Journal of Geochemical Exploration 140 (2014) 11–22

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/jgeoexp

Geochemical behaviors of boron and its isotopes in aqueous environment

of the Yangbajing and Yangyi geothermal fields, Tibet, China
Jianfei Yuan, Qinghai Guo ⁎, Yanxin Wang
State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, 430074 Wuhan, Hubei, PR China
School of Environmental Studies, China University of Geosciences, 430074 Wuhan, Hubei, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Fifty-two samples including geothermal well water, hot spring water, cold groundwater and river water were
Received 23 June 2013 collected from the Yangbajing and Yangyi geothermal fields to determine their boron concentrations and δ11B
Accepted 6 January 2014 values. The results show that the concentrations of boron in the geothermal waters range from 38.5 to
Available online 14 January 2014
165.4 mg/L, much higher than those of cold groundwaters and river waters (0.3–0.7 and 0.1–3.9 mg/L respec-
tively). The δ11B values are between −11.4 and −12.3‰ for the Yangbajing geothermal waters and between
Keywords:
Boron isotope
− 5.0 and −9.7‰ for the Yangyi geothermal waters, while those of the cold groundwaters are from −2.6 to
Geothermal water −4.8‰. The δ11B values and B/Cl ratios indicate that boron in geothermal water is mainly leached from reservoir
Aqueous environment host rocks, whereas magma degassing is possibly another source of boron. Although the dissolution of
Water–rock interaction tourmaline-rich granitic rocks is the primary factor controlling the boron concentrations and δ11B values of the
Geothermal wastewater Yangbajing and Yangyi geothermal waters, other secondary processes, e.g. CO2 degassing as well as subsequent
Contamination pH increase and precipitation of carbonate minerals, also affect the boron isotope fractionation occurring in the
reservoirs. In addition, the geothermal exploitation for electricity generation at Yangbajing had a significant
impact on geothermal water chemistry, which may have relations to boron isotopic fractionation as well. For
the Zangbo River flowing through the Yangbajing field, the boron isotopic geochemistry of river waters was
significantly influenced by geothermal wastewater near its drainage exit. However, the recharge of the tributaries
of the Zangbo River and the desorption of boron from river-bed sediments are major processes affecting the δ11B
values of river waters at the far downstream of the drainage exit. The results of this study validate that boron
and its isotopes can be used to trace the origin of geothermal water and to identify contamination induced by
geothermal wastewater drainage.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Boron can readily mobilize to aqueous environment during water–
rock interactions (Aggarwal et al., 2003; Dotsika et al., 2010;
Panagopoulos, 2009). It has two stable isotopes: 10B and 11B with natu-
ral abundance of about 19.8% and 80.2% respectively (Xiao et al., 2012,
2013b). Due to the marked difference in atomic mass between 10B
and 11B, isotopic fractionation can result in a distinct variation in the
11 10
B/ B ratios of boron-bearing media in geological and environmental
systems (Barth, 1998; Cary et al., 2013; Jiang, 2001; Jiang and Palmer,
1998; Kaliwoda et al., 2011; Louvat et al., 2011; Lu et al., 2012;
Marschall and Jiang, 2011; Muttik et al., 2011; Xiao et al., 2013a,
2013b; Zhao et al., 2011). For continental waters, the upper limit
of the δ11B value is 75‰ (Xiao et al., 2013b), while the lower limit
is − 27‰ (Pennisi et al., 2006). The approximate ranges of δ11B for
major boron reservoirs are: −9.7 to 6.8‰ for granites and fresh oceanic
⁎ Corresponding author at: School of Environmental Studies, China University of
Geosciences, 388 Lumo Road, Wuhan 430074, Hubei, PR China. Tel.: + 86 135 5411
6793; fax: +86 278 7436 235.
E-mail address: qhguo2006@gmail.com (Q. Guo).
basalts, −2 to 14‰ for altered oceanic basalts (Ishikawa and Nakamura,
1993; Vengosh et al., 1994a; Xiao et al., 2013b), 1.5‰ to 6.5‰ for
volcanic gases (Kanzaki et al., 1979), − 12 to 58‰ for marine boron,
− 32‰ to 26‰ for non-marine boron, − 17‰ to − 2‰ for igneous
rocks, and −34‰ to 22‰ for metamorphic rocks (Marschall and Jiang,
2011; Pennisi et al., 2006; Vengosh et al., 1994a; Xiao et al., 2013b).
