Applied Geochemistry, Vol. 5, pp. 541-554, 1990 0883-2927190 $3.00 + .

00
Printed in Great Britain Pergamon Press pie

A critical evaluation of the available measurements for the stable

isotopes of boron

R. L. BASSETF
Department of Hydrology and Water Resources, University of Arizona, Tucson, AZ 85721, U.S.A.

(Received 20 July 1989; accepted in revised form 5 February 1990)

Abstract--The reported measurements for the stable isotopes of B (~LB and "~B) in natural materials are
compiled, critically reviewed and evaluated. The selected values along with a discussion of the error,
indicate the potential exists for using B isotopes in interpreting geochemical environments. The isotopic
values for 611B range from -31%o for terrestrial rocks to +40%0 for sea water, relative to NBS SRM-951
which has a reported I IB/lOB ratio of 4.04362 +_ 0.00137 (2 o). Further, the isotope ratios generally form a
narrow cluster of values for specific rock types. In some instances the reported ~llB may be shifted
substantially from the mean of "unaltered" rock as a result of weathering or reaction such as the
progressive enrichment of 611B in marine sediments over time due to reaction with sea water.
An application of widespread interest is the use of B isotopes in environmental studies. Boron is a
contaminant derived from numerous sources such as municipal and industrial waste. The 611B in these
wastes or processed waters is often significantly different from the/~11B of the local ground-water, which
will likely reflect the blaB values of the nearby rocks. This modification by contaminated water can be
>20%o different from the 611B of the unaffected water, providing a useful tool in delineating the source of
contamination and the direction of migration.

INTRODUCTION et al., 1985). Solid source mass spectrometry pro-

Tr~E STABLEisotopes of B (11B and l°B) were identi-
fied by F. W. A s t o n as early as 1920, using a Positive
Ray Spectrograph, a precursor to the m o d e r n mass
spectrometer (AsToN, 1920), Subsequent investi-
gations by others sought to determine if a natural
fractionation of these isotopes could be identified in
rocks from a variety of geological environments.
THODE et al. (1948) reported a variation from 4.422 to
4.270 for the isotopic ratio of 11B/10B for nine samples
of geological origin. These data span a range of about
35%o, with an instrument precision of 1%o; conse-
quently, it was concluded to be sufficient evidence for
the existence of natural fractionation.
In direct contradiction to this conclusion, PARWELL
et al. (1956) relied on the analysis of 43 B-bearing
minerals and three samples of sea water, and con-
cluded that variation of 611B of less than a few per rail
was due to experimental error and was not geologi-
cally significant; unfortunately, they did not report
their actual data. They did note, however, that sea
water was about 2%0 heavier than the minerals exam-
ined. The rationale for their conflicting conclusion to
that of THODE et al. (1948), was that the earlier
observed variation was the result of both improper
sample preparation and of error associated with the
analysis of the B isotopes using BF 3.
The resolution of this controversy was driven by
the nuclear reactor program which was in need of
precise measurements for the l°B content of a variety
of materials, because l°B has a broad thermal neu-
tron cross section and is used as a m o d e r a t o r in
nuclear reactors to control the reaction (RAMAKUMAR
vided the needed precision, and eliminated the
uncertainty of mesurements with BF 3 in gas source
mass spectrometers. These precise measurements
demonstrated unequivocally the existence of a natu-
ral variation in the isotopic ratio of rocks from differ-
ent geological environments (HAAS et al., 1959;
McMULLEN et al., 1961; GORIS et al., 1961; FINLEY
and LEUANG,1961; FINLEY et al., 1962; SHIMA, 1962,
1963a; AGYEI and McMULLEN, 1968; SCHWARCZ et
al., 1969).
This paper summarizes and evaluates all available
published values for the liB/l°B ratios in natural
materials. Excluded from this summary are: 1. re-
cently reported ratios measured with the inductively
coupled plasma source-mass spectrometer ( I C P -
MS) because of the uncertainty in the analysis
(GREGOIRE, 1987a,b; DAVIDSON et al., 1990), and
2. the few ratios measured in gas source spec-
trometers, in which the analyte was BF 3 or BC13,
because of the well established unreliability of the
measurements. Also not included are the numer-
ous measurements performed on processed and syn-
thetic samples by the nuclear and medical indus-
tries.
Now almost thirty years after discussions over the
natural variation of B isotopes, the entire body of
published data is still sparse. Beyond the tabulation
of data for evaporites by SWIHARTet al. (1986), no one
has attempted to compile and evaluate the published
literature regarding this isotope pair; consequently,
no consistent interpretation is available. A thorough
search of the literature has resulted in the data
presented in this paper.

541
542 R . L . Bassett

Table 1. Summary of boron isotopic ratios and corrected d 11B values for naturally occurring rocks, minerals and waters
(relative to SRM NBS 951, UB/l°B 4.04362 _+ 0.00137)*

Sample Location lIB/roB dillB Ion Prep¶ Ref

Sea water
Arctic Ocean 1. surface 4.236 _+ 0.006 47.6 _+ 1.5 NaeBO ~- MB/IX (I)
Atlantic Ocean 1.70m 4.214 _+0.006 42.1 _+ 1.5 NaeBO ~ MB/IX (1)
2. surface (3)-~ nr 39.6 _+ 0.4 Cs2BO2~ IX (2)
Pacific Ocean l. surface 4.220 _+0,006 43.6 _+ 1.5 Na2BO ~ MB/IX (1)
2. surface 4.223 _+ 0.006 44.4 _+ 1.5 Na2BO ~- MB/IX (1)
3. surface 4.216 _+ 0.006 42.6 _+ 1.5 Na2BO + MB/IX (1)
4. surface (3)t nr 39.6 _+ 0,4 Cs2BO2~ IX (2)
5. 2500 m (3)t nr 39.4 _+ 0.4 Cs2BO ~- IX (2)
6. nr 4,071 _+ 0,023 6.8 _+ 6.0 Na2BO ~- MB (5)
7. Iwo-jima 4.207 _+0.008 40.4 _+ 2.0 Na2BO + MB (7)
8. Ogasawara 4.200 _+0,008 38.7 _+ 2.0 Na2BO + MB (7)

Bay water
Tokyo 1. nr 4.041 _+ 0.006 -0.7 _+ 1.5 Na2BO ] MB (3):~
2. nr 4.020 _+0.012 -5.8 _+ 3.0 Na2BO + EE (4,5)

