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GLOBAL BIOGEOCHEMICAL CYCLES, VOL. 16, NO. 4, 1072, doi:10.1029/2001GB001766, 2002

Global biogeochemical cycle of boron

Haewon Park1 and William H. Schlesinger
Division of Earth and Ocean Sciences, Nicholas School of the Environment and Earth Sciences, Duke University, Durham,
North Carolina, USA

Received 30 September 2001; revised 16 May 2002; accepted 4 June 2002; published 5 November 2002.

[1] The global Boron (B) cycle is primarily driven by a large flux (1.44 Tg B/yr) through
the atmosphere derived from seasalt aerosols. Other significant sources of atmospheric
boron include emissions during the combustion of biomass (0.26–0.43 Tg B/yr) and coal,
which adds 0.20 Tg B/yr as an anthropogenic contribution. These known inputs to the
atmosphere cannot account for the boron removed from the atmosphere during rainfall
(3.0 Tg B/yr) and estimated dry deposition (1.3–2.7 Tg B/yr). In addition to atmospheric
deposition, rock weathering is a source of boron (0.19 Tg B/yr) for terrestrial ecosystems,
and humans mine about 0.31 Tg B/yr from the Earth’s crust. More than 4.8 Tg B/yr
circulates in the biogeochemical cycle of land plants, and about 0.53–0.63 Tg B/yr is
carried from land to sea by rivers. The biogeochemical cycle of boron in the sea includes
4.4 Tg B/yr circulating in the marine biosphere, and an annual loss of 0.47 Tg B/yr to the
oceanic crust via a variety of sedimentary processes that collectively remove only a small
fraction of the total annual inputs to the oceans. Thus with our current understanding of
the global biogeochemistry of B, the atmospheric budget shows outputs > inputs, while
the marine compartments show inputs > outputs. Despite these uncertainties, it is clear
that the human perturbation of the global B cycle has more than doubled the mobilization
of B from the crust and contributes significantly to the B transport in rivers. INDEX
TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0330
Atmospheric Composition and Structure: Geochemical cycles; 1610 Global Change: Atmosphere (0315,
0325); 1615 Global Change: Biogeochemical processes (4805); 4825 Oceanography: Biological and
Chemical: Geochemistry; KEYWORDS: atmospheric deposition, biogeochemistry, biomass burning, boron,
geochemical cycles, human impacts, hydrothermal activity
Citation: Park, H., and W. H. Schlesinger, Global biogeochemical cycle of boron, Global Biogeochem. Cycles, 16(4), 1072,
doi:10.1029/2001GB001766, 2002.

1. Introduction 1987; Goldberg, 1997; Xu et al., 2001]. In seawater, equili-

brium reactions of B contribute to alkalinity and to the
[2] Boron (B) is an essential element for life and poten-
buffering of pH [Holmén, 2000]. Recent interest in the B
tially limiting to the growth of marine and freshwater
content of seawater stems from the observation that the
phytoplankton [Subba Rao, 1981] and to the growth of
isotopes of B (10B versus 11B) are fractionated during co-
land plants in certain habitats [Stone, 1990; Bernier and
precipitation in carbonates [Vengosh et al., 1991; Hemming
Brazeau, 1988]. B is essential for plant nitrogen assimila-
and Hanson, 1992]. The fractionation is pH-dependent,
tion [Camacho-Cristobal and Fontes, 1999], for the devel-
potentially allowing a reconstruction of the paleochemistry
opment of root nodules in N-fixing plants [Bolanos et al.,
of seawater and past variations in atmospheric CO2 content
1994], for the formation of polysaccharide linkages in plant
[Spivack et al., 1993; Sanyal et al., 1995; Pearson and
cell walls [O’Neill et al., 2001], and for a variety of other
Palmer, 2000].
processes in higher plants [Shelp, 1993]. It has recently
[3] The global cycle of B comprises terrestrial, marine,
been identified as a signaling mechanism in bacteria [Chen
and atmospheric components: the latter driven by a consid-
et al., 2002]. B is normally found as borate (BO3 3) in soils,
erable flux of gaseous B in the form of boric acid (H3BO3)
where its availability is controlled by interactions with soil
that is derived from seasalt aerosols. Although there have
carbonates and oxides/hydrous oxides of Fe and Al, in
been several attempts to balance a budget for B in the
reactions that are analogous to those for phosphate [Jin et al.,
oceans [You et al., 1993; Smith et al., 1995; Lemarchand et
al., 2000], none considers the exchange of B between
1
seawater and the atmosphere, which is potentially the
Now at Department of Geosciences, Princeton University, Princeton,
New Jersey, USA.
largest flux in its global cycle [cf. Fogg and Duce, 1985].
As is the case for many elements, the global cycle of B has
Copyright 2002 by the American Geophysical Union. been altered by human activities that currently extract >4
0886-6236/02/2001GB001766 Tg/yr ( = 1012 g/yr) of boron ores from the Earth’s crust