In hydrothermal fluids, the δ11B values vary from − 10.5‰ to 54.9‰
(Aggarwal et al., 2000, 2003; Lu et al., 2012; Vengosh et al., 1991,
1994b).
The isotopic signature of various boron sources may be preserved to
some extents in natural water systems, so δ11B can be used as a tracer to
identify the origin of boron dissolved in groundwaters and surface
waters (Chao et al., 2011; Voutsa et al., 2009). In recent years, with
the rapid development of analytical methods for boron concentration
and its isotopic ratio, they were widely utilized to investigate the geo-
logical genesis of geothermal systems and the dominant geochemical
processes affecting geothermal water chemistry. Mather and Porteous
(2001) made a study on the geochemical evolution of boron in UK
sandstone aquifers using both boron concentration and isotopic ratio;
Vengosh et al. (1991) employed boron isotope as an indicator to analyze
the evolution of brine and associated hot springs in the Dead Sea;

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http://dx.doi.org/10.1016/j.gexplo.2014.01.006
12 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22
Voutsa et al. (2009) delineated the distribution and origin of boron in
groundwaters from northern Greece; Pennisi et al. (2006) evaluated
the boron contamination occurring in the Cecina River alluvia aquifer
by use of boron and strontium isotopes; Louvat et al. (2011) investigat-
ed the geochemical behaviors of boron in the Guadeloupe hydrothermal
system. However, there has so far been a lack of systematic studies
concerning boron isotope fractionation in the high-temperature
hydrothermal systems of China with reservoir temperatures higher
than 200 °C.
The Yangbajing and Yangyi geothermal fields, marked with very
high reservoir temperatures up to 329.8 and 207.2 °C respectively
(Guo et al., 2007, 2009), belong to the Mediterranean–Himalayas geo-
thermal belt. Beneath either Yangbajing or Yangyi, there is a relatively
shallow magmatic heat source whose degassing has a significant impact
on the overlying hydrothermal system (Chen et al., 1996; Guo et al.,
2009; Nelson et al., 1996). Over the past three decades, quite a few stud-
ies have been conducted for depicting the regional geology, geothermal
geology and hydrogeology of the Yangbajing and Yangyi geothermal
fields (Cai et al., 1986; Duo, 2003; Shen and Wang, 1984; Tong and
Zhang, 1981). Recently, Guo (2012) and Guo et al. (2007, 2009, 2010)
have made a series of investigations in both fields. It is revealed that
the deep geothermal fluid below Yangbajing is formed via the uptake
of magmatic vapor by infiltrating snowmelt water, whereas the shallow
geothermal fluid is the result of mixing between deep geothermal fluid
and local cold groundwater. Boron, fluoride and arsenic contamination
of river waters resulting from the drainage of geothermal wastewater
by the Yangbajing power plants was assessed as well (Guo et al.,
2008). Although much effort has been taken for understanding the
geological and geochemical processes responsible for the formation of
Yangbajing and Yangyi geothermal waters, little systematic work was
carried out with a focus on the geochemistry of boron as well as its iso-
topes. Thus, in this study, the boron concentrations and 11B/10B isotopic
ratios were determined for the geothermal water, cold groundwater
and river water samples collected from Yangbajing and Yangyi to
delineate the geochemical origins of geothermal fluid as well as
dissolved boron, which is vitally important for the policy making of
local governments in terms of geothermal utilization and management.
2. Geology and hydrogeology setting
2.1. The Yangbajing geothermal field
The Yangbajing geothermal field, located in the Yangbajing fault
basin in front of the Nyenchen Tonglha Mountains (northwest to the
field) and the Tang Mountains (southeast to the field), is one of the
non-volcanic high temperature fields in Tibet. Two groups of normal
faults (the NNE–SSW and NE–SW stretching faults) are distributed in
front of the Nyenchen Tonglha Mountain and Tang Mountain, providing
space for the migration and storage of the geothermal fluids below
the Yangbajing field. The Yangbajing geothermal system consists of a
shallow and a deep reservoir. The bedrocks of the shallow reservoir
are Himalaya granite, and the overlying strata are made up of bolder
clay and silty clay. In contrast, the granitic mylonite and the fractured
granite constitute the deep reservoir, and its cap rocks are altered
granite and biotite granite. Besides, shallow groundwater with a burial
Table 1
Comparison of reservoir features between the Yangbajing and Yangyi geothermal fields.