Igneous rocks
Basalt: unaltered 1. Pacific (2)t nr - 3 . 7 _+ 0.6 CszBO2~ PH (2)
2. Pacific (2)¢ nr -2.25 _+ 0.4 Cs2B02~ PH (2)
Basalt: altered 1. Pacific nr 3.1 _+ 0.4 Cs2BO2r PH (2)
2. Pacific nr 9.2 _+ 0.4 Cs2BO2~ PH (2)
3. Pacific nr 5.5 _+ 0.4 Cs2BO2~ PH (2)
4. Pacific nr 8.1 -+ 0.4 CszBO2~ PH (2)
5. Pacific nr 3.1 _+ 0.4 Cs2BO ~ PH (2)
6. Pacific nr 0.1 _+ 0.4 Cs2BO ~ PH (2)
7. Pacific nr 2.5 _+ 0.4 CszBO ~ PH (2)
8. Hawaii 4.053 _+ 0.011 2.4 _+ 2.7 Na2BO~- MB (4,5)
9. Mohole 4.042 _+ 0.022 -0.4 _+ 5.4 NaeBO + MB (4,5)
Serpentinized I. Atlantic nr 12.5 _+ 0.4 Cs2BO + PH (2)
Peridotitcs
2. Atlantic nr 12.6 _+ 0.4 Cs2BO ~- PH (2)
3. Atlantic nr 8.3 _+ 0.4 Cs2BO2~ PH (2)
4. Atlantic nr 10.0 _+ 0.4 CseBO] PH (2)
Granite 1. Venezuela nr 1.6 _+ 0.4 Cs2BO ~ PH (14)
2. USGS G-1 4.065 _+ 0.015 5.3 _+ 3.8 Na2BO2~ MB (5)
Westerly, RI
Diabase 1. USGS W-1 4.047 _+0.014 (1.8 _+ 3.5 Na2BO f MB (5)
Centerville, V A
Gabbro (Insizwa, Republic
of South Africa)
1.213-427 m 4.105 _+0.008 15.2 _+ 2.0 Na2BO ~- MB (3)~
2. 4.092 _+0.044 12.0 _-2- 1.1 NazBO ~ MB (4,5)
3. 457-549 m 4.108 -+0.008 15.9 -+ 2.0 Na2BO ~- MB (3):~
4. 4.104 _+0.012 14.9 _+ 3.0 Na2BO ~- MB (4,5)
5. 579-640 m 4.102 _+0.002 14.4 _+ 0.5 Na2BO2~ MB (3)$
6. 4.100 _+0.008 13.9 _+ 2.0 Na2BO ~ MB (4,5)
Tourmaline:
Granite pegmatite 1. Nuristan, nr -5§ NazBO ~ SCF (15)
Afghanistan
2. Newry, ME nr -7§ NazBO + SCF (15)
(pink)
Newry, ME nr -9§ Na2BO~ SCF (15)
(green)
Newry, ME nr -9§ Na2BO ~ SCF (5)
(blue)
3. Greenwood, nr -9§ Na2BO ~ SCF (15)
ME
4. Kings Mtn., NC nr -12§ Na2BO + SCF (15)
Evaporites
Tincalconite 1. Searles Lake 4.068 _+0.012 6.0 _+ 3.0 NazBO ~- MB (12)

Continued
 Critical evaluation of stable isotopes of B 543

Table I. Continued

Sample Location I IB/mB d J1B Ion Prep¶ Ref

2. SearlesLake 4.072 _+0.012 7.0 _+ 3.0 NazBO2~ MB (12)

3. Argentina 4.033 _+ 0.006 -2.6 _+ 1.5 Na2BO + MB (3)$
Argentina 3.997 _+0.010 -11.5 ± 2.5 NazBO~- IX
4. Kashmir 4.005 _+0.008 -9.6 _+ 2.0 NazBO j MB (3)$
Kashmir 3.987 _+0.008 -14.0 _+ 2.0 Na2BO + IX
Ulexite 1. L. lnder, nr 31.7 _+ 5.0* Na2BO ~ SCF (13)
U.S.S.R.
2. Argentina 3.918 _+0.008 -31.3 _+ 2.0 NazBO f PH (9)
3. Argentina 4.069 _+0.010 6.3 _+ 2.5 Na2BO + IX (3)$
4. Turkey 4.073 _+0.008 7.3 _+ 5.0* NazBO + IX (3)$
5. Turkey nr -4.5 _+ 5.0* Na2BO~ SCF (13)
6. San Bernadino, nr -16.0 _+ 2.5 NazBO ~- SCF 113)
CA
Borax 1. Searles Lake 4.070 _+ 0.003 6.5 _+ 0.7 Na2BO ~ MB (10)
2. Searles Lake 4.069 _+ 0.003 6.3 _+ 11.7 Na2BO ~ MB (10)
3. Searles Lake 4.040 _+ 0.008 -11.9 _+ 2.0 Na2BO ~ MB (12)
4. Searles Lake 4.040 _+ 11.1116 -0.9 _+ 4.0 NazBO ~ MB (12)
5. California 4.244 _+ 0.022 49.5 ± 5.4 Na2BO ~ MB (4,5)
6. Boron, CA nr 0.3 ± 5.0* Na2BO + SCF (13)
Colemanite 1. Turkey 3.991 _+ 0.008 -13.0 _+ 2.0 NazBO ~ PH (3,9)*
2. Turkey nr -15.8 ± 5.11" Na2BO2~ SCF (13)
3. Argentinatl 4.1145 _+0.008 11.3 ± 2.0 Na2BO2~ IX (3):~
4. California 3.991 _+ 0.008 -13.11 _+ 2.0 Na2BO~- PH (3,9)
5. Turkey 3.98 _+0.006 -12.5 ± 1.5 Na2BO + IX (3)J;
Datolite 1. N. Caledonia 4.057 _+0.008 3.3 _+ 2.0 Na2BO ~ IX (3)$
2 Turkey+ 4.063 _+0.007 4.8 _+ 1.7 Na2BO ~ IX (3)$
lnyoite 1.Turkey 4.037 _+0.008 - 1 . 6 _+ 2.11 Na2BO ~ IX (3)+
2. U.S.S.R. 4.141 _+0.008 25.1 _+ 2.0 Na2BO2~ PH (9)
3. L. Inder, nr 24.2 ± 1.4" Na2BO ] SCF (13)
U.S.S.R.
4. Hillsborough, nr 22.3 _+ 3.11" Na2BO ~ SCF (13)
New Brunswick
5. Boron, CA nr -11.8 ± 1.4" Na2BO ~ SCF (13)
Inderite 1. Argentina 4.069 -+0.006 6.3 ± 1.5 Na2BO2~ IX (3)$
Pandermite 1.Turkey 4.069 -+0.010 6.3 _+ 2.5 Na2BO ~ MB (3):4
Hydroboracite 1. Argentina 4.0632 _+ 0.007 4.8 _+ 1.7 Na2BO ~ 1X (31~:
Howlitc 1. San Bernadino nr -21.9 _+ 1.0" Na2BO ] SCF (13)
CA
2. ,, 3.958 _+0.008 - 2 1 . 2 _+ 2.11 Na2BO + PH (9)
3. Windsor, NS nr 25.3 _+ 3.0* Na2BO + SCF (13)
Szaibclyitc 1. Canada 4.060 _+ 11./)1t8 4.1 +_ 2.0 Na2BO + PH (9)
Hambergitc I. Madagascar 4.022 _+11.008 -5.4 _+ 2.0 Na2BO~- PH (9)
Hilgardite I. Louann, LA nr 31.5 ± 1.4' Na2BO + SCF 113)
Boracite 1. Luneburg, FRG nr 20.7 ± 1.11" Na2BO~ SCF (13)
2. Hannover, FRG nr 18.2 _+ 1.11" Na2BO ~- SCF 1131
3. Louann, LA nr 29.5 ± 2.0+ NazBO + SCF (13)
Mcyerhoffcrite 1. Death Val. CA nr -8.1 _+ 2.0* Na2BO ~ SCF (13)
Kotoite 1. Korea 4.045 _+0.008 0.3 _+ 2.11 Na2BO ~ IX (3)~:

