive illitization of smectite) is considered. It fur-
ther suggests that some mineral-specific fractionation
reactions may follow a trend (Fig. 4) which is opposite
to the one proposed by Williams et al. (2001a).
3.2. Problems related to B fractionation trends
Unfortunately, none of the Williams et al. (2001b,c,d)
natural silicate–water data plot near or on the proposed
graph (Fig. 2). This raises doubts about their conclusion
that ‘‘there is a good agreement between the field results
and the experimentally derived B-isotope fractionation
curve indicating that it is a fair assessment of tempera-
ture dependence of B-isotope fractionations between sil-
icates and waters.’’ (Williams et al., 2001b). When
plotting data compiled from various publications in
the literature into the same diagram (Fig. 3), it appears
that these silicate–water systems are randomly scattered
over the diagram rather than linearly aligned with re-
spect to Dd11Bsilicate  d11Bfluid and temperature.
The deviation of natural silicate–water data (see
Fig. 3) from the proposed trend by Williams et al.
(2001a,b,c,d) and Hervig et al. (2002) is probably be-
cause B-isotope fractionation is very complex and min-
eral-specific and not solely a function of temperature,
as claimed by those authors. Below we discuss several
parameters that are likely to further influence the frac-
tionation behavior of B–water–silicate systems.
First, numerous workers have shown that B isotope
fractionation is a function of mineralogy, temperature,
and pH (e.g., Palmer et al., 1987; Hemming et al.,
1995; You et al., 1996). Specifically the pH is critical
for the B-fractionation, as at low pH all dissolved B is
essentially boric acid (B[OH]3) and at high pH all dis-
solved B is essentially borate ion (B[OH]4). A compre-
hensive study on the pH-dependence of B fractionation
in silicate–water systems is beyond the scope of this pa-
per for several reasons. First, the pH is not given for
the majority of the earlier studies. In addition, pH cannot
easily be obtained (or, in case of natural systems, be
reconstructed). Generally it is accepted that the lower
the pH, the lower the expected resulting d11B signature.
This effect could possibly be the reason for some of the
shift to more negative d11B signatures in the fluid seen
in hydrothermal tests with increasing temperature (e.g.,
You and Gieskes, 2001, pH starting value 7.3, pH end
6.4). We anticipate the Williams et al. (2001a) fluids to
show a similar trend, however, the d11B of those fluids
was not measured, instead d11B signatures were calcu-
lated by these workers (see above).
1043
There are other parameters which hamper hydrother-
mal experiment results such as those by You et al.
(1995), You and Gieskes (2001), and Williams et al.
(2001), and limit their suitability as analogues to natural
silicate–water systems. Hydrothermal experiments are
carried out under closed conditions, and, therefore, the
data from such experiments should only be extrapolated
to natural settings which are close to a closed system. As
only very few hydrothermal studies on B-isotope frac-
tionation have been conducted to date (You et al.,
1995; You and Gieskes, 2001; Williams et al., 2001a;
Hervig et al., 2002; Kopf et al., 2002), more studies need
to be carried out in order to determine whether a simple
linear relationship as established by Williams et al.,
2001a, can be applied to all silicate–water systems. Data
from the same authors (Hervig et al., 2002) hint towards
B-isotope fractionation systematics which apply only to
certain silicate minerals, or groups of minerals. For in-
stance, experiments on basalt and rhyolite melts show
different fractionation trends (Hervig et al., 2002) and
suggest that Si-content and possibly coordination of B
may be crucial players in B incorporation and fraction-
ation. Hervig et al. (2002) assume B in basaltic and rhy-
olitic glasses to be tetrahedrally coordinated, but this
assumption has not been proven yet. In addition, B spik-
ing (SRM 951, 2000 ppm, 0&) of basalt (as for the
hydrothermal test of Hervig et al., 2002) might also
cause an unnatural B-isotope fractionation behavior.
It can be observed that the basaltic and ryhyolitic frac-
tionation trends are different (Hervig et al., 2002, their
Fig. 3). Given the different mineralogical composition
of rhyolite and basalt, it is impossible to decide whether
mineralogy, Si-content, or the artificial spiking in the ba-
salt experiment are responsible for the different B frac-
tionation behavior observed.
Also experimental conditions, such as duration of the
hydrothermal test, fluid/rock ratio (and its variation
during the test; see Kopf et al. (2002)), and specifically
starting solution and silicate type or mineral composi-
tion might yield different results. Certainly, strong spik-
ing of the fluid in a hydrothermal test with 10B causes a
fractionation behavior of B which is not only non-repre-
sentative for natural settings, but equally non-applicable
in any interpretation. For instance, both You et al.
(1995) and You and Gieskes (2001) used fluids with a
d11B ratio of 990& at the beginning and 100&
at the end of the experiment. Such d11B signatures do
not exist in nature, and we suspect that oversaturation
of the fluid with 10B may cause artifacts regarding incor-
poration of the light vs. heavy species, and results in a
shift to positive d11B values which is not necessarily
meaningful. In contrast, d11B of unspiked testing solu-
tions becomes more negative with increasing tempera-
ture (You et al., 1995; Kopf et al., 2002). The latter
trend nicely matches data from natural settings where
deep-seated fluids in subduction zone decollement zones
1044 A. Deyhle, A.J. Kopf / Physics and Chemistry of the Earth 30 (2005) 1038–1046
show similar shifts to more negative d11B (You et al.,
1993; Kopf et al., 2000).
Not only temperature, pH (or, more generally speak-
ing, the chemical composition of the fluid), the presence
of organic matter, and mineralogy are factors responsi-
ble for B fractionation, but also pressure has been
named as a possible influence (Palmer et al., 1992; Her-
vig et al., 2002). Finally, the fluid/rock ratio should also
be taken into consideration and could possibly influence
the extent of reaction/fractionation between fluid and
rock. The effects are hard to anticipate, since natural
sediments and rocks have high initial porosities and
are hence reactive; on the other hand, burial causes a
T-increase (in the then compressed rock with lower
porosity), which also enhances fluid–rock interaction.
Hydrothermal compression tests, where P is continu-
ously increased in parallel experiments at various tem-
peratures, have been carried out to illuminate the
counteracting processes of PT-increase and porosity
reduction and their effect on B geochemistry. At the
range of temperatures (20–150 °C) and pressures (0–
80 MPa) regarded, B fractionation during deformation
of fluid-saturated rock can be separated (Kopf et al.,
2002). However, additional work on geomaterials other
than clay-rich sediments has to be done in the future to
more fully understand boron in silicate–water systems.
4. Conclusion
Results from two decades of intensive studies of the
geochemistry of boron and its isotopes have led to the
conclusion that the isotope fractionation of boron is
probably mineral specific and is additionally influenced
by other parameters such as pH, fluid/rock ratio, and
pressure (c.f., Figs. 3 and 4). This suggests that the use
of the boron isotopes for geothermometry is probably
not possible without narrowing down the conditions
that have affected the isotope fractionation processes
(Williams et al., 2001a,b). This first comprehensive com-
pilation presented in Fig. 4 points to potential problems,
and does not allow any definite conclusions regarding
the influence of the most prominent players in B isotope
fractionation in natural silicate–water systems. There-
fore, we suggest that care has to be taken when using
fractionation trends as geothermometers. To better an-
swer these questions, further careful studies would have
to be conducted which include different pressures, pHs,
sample compositions/mineralogy, and temperatures.
Acknowledgements
The authors thank Sonia Tonarini and Joris M. Gies-
kes for their helpful criticism and expert comments on
our compilatory work. We also acknowledge the edito-
rial support by Andrea Dini and Cedric Corteel.
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