Marine Chemistry 62 Ž1998.

1–14

11
Br10 B variations of dissolved boron in a freshwater–seawater
mixing plume žElbe Estuary, North Sea /
),1
Susanne Barth
Department of Earth and Space Sciences, State UniÕersity of New York at Stony Brook, Stony Brook, NY 11794-2100, USA
Received 31 July 1997; accepted 4 February 1998

Abstract

This study is the first to utilize the boron isotopic composition Ž d11 B., in combination with elemental concentrations Žlike
B, Na, and Cl. and salinity, as a sensitive tracer for discerning distinct solute sources and constraining geochemical
processes in a freshwater–seawater mixing plume. Two distinct series of water samples, collected in the Elbe Estuary and
North Sea ŽGermany. in September 1994 and during an extreme winter flood event in February 1995, have been examined.
Boron isotopic compositions and B concentrations have been determined by negative thermal ionization mass spectrometry
with analytical uncertainties of "0.3‰ Ž2 smean . and "1% Ž2 s ., respectively. The least saline brackish water Žsalinity of
- 0.50. shows a d11 B value of q23.9‰ Ž0.25 mg Brl., at variance with seawater from the open marine North Sea Žsalinity
of 34.70., which is characterized by a d11 B value of q40.3‰ Ž4.7 mg Brl.. The effects of admixture of immense amounts
of rainwater during the centennial flood Žin February 1995. relative to less extreme meteorologic conditions prevailing
earlier Žin September 1994. are documented in this study. The flood event led to considerable 11 B enrichment in the
freshwater–seawater mixing plume Žrecorded by a shift on the order of d11 B f 14‰ at 0.25 mg Brl in the least saline
brackish water., accompanied by comparatively minor changes in elemental abundances. Well-defined correlations among
d11 B values, B concentrations, and salinity are interpreted in terms of binary mixing between riverine input waters and North
Sea seawater by a process of straightforward dilution. These relationships favor a model of conservative behavior of boron
during estuarine mixing, without involving significant interactions between dissolved and adsorbed boron. q 1998 Elsevier
Science B.V. All rights reserved.

Keywords: boron isotopes; estuarine mixing; brackish water; seawater; Elbe Estuary; North Sea

1. Introduction sphere. Boron isotopes are potentially useful tracers

for discerning distinct solute sources in natural
Boron isotope geochemistry holds considerable aquatic systems since Ž1. boron is highly soluble in
promise for providing new insight into a variety of aqueous solutions and, hence, an ubiquitous minor or
geochemical processes in the lithosphere and hydro- trace constituent in nearly all water types, and Ž2. the
relatively large mass difference between the two
) stable isotopes of boron, 10 B and 11 B, leads to a
Address for correspondence: Reichenbachstrasse 7, D-72766
Reutlingen, Germany. Fax: q49-7121-434381.
wide range of boron isotope variations in nature
1
¨ Geologie und Palaontologie,
Present address: Institut fur ¨ Uni- Ž d11 B f 90‰, Barth Ž1993.; for d notation see be-
¨ Tubingen,
versitat ¨ ¨
D-72076 Tubingen, Germany. low.. Natural waters Žseawater, river water, rainwa-

0304-4203r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII S 0 3 0 4 - 4 2 0 3 Ž 9 8 . 0 0 0 2 3 - 1
2 S. Barthr Marine Chemistry 62 (1998) 1–14