Metamorphic rocks
Tourmaline:
Metapelite 1. L. Ste-Marie nr +22.§ Na2BO ~ SCF (15)
Quebec
2. Balmat, NY nr +12.§ Na2BO~" SCF (15)
3. Sar e Sang nr +3.§ Na2BO ~ SCF (15)
Afghanistan
4. Marlene Supra, nr -9.§ Na2BO ] SCF (15)
W. Greenland

Continued
544 R . L . Bassett

Table l. Continued

Sample Location alB/l°B dUB Ion Prep¶ Ref

5. Isua Supra, nr -22.§ Na2BO2+ SCF (15)

W. Greenland
Metapelite/ 1.Pierrepont, nr + 13.§ Na2BO ~ SCF (15)
Marble NY
2. S Baptiste nr +9.§ Na2BO ~ SCF (15)
Lake Road,
Ontario
3. G o u v e r n e u r , nr +7.§ NazBO ~ SCF (15)
NY
Marble Contact 1. Hamburg, NJ nr +4.§ NazBO ~ SCF 05)
2. Amity, NY nr +3.§ NazBO ~- SCF (15)
3. Sterling Hill, nr +1 .§ NazBO ~- SCF (15)
NJ
4. Johnstown, NY nr -1.§ NazBO ~ SCF (15)
Unspecified 1. Finland (2)t 4.007 4- 0.002 -9.1 4- 0.5 NazBO ~ nr (3),
Slate 1. Paleozoic 4.104 _+0.023 14.9 _+ 5.7 NazBO2~ MB (5)
2. Littleton, NH nr 11.0 Na2BO ] MB/IX (1)

Extraterrestrial
Meteorites:
Iron 1. Toluca 3.850 _+ 0.011 -48. _+ 2.7 Na2BO ~ MB (4,5)
Chondrite 2. Richardson 3.815 _+0.015 -58. _+ 3.7 Na2BO J MB (4,5)
3. Ehole 3.820 _+0.02 -55. _+ 4.9 NazBO ~ MB (4,5)
4. Achilles 3.902 _+0.007 -36. _+ 1.7 Na2BO2~ MB (4,5)
Achondrite 5. Pasamonte 3.960 _+0.008 -21. _+ 2.0 Na2BO ~ MB (4,5)
Lunar Regolith:
1. Luna 16 3.73 _+ 0.05 -124.6 _+ 12.4 nr nr (6)
2. Luna 16 3.69 _+ 0.05 -77.7 _+ 12.4 nr nr (6)
3. L u n a 16 3.54 _+ 0.04 -87.5 _+ 10. nr nr (6)
Geothermal waters
Japanese Hot I. Kusatsu-Yub. 4.086 _+0.008 10.5 _+ 2.0 Na2BO ~- MB (11)
Springs 2. Kusatsu-Jizo 4.091 _+0.008 11.7 _+ 2.0 Na2BO ~- MB (11)
3. Bandaiko 4.082 _+0.008 9.5 _+ 2.0 Na2BO2~ MB (11)
4. Manza-Yub. 4.092 _+0.008 12.0 _+ 2.0 Na2BO2~ MB (11)
5. Manza-Kar. 4.086 _+ 0.007 10.5 _+ 1.7 Na2BO ~" MB (11)
Fumaroles
Condensate
Satsuma lwo-jima: 1. T > 465 (11)¢ 4.0659 + 0.0033 5.5 -+ 0.8 Na2BOj ~ MB (8)
andesite caldera 2. 100 < T 4.0654_+ 0.0081 5.4 + 2.0 Na2BO2~ MB (8)
(T in °C) T < 465 (13)~
NE Japan Arc: 1. 105 < T 4.068 +_ 0.0031 6.0 _+ 0.8 Na2BO~ MB (7)
<890 (7)*
Mid Japan Arc: 1.197 < T 4.0988 _+ 0.0059 13.7 _+ 1.5 Na2BO~ MB (7)
<281 (4)t
L. Japan Arc: 1.97 < T 4.1066_+ 0.(1231 18.0 _+ 5.7 Na2BO~ MB (7)
<245 (5)t
Sassolitc l. Japan 4.097 _+0.010 13.2 _+ 2.5 Na2BO ~- MB (3),
2. Japan 4.073 _+0.008 7.3 _+ 2.0 Na2BO2~ IX (3),
Soffionis Boric 1.Larderello 4.114 _+0.015 17.4 _+ 3.7 Na2BO ~- IX (3),
Acid Vapor lta[y (2)t
 Critical evaluation of stable isotopes of B 545

ANALYTICAL M E T H O D S
All m e a s u r e m e n t s evaluated here were obtained using
solid source mass spectrometry. Error attributable to the
instrument performance is small; the reported internal
precision using known standards is generally <2-3%o. The
published literature for B isotopic ratios and their reported
precision for natural materials are summarized in Table 1.
The majority of errors can be attributed to one of the
following sources: 1. the B extraction m e t h o d and sample
treatment; 2. isobaric interference during analysis; 3. isoto-
pic fractionation on the filament; 4. uncorrected machine
bias.
Sample preparation
Methods used to extract B from minerals can contribute
significantly to m e a s u r e m e n t errors. The magnitude of
these errors is difficult to determine from published work
alone. The only direct comparison between the two most
c o m m o n methods, methyl borate distillation and ion
exchange, was done by AGYEI and MCMULLEN (1968). All of
t h e rock samples used in their analyses were initially dis-
solved quantitatively by the addition of HCI or N a O H . The
B was then extracted either by distilling the solution in the
presence of methyl alcohol, forming volatile methyl borate,
or by using in sequence a cation exchange then an anion
exchange resin to remove the interfering solute, leaving
boric acid in solution.
Sodium hydroxide was then added to the remaining
solutions to precipitate sodium borate. Recoveries ranged
from 80% to 90% using methyl borate and 72% to 95%
using ion exchange. As can be seen from Table l, both
m e t h o d s were used to examine three samples, tincalconite
from Argentina and Kashmir, and sassolite from Japan. All
thrcc samples differed in the final m e a s u r e d ratio o f 6 ii B by
8.9, 4.4 and 5.9%0, respectively. The m e a n for the values is
6.4%0 lighter using the ion exchange method.
Ion exchange
The separation of isotopes using an ion exchange m e t h o d
is a well established procedure both experimentally and
theoretically (LONDON, 1961; UREV, 1947). The technique
works somewhat successfully for several light isotopes but is
not useful for elements with high masses (HARDY, 1976).
The fractionation in ion exchange reactions, as would be
expected, generally results in the heavier isotope becoming
enriched in the condensed phase. The fractionation factor
(a) describes the partitioning between phases, using Li as an
example:
(6Li]7Li)Resin
ct = (6Li/7Li)A q. . . . . '
The a values are typically in the range of 1.002-1.022 for
Li and 1.026-1.055 for N (BENEDICT et al., 1981). In an i o n
exchange or adsorption process the lighter isotope should
be enriched in the aqueous phase while the heavier isotope
is kinetically preferred on the resin surface. The B system is
somewhat enigmatic in this regard because it apparently
exhibits a reverse behavior.
Several workers have suggested (YONEDA et al., 1959;
KAKIHANA et al., 1977; AGVE1 and McMULLEN, 1968;
SCHWARCZ et al., 1969) that in the B system the adsorption
process enriches the heavier isotope in the aqueous phase
and that this m e c h a n i s m is responsible for the observed
6~1B values for sea water which are so much heavier than
terrestrial B (Table 1). The experimental work of SHERGINA
and KAMINSKAYA(1967) clearly demonstrated this behavior
in a column study. In their work, KAKIHANAet al. (1977)
suggested that this reversed behavior is the result of the
aqueous fractionation which occurs when boric acid dis-
sociates to the borate anion and reconfigures from a trigonal
to a tetrahedral structure:
B(OH)3 + H 2 0 ~ B ( O H ) 4 + H + pK = 9.2.
A fractionation factor of 1.0194 at 25°C, for the aqueous
species was originally reported by KOTAKAet al. (1973). This
a q u e o u s structural reconfiguration depletes liB in the
borate anions. Subsequently, KAKIHANAet al. (1977) deter-
mined the aqueous fractionation factors over the tempera-
ture range of 0°-50°C (1.0206-1.0177). This is significant for
solutions in which boric acid is partially dissociated, and the
sorption mechanism favors one B species over another. As
shown by BASSET]" (1976), the adsorption on clay surfaces
does favor the retention of the borate anion. PALMERet al.
(1987a) suggested that this is likely to be important for sea
water, such that as borate sorbs, the ocean water becomes
slightly enriched in liB. At high pH values (>9) used in
extraction methods, the majority of B is present as the anion
and the aqueous configurational fractionation is not import-
ant. At low pH values the same would be true; all the B is
present as the acid and little if any sorption occurs except in
circumstances where the adsorption or precipitation of
some mineral phase reconfigures from the neutral boric acid
to the anion on the surface.
For those circumstances in which both species are present
as a significant mole fraction of the total B in solution, the
sorbent will then disproportionately remove more of the
lighter isotope. PALMERet al. (1987a) suggest that fraction-
ation may again occur when the trigonal boric acid sorbs
onto the clay mineral surface as the tetrahedral anion,
adding to the observed enrichment of liB in the solution
phase.
An understanding of this mechanism allows us to evaluate