20 - 1

20 - 2 PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON
Figure 1. Model for the global biogeochemical cycle of boron.
[U.S. Geological Survey (USGS ), 2000]. Large amounts of
B are used in the manufacture of borosilicate glass, deter-
gents, and fire extinguishing materials, and in the disposal
of nuclear waste.
[4] Here we provide a compilation and synthesis of data
from the literature, leading to a pictorial model for the
global biogeochemical cycle of B (Figure 1). In this
compilation, we describe the uncertainty associated with
estimates of the major fluxes of boron, while assuming
that errors in the minor fluxes do not alter the global
picture. Where we have incorporated the data of previous
authors, we have retained the number of significant digits
published in their work. This quantitative synthesis of the
global B cycle offers context to assess the current human
impact and to identify areas of uncertainty in our current
understanding.
2. Literature Review and Results
2.1. Atmospheric Flux
2.1.1. Inputs
2.1.1.1. Seasalt Aerosols
[5] The gas-phase concentration of B in the atmosphere,
which is assumed to be boric acid vapor (H3BO3) [Anderson
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et al., 1994], is nearly always higher than the Henry’s Law
prediction of the concentration in equilibrium with dis-
solved B(OH) 3 in seawater (4.6 mg B/kg; Holland
[1978]). The higher concentration of B in the atmosphere
is thought to be derived from the evaporation of boric acid
vapor from seasalt aerosols as they dry. As a result, B/Na in
seasalt aerosols is normally about 5.6 times less than B/Na
in seawater [Rose et al., 2000a]. Despite this partitioning
into gaseous and particulate phases, the total input of B to
the atmosphere can be calculated from estimates of the
formation of seasalt aerosols, assuming that there is no
fractionation of ions during the injection of bubbles to the
atmosphere, as suggested by Fogg and Duce [1985; cf.
Glass and Matteson, 1973].
[6] The annual production of seasalt aerosols is estimated
at 10  1015 g/yr [Möller, 1990] to 11.7  1015 g/yr [Gong
et al., 1997]. Both estimates are compatible with an earlier
estimate of 8 –22  1015 g/yr for the annual dry deposition
of seasalt over the world oceans [Erickson and Duce, 1988].
With an average seawater salinity of 35%, the annual input
of B to the atmosphere could range from 1.0 to 2.3 Tg B/yr.
A similar calculation, using the Cl budget for the atmos-
phere [Graedel and Keene, 1995] and a chlorinity ratio of
0.00024 in seawater, yields an estimate of 1.44 Tg B/yr. We
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PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON 20 - 3

use the median of these values, 1.44 (1.0 – 2.3) Tg B/yr, in
our budget for B in the atmosphere.
2.1.1.2. Volcanoes
[7] Citing a single value for the B/SO2 ratio in volcanic
emanations, Fogg and Duce [1985] calculated the gaseous
flux of B from volcanoes as 2.1 Tg B/yr, based on an estimate
of the annual flux of SO2 from volcanoes worldwide.
Anderson et al. [1994] gathered additional data that indicated
that the B/SO2 ratio of 0.14 available to Fogg and Duce was
unusually high. Anderson et al. used a mean B/SO2 ratio of
0.02 from Mount St. Helens to calculate global volcanic
emissions of 0.24 Tg B/yr, using an estimate of 10 TgS/yr as
the annual flux of SO2 from volcanoes [Bates et al., 1992].
Our compilation of data (Table 1) indicates a median B/SO2
ratio of 0.0011(weight/weight) in volcanic emissions and a
global flux of 0.022 Tg B/yr from this source.
[8] A similar approach can be followed using the B/Cl
ratio in volcanic gases and the estimate of 2 Tg/yr of Cl
emitted from volcanoes [Graedel and Keene, 1995]. Both B
and Cl are partitioned into the gaseous phase in high-
temperature geothermal systems [Arnórsson and Andrés-
dóttir, 1995]. A compilation of B/Cl ratios in volcanic gases
shows a median ratio of 0.0084 (Table 1), and a global
estimate of B emission of 0.017 Tg/yr from volcanoes. With
the assumption that all gaseous B and Cl emitted by
volcanoes are subsequently captured and deposited in their
ash, Koutz [1971] estimated that volcanoes contribute 0.01
Tg B/yr to the atmosphere: not only about half as large as
the estimates presented here, but also much lower than
previous values.
[9] The global flux of B from volcanoes to the atmosphere
is undoubtedly varying from year to year, but our estimate of
gaseous emissions, 0.017 – 0.022 Tg B/yr, provides the likely
range of values for the annual volcanic flux to the atmos-
phere. The B fluxes derived from the gaseous ratios of B/Cl
and B/SO2 seem to agree well and are much lower than
previous estimations. Given this small flux, we have not
attempted to provide an uncertainty estimate for it.
[10] Fogg and Duce [1985] estimated the B flux in
volcanic particulates as 0.0003 Tg B/yr by taking the
volcanic particulate emission as 4 – 150 Tg/yr and its B
concentration as 30 ± 9 (standard error, SE) ppm. Anderson
et al. [1994] estimated the global flux as 0.21 Tg B/yr based
on the concentration of B in volcanic particulates collected
from Mount St. Helens. The annual volcanic dust produc-
tion is estimated as 35 Tg/yr [Jonas et al., 1995]. Using
6.27– 13.4 ppm as the mean values for the B concentration
in volcanic ash [Anderson et al., 1994], the global boron
flux via volcanic particulates lies between 0.00022 and
0.00047 Tg B/yr. This new estimate is very small compared
to the emission of gaseous B from volcanoes, and it can be
ignored in the global budget.
2.1.1.3. Eolian Dust
[11] Tegen and Fung [1995] estimated the annual produc-
tion of particulates from wind erosion, i.e., global eolian
dust, as 3000 Tg/yr, at the upper limit of a compilation of
estimates by Duce [1995]. Although some sedimentary
deposits have higher concentrations, we assume that the B
concentration in soil is similar to the mean B concentration
of the continental crust, 11 ppm [Wedepohl, 1995], so the

Table 1. Ratio of Boron to Cl and SO2 Gases Collected From Various Volcanic Regions
Site Emissions Description Ratio B/Cl (wt/wt)a Ratio B/SO2 (wt/wt) Reference
North America
5
Kilauea, Hawaii plume <6.4  10 Anderson et al. [1994]
4
plume <1.7  10 Anderson et al. [1994]
Mt. St. Helens, Wash. active vent 0.0016 Anderson et al. [1994]
>0.06 Anderson et al. [1994]

Central America
Poas fumaroles <4.3  10 5 Anderson et al. [1994]
Costa Rica 2.6  10 5 Anderson et al. [1994]
El Chichon, Mexico lake fumes 0.19 Anderson et al. [1994]
0.90 Anderson et al. [1994]

Japan
Hokkaido gaseous 0.053 0.038 White and Waring [1963]b

Russia, Kamchaka
Shelveluch Volcano center crater, 1953 0.0003 0.0062 White and Waring [1963]b

New Zealand
Wairakei area steam 0.0126 Hulston and Lupton [1996]
Ohaaki-Broadlands well-bleeding 0.036 Hulston and Lupton [1996]

Iceland
Hekla, Iceland eruption in 1947 0.00126 0.0006 White and Waring [1963]b

Other Region
crator 0.0115 0.0253 Basharina [1965]b
c
Median 0.0084 0.0011
a
wt/wt = weight(g)/weight(g).
b
From Koutz [1971].
c
Arithmetic mean of the total samples.