Fig. 1. Ža. Map showing the location of the Elbe Estuary in the southeastern part of the North Sea. Žb. Map showing the location of sampling
stations ŽA to L. along the freshwater–seawater mixing zone ŽElbe Estuary, North Sea.. Individual sample numbers are listed in Tables 1–3
and used throughout the text.
 S. Barthr Marine Chemistry 62 (1998) 1–14
ter, groundwater, saline formation water, brines, and
geothermal fluids. encompass a large range in d11 B
of f 76‰, from y16‰ ŽVengosh et al., 1991. to
q60‰ ŽVengosh et al., 1994..
Dissolved boron in aqueous solutions is predomi-
nantly present as undissociated boric acid, BŽOH. 30
Žtrigonal species., and as the borate anion, BŽOH.y 4
Žtetrahedral species.. The ionization of boric acid,
0 y
B Ž OH . 3 q H 2 O m B Ž OH . 4 q Hq
has been experimentally studied by Hershey et al.
Ž1986.. Adsorption experiments, involving either B-
specific ion-exchange resin ŽKakihana et al., 1977.
or natural clays Že.g., Schwarcz et al., 1969; Palmer
et al., 1987. have shown that 11 B and 10 B are
preferentially partitioned into the BŽOH. 30 and
BŽOH.y 4 species, respectively, such that according to
the exchange reaction
0 y 0
10
B Ž OH . 3 q a-Al 2 O 311 B Ž OH . 4 m11B Ž OH . 3
y mixing plume. I report here precise boron isotope
q a-Al 2 O 310 B Ž OH . 4
the isotopic equilibrium between the adsorbed and
dissolved boron species lies to the right. The 11 B
enrichment of seawater, characterized by a d11 B
value of f q39.5‰ ŽSpivack and Edmond, 1987.,
by about 40–50‰ relative to average continental
crust is mainly attributed to isotopic fractionation
associated with differential uptake of the two domi-
nant boron species during adsorption of B onto
active surfaces in the marine environment Že.g.,
Schwarcz et al., 1969; Spivack and Edmond, 1987;
Palmer et al., 1987.. The boron isotopic composition
of seawater is world-wide constant due to the long
residence time of boron in seawater Žabout 10 Ma
ŽHolland, 1978. or 16 Ma ŽTaylor and McLennan,
1985... As mixing of deep ocean water takes place
on a time scale of about 1000 years ŽHolland, 1978.,
boron is homogeneously distributed in the oceans.
The potential of boron isotopes for tracing geo-
chemical processes in a variety of geological envi-
ronments has been shown by a number of studies
which considerably increased over the past 10 years
Žsee reviews by Bassett, 1990; Barth, 1993; Palmer
and Swihart, 1996; Leeman and Sisson, 1996., mainly
as a consequence of the development and improve-
ment of diverse analytical methods applicable for
boron isotope analysis Žrecent reviews by Aggarwal
and Palmer, 1995; Swihart, 1996.. Determination of
3
the boron isotopic composition in natural surface
waters that may have B concentrations as low as in
the m grl range, however, still suffers from analyti-
cal difficulties which account for the world-wide
sparse data base available for river water Ž3 values;
Vengosh et al., 1995. and rainwater Ž6 values; Spi-
vack, 1986; Xiao et al., 1992; Eisenhut and Heumann,
1997..
In view of the enormous difference recorded be-
Ž 1.
tween the boron isotopic compositions of seawater
and average continental crust, boron isotope system-
atics are expected to be a potentially useful tracer
particularly at the freshwater–seawater interface of
the oceans where natural waters with largely differ-
ent chemistries are subject to mixing processes. This
study is the first to utilize the boron isotopic compo-
sition, in combination with elemental concentrations
Žlike B, Na, and Cl. and salinity, as a tracer for
constraining geochemical processes in an estuarine
Ž 2. and chemical data for two distinct series of water
samples which have been collected in the Elbe Estu-
ary and North Sea ŽGermany. in September 1994
and during an extreme winter flood in February 1995
ŽFig. 1a,b.. The purposes of this study are mainly Ž1.
to investigate the sensitivity of 11 Br10 B ratios in the
estuarine mixing plume to varying hydrologic condi-
tions, encountered at the study site in September
1994 and during the centennial flood in February
1995, and Ž2. to examine whether during estuarine
mixing boron behaves conservatively, as would be
expected in the case of simple binary mixing be-
tween fresh and saline waters Žstraightforward dilu-
tion., or, alternatively, non-conservatively due to
interactions between dissolved and adsorbed boron.
Integration of boron isotopic and chemical data pro-
vides a unique possibility to study the application of
boron isotope geochemistry for constraining mixing
processes between distinctly different sources of dis-
solved boron Žmarine vs. non-marine. and the effects
of waterrrock interactions in the estuarine environ-
ment.
2. The February 1995 flood event
At the beginning of 1995, extremely heavy and
long-lasting rainfall led to one of the biggest floods
4 S. Barthr Marine Chemistry 62 (1998) 1–14
ever recorded in Germany, France, Belgium, and
The Netherlands Že.g., Bronstert, 1996; Caspary,
1996; Savenije, 1996.. The centennial flood has been
related to an intense cyclonic west circulation over
the eastern part of the North Atlantic, known to be a
meteorological prerequisite for most winter floods in
Europe during the past decades Žvan Meijgaard,
1996.. This scenario triggered a series of frontal
disturbances which penetrated deep into the Euro-
pean continent bringing excessive amounts of pre-
cipitation. Since storage of the immense water masses
in the Žpartly frozen and saturated. soils was not
Fig. 2. Variations in Ža. the runoff of the Elbe River, monitored
over a period from August 1st, 1994 to April 1st, 1995 at station
‘Neu Darchau’ Ž536.4 km., located upstream of Hamburg, and Žb.
electric conductivity, monitored over the same period for the Elbe
River at stations ‘Bunthaus’ Ž609.8 km. and ‘Seemannshoft’ ¨ about 20–40 m and 40–150 m in the southern and
Ž628.9 km., both located in Hamburg, and Elbe Estuary at station
‘Grauerort’ Ž660.5 km., located downstream of Hamburg ŽARGE
ELBE, 1994r95.. Note the extreme peak in runoff of the Elbe
River during the February 1995 flood and related decrease in
electric conductivity, discernible both in the input river water and
estuarine mixing plume.
possible, many large rivers rose dramatically to flood
levels due to instantaneous surface runoff ŽChbab,
1996; Ulbrich and Fink, 1996..
During the extreme February 1995 flood, the
runoff of the Elbe River, measured at station ‘Neu
Darchau’ Žlocated upstream of Hamburg., increased
within only a few days from 1488 m3rs on February
1st to a peak value of 2165 m3rs on February 9th,
corresponding by way of example to a 4.6 fold
increase in relation to a ‘normal’ runoff of 473 m3rs
measured on September 1st, 1994. The variations in
the runoff of the Elbe River, monitored from August
1st, 1994 to April 1st, 1995, are illustrated in Fig. 2a.
The effects of such extreme precipitation on water
chemistry are evidenced by a decrease in electric
conductivity, discernible both in the input river water
Žfrom 1080 m Srcm to 649–753 m Srcm at station
‘Bunthaus’ and from 1060 m Srcm to 663–787
m Srcm at station ‘Seemannshoft’,¨ both located in
Hamburg, on September 1st, 1994 and during Febru-
ary 1st to February 9th, 1995, respectively., and
estuarine mixing plume Žfrom 1980 m Srcm on
September 1st, 1994 to 882–1100 m Srcm during
February 1st to February 9th, 1995 at station
‘Grauerort’, located downstream of Hamburg.. The
variations in electric conductivity, monitored for the
Elbe River and Elbe Estuary for the 8 month period
mentioned above are shown in Fig. 2b.
3. Description of the study site
The Elbe River, one of the main rivers in Middle
Europe with a flow volume of 1.4 = 10 13 lryear has
its source in the Bohemian mountain range and takes
its course across Germany where it enters the North
Sea ŽFig. 1a., reaching a width of about 15 km in the
estuary region near Cuxhaven ŽFig. 1b.. The North
Sea is a marginal shelf sea which covers an area of
about 575 000 km2 between the European continent,
the British Isles, and Scandinavia. Influx of Atlantic
seawater into the North Sea basin, reaching depths of
northern parts, respectively, occurs mainly through
the Channel as well as the passages between Scot-
land, the Shetland Islands, and Norway.
Brackish water and seawater samples from the
Elbe Estuary and North Sea have been collected in
 S. Barthr Marine Chemistry 62 (1998) 1–14 5