Notes to Table 1:
*All error was reported as 2 o at the 95% confidence limit, or was not explicitly stated in which case the standard 2 o
representation was assumed, except for Shima who stated only that the correlation factor was three times the standard
error, and Swihart who reported all data as 1 SD internal error, which have been converted to 2 o in this tabulation.
Multiple analyses.
SError is probably _+6%o (2 o), see text.
§The reported standard deviation ranged from _+1.5 to _+1.7%o for the 18 samples analyzed on two different instruments,
error was not specified for the individual analyses (15).
¶ M B methyl borate extraction; IX ion exchange; EE ether extraction; PH pyrohydrolysis; SCF sodium carbonate flux
followed with ion exchange.
!lAlso contains inyoite.
nr not reported.
References: 1. SCHWARCZetal. (1969); 2. SPIVACKand EDMOND (1987); 3. AGYEI and MCMULLEN (1968); 4. SHIMA(1962);
5. SIJIMA ( 1963a); 6. EUUSTER (1974) ; 7. NOMURAetal. (1982); 8. KANZAK1etal. (1979); 9. FINLEYetal. ( 1962); 10. FINLEY and
LEUANC (1961): 11. KAKIHANAetal. (1987); 12. McMULLENetal. (1961); 13. SwIHaavetal. (1986); 14. SPlVACKetal. (1987);
15. SWlHARTand MOORE (1989).
546 R . L . Bassett

better the sample preparation methods where ion exchange
is part of the procedure. For studies in which ion exchange is
part of the extraction mechanism, the recovery must be as
quantitative as possible, as is noted in SPIVACKand EDMOND
(1986) and BASSETr et al. (1990). During anion exchange
extraction, when the solution pH is near neutral, and boric
acid is predominantly a neutral species, if some B as borate
were being inadvertently removed from solution along with
other anions, then the lighter isotope would be favored on
the anion exchange resin as borate. The net result would be
heavier values for the B subsequently precipitated from the
remaining solution. This is the reverse of what is observed in
the previous study. Therefore the discrepancy between the
methods may not be due to the ion exchange extraction
reaction, but rather to fractionation during the methyl
borate distillation.
The distillation extraction when done quantitatively is an
accurate method (KANZAKI et al., 1979; SPWACK and
EDMOND, 1986; LAND and MACPHERSON,1989) without
fractionation; however, MARTIN and HAYES (1952) indi-
cated that incomplete extraction may occur. It is suggested
here that because the recoveries of B were so low in the
work by AGYEI and McMULLEN (1968) the methyl borate
data may be too high by as much as 6.4%0, which is the mean
difference between the two methods, and that the ion
exchange data are probably more accurate. Owing to the
fact, however, that both methods could contribute error,
and we observe only the net difference between them, it is
recommended that these data be viewed with potential 2 cr
error of about +_6%0.
Boron can be extracted quantitatively from rock samples
without incurring mass fractionation by using ion exchange
resins. SWIHARTet al. (1986), SPwAcg and EDMOND (1987),
BASSE'rr et al. (1990) all employed some variation of the ion
exchange procedure and verified the procedure by using the
NBS 951 isotope standard which demonstrated that no
fractionation occurred. The key to accuracy is the preven-
tion of contamination from impurities and in the obtaining
of a high recovery percentage.
Isobaric interference
The majority of the isotopic measurements conducted to
date rely on the detection of the sodium borate ions
(Na2 I1BO~ and Na2 I°BO~) which have masses ( m / e 89
and 88) which are isobaric with Sr ( m / e 88). There is the
potential for interference when Sr is present, however, the
magnitude of this is obviously dependent on sample purity.
No evaluation of error can be made relative to the presence
of Sr interference; however, it is suggested this problem be
alleviated in the future by either analyzing for Sr or employ-
ing one of the subsequently discussed methods.
To avoid this potential interference with Sr and to mini-
mize fractionation by using a heavier ion, SPIVACK and
EDMOND (1986) proposed a procedure which allowed them
to measure B isotol~e ratios with cesium borate ions
(Cs 2 I1BO~ and Cs2 "BO~-) at masses 309 and 308. The
resultant analyses had a reported standard deviation of
+_0.12%o.
ZEININGER and HEUMANN (1983), and BASSErr et al.
(1990) have shown that B analyzed in the negative ion mode
(1 iBO 2 and I°BO2 ions at masses 43 and 42) is virtually free
from any isobaric interference, with external precisions of

Table 2. Standards and correction factors used to determine the absolute B isotopic
ratio in natural samples ( O R N L - A 4.270, ORNL-B 3.956, K A P L 3.661, NBS SRM
951 4.04362)