Yangbajing deep reservoir
The maximum reservoir temperature (°C) 329.8
Reservoir lithology Himalayanian granitic mylonite
and fractured granite
Cap rocks Intensively eroded Himalayanian
granite and biotite granite
Reservoir thickness (m) About 900
depth of 10–20 m and stream waters recharged by snowmelts water
from the Nyenchen Tonglha Mountains occur within the field as well.
The Zangbo River winding towards the east on the southeast part of
the geothermal field is the major surface water in the Yangbajing field.
The Yangbajing geothermal field falls into a temperate semiarid
monsoon climate area, with an annual air temperature of 2.5 °C in
the past 40 years and an average value of 0.597 atm for atmospheric
pressure. The mean annual rainfall in the area is 382.8 mm with 65%
of the total in July and August.
2.2. The Yangyi geothermal field
The Yangyi geothermal field, with altitude between 4550 and
5050 m, is located to the west of the Yangyi village, Tibet. The topogra-
phy of the field is high in the west and the south, low in the east and the
north. The reservoir consists of Himalayanian biotite granite and biotite
granite porphyry, and the cap rocks are altered volcanic rock granite
porphyry. Quaternary sediments including gravel, sand, and silty clay
are widely distributed in the geothermal field. There are three groups
of faults distributed in this area, including N–S stretching faults,
NE–SW or nearly E–W stretching faults and NW–SE stretching faults.
The major river in the field is the Luolang River, flowing from south to
north and converging into the Lhasa River.
The Yangyi geothermal field is characterized by a semiarid plateau
meadow climate, mean annual air temperature of 1.1 °C, and atmo-
spheric pressure ranging from 0.544 to 0.570 atm. The average annual
rainfall is 414.1 mm, with 85% rainfall in July and September. The
geographical and climate features of the Yangyi field are very similar
to those of the Yangbajing geothermal field (Table 1).
3. Sampling and analysis
3.1. Field sampling
Fifty-two samples, including forty from the Yangbajing and twelve
from the Yangyi geothermal field, were collected in and around the
two fields in August and September of 2007. The sampling locations
are shown in Fig. 1. When sampling, all water samples were filtered
through a 0.45 μm filter in situ, and then stored in new 350 mL polyeth-
ylene bottles. Those polyethylene bottles had been rinsed by deionized
water twice before sampling. Unstable parameters including water
temperature (T), pH and electrical conductivity (EC) were determined
on site using the 5-Star multi-parameter water quality analyzer
(520M-01 model, Thermo Electron Corporation, USA). The water
samples for metal element analysis were acidified to pH b 2 using
14 M HNO3, whereas those for anion analysis were not.
3.2. Lab analysis and data processing
Alkalinity was measured on the sampling day with the Gran titration
− − −
method. The concentrations of SO2−4 , Cl , Br and F were determined
using ion chromatography (model DX-120, Dionex), and Ca2+, Mg2+,
Na+, K+, B, As, Li and Sr using ICP-AES (IRIS INTRE IIXSP) and ICP-MS
(Agilent 7500a plasma mass spectrometer) within 2 weeks after
Yangbajing shallow reservoir Yangyi geothermal reservoir
173.0 207.2
Quaternary sandstones Himalayanian biotite granite
and biotite granite porphyry
Quaternary boulder clay and silty clay Intensively eroded Miocene
volcanic rocks
About 100 400–500
 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22
Fig. 1. Simplified maps and sampling locations of the Yangbajing and Yangyi geothermal
fields.
sampling. In most cases, analytical uncertainties for major and trace
elements are below ±5%.
Boron separation and isotopic ratio measurement were conducted at
the State Key Laboratory for Mineral Deposits Research of Nanjing
University (China). Firstly, boron was isolated from solution sample
via a three-column ion-exchange procedure, i.e. the first mixed resin
column (cation-exchanger H+ form and anion-exchanger HCO− 3 form,
the former: AG50W × 8H+ — Form Resin, USA, 0.037–0.074 mm; the
later: Ion Exchanger II, Germany, 0.18–0.25 mm), the peristaltic pump
coupled boron specific resin column (Amberlite IRA 743, USA, 0.125–
0.149 mm), and the second mixed resin column (cation-exchanger
H+ form and anion-exchanger HCO− 3 form, as mentioned above). The
full recovery of boron from the solution with complex matrices was
about 99%. Then the extracted boron solution containing approximately
1 μg B was mixed with a CsCO3 solution to get a Cs:B ratio ranging from
0.5 to 2. The mixed solution was evaporated at low temperature
13
(b60 °C) until a few μL remained, and finally loaded with graphite slurry
on to a Ta filament.