Table 1
Sampling sites of brackish water and seawater ŽElbe Estuary, North Sea.
Samples Date Time Longitude Latitude Site Water depth Sampling depth
ŽE. ŽN. Žm. Žm.
September 1994
X X
9567 01-09-1994 08:05 09809.1 53852.6 A 12 4
X X
9572 01-09-1994 08:53 09809.1 53852.6 A 12 4
X X
9566 01-09-1994 09:52 09803.7 53852.6 C 11.5 4
X X
9563 01-09-1994 10:43 09801.1 53851.8 D 12.4 4
X X
9569 01-09-1994 11:30 08857.8 53851.2 E 12.5 4
X X
9568 01-09-1994 12:30 08846.0 53851.4 F 12 4
X X
9562 01-09-1994 14:50 08846.0 53851.4 F 12 4
X X
9547 01-09-1994 23:15 08846.0 53851.4 F 12 4

February 1995
X X
BRU01 01-02-1995 14:05 09807.2 53852.6 B 17 10
X X
CUX01 09-02-1995 14:12 08844.6 53851.8 G 19 10
X X
4201 09-02-1995 12:12 08827.2 53859.4 H 19 10
X X
03 01-02-1995 17:10 08828.0 53859.5 I 11 7.5
X X
3401 07-02-1995 09:43 07844.9 54814.9 J 33 10
X X
1101 04-02-1995 10:20 06854.9 54840.0 K 40 10
X X
0201r4 02-02-1995 10:25 05805.1 55812.0 L 42 10

depths of 4–10 m at 12 stations along the cruise
track of the research vessel Gauss on September 1st,
1994 and from February 1st to February 9th, 1995.
The sampling stations along the estuarine mixing
zone, labelled A to L, are shown in Fig. 1b, together
with individual sample numbers. Descriptions of the
water samples collected during the September 1994
and February 1995 surveys are given in Table 1.
4. Analytical techniques
4.1. Precise analysis of 11 Br10 B ratios by NTIMS
(negatiÕe thermal ionization mass spectrometry)
Natural water samples were filtered through 0.45
m m membranes and stored under refrigeration. The
11
Br10 B isotopic ratios of the water samples were
measured by NTIMS using an NBS design 15 cm
radius-of-curvature 608 sector solid-source mass
spectrometer at the State University of New York at
Stony Brook ŽUSA.. This technique is characterized
by high analytical sensitivity, and, hence, is the
preferred technique for isotope analysis of natural
waters which may have B concentrations as low as
in the m grl range. The water samples were loaded
directly onto rhenium filaments, without separation
of boron prior to analysis, but with addition of B-free
seawater and 1 M HCl as loading reagents Žanalyti-
cal procedure as outlined by Hemming and Hanson,
1994 and Barth, 1997a..
It is demonstrated here that boron isotopic compo-
sitions of natural waters Žfilament loads of 1–10 ng
B. can be measured by NTIMS with an analytical
uncertainty of "0.3‰ Ž2 smean , corresponding to
2 srn0.5, where n s 3 to 8 replicate analyses.. The
excellent analytical precisions obtained on the water
samples and the NIST SRM-951 boric acid standard
Ž"0.7‰ Ž2 sm ., n s 5; Barth, 1998. demonstrate
that the measurements were not affected by isobaric
interferences resulting from cyanogen ŽCNO..
The boron isotopic compositions of the water
samples are reported as d11 B values Žin per mil.
relative to a mean 11 Br10 B ratio of 4.00125 mea-
sured for the NIST SRM-951 standard ŽBarth, 1998.,
where
d11 B Ž ‰ . s ½ Ž 11 Br10 B . Sample
r Ž 11 Br10 B . NIST SRMy951 Standard y 1 5
= 10 3 Ž 3.
6 S. Barthr Marine Chemistry 62 (1998) 1–14