20 - 4 PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON
flux of B to the atmosphere is estimated as 0.033 Tg B/yr.
For the assessment of the Intergovernmental Panel on
Climate Change, Jonas et al. [1995] indicate a global flux
of soil aerosols on the order of only 1500 Tg/yr, which
would indicate a B flux of 0.017 Tg/yr to the atmosphere
from this process. Neither estimate offers a significant flux
of B to the atmospheric budget.
2.1.1.4. Emissions From Vegetation
[12] Nriagu [1979] estimated the total particulate emis-
sion by plants as 75 Tg/yr [Fogg and Duce, 1985]. If the
mean boron concentration in plant tissues is about 50 ppm,
then each year 0.004 Tg B/yr would be emitted to the
atmosphere by plant-derived aerosols, which would make
only a minor contribution to the atmospheric budget.
2.1.1.5. Fossil Fuel Burning
[13] Global coal combustion has increased from 3200 Tg/yr
in 1976 to 4700 Tg/yr in 1999 [Energy Information Admin-
istration, 1999], possibly leading to an increase in the
gaseous emission of B from coal combustion to as much as
0.18 Tg/yr in 1999 (calculated following the works of Fogg
and Duce [1985] and Anderson et al. [1994]). Anderson et al.
estimated that particulate emissions of B from worldwide
coal combustion add 0.013 Tg B/yr to the atmosphere. Thus
we estimate that present-day B release from coal combustion
is likely to be about 0.20 Tg/yr.
[14] World petroleum consumption in 1999 was about
3300 Tg/yr [Energy Information Administration, 1999] and
this released 0.00049 Tg B/yr to the atmosphere [Anderson
et al., 1994]: a minor contribution to the global budget for B
in the atmosphere.
2.1.1.6. Biomass Burning
[15] Andreae and Merlet [2001] estimate the annual
combustion of biomass as 8600 Tg/yr (= 3870 Tg C)
globally – in the range of earlier estimates from 2000 to
5000 Tg C/yr [Crutzen and Andreae, 1990; Hao and Liu,
1994]. This new value represents the sum of carbon released
during deforestation, natural biomass fires, biofuel burning,
charcoal making, charcoal burning, and the combustion of
agricultural residues. Assuming that the boron concentration
in biomass ranges from 30 to 50 ppm [Nriagu, 1979], the
boron flux to the atmosphere from biomass burning lies
between 0.26 and 0.43 Tg B/yr.
2.1.1.7. Other Human Activities
[16] During the mining and processing of boron-containing
minerals, dust and gaseous boron are released to the atmos-
phere, which are quantified as about 0.003 Tg B/yr by Argust
[1998], and 0.009 Tg B/yr by Anderson et al. [1994]. About
2.3  1012 g /yr of boron-containing compounds are used in
the world [Lyday, 1982]. Considering 30% of anhydrous
boric acid (B2O3) and 11% of borax (Na12B4O7
10H2O) is
boron, Argust estimated the global industrial use of B at 0.31
Tg/yr. Anderson et al. estimated that the release of B to the at-
mosphere during manufacturing would be about 0.02 Tg/yr.
They also estimated the boron release to the atmosphere by
incineration as 0.045 Tg B/yr using the global amount of
materials incinerated each year, as estimated by Nriagu
[1989]. The sum of these industrial activities is likely to
release about 0.07 Tg B/yr to the atmosphere.
[17] All estimates of the atmospheric release of B are
based on an assumption that B is mainly in vapor form of
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boric acid in the atmosphere. Some boron halogens such as
BF3, BCl3, and BBr3 may be produced during biomass
burning, fossil fuel combustion, incineration, and manufac-
turing. Most of these are heavier than the density of air or/
and quickly convert into B(OH)3 in the atmosphere [Braker
and Mossman, 1980].
2.1.2. Outputs
2.1.2.1. Rain Precipitation (Wetfall)
[18] The concentration of B in rainfall has been measured
in many places worldwide over the last 30 years. As
summarized in Table 2, rainwater from continental sites
contains less B than that from coastal and marine sites.
Multiplying the mean concentration of B in marine rain (10
± 2.3 (SE) ppb) by an estimate of the annual precipitation
over the oceans [Chahine, 1992] indicates 3.87 ± 0.89 (SE)
Tg B/yr as the annual flux of B in wet deposition over the
ocean. Since the values in this limited data set are not
normally distributed, we prefer to use the median concen-
tration (6.6 ppb), which yields an estimate of 2.54 Tg B/yr
for wet deposition over the oceans: at the lower end of the
range estimated by both Fogg and Duce [1985] and
Anderson et al. [1994]. The wet deposition over the con-
tinents, calculated with either the mean, 4.89 ± 1.2 (SE)
ppb, or median (4.35 ppb) value, is estimated as about 0.50
Tg B/yr (Table 2).
2.1.2.2. Dry Deposition of Particulate Boron
[19] B exists as both particulates (Bp) and gases (Bg) in
the atmosphere, with a 1:4 ratio between these forms over
the land and a 1:22 ratio over the ocean (Table 3).
Particulate B exists with concentrations of 2 ± 0.44 (SE)
ng/m3 over the remote oceans and 4.5 ± 1.03 (SE) ng/m3
over the continents. These particles are removed by wet and
dry deposition. On land, dry deposition of various substan-
ces is often equal to the wet deposition [Schlesinger, 1997],
so the global dry deposition of B on land could be as large
as 0.50 Tg B/yr. This estimate is likely to represent the
upper limit, as larger values are incompatible with the mass
balance budget for B in the atmosphere.
[20] Erickson and Duce [1988] estimated the amount of
seasalt aerosols removed from the atmosphere by dry
deposition over the world’s oceans as 0.8 – 2.2  1016
g/yr globally. Assuming that the majority of the atmospheric
particulates over the oceans are from seasalt aerosols, and
that the total aerosol content of the marine atmosphere and
its B concentration (Bp) are about 10,000 and 1.0 ng/m3 atm
(Table 3), respectively [Warneck, 1988], the dry deposition
of particulate B over the oceans would be 0.8– 2.2 Tg/yr.
This estimate for dry deposition of B at sea is about 10– 30
times larger than the global estimate of dry deposition (0.07
Tg B/yr) calculated by Anderson et al. [1994], using 0.2
cm/s as the dry deposition velocity [McCarthy, 1988]. The
aerosol content of the marine atmosphere shows great
spatial and temporal variation, so better estimates of the
dry deposition of B will require further study [Jahiruddin et
al., 1998].
2.1.2.3. Gaseous B Absorption Into the Seawater
[21] At 25
C, the concentration of boric acid vapor in the
atmosphere over the oceans predicted with Henry’s law con-
stant (H = 5  10 9g mair 3/g mseawater 3) is 20 ng/m3
[Duce, 1996], while field measurements report 40– 50 ng/m3
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PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON 20 - 5