Boron isotope ratios were determined using positive thermal ioniza-
tion mass spectrometry (Jiang, 2001; Yan et al., 2013) and expressed
conventionally in relation to the NIST SRM 951 boric acid reference
material. It is converted to a δ11B notation as below:
11
!
11 B=10 BSample
δ B¼ 11
−1  1000‰:
B=10 BStandard
The average 11B/10B ratio of NIST SRM 951 is 4.0514 ± 0.1‰ (2σ). A
11
δ B value of −0.3‰ for NIST SRM 951 through the same pretreatment
procedure was obtained, indicating that little isotopic fractionation oc-
curred during the extraction procedure. Most water samples were ana-
lyzed in duplicate, with an average precision better than ±0.3‰ (2σ).
4. Results and discussion
4.1. Boron concentration
4.1.1. Yangbajing
The chemical constituents in the samples with respect to the relative
contents of major cations and anions are illustrated in Table 2 and Fig. 2.
Bicarbonate is the dominant anion in cold groundwater and river
waters, while that in geothermal waters is chloride. Sodium and calcium
are the primary cations for geothermal water and cold water samples
respectively. The boron concentrations in geothermal water, cold
groundwater and river water samples range from 42.6 to 165.4 mg/L,
0.2 to 0.7 mg/L, and 0.0 to 1.8 mg/L respectively. It is obvious that
boron is much more enriched in geothermal waters than in cold
groundwaters and river waters. Moreover, the boron concentration of
geothermal water from deep reservoir (well ZK4001) is higher than
those from shallow reservoir (wells ZK05, ZK 302, ZK329, ZK357 and
ZK 359) (see the details in Table 2). Despite the distinct difference of
boron concentration between deep and shallow geothermal fluids, a
remarkable linear relationship of boron as well as EC, Cl, K, Na, Li and
As among all water samples can be identified (Fig. 3). It implies that
both deep and shallow reservoirs beneath the Yangbajing field belong
to the same hydrothermal system, and the geothermal waters from
shallow reservoir may be formed by the mixing between those from
deep reservoir and local cold groundwaters. Boron is a conservative
element like chloride in a geothermal system, especially in high-
temperature geothermal systems, and therefore its concentration
can be used to calculate the mixing ratios of deep geothermal water in
the shallow geothermal water samples. Thus a binary mixing model
(Eq. (1)) with two endmembers (cold groundwater represented by
sample YBJ-C-4 and deep geothermal fluid by sample ZK4001) was
proposed, based on which the mixing ratios of deep geothermal fluid
in all geothermal samples collected from shallow wells were estimated
to be between 25.7 and 41.0%.
4.1.2. Yangyi
The geothermal waters collected from the geothermal wells at
Yangyi (YYT-5, YYT-6, YYT-7 and YYT-8) are Na–HCO3 type, while the
geothermal spring samples (YYT-1, YYT-2, YYT-3 and YYT-4) are
Na–SO4–Cl or Na–Cl–SO4 type. Different from the geothermal samples,
the Luolang River waters are Ca–HCO3 type. The concentration of
SO2−
4 in geothermal water may be controlled by the oxidation of H2S
or pyrite and/or the dissolution of gypsum (Mather and Porteous,
2001). Zhao et al. (1998) pointed out that H2S was detected in the
steam phase separated from some geothermal well discharges at
Yangyi. Thus, the oxidation of H2S is more likely to contribute to the
elevation of SO24 − concentration of the Yangyi geothermal waters.
The boron concentrations of the geothermal waters from Yangyi are be-
tween 38.5 and 45.7 mg/L, similar to those from the shallow reservoir of
14 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22

Table 2
Physical and chemical parameters of water samples collected from Yangbajing and Yangyi (in mg/L, except for T in °C, EC in μs/cm, and δ11B in ‰).