4.2. Determination of B concentrations by NTIMS 5. Results

isotope dilution and ICP-OES
B concentrations of the water samples have been
determined by NTIMS isotope dilution with an ana-
lytical uncertainty of "1% Ž2 s ., using the NIST
SRM-952 standard Ž10 B-enriched boric acid. as a
spike. Comparison of the B concentrations, deter-
mined by NTIMS isotope dilution and ICP-OES
Žwithout use of matrix-matched standard solutions.,
shows fairly good correspondence for water samples
in the low concentration range Že.g., brackish water
BRU01.. At variance, water samples in the higher
concentration range Že.g., seawater 0201r4. reveal a
shift towards apparently lower B concentrations de-
termined by ICP-OES as compared to NTIMS iso-
tope dilution. The deviation in B concentration in-
creases systematically with increasing salinity and
Na concentration Ž r s 0.90.. These relationships in-
dicate that B concentration analysis of natural water
samples by ICP-OES may be strongly affected by
matrix effects, giving rise to a deviation on the order
of 10 to 20% if working without matrix-matched
standard solutions, at variance with NTIMS isotope
dilution which is virtually unaffected by such effects
ŽBarth, 1997b..
Salinity and electric conductivity data, total sus-
pended sediment ŽTSS. contents, Na and Cl concen-
trations, as well as NarCl and BrCl molar ratios of
the brackish water and seawater samples from the
Elbe Estuary and North Sea are listed in Table 2.
Boron isotopic compositions Žmeasured 11 Br10 B ra-
tios and calculated d11 B values. and B concentra-
tions of the water samples are given in Table 3.
The water samples analyzed for the present study
comprise a large range in salinity Ž- 0.50–34.70.,
electric conductivity Ž2623–53 100 m Srcm., and
TSS contents Ž1.82–33.14 mgrl.. The least saline
brackish water sample ŽBRU01; salinity of - 0.50.
shows the lowest concentrations of Na Ž0.39 grl.
and Cl Ž0.51 grl., and highest molar ratios of NarCl
Ž1.18. and BrCl Ž16.1 = 10y4 .. At variance, the
most saline water sample Ž0201r4; salinity of 34.70.,
deriving from the sampling site most remote from
the land Žsite L; see inset in Fig. 1b., is characterized
by the highest concentrations of Na Ž11.2 grl. and
Cl Ž20.0 grl., and lowest molar ratios of NarCl
Ž0.86. and BrCl Ž7.7 = 10y4 .. This sample is repre-
sentative for seawater from the open marine North
Sea as evidenced by chemical characteristics which

Table 2
Chemical data of brackish water and seawater ŽElbe Estuary, North Sea.
Samples Salinity a Electric conductivity TSS Nab Cl NarCl BrCl c
Ž m Srcm. Žmgrl. Žgrl. Žgrl. ŽM. ŽM. Ž=10y4 .
9567 3.10 y 13.12 1.35 y y y
9572 4.50 y 24.76 1.66 y y y
9566 8.81 y 33.14 2.61 y y y
9563 10.81 y 19.60 3.57 y y y
9569 13.53 y 15.90 4.35 y y y
9568 21.41 y 1.82 6.70 y y y
9562 17.04 y 10.32 5.45 y y y
9547 24.46 y 2.28 8.27 y y y
BRU01 - 0.50 2623 y 0.39 0.51 1.18 16.1
CUX01 3.92 7200 y 1.24 2.00 0.96 9.8
4201 20.50 35 100 y 7.17 11.0 1.01 9.2
03 26.90 44 000 y 9.34 15.0 0.96 8.5
3401 32.50 49 900 y 10.8 18.0 0.93 8.2
1101 33.70 51 300 y 11.0 19.0 0.89 8.3
0201r4 34.70 53 100 y 11.2 20.0 0.86 7.7
a
Salinity determined by salinometer Ž"0.01‰.; a value of 0.50 Ždetection limit. is assumed to approach the actual salinity of sample
BRU01.
b
Na concentrations determined by ICP-OES Žsee Barth, 1997b..
c
B concentrations determined by NTIMS isotope dilution Žsee Table 3..
 S. Barthr Marine Chemistry 62 (1998) 1–14 7

Table 3
Boron isotopic compositions and B concentrations of brackish water and seawater ŽElbe Estuary, North Sea.
11
Samples Br 10 B ratios 11
Br 10
B d 11 B a 2 smb Bd Be
mean Ž‰. Ž‰. w n x c Žmgrl. w n xc Žmgrl.
Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7 Run 8
9567 4.1203 4.1178 4.1224 y y y y y 4.1202 29.7 0.53 w3x 0.64 w1x 0.55
9572 4.1288 4.1316 4.1306 y y y y y 4.1303 32.3 0.32 w3x 0.76 w1x 0.68
9566 4.1441 4.1463 4.1457 y y y y y 4.1454 36.0 0.26 w3x 1.3 w1x 1.1
9563 4.1491 4.1479 4.1478 y y y y y 4.1483 36.8 0.16 w3x 1.5 w1x 1.3
9569 4.1528 4.1501 4.1535 y y y y y 4.1521 37.7 0.41 w3x 1.9 w1x 1.6
9568 4.1602 4.1606 4.1637 y y y y y 4.1615 40.0 0.43 w3x 2.9 w1x 2.3
9562 4.1573 4.1597 4.1602 y y y y y 4.1591 39.5 0.35 w3x 2.3 w1x 1.9
9547 4.1620 4.1597 4.1611 y y y y y 4.1609 39.9 0.26 w3x 3.4 w1x 2.8
BRU01 4.0971 4.0943 4.0988 y y y y y 4.0967 23.9 0.52 w3x 0.25 w1x 0.22
CUX01 4.1351 4.1378 4.1362 y y y y y 4.1364 33.8 0.31 w3x 0.60 w1x 0.54
4201 4.1624 4.1613 4.1615 y y y y y 4.1617 40.1 0.13 w3x 3.1 w1x 2.5
03 4.1625 4.1648 4.1642 y y y y y 4.1638 40.6 0.27 w3x 3.9 w1x 3.1
3401 4.1601 4.1644 4.1646 y y y y y 4.1630 40.4 0.58 w3x 4.5 w1x 3.6
1101 4.1652 4.1655 4.1639 4.1655 y y y y 4.1650 40.9 0.16 w4x 4.8 w1x 3.7
0201r4 4.1622 4.1616 4.1618 4.1635 4.1639 4.1635 4.1614 4.1628 4.1626 40.3 0.15 w8x 4.7 w4x 3.8
a
B isotope values given as d values Žin per mil. relative to a 11 Br10 B ratio of 4.00125 measured for the NIST SRM-951 boric acid
standard ŽBarth, 1998..
b
Analytical uncertainties of 11 Br10 B measurements calculated using the 2 sme an , corresponding to 2 srn0.5 , where n s 3 to 8 replicate
analyses.
c
Number of mass spectrometric 11 Br10 B measurements.
d
B concentrations determined by NTIMS isotope dilution with an analytical uncertainty Ž2 s . of "0.9% Žsample 0201r4..
e
B concentrations determined by ICP-OES with an analytical uncertainty Ž2 s . of "5% Žsee Barth, 1997b..