Standard Measured Correction applied

Source extracted Standard ratio to samples

McMULLEN et al. yes ORNL-A 4.249 yes

(1961) yes ORNL-B 3.936
FINLEY et al. no KAPL 3.665 no
(1962)
SHIMA (1962) no ORNL-B 3.958 no
3.950
SHIMA (1963a) no ORNL-B 3.958 no
3.950
A~YEI and McMULLEN no ORNL-A 4.243 yes
(1968) no ORNL-B 3.932 yes
no ORNL-A 4.287 yes
no ORNL-B 3.969 yes
SCHWARCZet al. (1969) no nr nr no
(see text)
SWIHART et al. yes NBS 951 4.0447 yes
(1986)
NOMURA et al. yes NBS 951 4.050 no
(1982)
KANZAKI et al. yes NBS 951 4.050 no
(1979)
SPlvACr and EDMOND yes NBS 951 4.04558 yes
(1986)
SWIHART and MOORE yes NBS 951 4.0449 yes
(1989) 4.0401 yes
BASSETr et al. yes NBS 951 4.0444 yes
(1990)
 Critical evaluation of stable isotopes of B
<0.9%o. As can be seen from the data presented in Table 1,
the majority of the measurements were made using the
positive sodium borate ions and no indication of correction
for Sr interference was ever noted.
Mass fractionation
The details of the decomposition reaction for borate on
the filament are not well understood, but it is known that the
ion beam intensity and the specific molecular species emit-
ted is a function of the rate of warm up and the temperature
of the filament. For example, sodium borate loaded on a Re
filament will decompose into the NazBO~- at temperatures
of 750°C generating an ion current of 10-12 to 10-11 A;
whereas at a temperature of -I900°C, the negative ion
BO~- is produced with comparable or greater ion beam
current (ZEIr~IN6ER and HEtn~Ar~N, 1983; BASSE~ et al.,
1990). A complicating factor to this process is the mass
fractionation which occurs on the filament over certain
temperature ranges. No assessment of this source of error
can be made at present for the published isotope ratios,
because the filament temperatures or currents are not noted
in most of the papers reviewed, and because there is no third
isotope against which this fractionation can be compared, as
is done with other isotopes such as Sr.
Machine bias
The fractionation due to the method of sample prep-
aration or due to machine bias between different instru-.
ments, can be corrected if known standards are taken
through the same preparation procedure as are the samples.
Early workers did not have established standards with well-
known B isotopic ratios. Frequently, laboratories analyzed
synthetic standards and relied on interlaboratory compari-
son to determine the mean value, which then could be used
to evaluate the accuracy of their machine. The bulk of the
published isotope data reviewed here is derived from the 10
publications listed in Table 2. The papers published after
1970 give data which have been measured relative to the
National Bureau of Standards, Standard Reference
Material No. 951 (NBS SRM-951) which is a well character-
ized boric acid with a reported isotopic ratio of 4.04362 +
0.00137 (CANTANZAROet al., 1970).
The published ratios from these later studies should be
considered to be highly reliable for two reasons: 1. the error
caused by machine bias has been corrected using the NBS
SRM-951 standard; and 2. the standard was also taken
through the extraction procedure to evaluate mass fraction-
ation during sample preparation.
= I
Borax
Seawater
J 1 (71
Tokyo Bay ' -
Basalt
Gabbro
-1'o o 1'o
6"B
FI6. 1. Comparison of 611B values reported by SHIMA(1962, 1963) (A) with error shown as error bars;
data from other workers is designated with (o) for comparable materials, with error shown as circles. Data
are from Table 1, large vertical arrows indicate categories likely intended by Shima (see text).
547
Earlier work is more difficult to evaluate. It is interesting
to note that much of the initial work was done by associates
of the McMaster University isotope laboratory. In fact, five
of the six pre-NBS SRM-951 papers calibrated their instru-
ments using the same synthetic standards obtained from
Oak Ridge National Laboratory with the following absolute
values for the 11B/l°B ratio (ORNL-A, 4.270 or ORNL-B,
3.956). The data in Table 2 identify the standard used for
calibration, the measured value, and whether the correction
factor was applied to the data. It should be noted that the
procedure used by SCHWARTZet al. (1969) is not specifically
described but the authors indicate that their procedure was
essentially the same as that of AGYEI and McMULLEN
(1968).
All of the workers reported a correction factor which
would indicate that the instrument has an accuracy for the
ratio within +0.006 (+_ 1.5%0) as the worst case. This must be
tempered by the fact that only McMULLENet al. (196l) took
the standards through the extraction procedure. There are
clearly some problems with sample preparation procedures
because of the large difference between the reported values
for the same minerals using different extraction procedures
as discussed above (AGvE1 and McMULLEr% 1968). The
conclusion is that uncorrectable mass fractionation exists
primarily in the preparation steps as evidenced in the
comparison of the two methods by AGVEI and McMULLEN
(1968). All reported ratios which are not corrected or at
least evaluated by comparison with standards taken through
the extraction and separation procedure are less reliable,
possibly by several per rail.
REVIEW OF PUBLISHED DATA
Sea water
T h e r e are eleven values r e p o r t e d for sea w a t e r
f r o m t h r e e oceans ( s o m e r e p o r t e d values are the
m e a n values of several replicate analyses), the Arc-
tic, Atlantic and Pacific (Table 1). Most are surface
water samples, others are unclassified or w e r e taken
at d e p t h s of either 70 or 2500 m. The data all agree
within a few per rail of each o t h e r and indicate that
the oceans have sufficient mixing to maintain a
reasonably constant worldwide ratio.
The only serious discrepancy is with the value
r e p o r t e d by SHIMA (1963a). This value is a b o u t 32%0
too light in c o m p a r i s o n with the o t h e r r e p o r t e d
I = I
rr~--=~t (71
"~9 points
2'o 3'0 go 5'o
548 R.L. Bassett
measurements. The ratios determined by SHIMA
(1962, 1963a) for Tokyo Bay water, basalt and gab-
bro, agree reasonably well with those ratios reported
by other workers for similar materials (Table 1). This
large discrepancy between the value of 6.8%0
reported by SHIMA (1963a) for sea water, and all the
other values near 40%0 is likely to be either incorrect,
or may represent a sample collected close to the
coast, though he leaves the sample location unidenti-
fied. The only other water sample analyzed by Shima
was Tokyo Bay water. If this Pacific Ocean water
sample were collected near enough to the coast so
that it was influenced by the water in Tokyo Bay,
which has a much lighter ratio, then the sample could
have an isotopic ratio representing a mixture of the
two. It could be assumed that the bay and nearby
reaches of the ocean are significantly affected by
terrestrial contribution from fluvial discharge.
I would like to suggest an alternative explanation
for this anomalous value, If all of the measured ratios
obtained by SHIMA (1963a) are plotted, along with
comparative values from other researchers (Fig. 1),
two things become apparent. First, the values ob-
tained by Shima for basalt, gabbro and Tokyo Bay
water are close to the values given by others, within
experimental error; the large discrepancy exists for
borax and sea water. Second, if one compares the
borax and sea water categories, it appears that these
two discrepant numbers represent samples that may
have been reversed either during analysis or in
reporting. If one simply transfers these reported
numbers to the opposite category, they align with
other reported values equally as well as do all the rest
of Shima's data. Although this is not definitive, it
explains why Shima's values for borax and sea water
are both >30%0 different from other workers, and
shifted in opposite direction. In SWIHARTet al. (1986),
these authors chose to disregard Shima's value for
borax without justification. Neither the borax nor the
sea water value can be considered reliable as
reported; however, the above explanation provides a
mechanism whereby the experimental methods and
procedures used by Shima can still be considered
reliable, and his other data useful, yet still account for
the extremely large discrepancy for borax and sea
water.
The values of SCHWARTZ et al. (1969) are also
probably high because the reported precision for
their data is large compared to the more precise
values from SPIVACKand EDMOND (1987). The mean
for worldwide ocean water, using all the other
reported ratios, but excluding the value from Shima,
is 41.8%o. In view of the fact that the technique
followed by SPIVACKand EDMOND (1987) yielded an
accurate and precise value which surpasses that of the
other investigators, and gives values which are
encompased within the error of several other
workers, the true value for modern sea water is likely
to be closer to their value of -40%0. Owing to the fact
that the 6HB for the Atlantic and Pacific Oceans
reported by SCHWARCZet al. (1969) are high relative
tO SPIVACKand EDMOND (1986) by 2-4%0, it should
also be assumed that their value for 611B of the Arctic
of 47.6 should similarly be in question by that
amount, which would lower a corrected value more
toward the values for the other oceans.
Igneous rocks
Basalt. Isotopic ratios have been measured for
both unaltered and weathered basalt; however, in all
cases the source for samples analyzed to date is from
submarine basalt flows. No values have been pub-
lished for terrestrial basalts. Fresh and altered basalts
from the East Pacific Rise (EPR) were examined by
SPWACK and EDMOND (1987), and the following
differences were noted: 1. the 611B shifted from
<0%0 ( - 3 . 7 to - 1.5) for fresh basalt to values signifi-
cantly heavier (0.1-9.2) in altered rocks; 2. the B
content increased from <0.5 ppm to 8.9~59 ppm; and
3. the altered rocks were characterized by palagoni-
zation of glass. StoMA (1962, 1963a) reported two
values for basalt (Table 1), one for Hawaii and one
for Mohole, with no definitive information regarding
location. The Mohole sample was probably collected
from the Gaudalupe site which is about 240 km off
the Baja California coast. The corehole EM-7 was
drilled in 1961 and bottomed in Tertiary-age basalt
177 m below the sediment-ocean water interface.
Zeolite and palagonite were reported to be in the
basalt which indicates alteration had already begun
(ENGEL and EN6EL, 1961). In addition, the B content
was 3.2 ppm, further substantiating the alteration
process as noted by SPWACKand EDMOND (1986). The
reported 611B for Mohole basalt fits well with other
values for altered basalt and is so designated in Table
1. Similarly, the basalt from Hawaii is considered
altered, based strictly on the reported 611B and the
elevated B concentrations. In conclusion, the fresh
basalt has the lowest 6 lIB value (slightly negative)
and is progressively enriched with ~1B during reac-
tion with sea water.
Serpentinized peridotites. These are ultramafic
rocks dredged from the sea floor which have reacted
with sea water at elevated temperatures and incor-
porated heavier "marine" B; a discussion of the
reactions and suspected mechanisms is given in SPI-
VACKand EDMOND (1987). NO other values have been
reported for comparison.
Gabbro. These samples are from Insizwa, Repub-
lic of South Africa and are apparently primary in
origin. They were obtained from depths of 213-640
m. The isotopic measurements were done both by
SHIMA (1962) and AGYEI and McMULLEN (1968) on
the same samples. The difference between the
reported values, though small, is most likely simply
analytical error. AGYEI and McMULLEN (1968) cor-
 Critical evaluation of stable isotopes of B 549