Code T pH EC Ca Mg Na K HCO3 SO4 Cl CO3 F Br Sr Li As B δ11B

YBJ-C-4 11.1 8.53 100.0 13.8 1.55 4.1 0.56 46.4 9.1 2.0 0.8 0.79 0.10 0.08 0.00 0.01 0.3 −2.60
YBJ-M-1 18.4 8.38 86.1 11.9 1.08 6.0 0.28 33.7 12.2 2.4 0.5 0.74 0.08 0.06 0.00 0.02 1.1 –
YBJ-M-2 11.5 8.58 88.2 14.1 1.11 2.3 0.25 27.5 15.6 2.2 0.5 0.49 – 0.06 0.00 0.02 0.7 −4.80
YBJ-M-3 14.7 8.63 73.7 13.3 0.39 1.9 0.23 27.9 10.8 2.1 0.7 0.49 – 0.06 0.00 0.01 0.6 –
YBJ-M-4 18.8 8.48 75.2 11.5 0.99 2.1 0.24 26.4 13.4 1.8 0.5 0.58 0.07 0.06 0.00 0.02 0.5 –
YBJ-M-5 18.3 8.45 91.0 14.5 1.15 2.4 0.33 28.8 16.8 1.8 0.5 0.55 – 0.07 0.00 0.02 0.4 –
YBJ-M-6 13.6 8.54 89.0 15.0 1.51 1.5 0.27 41.0 8.0 1.7 0.8 0.44 – 0.06 0.00 0.01 0.4 –
YBJ-M-7 18.1 8.30 702.5 46.6 7.64 112.6 11.88 178.2 20.8 130.1 2.9 5.31 0.85 0.24 1.62 1.05 18.6 –
YBJ-M-8 12.2 7.32 76.8 12.4 1.05 0.9 0.40 24.1 15.6 1.8 0.0 0.56 – 0.05 0.00 0.01 0.3 –
YBJ-S-1 12.1 6.31 105.6 15.4 2.20 4.2 0.90 51.9 9.4 2.2 0.0 0.43 – 0.11 0.01 0.02 0.13 −7.30
YBJ-S-2 12.9 6.19 106.2 15.1 2.23 3.4 0.85 51.3 9.5 2.2 0.0 0.41 – 0.11 0.01 0.01 0.1 –
YBJ-S-3 19.4 8.05 224.1 15.2 2.07 26.1 2.48 67.2 12.6 24.1 0.5 1.31 0.10 0.12 0.19 0.20 3.9 −8.80
YBJ-S-4 15.3 8.63 116.8 14.8 2.08 5.3 0.97 49.4 8.7 3.9 1.2 0.46 0.06 0.11 0.02 0.04 0.5 –
YBJ-S-5 15.0 9.07 112.4 15.5 2.19 4.4 0.90 44.4 10.1 4.9 3.1 0.57 0.04 0.11 0.02 0.04 0.3 –
YBJ-S-6 15.0 8.96 120.3 15.0 2.02 5.8 0.99 43.1 11.8 4.7 2.3 0.53 0.06 0.11 0.03 0.04 0.6 –
YBJ-S-7 10.2 7.17 70.3 11.1 2.31 1.9 1.68 26.5 19.6 1.8 0.0 0.60 – 0.06 0.01 0.01 0.0 –
YBJ-S-8 10.1 7.64 70.8 10.7 2.04 1.8 1.57 22.5 19.3 1.8 0.0 0.58 – 0.06 0.01 0.01 0.0 –
YBJ-S-9 11.3 8.95 86.8 11.5 1.73 3.6 1.46 30.2 14.4 3.8 1.3 0.44 – 0.07 0.01 0.01 0.3 –
YBJ-S-10 13.3 7.36 69.8 10.1 1.67 2.1 1.27 31.5 10.7 1.8 0.0 0.6 – 0.06 0.00 0.01 0.0 –
YBJ-S-11 12.1 7.95 117.8 14.3 2.09 8.2 0.97 53.3 11.0 6.1 0.3 0.45 – 0.11 0.02 0.03 0.5 –
YBJ-S-12 12.3 8.01 118.3 14.4 2.15 8.8 1.02 55.6 15.8 4.2 0.3 0.48 – 0.11 0.02 0.04 0.5 −10.3
YBJ-S-13 12.4 8.17 118.2 14.5 2.24 6.9 1.01 55.3 10.4 4.2 0.4 0.48 – 0.11 0.02 0.04 0.5 –
YBJ-S-14 20.3 8.35 278.1 24.7 3.72 22.6 1.52 87.1 17.3 16.0 1.6 1.13 0.15 0.19 0.07 0.07 1.8 −10.4
YBJ-S-15 20.9 8.25 171.8 16.2 2.47 11.3 1.36 49.7 15.0 9.1 0.6 0.62 0.14 0.13 0.06 0.06 1.3 −10.6
YBJ-S-16 13.1 8.40 108.5 14.4 2.18 7.2 0.95 55.8 11.4 5.1 0.8 0.61 0.09 0.11 0.04 0.05 0.4 –
YBJ-S-17 12.9 7.65 122.4 13.5 1.45 9.6 1.18 51.7 13.4 4.8 0.1 0.59 – 0.08 0.02 0.01 0.4 –
YBJ-SD-1 17.4 7.45 195.7 24.6 2.43 15.6 1.97 110.0 5.7 3.7 0.2 0.69 0.08 0.17 0.04 0.37 0.8 –