compare well to those of average seawater Žsalinity
of 35, NarCl ŽM. s 0.86, BrCl ŽM. s 7.8 = 10y4 ;
Holland, 1978.. The d11 B values and B concentra-
tions of the water samples analyzed in this study
show large variations from q23.9 to q40.9‰ and
0.25 to 4.8 mgrl, respectively. Among these, sam-
ples BRU01 and 0201r4 are characterized by d11 B
values of q23.9‰ Ž0.25 mg Brl. and q40.3‰ Ž4.7
mg Brl., respectively.
6. Discussion
6.1. Tracing estuarine mixing by boron isotope sys-
tematics: a case study in the Elbe Estuary
Two distinct series of water samples, collected in
the Elbe estuarine mixing plume during surveys in
September 1994 and February 1995, define strong
positive linear correlations between elemental con-
centrations Žsuch as Na, Cl, and B. and salinity
Ž r G 0.996; Fig. 3a,b., with the least saline brackish
water samples of each series showing only minor
differences in Na and B concentrations at a given
salinity. At variance, boron isotope systematics ap-
pear to be more sensitive to varying compositions of
the input waters and, hence, reveal the presence of
two distinctly different mixing trends prevailing in
the estuary in September 1994 and February 1995.
Binary mixing curves between d11 B values and B
concentrations ŽFig. 4., corresponding to negative
linear correlations between d11 B and 1rB concentra-
tion Ž r G 0.995; Fig. 5., can be modeled by involv-
ing as ‘endmembers’ Ž1. samples 9567 Ž d11 B s
q29.7‰, 0.64 mg Brl. and 9547 Žq39.9‰, 3.4 mg
Brl., and Ž2. samples BRU01 Žq23.9‰, 0.25 mg
Brl. and 0201r4 Žq40.3‰, 4.7 mg Brl. for the
September 1994 and February 1995 surveys, respec-
tively. The response of the boron isotopic system to
varying endmember compositions of the input wa-
ters, exemplified by the pronounced shift in d11 B
8 S. Barthr Marine Chemistry 62 (1998) 1–14

Fig. 4. d11 B vs. B concentration diagram for brackish water and

seawater from the Elbe Estuary and North Sea Ždata from Table
3.. The binary mixing curves are calculated as follows: d11 B mix
s B I Pd11 B I PF q B II Pd11 B II P Ž 1y F . rB mix and B mix s
 4
B I Ø F qB II Ø Ž1y F ., where B I , B II , and B mix are B concentra-
tions, and d11 B I , d11 B II , and d11 B mix are d11 B values of the
waters from the Elbe Estuary ŽI. and North Sea ŽII. components
and the mixture, respectively. Fractions Ž F . of components I are
expressed by numbers along the mixing curves.

Fig. 3. Ža. Na and Cl concentrations and Žb. B concentrations vs.

salinity Ž S . for brackish water and seawater from the Elbe Estuary
and North Sea Ždata from Tables 2 and 3.. Strong positive
correlations are defined for water samples collected in September,
1994 ŽNa s 0.32 Sq0.13, Bs 0.13 Sq0.18. and February, 1995
ŽNa s 0.33 Sq0.09, Cl s 0.56 Sy0.10, Bs 0.14 Sq0.17..
BRU01. The shift of 13.6‰ Žat 0.25 mg Brl. can
only be interpreted in terms of largely varying boron
isotopic compositions of the input waters during the
two distinct surveys.

recorded in the estuarine mixing plume during the

two distinct surveys, is discussed in more detail
below.