rect their measurements to absolute values based on Table 3. Compilation of the 6HB values of evaporite
the ORNL standards, and StoMA (1962) does not minerals, associated by location and geological age, and
report that his values are corrected; consequently, segregated into marine and non-marine origin (data from
Table 1)
the former values are considered more reliable.
These values of 12-15%o seem high compared to the
other mafic rocks and could represent rocks that have Mineral Formula 61 l B
been altered by sea water; no detail studies are
available at the present time. Marine
Louann Salt, LA, U.S.A. (Jurassic)
Granite, Two granites have been analyzed: 1. the Hilgardite Ca2CI(BsOs)(OH)2 31.5
first value is for G-l, a U.S.G.S. standard reference Boracite Mg3CI(B7013) 29.5
sample of Permian age, the Westerly Granite in Lake Inder, Kazakhstan, U.S.S.R. (Permian)
Rhode Island; and, 2. a granite sample of Precam- Inyoite Ca2B6011" 13HzO 23.3
brian age from the Guyana Shield, Orinoco Basin, Inyoite Ca2B6Oll' 13H20 24.2
Ulexite NaCaBsO9. 8HzO 31.7
Venezuela. The standard deviation for the measure-
ment of G-1 is large and is broad enough to include Hanover and Luneberg, F.R.G. (Permian; Zechstein)
Boracite Mg3CI(BTOI3 ) 18.2
the more precise value for the Venezuelan sample. Boracite Mg3CI(BTOj3 ) 20.7
So few igneous rocks have been analyzed to date that
Hillsborough, New Brunswick, Canada (Mississippian)
little can be concluded from these preliminary num- Inyoite Ca2B6OIl" 13H20 22.3
bers other than that the fact that granitic rock is
slightly more enriched in liB than the unaltered Windsor, Nova Scotia, Canada (Mississippian)
Howlite Ca2B304(OH)zSiBzOs(OH)325.3
basalts, but the error is large (Table 1).
Non-marine
Tourmaline from granite pegmatites. SWIHARTand Searles Lake, CA, U.S.A. (Late Quaternary)
MOORE (1989) reported six values for B isotopes in Borax Na2B407- 10H20 6.5
tourmalines from granitic pegmatites. Even though Borax Na2B407. 10H20 6.3
tourmalines have historically been useful in petrolo- Borax Na2B407 • 10H20 -0.9
Borax NazB407-10H20 -0.9
gical evaluations of ore deposits and event recon- Tincalconite Na2BaO7-5H20 6.0
struction, it is not clear that B isotopes measured for Tincalconite NazB407-5H20 7.0
tourmaline can be usefully interpreted at present.
Boron, CA, U.S.A. (Middle Miocene)
The 611B values are lighter than other reported Inyoite CazB6Oll • 13H20 - 11.8
values for granite or volcanic rocks and will require Borax Na2B407-10H20 0.3
further investigation. SWIHART and MOORE (1989) San Bernadino, CA, U.S.A. (Middle Miocene)
suggested the influence of a mantle component must Howlite Ca2SiBsOg(OH)s -21.9
be considered, because the values are so depleted in Ulexite NaCaBsO0-8HzO - 16.0
liB.
Death Valley, CA, U.S.A. (Late Miocene)
Colemanite CazB6Ol1-5H20 -13.0
Meyerhofferite CazB6011"7H20 -8.1
Evaporite minerals Argentina (non-specific) (Tertiary)
Tincalconite NazB407-5H20 -2.6
SWIHART et al. (1986) noted a clear distinction Tincalconite NazB407•5H20 - 11.5
Ulexite NaCaBsO9. 8H20 6.3
between the mean values of 61IB of marine and Colemanite CaeB601~•5H20 0.3
non-marine evaporites, and attributed this to the Inderite MgzB6Oxo. 15H20 6.3
contribution of the much heavier 611B of sea water. Hydroboracite CaMgB60 t ~.6H20 4.8
In contrast, continental evaporites derive their B Argentina (Salar Caucham) Thermal Springs and
from the weathering of a variety of rock types and Volcanics (Tertiary)
often have volcanic or thermal spring contributions. Ulexite NaCaBsO 9. 8H20 - 31.1
Boron derived from the weathering of volcanic rocks Kashmir, lndia
will undoubtedly result in a much lighter value for the Tincalconite N a z B 4 0 7 •5 H 2 0 -9.5
611B of the resultant evaporite minerals than would Tincalconite Na2B407-5H20 - 14.0
be expected from a marine source. The minerals from Turkey (Late Tertiary)
Table 1 which can be attributed to evaporitic environ- Ulexitc NaCaBsO 9. 8H20 7.3
Ulexite NaCaBsO9. 8H20 -4.5
ments are listed in Table 3 according to marine and Colemanite Ca2B6O11.5H20 -13.0
non-marine origin, and further segregated by loca- Colemanite Ca2B6011"5H20 - 15.0
tion and geological age. Colemanite CazB6Ol1.5H20 -15.8
Datolite CaBSiO4(OH) 4.8
Marine evaporites. The 611B contribution of sea Inyoite CaB6Oj i • 13H20 - 1.6
Pandermite Ca4Bl0Olg.7H20 6.3
water is readily seen in the minerals listed in Table 3;
all values are heavier than any reported volcanic rock New Caledonia (NE Australia)
Datolite CaBSiO4(OH ) 3.3
or terrestrial evaporite. In addition to this obvious
550 R.L. Bassett