Table 2. Boron Concentration in Rainwater From Various Regions

Sample Areas Description [B], ppb (Mean) Reference
Continental Sites
Mississippi, USA continental 6.8 Boyd and Walley [1972]
Aiken, SC, USA continental 6.3 Boyd and Walley [1972]
Niwot ridge, Colo., USA continental 6.6 Fogg and Duce [1985]
College Park, Md., USA continental 1.0 Anderson et al. [1994]
Guildford, Surrey, UK inland 8.67 Mather and Porteous [2001]
Blewbury, Oxfordshire, UK inland 5.7 Mather and Porteous [2001]
Inverey, UK inland 10 Neal et al. [1997]
Himalaya continental 0.97 Rose et al. [2000b]
(At elevations over 1000 m) continental 15
continental 3
continental 0.97
continental 0.97
continental 0.97
Czech Republic continental 1.5 Kockova et al. [1998]
Mediana 4.35
Wetfall over the continents 1.1  1017 L/yr  4.4 ppb 0.48 Tg B/yr

Marine/Coastal Sites
Banchory, UK coast 26.4 Neal et al. [1997]
Isle of Wight, UK coast 15.8 Mather and Porteous [2001]
Narrangansett, R. I., USA coast 3.3 Fogg and Duce [1985]
American Samoa, USA open ocean 3.3 Boyd and Walley [1972]
Fogg and Duce [1985]
Enewetak, USA open ocean 4.5 Boyd and Walley [1972]
Fogg and Duce [1985]
Gulf Coast, Fla., USA (winter) coast 11.9 Martens and Harriss [1976]
Gulf Coast, Fla., USA (summer) coast 8.5 Martens and Harriss [1976]
Japan open ocean 4.7 Nishimura et al. [1973]
Lincoln, New Zealand coast 22.7 Herrmann [2001]
Barrytown, New Zealand coast 11.9 Herrmann [2001]
Mediana 6.6
Wetfall over open ocean/coast 3.85  1017 L/yr  6.6 ppb 2.54 Tg B/yr
a
Median is used due to the skewed data distributions. The mean values for continental and marine sites are 4.89 ± 1.16
(SE) ppb and 10.06 ± 2.3 (SE) ppb, respectively.

(Table 3). Therefore, the oceans would seem to serve as a
sink for gaseous boron (Bg) [cf. Nishimura and Tanaka,
1972]. This flux has been estimated at 1.6 Tg B/yr by Duce
using the dry deposition flux equation expressed as FA =
VdDCa where FA is the mass flux (mg/m2/s), Vd is the dry
deposition velocity for the chemical, and DCa is the
concentration difference of the chemical between the ocean
and the atmosphere (ng/m3). Duce [1996] and Anderson et
al. [1994] estimated DCa as 30 ng/m3 using the expected
boron concentration in the marine atmosphere of 20 ng/m3
derived by H at 25
C. When the temperature is lower than
20
C, however, Fogg and Duce [1985] show that seasalt
should become a ‘‘sink’’ for the boric acid gases. At the
mean temperature of Earth, 15
C, DCa would be three times
lower (i.e., 10 ng/m3) than at 25
C and the global flux to the
sea surface would be 0.5 Tg B/yr. Although our new
estimate of the flux of B gas from the atmosphere to the
world’s oceans is relatively small, we might expect some
geographic variation in its magnitude.
2.1.2.4. Atmospheric Deposition, Summary
[22] Even if we assume that there is no net flux of gaseous
boron to the sea, the total outflow of B from the atmosphere,
4.3 Tg B/yr, is at least two times greater than the known
sources of B in the atmosphere (Table 4). Uncertainties in
estimates of some of the larger flux terms do not preclude a
balanced budget. Since the mean residence time for B in the
atmosphere is only 5 – 13 days [Duce, 1996], the reasons for
an imbalance are unclear, but better estimates of the sources
and sinks of B in the atmosphere must await further
investigation.
2.2. Land Flux
2.2.1. Input
2.2.1.1. Weathering
[23] Besides wet deposition, which we have already
examined as part of the atmospheric budget, the other
major source of boron on land derives boron from rock
weathering, largely from carbonate rocks [You et al., 1993].
Garrels and MacKenzie [1971] estimated the amount of
chemical weathering as 3.93  1015 g/yr, which yields a
weathering flux of 0.043 Tg B/yr using the mean B
concentration of 11 ppm in the continental crust [Wede-
pohl, 1995]. Similarly, the boron mobilized by mechanical
weathering is estimated as 0.15 Tg B/yr, using the global
estimate of mechanical weathering and the mean concen-
tration of B in the continental crust [Milliman and Meade,
1983].
2.2.1.2. Anthropogenic Mobilization
[24] Borax and anhydrous boric acid are the most com-
monly used B compounds in industry. They play an
important role in the global boron budget since the pertur-
bation caused by intensive human mining of B contributes
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20 - 6 PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON

Table 3. Atmospheric B Concentration Over Continent and Ocean

Range (mean) Total [B], ng/m3 Reference
3 3
Bg, ng/m Bp, ng/m
Continental
College Park, Md. 5.4 – 22.9 (13.2) 4.7 – 10.7 (6.3) 19.5 Anderson et al. [1994]
5.0 – 30.4 (14.8) 0.5 – 8.8 (4.4) 19.2
5.1 – 32.2 (20.7) 3.2 – 6.7 (4.8) 25.5
Gaithersburg, Md. 1.0 – 9.2 (4.0) 0.6 – 13.6 (6.1) 10.1 Anderson et al. [1994]
1.0 – 9.2 (4.0) 1.0 – 2.6 (1.8) 5.8
Fairbanks, Alaskaa 0.2 – 0.9 (0.5) 5.2 – 17.6 (12.2) 12.7 Anderson et al. [1994]
Eastern, Ohiob 14 – 223 (77) 0.02 – 6.7 (1.9) 78.9 Fogg and Duce [1985]
Bellevue, Colo. 1.4 – 35 (16) 0.1 – 3.3 (1) 17 Fogg and Duce [1985]
... 1.3 – 4.3 (2.6)
Niwot Ridge, Colo. ... 2.8 – 6.0 (4.1) Fogg and Duce [1985]
Meanc 18.7 ± 8.68 4.5 ± 1.03 23.6 ± 8.19

Coastal Sites
Wallops Is, Va. 70.3 2.9 73.2 Anderson et al. [1994]
Lewes, Del. 3.5 3.7 7.2 Anderson et al. [1994]
La Jolla, Calif. 35 – 167 (71) 0.71 – 4.7 (2.7) 73.7 Fogg and Duce [1985]
Narragansett, R. I. 4.1 – 199 (48) 0.01 – 7.8 (2.1) 50.1 Fogg and Duce [1985]
Canterbury Plain, New Zealand 23.8 Hermann [2001]
(Springston/Lincoln)
Intramontane basin, New Zealand 17.3 Hermann [2001]
(Cass/Craigieburn)
West coast, New Zealand 55.1 Hermann [2001]
(Barrytown)
Tokyo Bay, Japan 42.5 (n = 2) Miyata et al. [2000]

Remote Marine Sites

High Point, Bermuda 10.5 1.1 11.6 Anderson et al. [1994]
Cape Kumukahi, Hawaii 25 0.5 25.5 Anderson et al. [1994]
Oahu, Hawaii 65 – 117 (97) 0.18 – 1.2 (0.56) 97 Fogg and Duce [1985]
American Samoa 1.5 – 5.2 Fogg and Duce [1985]
Open Ocean, Japan 88 (n = 14) Miyata et al. [2000]
Mean 46.5 ± 13.2 2.11 ± 0.44 47.1 ± 8.87
a
As indicated by the authors.
b
Polluted site.
c
Means are used with standard error.

B to its global cycle. The USGS [2000] recently estimated boric acid, borax, colemanite, and ulexite, is about 4.4 Tg
the global reserves of boron ores as about 170 Tg, which B [USGS, 2000], resulting in 0.31 Tg B/yr entering indus-
contain 30– 60 Tg B as determined by Argust [1998]. The trial use [Argust, 1998]. About half of processed boron is
annual extraction of boron-containing minerals, such as used in the manufacture of glass, fiberglass, and ceramics,
while the remainder is consumed in products that potentially
increase the supply of B that circulates in the environment
Table 4. Atmospheric Budget of Boron
[Argust, 1998]. For example, 6% of the total production is
Sources Budget, Tg B/yr used in making soap and detergent, 4% in making fire
Volcanoes (gas) 0.017 – 0.022 retardants, and 3% in making agricultural products. The
Soil dust 0.017 – 0.033 total human extraction of B from the Earth’s crust is
Plant aerosols 0.004 approximately 1.5 times that mobilized from the Earth’s
Fossil fuel combustion 0.20
Biomass burning 0.26 – 0.43
crust by rock weathering (Table 5).
Other human activities 0.07 2.2.2. Output
Seasalt 1.44 ± 0.9 2.2.2.1. River Discharge
Total 1.1 – 3.1 [25] The amount of dissolved boron transported in rivers
Sinks Budget, Tg B/yr has been estimated by Harriss [1969], Seyfried et al.
Wetfall [1984], and Lemarchand et al. [2000], with estimates
Land 0.5 ranging from 0.38 to 0.48 Tg B/yr. The suspended sediment
Sea 2.54 delivered to oceans is 13.5  1015 g/yr [Milliman and
Meade, 1983] and the mean boron concentration in crustal
Dryfall
Land 0.5 materials is about 11 ppm [Wedepohl, 1995], so the
Sea expected amount of boron flux via river particulates is
(Bp) 0.8 – 2.2 about 0.15 Tg B/yr. Thus the total transport of boron in
(Bg) 0.5 rivers removes about 0.53– 0.63 Tg B from the Earth’s land
Total 4.84 – 6.24
surface each year.
 19449224, 2002, 4, Downloaded from https://agupubs.onlinelibrary.wiley.com/doi/10.1029/2001GB001766 by Cochrane Greece, Wiley Online Library on [28/12/2022]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON 20 - 7