6.2. The sensitiÕity of 11 Br10 B ratios in the estuarine

mixing plume to Õarying hydrologic conditions

Based on the distinctly different mixing lines

between d11 B and reciprocal B concentration values,
defined by water samples of the September 1994 and
February 1995 surveys ŽFig. 5., a d11 B value of
q10.3‰ can be calculated for the September 1994
series at a given B concentration of 0.25 mgrl,
corresponding to the lowest B concentration mea-
sured for the least saline brackish water of the Fig. 5. d11 B vs. 1rB concentration diagram for brackish water
and seawater from the Elbe Estuary and North Sea Ždata from
February 1995 series Žsample BRU01.. This extrapo- Table 3.. Strong negative correlations are defined for water sam-
lated d11 B value is significantly lower as compared ples collected in September 1994 Ž d11 Bsy8.04 1rBq42.43.
to the d11 B value of q23.9‰ measured for sample and February 1995 Ž d11 Bsy4.43 1rBq41.50..
 S. Barthr Marine Chemistry 62 (1998) 1–14
Although pollution of the Elbe River, draining
densely populated and industrialized catchment ar-
eas, is well known and has recently been substanti-
ated by the detection of a positive gadolinium
anomaly in shale-normalized rare earth element pat-
terns ŽBau and Dulski, 1996., anthropogenic effects
are unlikely to have a major control on the shift in
d11 B observed in the estuarine mixing plume. An-
thropogenic boron compounds, mainly industrially
manufactured sodium perborate, a bleaching agent
added to a variety of detergent formulations and
cleaning products, are characterized by a restricted
range in d11 B of y4.9 to q3.1‰ ŽXiao et al., 1988;
Vengosh et al., 1994; Eisenhut et al., 1996; Barth,
1998.. These values are within the d11 B range of
y5.4 to q10.2‰ of natural sodium borate minerals
from non-marine evaporite sequences in the USA
and Turkey ŽMcMullen et al., 1961; Swihart et al.,
1986; Xiao et al., 1988; Oi et al., 1989; Palmer and
Helvaci, 1995. used as raw material for world pro-
duction of commercial boron products ŽHarben and
Bates, 1984.. Hence, discharge of domestic aqueous
effluents, enriched in water-soluble boron com-
pounds of anthropogenic origin, would contribute to
a downward shift in d11 B of the brackish water in
the estuarine mixing plume. This would imply that at
the study site an anthropogenic impact would have
been considerably more pronounced in September
1994 than in February 1995 which seems unlikely
and is devoid of any other evidence.
Alternatively, admixture of a 11 B-rich component
in February 1995 may explain the observed shift to
higher d11 B values in the estuarine mixing plume
relative to September 1994. In view of the extreme
flood event in February 1995, which is well docu-
mented by a vast amount of physical and chemical
data Žsee Fig. 2., it may be argued that this 11 B-rich
component is represented by rainwater. It is well
known that boric acid vaporizes from the sea surface
into the atmosphere, and that most of the boron in
the atmosphere and rainwater originates from this
process ŽGast and Thompson, 1959.. Hence, the
ocean is not a sink ŽNishimura et al., 1973. but a
source for atmospheric boron ŽFogg and Duce, 1985..
The major global sources of atmospheric boron,
which consists primarily in gaseous Žrather than in
particulate. form, appear to be Ž1. seawater by pro-
duction of sea salt aerosol during bubble bursting at
9
the sea surface Žmarine spray., Ž2. dissolved compo-
nents in the form of volcanic emissions, and Ž3.
products generated by anthropogenic activity, mainly
during coal combustion and agricultural burning
ŽFogg and Duce, 1985.. Large isotopic variations are
expected for boron in the atmosphere and rainwater,
since the principal boron sources are characterized
by largely different d11 B values: Ž1. vapor produced
during seawater evaporation with d11 B values of
q22.7 to q37.3‰ ŽXiao et al., 1998., Ž2. volcanic
gases with d11 B values of q2.3 to q21.4‰
ŽKanzaki et al., 1979; Nomura et al., 1982., and Ž3.
fly ash leachates with d11 B values of y19.2 to
q15.8‰ ŽDavidson and Bassett, 1993.. This vari-
ability is reflected in the wide compositional range
of rainwater, documented by d11 B values of q0.8 to
q35‰ for rainwater from the Pacific Ocean
ŽSpivack, 1986., q16.7‰ for rainwater from Qing-
hai, China ŽXiao et al., 1992., and q13.1‰ for
rainwater from SE Germany ŽEisenhut and Heumann,
1997.. Boron isotopic systematics of rainwater are
still poorly constrained Žby only 6 values mentioned
above., mainly due to highly demanding analytical
techniques required for mass spectrometric analysis
of aqueous samples with B contents as low as in the
m grl range, such as typical for rainwater Žnormal
range of 0.3 to 15 m g Brl according to Fogg and
Duce Ž1985., except for a high value of 0.50 mg Brl
reported by Xiao et al. Ž1992... In view of the
variability of the boron isotopic composition of rain-
water, a model involving 11 B-rich rainwater, influ-
enced by a ‘marine’ boron component, may plausi-
bly explain the observed shift to higher d11 B values
in the estuarine mixing plume during the February
1995 flood relative to less extreme hydrologic condi-
tions. New experimental results by Xiao et al. Ž1998.
on the fractionation of boron isotopes during evapo-
ration-related phase separation of coexisting vapor
Žq22.7 to q37.3‰. and seawater Žq38.8‰. pro-
vide constraints on the generation of isotopically
heavy boron during seawater vaporization. Such
11
B-rich atmospheric boron may have played a par-
ticularly important role during the extreme February
1995 rainfall, in agreement with the meteorologic
conditions relating this event to an intense cyclonic
west circulation over the eastern part of the North
Atlantic and subsequent frontal disturbances which
penetrated deep into the European continent.
10 S. Barthr Marine Chemistry 62 (1998) 1–14
6.3. ConserÕatiÕe or non-conserÕatiÕe behaÕior of
boron during estuarine mixing?
Adsorption of boron onto active surfaces, prefer-
ably clay minerals, may be expected to be an impor-
tant process particularly at the freshwater–seawater
interface of the oceans where stirring by tidal cur-
rents often produces a high concentration of sus-
pended sediment in the estuarine water. Initial inter-
est in such a process centered around the possible
use of B contents of clay minerals Žmainly illite. as