ZK329 86.0 6.06 1462.0 1.5 0.01 272.8 28.01 227.0 48.6 309.3 0.1 9.99 1.51 0.08 3.19 1.14 42.6 −12.0
ZK359 86.0 6.57 2026.0 2.7 0.01 392.6 45.67 316.1 60.0 442.0 0.5 12.99 3.00 0.14 5.15 2.65 61.3 −11.4
ZK357 86.0 6.58 2051.0 1.7 0.02 381.0 42.75 307.7 57.5 420.3 0.4 13.02 1.39 0.16 4.91 2.53 59.5 −12.3
ZK05 86.0 6.73 1983.0 6.8 0.03 381.8 40.85 284.0 57.4 405.9 0.6 13.20 1.68 0.23 4.74 2.53 59.2 −12.0
ZK4001 86.0 6.37 4350.0 1.6 0.02 785.4 153.90 385.3 28.6 1073.0 0.6 28.51 9.13 0.33 17.42 6.82 165.4 −11.9
ZK302 86.0 6.76 2278.0 2.5 0.02 446.0 54.48 376.2 62.1 493.8 0.9 14.06 1.43 0.16 6.23 2.90 67.9 −11.6
YBJ-W-1 86.0 8.89 2119.0 1.7 0.00 407.6 47.63 147.9 61.6 464.1 43.6 14.01 1.44 0.11 5.39 2.68 63.2 −12.8
YBJ-W-2 25.0 9.65 983.0 6.8 0.56 189.0 17.01 95.3 41.1 186.5 31.8 8.75 1.18 0.11 2.03 1.65 29.1 –
YBJ-W-3 17.8 8.30 129.5 12.9 1.48 8.3 1.16 34.9 20.0 6.9 0.4 0.77 0.12 0.08 0.04 0.06 1.3 –
YBJ-W-4 60.4 7.96 2380.0 3.3 0.10 442.2 63.27 292.3 59.7 560.7 6.1 12.73 1.99 0.16 7.26 3.18 75.2 –
YBJ-X-1 2.7 8.82 3.3 0.2 0.40 1.4 0.00 2.4 0.5 1.7 0.1 0.00 0.05 0.00 0.00 0.01 0.2 –
YBJ-X-2 3.3 8.78 3.1 0.3 0.36 1.5 0.00 3.0 0.6 1.7 0.0 0.00 – 0.00 0.00 0.00 0.2 –
YBJ-X-3 9.2 7.59 45.4 4.9 1.60 1.6 0.11 16.7 7.4 1.8 0.0 0.32 – 0.03 0.00 0.02 0.2 –
YYC-1 16.0 7.62 104.0 15.6 2.51 5.0 0.47 60.3 5.0 1.9 0.2 0.32 0.71 0.12 0.01 0.02 0.7 –
YYC-2 13.3 7.14 80.6 12.5 1.63 4.0 0.36 51.3 3.1 1.8 0.0 0.19 – 0.07 0.00 0.01 0.6 −1.0
YYC-3 13.6 7.16 89.8 11.8 1.76 4.8 0.46 45.8 7.3 2.3 0.0 0.25 – 0.08 0.02 0.02 0.6 –
YYC-4 13.8 7.87 100.3 12.8 2.26 5.5 0.53 46.6 8.9 2.7 0.2 0.31 – 0.10 0.03 0.03 0.7 −3.9
YYT-1 84.0 9.19 1958.0 3.8 0.95 374.2 24.02 178.7 225.3 169.2 100.2 20.37 0.92 0.33 7.78 1.95 40.8 −5.4
YYT-2 79.0 9.21 2096.0 1.4 0.87 430.0 25.04 223.1 244.8 174.9 119.0 21.58 1.01 0.27 8.41 2.01 42.4 –
YYT-3 86.0 9.42 2236.0 1.1 1.06 432.8 29.33 148.1 253.4 182.4 152.2 22.70 0.96 0.23 9.11 2.14 44.6 –
YYT-4 88.0 9.12 2106.0 1.5 0.97 439.8 24.67 241.8 241.8 173.8 126.9 22.28 0.81 0.16 8.50 1.97 41.4 −5.0
YYT-5 84.0 8.03 1864.0 18.7 1.16 398.0 19.93 515.3 224.5 161.5 24.7 13.08 0.00 0.61 5.74 1.67 38.5 −6.5
YYT-6 89.0 7.96 2320.0 6.5 0.96 489.6 56.47 645.0 255.5 182.5 28.7 20.46 5.12 0.47 10.46 2.06 45.5 –
YYT-7 84.0 7.93 2212.0 6.6 0.94 478.8 50.57 639.2 247.3 180.2 23.5 20.03 0.89 0.43 9.51 2.08 44.0 −9.7
YYT-8 86.0 8.02 2512.0 25.8 0.95 597.0 41.21 815.3 254.8 184.6 51.1 13.00 – 0.83 6.64 2.11 45.7 −6.7