Table 5. Land Budget of Boron seawater flow rate from hot springs which have an average
Sources Budget, Tg B/yr
B concentration of 5.5 ppm. Our global estimate of the
high-temperature flux, 0.08 Tg B/yr, is derived as the mean
Atmospheric deposition
Wetfall 0.5
of these available values. In addition, fluid expelled from
Dryfall 0.5 accretionary prisms in subducting crust is estimated to carry
Rock weathering (chemical and mechanical) 0.193 about 0.02 Tg B/yr, another mechanism that releases B to
Mining extraction the ocean [Lemarchand et al., 2000]. These inputs are small
Mobile 0.15 compared to the delivery of B in rivers and by wetfall and
Immobile (e.g., glass) 0.16
Total 1.5 dryfall on the ocean’s surface.
2.3.2. Outputs
Sinks Budget, Tg B/yr
[30] Most studies of the geochemical cycle of boron in the
Rivers 0.53 – 0.63 oceans have identified six outputs: incorporation in carbonate
Plant aerosols 0.004
Dust 0.017 – 0.033 minerals, deposition in estuaries and sediment adsorption,
Biomass burning 0.26 – 0.43 pore water burial, low-temperature hydrothermal flux, sili-
Incineration 0.07 cate formation, and the preservation of sedimentary organic
Fossil fuel combustion 0.2 matter (Table 6). These are the long-term removals of B from
Landfill 0.29
Total 1.37 – 1.66
the seawater. However, as we shall see, seasalt production
removes a greater amount of boron (1.44 Tg B/yr) from the
ocean than removed by all of these combined together, and it
transfers B through the atmosphere to the land. Thus it should
2.2.2.2. Human Influences not be omitted from the list of oceanic outputs. Our view of
[26] Of the worldwide industrial consumption of boron, the global boron cycle, which includes transfers between the
0.31 Tg B [Argust, 1998], about 0.04 Tg B is released to the atmosphere and the oceans, is analogous to recent treatments
environment as a result of the use of soap and detergent (6%), of the global cycles of Cl [Graedel and Keene, 1995] and S
fertilizer (3%), and application of fire retardant (4%). Since [Brimblecombe et al., 1989], which also consider seawater-
most of these products are discharged into the rivers, we derived fluxes with short mean residence time in the atmos-
estimate that about 7% of the fluvial discharge of B is a phere.
consequence of human usage. An anthropogenic discharge of 2.3.2.1. Incorporation in Marine Carbonates
boron into rivers (0.025 Tg B/yr) was estimated by Lemarc- [31] Vengosh et al. [1991] provided the highest estimate
hand et al. [2000], who also suggested that about 7% of the of boron uptake by the precipitation of marine CaCO3,
total river content of boron has an anthropogenic origin. because their estimate of the boron concentration in normal
[27] The majority of boron products are likely to stay carbonates is about two times higher than other values
within the human society (e.g., 53% in glass industry), but reported in the literature. Spivack et al. [1987] indicated
they may return to the soil and to the groundwater after that the average boron content of limestones cannot be
being discarded and buried in landfills. Argust [1998] taken as representative of biogenic carbonates, due to the
estimated the amount of boron that enters landfills as 0.29 presence of even small amounts of clay contaminant.
Tg B/yr. Spivack et al. report B concentrations of 9 – 15.1 ppm in
2.2.2.3. Biogeochemical Cycling carbonates, using data from Furst et al. [1976], who
[28] The average B content in terrestrial organic matter is recovered samples precipitated directly from seawater.
between 30 and 50 ppm [Stone, 1990]. The global terrestrial
net primary production is reported by Field et al. [1998] as
56.4 Pg C/yr, so the global plant uptake of boron from soils Table 6. Ocean Budget of Boron
can be calculated as 4.5 Tg B/yr. Once used by plants, most
boron is fixed into cell walls and is not recycled internally. Sources Budget, Tg B/yr
Some B is returned to the atmosphere in the emission of Sea wetfall 2.54
plant aerosols or during biomass burning, but the majority is Sea dryfall 0.8 – 2.2
Gaseous adsorption 0.5
returned to the soil when plants die. Thus the internal
biogeochemical cycle of B on land is several folds larger River
than the inputs and outputs from the continents (Table 5). Dissolved 0.38 – 0.48
Particulates 0.15
2.3. Oceanic Flux High T-hydrothermal 0.08
2.3.1. Inputs Fluid expelled 0.02
Total 4.47 – 5.97
2.3.1.1. High-Temperature Hydrothermal Flux and
Expelled Fluid Sinks Budget, Tg B/yr
[29] In addition to atmospheric inputs and the riverine Carbonates 0.04
flux just described, You et al. [1993] suggested that high- Marine sediment 0.18
Silicates 0.004 – 0.032
temperature hydrothermal vents are a significant source of Pore water 0.006
boron to ocean waters. Spivack and Edmond [1987] and Low T-flux 0.08 – 0.27
You et al. estimated the boron flux through hydrothermal Organic burial 0.014
vents as 0.004 – 0.042 Tg B/yr, while Seyfried et al. [1984] Seasalt 1.44 ± 0.9
Total 0.86 – 2.88
estimated it as 0.13 Tg B/yr. Seyfried et al. used the