paleo-salinity indices Že.g., Harder, 1970.. Subse-
quent work demonstrated, however, that the B abun-
dance of marine and freshwater estuarine sediments
are indistinguishable when normalized to the per-
centage of clay present ŽDewis et al., 1972.. The
uptake of boron by adsorption from seawater, esti-
mated to amount about 9 = 10 9 moles per year
Žassuming that the sediments transported by the Mis-
sissippi River are representative of the global input
to the oceans; Spivack et al., 1987., is associated
with isotopic fractionation. The extent to which the
11
Br10 B ratio of dissolved boron can be changed by
such kind of adsorption-related fractionation of boron
isotopes, in which the light isotope, 10 B, is preferen-
tially incorporated into the adsorbed phase, may be
addressed by a simple model calculation. Assuming
completely reversible interaction and fluid–solid
equilibrium, the d11 B value of the modified water
Ž d11 B Mo dified Water ., after having reached equilibra-
tion, may be expressed by
d11 B Mo dified Water
11
s žd B Original Water q 1000 r Ž a y a X q X .
/ 1987.. Applying Eq. Ž4. by taking into account the
y 1000
11
ŽVengosh et al., 1994., where d B Original Water is the
d11 B of the original water, a is the boron isotope
fractionation factor between adsorbed and dissolved
boron, and X Žthe fraction of boron which remains
in solution. corresponds to X s 1rŽ1 q K d ., with
K d being the distribution coefficient of boron ad-
sorption expressed as K d s wBxSedimentrwBx Water . The
isotope fractionation factor a between two phases A
Žadsorbed boron. and D Ždissolved boron. is defined
as aAy D s R A rR D , where R s11 Br10 B, and the
relative 11 B enrichment is DAy D s 10 3 ln aAyD
sf dA y d D .
Isotope fractionation between the two dominant
boron species, experimentally studied by the adsorp-
tion of boron from boric acid solution onto ion-ex-
change resin, is an effective process capable to pro-
duce a values on the order of 0.980–0.983 ŽT s 0–
608C; Kakihana et al., 1977.. Fractionation factors of
0.957–0.974 have been determined for boron adsorp-
tion involving natural clay minerals Žillite. and syn-
thetic seawater ŽT s 238C; Schwarcz et al., 1969.,
similar to a values of 0.967–0.978 obtained for
interaction of Mississippi delta clays with seawater
ŽT s 5–408C; Palmer et al., 1987.. Examination of
the adsorption behavior of boron during interaction
of Mississippi delta clays with seawater revealed that
fractionation factors Ž a . and distribution coefficients
Ž K d . systematically increase with increasing pH since
clays have a stronger adsorption affinity for BŽOH.y 4
relative to BŽOH. 30 ŽPalmer et al., 1987.. This rela-
tionship is consistent with previous studies of boron
adsorption on pure clay minerals relating the pH
dependence of K d to the speciation of dissolved
boron Že.g., Keren and Mezuman, 1981.. For a model
calculation aimed at evaluating the magnitude of 11 B
enrichment of dissolved boron which can be achieved
by such an adsorption process, a –K d pairs of Ž1.
0.970 and 2.15, and Ž2. 0.975 and 2.85, experimen-
tally determined at pH values of 7.15 and 8.15,
respectively Žat 58C; Palmer et al., 1987., may be
used. Among these, the latter fractionation factor
corresponds fairly well to those determined for the
interaction between Mississippi clay sediments and
seawater Ž0.974 " 0.003. and between deep sea sedi-
ments and seawater Ž0.976 " 0.001. ŽSpivack et al.,
a –K d pairs mentioned above for pH values of 7.15
Ž 4. and 8.15 ŽPalmer et al., 1987., an original d11 B
value of 0‰ could be shifted to values of f q21‰
and f q19‰, respectively.
However, adsorption-related fractionation of boron
isotopes, leading to 11 B enrichment of dissolved
boron, is always linked to removal of elemental
boron from solution. Consequently, if during estuar-
ine mixing adsorption of boron is considered as a
relevant process, removal of boron from solution
should be evidenced by comparing the measured B
concentrations with any conservative index of mix-
ing, like salinity. In such a case, B concentration and
salinity data of the estuarine waters would be ex-
 S. Barthr Marine Chemistry 62 (1998) 1–14
pected to deviate from a theoretical dilution line,
corresponding to a straight line joining the endmem-
bers of the mixing series, and the extent of deviation
should be a measure of the amount of boron re-
moved. Based on a non-linear mixing relationship
between B concentration and salinity, removal of
boron on the order of 25–30% by uptake on sus-
pended sediment has been reported for the Alde
River, a small river in England entering the North
Sea ŽLiss and Pointon, 1973.. At variance, large
tropical rivers such as the Zaire ŽKongo. River in
Africa and Magdalena River in South America, en-
tering the equatorial Atlantic and the Caribbean Sea,
respectively, show excellent linear fits of the boron
and salinity data, which strongly support that
straightforward dilution, without involving intensive
reactions between dissolved boron and solid phases,
is controlling the behavior of boron in the estuarine
mixing plumes ŽFanning and Maynard, 1978.. Fur-
ther evidence indicating that boron adsorption is not
a crucial mechanism during estuarine mixing of fresh
and saline waters comes from studies of the Chiku-
gogawa River in Japan ŽHosokawa et al., 1970. and
Mackenzie River in Canada ŽDewis et al., 1972..
Freshwater–seawater mixing in the Elbe Estuary
is documented by strikingly well-correlated relation-
ships between elemental concentrations and salinity
ŽFig. 3a,b.. Least-squares regressions of the B con-
centration and salinity data to straight lines, yielding
correlation coefficients Ž r . of 0.998 for both the
September 1994 and February 1995 surveys, signify
strong adherance of the data fits to linearity ŽFig.
3b.. Even boron isotopic compositions, known to be
much more sensitive to adsorption effects as com-
pared to B concentrations, show no significant devia-
tion from calculated mixing curves in d11 B vs. B
concentration representation ŽFig. 4., evidenced by
linear correlations between d11 B and reciprocal B
concentration values defined by correlation coeffi-
cients Ž r . of 0.995 and 0.999 for the September 1994
and February 1995 series, respectively ŽFig. 5.. Simi-
larly, strongly linear correlations between d11 B and