association, two specific characteristics should be
explored.
First, there are no experimentally determined frac-
tionation factors for the distribution of B isotopes
between the aqueous phase and precipitated evapor-
ite minerals. Most of these evaporite minerals are
either primary precipitates from an evaporating brine
o r represent a recrystallization event. In either case,
the bulk of the mass of B should have been derived
from ocean water, rather than meteoric water, even
in the case of secondary recrystallization, because of
the fact that most meteoric water has extremely low
values for B concentration and would introduce only
a small mole fraction of the total B content. If we
assume that there is no substantial fractionation, or
that the fractionation is constant for given minerals
during precipitation of B as borate during evapor-
ation from B-enriched brines, then the isotopic ratio
recorded in these rocks is correlative to the sea water
ratio.
Second, the minerals analyzed span a time frame
from the Mississippian to the Jurassic. In addition to
these data, the value for modern sea water is also
known. If these data are plotted with respect to
geological age, a trend toward heavier values from
the late Paleozoic to the present is immediately
obvious (Fig. 2). This implies that these evaporites
have recorded the process of enrichment of the
heavier isotope in sea water from the Mississippian to
the present.
As discussed earlier, several researchers have
suggested that removal of B by adsorption on clays
attenuates the total B content of sea water; and
because the adsorption of B tends to favor the light
isotope this may at least partially explain the rela-
tively heavy 6 n B value for sea water. The evidence
presented here indicates that this enrichment process
is correct and that the effect is documented in marine
evaporites as being progressive over time, possibly in
the range of 20%0 since the Mississippian. Our labora-
tory is determining fractionation factors for a number
of minerals in order to investigate this process, and it
is unlikely that the historical oceanic enrichment will
be understood until many more isotope analyses have
been made.
It should also be noted that boracite samples of
Jurassic and Permian age have been analyzed; two
samples from the Zechstein, one from the Gulf
Coast. The Louann salt is a relatively pure marine
bedded salt; the boracite and hilgardite samples were
found to be part of the residuum and probably
represent primary precipitates; however, LAND et al.
(1988) have documented a change in the 87Sr/86Sr
ratios in the Louann salt which likely occurred during
deformation. KUHN (1968) reported that the boracite
from the Zechstein also appears to be of primary
origin, is widely distributed in the salt, and can be
reasonably assumed to have been derived from sea
water. The 611B difference between Jurassic and
Permian boracite is >9%0, strongly suggesting that
the sea water value has changed with time. If a
fractionation factor is intrinsic to the partitioning
between sea water and the mineral, in this case it
could be assumed to be nearly the same; conse-
quently, the conclusion of enrichment over time is
further supported.
Non-marine evaporites. The data for B isotopes of
continental evaporite minerals are less definitive.
There is clearly a contrast with marine samples; in
fact, many of the minerals have negative 611B values.
Continental sources of water are much more variable
than is the marine environment. Each deposit re-
quires a close examination of the depositional his-
tory. Even in well characterized systems such as the
Tertiary to Quarternary borate region of Searles
Lake, California, the water source is known to have
alternated between mountain-front runoff and per-
iodic flood discharges from saline lakes upstream
from Searles Lake. Some fraction of the B was
derived from the weathering of volcanic rocks in the
Sierra Nevada while other fractions of the solute load

Modern Seowoter
4C
i .--~"

[o Lo., I,~., ,H. . . . . . .

3C
6"8 IHo ._-Ii Lake .- -- --
",r,- ~ li',?~" ,, .o.o°..
2C B ~.- H Hilgordlte
B Ziohste~ Ho
i Howlite
: I Inyoite
1 : U Ulex|te
I

300 200 1 O0 Present

MilHons of Yeors B e f o r e P r e s e n t

Fro. 2. Trend of increasing 6riB in sea water over geologicaltime as evidenced by evaporite minerals (data
from Tables 1 and 3).
 Critical evaluation of stable isotopes of B
came from thermal springs or discharge from lakes
fed by thermal springs. Clearly, the source for the B
could have a large range of 611B values.
At present, speculation on the variability of values
from specified deposits would be premature without
the benefit of more analyses, the hydrogeological and
surface water record, depositional history, and a
better understanding of fractionation factors during
evaporation.
Metamorphic rocks
The only published values for metamorphic rocks
are for tourmalines and for one analysis for slate.
SWIHARXand MOORE (1989) have recently published
12 new values for tourmaline from metasedimentary
environments; a clear distinction can be seen be-
tween tourmalines in metasedimentary rocks with a
marine source which have values for 611B between
- 1 and +22%0, and tourmaline from submarine
(-22%o) and exhalative origin (-9%o).
The 611B are reported to 1 e standard deviation of
-1.7%o and should be considered reliable because
the extraction procedures were quantitative and in-
cluded the NBS standard in the evaluation as
reported earlier (SWIHARTe t al., 1986).
Other values for tourmalines have been reported
(SHIMA, 1963b; MALINKOet al., 1982; PALMERel al.,
1987b). Though MALINKO et al. (1982) provide 73
values for the 11B/10B ratios of borosilicates and a few
borates, the data cannot be used here because no
standard with a known ratio was run with the samples
and none of the minerals they analyzed have been
analyzed by others. As a result, the ratios canot be
corrected or compared to other published values.
SHIMA (1963b) reported seven values for the 1i B/10B
ratio ranging from 3.997 to 4.099 (the 611B relative to
NBS 951 is - 1 1 . 5 to +13.7). These are within the
range of values given by SWIHARTand MOORE (1989),
but too little geological information is provided to
classify them with the other metasedimentary and
pegmatitic tourmalines. In a brief abstract, PALMERet
al. (1987b) noted that they have analyzed tourma-
lines from both stratabound and strataform massive
sulfide deposits samples from more than 30 locations.
The 611B values are not individually given but range
from + 10.5 to -22.8%0. The authors state that there
is no correlation with age, size or mineralogy of the
specific deposit, but there is a relation to the lithology
of the host deposit.
Meteorite and lunar samples
Fortunately, a few ratios have been published for
meteorites from the work of StoMA (1962, 1963a).
The error that he reports for the analysis is small
enough that it is clear that the meteoric isotopic ratios
are significantly depleted in ii B relative to terrestrial
551
samples as are the lunar samples analyzed by EUGS-
TER (1974).
SELECTED VALUES
The reviewed and selected values for 611B are
shown in Fig. 3. In many cases only one value for the
specific mineral is reported in the literature; conse-
quently, these values are selected if the experimental
procedure appears reasonable. For reported values
in which the extraction procedure is in question, for
which other more reliable comparative data exist, or
other uncertainties exist regarding the true value, the
611B measurement if shown, is signified by a small
filled circle. Actual standard deviations reported by
the authors are listed in Table 1 but are not included
in Fig. 3.
Such a sparse data set is still too incomplete to be
used for computing mass balances and global geo-
chemical cycles. Substantial fractionation and redis-
tribution of B isotopes is evident as a result of both
terrestrial and marine geochemical processes, such as
weathering of igneous rocks and transport of solute
to evaporite lakes, reaction of basalts and marine
sediments with sea water, recrystallization in meta-
morphic and hydrothermal fluids, and diagenetic
processes active in sedimentary basins. New and
more precise 611B values will undoubtedly more
clearly define the mechanisms responsible for the
isotopic redistribution in many geochemical environ-
ments.
ENVIRONMENTAL IMPLICATIONS
It is well known that B is present in both ground-
water and surface water in almost all environments.
The 611B in ground-water may be a useful tool for
interpreting the source and possibly the flow path of
the water in the system of interest. The ground-water
will contain B derived from such processes as weath-
ering, diagenesis and mineral dissolution along the
flow path, and perhaps even some contributions from
organic material to name only a few sources. Though
the natural fractionation of B isotopes may extend
over a wide range of 611B values, based on a limited
number of analyses, it appears that the values in
shallow aquifers may fit within a narrow range for
local-scale problems.
Isotopic ratios for B may prove to be a useful
method for determining the presence and even the
extent of contamination in an aquifer, because indus-
trial and municipal sources of waste water often
contain B at elevated concentrations. For example,
municipal waste water, leachate from coal-fired
power plants, geothermal water, oil field brines, etc.,
all produce water containing B in the ppm range. In
contrast, most ground-water contains B at concen-
trations <1 ppm. Recent studies have determined
that B from utility waste, for example, may have 611B
values >20%o depleted in 11B compared to the native
552 R.L. Bassett