20 - 8 PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON
Pennisi et al. [2000] report the mean concentration of B in
marine carbonates as 12.5 ppm. An upper-limit estimate for
boron removal from ocean waters is provided by the total
carbonate production, 3200 g CaCO3/yr by Milliman
[1993], which would carry 0.04 Tg B/yr, intermediate
between the prior estimates of Spivak et al. [1987]
(0.005 – 0.012 Tg B/yr) and Vengosh et al. [1991] (0.064
Tg B/yr). We do not consider aragonite or dolomite as a
boron sink because aragonite is more easily dissolved than
calcite, and only small amounts of dolomite are deposited
in today’s oceans.
2.3.2.2. Deposition in Estuaries and Sediment
Adsorption
[32] Liss and Pointon [1973] first noted the removal of B
during the mixing of river and seawaters. Spivack et al.
[1987] estimated estuarine removal as about 0.099 Tg B/yr,
which includes B removed in estuaries before their waters
enter the oceans and/or during mixing of water in tidal
areas. In addition to boron buried in estuarine sediment,
dissolved boron is adsorbed on clay minerals and added to
marine sediments globally. Estimates of the boron removal
by clay adsorption agree within a factor of three among
different studies [Seyfried et al., 1984; Vengosh et al., 1991;
Smith et al., 1991], with a mean flux of 0.18 Tg B/yr, which
we take as the best estimate of the total removal of B from
the oceans by this process.
2.3.2.3. Pore Water Burial
[33] Pore water burial has also been suggested as a
mechanism of boron removal from seawater, estimated by
Spivack and Edmond [1987] at 0.008 Tg B/yr. If the pore
water burial of B and Cl is proportional to their concen-
tration in seawater and 25 Tg Cl/yr is buried by this process
globally [Berner and Berner, 1996], then we estimate that
0.006 Tg B/yr is removed from the oceans by pore water
burial each year. Both estimates constitute only a minor flux
in the global B cycle.
2.3.2.4. Low-Temperature Hydrothermal Flux
[34] Low-temperature hydrothermal circulation captures
soluble elements from seawater in the oceanic crust.
Although estimates of the removal of B from seawater by
this process range from 0.08 to 0.27 Tg B/yr, the prepon-
derance of values is found at the lower end of this range
(Table 7). This estimate of the removal of B in low-
temperature hydrothermal systems may be too low as
recent studies have identified considerable areas of off-axis
hydrothermal activity [Kelley et al., 2001] that may repre-
sent additional B sinks. In any case, considering the
balance of high- and low-temperature processes, hydro-
thermal systems seem to provide a net sink of B from the
oceans.
Table 7. Literature Review of Low T-Flux Estimation
Low T-Flux Estimation, Tg B/yr Reference
Experimental value 0.16 – 0.19 Seyfried et al. [1984]
0.14 Spivack and Edmond [1987]
0.083 Thompson [1983]
0.27 Smith et al. [1995]
0.11 You et al. [1993]
Estimate 0.08 – 0.27 This study
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2.3.2.5. Biogenic Silicates
[35] Silicate formation by biogenic processes also removes
boron from the seawater, burying it into marine sediment.
Tréguer et al. [1995] provided an estimate of the input of
dissolved Si to the world’s oceans, 171 Tg Si/yr, largely
derived from chemical weathering of the land surface.
Assuming a steady state Si concentration in seawater, this
new estimation of Si input would indicate a loss of about
0.03 Tg B/yr by incorporation in marine silicates, calculated
assuming 84 ppm of B in silicates [Pennisi et al., 2000].
Earlier, assuming B content of 75 ppm in diatomaceous
material, Harriss [1969] estimated that the production of
biogenic silicates carries 0.027 Tg B/yr to marine sediments.
[36] Alternatively, Spivack et al. [1987] suggested 11 ppm
of boron in biogenic opal. Given this concentration, they
estimated the removal of boron from the oceans by the
formation of biogenic silica at 0.0038 Tg B/yr. Tréguer et al.
[1995] estimated that only 3% of the gross production of
biogenic silicates is preserved in marine sediments, which
would carry 0.004 – 0.032 Tg B/yr to the sediments, depend-
ing on assumptions regarding the B content of opal. Thus
for the global budget, we estimate that the formation of
biogenic silicates in the oceans carries <0.03 Tg B/yr to
marine sediments.
2.3.2.6. Biogeochemical Cycling and the Organic Sink
[37] Biological uptake of boron by primary production was
proposed as an important sink for boron in ocean [Harriss,
1969]. However, most organic materials are degraded
quickly in the oceans, so biotic uptake should be considered
as a form of internal cycling that does not contribute to the
long-term removal of B from seawater. Pennisi et al. [2000]
estimated a boron concentration of 43 ppm in marine
organisms. Assuming marine net primary production is
48.5  1015 g C/yr [Field et al., 1998], with a carbon content
of 50%, 4.3 Tg B/yr must circulate in the internal biogeo-
chemical cycle of boron in ocean. If 0.157  1015 g C/yr
represents the net incorporation of organic carbon into
oceanic sediments [Berner, 1982], then the estimated boron
deposition in organic sediments will be about 0.014 Tg B/yr.
3. Discussion
[38] Tables 4 – 6 summarize the boron budget in each
realm of its global cycle. The budget for land is remarkably
well balanced, whereas for the atmosphere outputs > inputs,
as has been noted previously [Duce, 1996].
[39] We believe that the annual deposition of B in
precipitation (wetfall) is the best-known value in the atmos-
pheric budget. By itself, the flux in wetfall is roughly
double the estimate of the largest input to the atmosphere:
1.44 Tg B/yr from seasalt aerosols (Table 4). It is possible
that we have overestimated the wet and/or dry deposition of
B from the atmosphere, particularly over the oceans. How-
ever, the imbalance in the atmospheric budget for B would
persist, even if the B content of marine rains is half of the
average value that we derive from available data (Table 2).
By using the Bg and Bp concentrations from Table 3, we
calculated the pool of Bg = 0.14 Tg B, and Bp = 0.024 Tg B
in the troposphere, and the mean residence time of boron in
the atmosphere is 14– 21 days (11 – 18 days for Bg and 2 – 3

PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON
Table 8. Comparisons of Sources of Materials to the Global Atmospherea
Element Anthropogenic
Industrial/Fossil fuel Biomass Burning
SO4 (S) 90 1.89
B 0.26 0.35
C1 5 0.5
a
All data in Tg/yr, with those for S and Cl taken from Schlesinger [1997].
days for Bp, respectively). Given these short mean resi-
dence times, we suspect that we have underestimated or
overlooked other processes that may contribute B to the
atmosphere.
[40] We used several different approaches to estimate the
seasalt injection of B to the atmosphere. These show good
agreement, and we believe this estimate is well constrained.
In previous work, Fogg and Duce [1985] estimated 1.5 Tg
B/yr as the amount of boron reaching the atmosphere from
volcanoes. However, the additional data compiled here
indicate that the contribution of B to the atmosphere by
volcanoes is relatively small. Among other potential sour-
ces, higher fluxes of B to the atmosphere from human
activities are incompatible with the widespread observation
that the B content of rainfall is greater over the oceans.
Clearly, resolution of the atmospheric budget for B will
require further study.
[41] Imbalance in the budget for B in the oceans derives
from an imbalance in the large fluxes of B between the
oceans and the atmosphere. Indeed, without these fluxes,
the input in river flow closely balances the sum of various
outputs by sedimentary processes and hydrothermal alter-
ation, as noted by Harriss [1969] and Lemarchand et al.
[2000]. Nevertheless, a global budget must include the
atmospheric flux, because a small amount of B moves
through the atmosphere to the land surface, where it
contributes to the B circulation in vegetation and to the
B content of stream waters [Rose et al., 2000b; Jahiruddin
et al., 1998]. The net transport of B through the atmos-
phere to land is estimated as 0.012 Tg B/yr, assuming that
the transport of B is proportional to the net landward
transport of Cl from seasalt aerosols [Graedel and Keene,
1995]. In future work, identification of a large and hitherto
unknown flux of B from seawater to the atmosphere would
allow simultaneous reconciliation of both the atmospheric
and marine compartments in the global biogeochemical
cycle of B.
[42] The oceans are the largest global reservoir for boron,
and many studies show that the boron concentration in the
ocean has been constant for the last 10 Myr [Lemarchand
et al., 2000]. The estimated boron mass in the ocean
reservoir assuming a uniform concentration of 4.6 mg/l of
boron in seawater is about 6.2  106 Tg. Relative to total
outputs, which include the seasalt injection to the atmos-
phere, we suggest that B in seawater has a mean residence
time of 3.3 Myr, shorter than recent estimates of 20 Myr by
Spivack and Edmond [1987] and 14 Myr by Lemarchand et
al. [2000]. This shorter mean residence time for B has
implications for the use of B isotopes in carbonates to
estimate changes in the pH of seawater during paleoclimates
[Royer et al., 2001].
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20 - 9
Natural Ratio
Seasalt Continental Dust Volcanic Anthropogenic: Natural
144 8 10 0.57
1.44 0.03 0.02 0.41
6000 2 0.00092
[43] As is the case for many biogeochemical cycles, the
circulation of B within the terrestrial and marine biospheres
is much greater than the annual net inputs and outputs from
these realms. This situation usually arises when limited
supplies of an element are available for plant uptake,
leading to the evolution of efficient internal biogeochemical
cycling in the ecosystem. Subba Rao [1981] shows B
limitations to the growth of marine phytoplankton, but in
the North Pacific Ocean, the depth distribution of B in
seawater indicates conservative behavior, suggesting that
the B concentration is unlikely to be controlled by the
growth of phytoplankton [Nozaki, 1996].
[44] Known global reserves of B will supply current
human demand for about 100 years. A large proportion of
the human production of B is sequestered in the manufac-
ture of borosilicate glass, and only about half of the human
mobilization of the B from the Earth’s crust would be
expected in mobile forms that contribute to the B content
of surface waters. B from atmospheric deposition plus a
smaller amount mobilized from rock weathering can easily
account for the annual B transport in rivers. The mass of
boron on the land surface is about 2200 Tg B, calculated by
taking the mean boron concentration of 11 ppm in soils and
the mass of surface soil (2.2  108 Tg; Chameides and
Perdue [1997]). This indicates 1700 years as the mean
residence time of boron on the land surface (2400 years
without the human perturbation), calculated using either the
estimated inputs or outputs of boron from the Earth’s land
surface.
[45] The human impact on the global biogeochemical
cycle of B rivals that seen for other elements of interest to
modern society: e.g., N, P, and S. Human activities have a
major impact on the transport of S through the atmosphere
(Table 8). The impact on B is slightly less severe, but the
atmospheric burden of B is clearly elevated compared to
that of a conservative element such as Cl. Potential human
contributions to the B transport in rivers rival those for P,
although both are much less than the human impact on
riverine N transport (Table 9). The world’s oceans are likely
to have experienced a net increase in dissolved B concen-
tration, albeit a minor percent change, since the beginning
of the Industrial Revolution. The global biogeochemical
Table 9. Anthropogenic Transport in World Riversa
Element River Transport World Industrial Ratio:
Production Anthropogenic/Natural
B 0.53 – 0.63 0.31 0.5
N 35 100 2.86
P 21 12 0.57
a
N and P data are procured from Schlesinger [1997].

20 - 10 PARK AND SCHLESINGER: GLOBAL BIOGEOCHEMICAL CYCLE OF BORON
cycle of B is worthy of further study, with investigations
focused on the processes that control the flux of B through
the atmosphere.
[46] Acknowledgments. We thank Robert Duce at Texas A&M Uni-
versity, Richard Birnie of Dartmouth College, John Hulston at the Institute
of Geological and Nuclear Sciences, Fred Anderson at University of
Chicago, and Bill Rose at Michigan Technical Institute for their advice
and help in completing this study.
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