reciprocal salinity values Žnot shown. are defined by
water samples collected in September 1994 Ž r s
0.983. and February 1995 Ž r s 0.958.. Another ar-
gument providing further evidence against signifi-
cant adsorption-related effects during the estuarine
mixing process comes from the slopes of the regres-
11
sions calculated for the B concentration vs. salinity
relationships, which become 0.232 and 0.244 for the
September 1994 and February 1995 series, respec-
tively, when multiplied by the salinity–chlorinity
ratio of seawater Ž1.80655.. These values compare
favorably to values reported for seawater Že.g.,
0.222–0.264 with 0.240 on average, Culkin, 1965;
0.230, Riley and Chester, 1971; 0.232, Uppstrom, ¨
1974., and for the estuarine waters of the Zaire
ŽKongo. River and Magdalena River for which a
conservative behavior of boron has been evidenced
Ž0.231; Fanning and Maynard, 1978.. These relation-
ships, in connection with the observation that both B
concentrations and d11 B values in the Elbe Estuary
are predictable from salinity, can only be interpreted
in terms of a conservative behavior of boron during
the estuarine mixing process.
A variety of physical and chemical factors may
influence the behavior of boron in estuaries. Among
these, temperature effects appear to be of no account
since conservative behavior of boron has been found
in estuaries located in a broad band between f 58S
to f 708N Že.g., Hosokawa et al., 1970; Dewis et al.,
1972; Fanning and Maynard, 1978., with the Elbe
Estuary being located in between at f 548N Žsee
Fig. 1b.. The suspended load cannot be considered
as a factor controlling the degree of boron adsorption
either, since large ranges in total suspended sediment
ŽTSS. contents are encountered in rivers with conser-
vative behavior of boron such as the Zaire ŽKongo.
River Ž32–52 mgrl. and Magdalena River Ž200
mgrl. ŽFanning and Maynard Ž1978. and references
therein. as well as in the mixing plume of the Elbe
River Ž2–33 mgrl; Table 2., similar to the range of
values reported for the Alde River Ž10–80 mgrl;
Liss and Pointon, 1973.. Coastal circulation, related
to re-suspension by tidal currents, implying pro-
longed interaction of the estuarine waters with the
suspended load, may largely be excluded as a crucial
factor favoring adsorption, since in spite of similar
tidal conditions prevailing in the North Sea, dis-
tinctly different behavior of boron is found in the
mixing plumes of the Alde River and Elbe River. A
possible influence on the behavior of boron in estuar-
ies may, however, be ascribed to the magnitude of
riverine input, a factor by which the small Alde
River is clearly distinguished from large rivers with
enormous flow volumes like the Zaire ŽKongo. River,
12 S. Barthr Marine Chemistry 62 (1998) 1–14
representing the second largest river world-wide Ž1
= 10 15 lryear., and Magdalena River Ž2 = 10 14
lryear., discharging roughly as much as the
Columbia River or Indus River ŽFanning and May-
nard, 1978., as well as the Elbe River Ž1.4 = 10 13
lryear.. Since the flow volume of a river is related
to the rivers’ length and size of catchment area, it
may be presumed that an increase in these factors
may be paralleled by an increasing efficiency of
boron adsorption, mainly due to prolonged interac-
tion of the river water with the suspended load.
Hence, such river water may be assumed to have
already achieved complete equilibrium between dis-
solved and adsorbed boron before entering the estu-
ary, where it undergoes simple mixing with the
marine endmember.
7. Conclusions
The boron isotopic composition, in combination
with elemental concentrations Žlike B, Na, and Cl.
and salinity, has been utilized for the first time in
this study as a sensitive and useful tracer for discern-
ing distinct solute sources and constraining geochem-
ical processes in an estuarine mixing plume. The
effects of admixture of immense amounts of rainwa-
ter during an extreme winter flood event, producing
considerable 11 B enrichment in the freshwater–
seawater mixing plume Žrecorded by a shift on the
order of d11 B f 14‰ at 0.25 mg Brl in the least
saline brackish water., accompanied by compara-
tively minor changes in elemental abundances, are
documented for the Elbe Estuary. The sensitivity of
the boron isotopic system to prevailing meteorologic
conditions has implications for hydrologic andror
environmental studies applying boron isotope sys-
tematics to surface aquatic systems, particularly along
the coast where an increased likelihood of a dominat-
ing marine boron source in precipitation may be
anticipated.
Adsorption of boron onto active surfaces in the
estuarine environment cannot be regarded as a major
mechanism in the investigated freshwater–seawater
mixing plume since well-defined correlations among
d11 B values, B concentrations, and salinity can only
be interpreted in terms of straightforward dilution,
thus favoring a model of conservative behavior of
boron during estuarine mixing. Hence, adsorption of
boron onto suspended matter is to be expected as an
important process upstream in the river where equi-
librium between dissolved and adsorbed boron ap-
pears to be achieved before entering the estuary.
Such a model may be considered for the Elbe Estu-
ary where the riverine input water undergoes simple
binary mixing with North Sea seawater, which is
characterized by a boron isotopic composition that is
indistinguishable from the signature of the world
oceans.
Acknowledgements
The present paper greatly benefited from con-
structive comments and thorough reviews by J. Ag-
garwal and Y.-K. Xiao. Y.-K. Xiao is sincerely
thanked for generous provision of unpublished ex-
perimental data. Valuable editorial comments by P.S.
Liss are acknowledged. My thanks are due to G.N.
Hanson for the access to the mass spectrometer at
the State University of New York at Stony Brook,
USA, and to N.G. Hemming for his advice during
NTIMS analysis. G.H. Swihart and M. Bau are
thanked for suggestions during an earlier stage of the
work. I am grateful to D. Schmidt and W. Gerwinski
for arranging the collection of water samples, and for
providing chemical data M. Bergemann is thanked
for his help. Support of this work by the Deutsche
Forschungsgemeinschaft ŽDFG. is gratefully ac-
knowledged.
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