ground-water (BAssETr and DAVIDSON, 1990; DAVID-
SON, 1989). This easily detectable shift in 611B of
mixed waters from that of the background ground-
water, is providing a useful tool in delineating the
source of the contaminants in the affected water.
It is also now suspected that a variety of stable
isotopes will be useful in deciphering the diagenetic
sequences that are forming in sedimentary basins.
Isotopic ratios such as S7Sr/86Sr, 180/160, 13C/12C,
11B/l°B, D/H and perhaps 7Li/6Li should greatly
enhance our interpretive ability (LAND and MAC-
PHERSON, 1989). They report values for 6UB from
Miocene brines which range from +25 to +40%0,
resembling sea water rather than shallow aquifers of
deep seated fluids (LAND and MACPHERSON, 1989).
Additional extensive sampling from deep sedimen-
tary basins should provide a more definite analysis of
the relation between lithology and the 611B values of
the associated fluids.
CONCLUSIONS
The movement of B through its global geochemical
cycle has been of interest for decades. The isotopic

i
Seawater:
Arctic i °
I •o
Atlantic
Io0ooo
Pacific I
Marine Evaporites:
Hilgardite
Boracite
Inyoite 0
Howlite
Ulexite
Tourmaline (marine):
Metapelite 0 0 0 ~ 01

Marble
I
Metamorphics: I
Slate • • E
P
Igneous: t
Basalt (altered/marine) I °°•° I
Basalt (unaltered)
Diabase II • I
I I
Gabbro
I I
Granite i • • I
i
Thermal Waters (etc.): I

Hot Springs (Japan) I m I

I
Fumarole Condensate
Sazsolite
ill • °I I

Boric Acid vapor I

1 •I
I
Evaporites ( n o n - m a r i n e ) : I
I
Tincalconite I ooo
Ulexite Io o 0 o• I
Borax CO •
Colemanite 00~
Oatollte
Inyoite LEGEND
Inderite o o

Pandermanite o Selected or
Hydroboracite o Only value:
Howlite (E) • >NBS 951
Szaibelyie o <NBS 951
Hambergite 0
Meyerhofferite 0 o Reported but
Kotoite less reliable
Meteorites:
iron
Chondrite O0 0
Achondrite 0
Lunar:
Regolith < ( - - 1 2 5 tO - - 8 8 )
[ I I I I I I 1 I
-60 -50 -40 -30 -20 -10 10 20 50 40

6',B

FIG. 3. Selected values for 611B for natural materials indicated by large circles, less reliable values
generally with large standard deviation are presented as small closed circles.
 Critical evaluation of stable isotopes of B
f r a c t i o n a t i o n of XlB/l°B offers the p o t e n t i a l for
f u r t h e r d e t e r m i n i n g sources a n d for u n d e r s t a n d i n g
the processes which p a r t i t i o n B as it m o v e s from the
terrestrial to the m a r i n e e n v i r o n m e n t , or redistri-
butes within the m a r i n e cycle. Difficult extraction
p r o c e d u r e s and analytical u n c e r t a i n t y have histori-
cally p r e v e n t e d the a c c u m u l a t i o n of a large n u m b e r
of m e a s u r e m e n t s , a n d the available p u b l i s h e d data-
base is still r a t h e r small.
A v a i l a b l e d a t a h a v e b e e n compiled, reviewed, a n d
e v a l u a t e d , a n d the results indicate a clear distinction
b e t w e e n several e n v i r o n m e n t s . M a r i n e and non-
m a r i n e sources are distinct; processes of w e a t h e r i n g ,
alteration a n d a d s o r p t i o n are clearly reflected in t h e i r
isotope ratios. T h e global sea w a t e r reservoir of B
may have b e c o m e e n r i c h e d in l i B o v e r geological
time b a s e d on analysis of m a r i n e b o r a t e s . T h e exact
m e c h a n i s m is u n c l e a r but m a y b e the result of reac-
tion with m a r i n e sediments. It is also possible that the
implication of a historical t r e n d is skewed by evapor-
ite diagenesis which may have altered the b o r a t e s
over time.
T h e b e n c h m a r k data base is useful as a r e f e r e n c e
for future studies a n d can be e x p a n d e d as m o r e data
for I1B are m a d e available. C o n s i d e r a b l e e r r o r exists
in m a n y of the r e p o r t e d analyses, generally of the
o r d e r of 2-6%0. B e t t e r analytical m e t h o d s recently
p r e s e n t e d by several a u t h o r s indicate that accurate
and precise values are n o w achievable ( b e t t e r t h a n
1%o) a n d in the near future will be used to e x p a n d ,
considerably, o u r k n o w l e d g e of the I IB/I°B distri-
b u t i o n for natural materials.
Acknowledgements--1 am grateful to Dr Austin Long of the
Geoscicnce Department, Dr Stanley Davis of the Hydro-
logy and Water Resources Department of the University of
Arizona and Dr Lynton Land at the University of Texas for
critically reviewing the manuscript. The support of the
American Chemical Society, Petroleum Research Fund
(PRF 20448-AC2) which provided partial funding for thc
work is also gratefully acknowledged.
Editorial handling: Y. K. Kharaka.
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