Notes: the sampling code as “YBJ” is collected from the Yangbajing geothermal field, and “YBJC-”: cold groundwater, “YBJM-” and “YBJ-SD-”: stream water, “YBJS-”: river water, “YBJX-”:
snow-melting water, “YBJW-”: thermal wastewater, “ZK”: well number; the sampling code as “YY” is collected from the Yangyi geothermal field, and “YYC-”: river water, “YYT-”: thermal
water.

the Yangbajing geothermal system (Table 2). The concentration ranges
of several other chemical constituents (e.g. Cl, Na, K and F) in the geo-
thermal waters from Yangyi and the shallow Yangbajing reservoir are
also in the same level (Table 2).
The boron concentrations of the Luolang River waters range from 0.6
to 0.7 mg/L, a little higher than the corresponding Drinking Water
Standard (0.5 mg/L) recommended by the World Health Organization.
The elevated concentration of boron in the river waters was induced
by the discharge of the Yangyi geothermal waters (Guo et al., 2009).
4.1.3. Statistic analysis
In order to examine the possible correlation among the measured
physical and chemical parameters of geothermal water, their correlation
coefficients have been calculated and presented in Table 3. It shows that
boron is positively correlated with T, EC, Na, K, Cl, F, Li, and As, while
negatively correlated with Ca and Mg. The significant correlations be-
tween boron and Cl or As can probably be attributed to their common or-
igin (Voutsa et al., 2009; Zhang, 1998). However, as the geothermal
fluids flow upward to near surface, CO2 degassing may happen due to
pressure decrease, causing the transformation of HCO− 2−
3 to CO3 and sub-
2+ 2+
sequent precipitation of Ca and Mg . Thus, boron has negative rela-
tions with Ca and Mg.
Hierarchical cluster analysis was employed to classify the water
samples into three groups (Fig. 4): group A corresponds to cold ground-
water, stream water, snowmelt water, river water and some geo-
thermal wastewater samples collected from Yangbajing (YBJW-2 and
YBJW-3) with boron concentration less than 4 mg/L (except for
YBJW-2 whose boron concentration is 29.1 mg/L); group B comprises
the geothermal water samples from both Yangbajing and Yangyi with
boron concentrations between 38.5 and 67.9 mg/L; and group C is
 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22
Fig. 2. Langelier and Ludwig diagram presenting the major constituents of water samples
( : geothermal water from Yangbajing, : geothermal water from Yangyi, ●: cold water
including river water, cold groundwater and snow-melting water).
represented by the geothermal water sampled from the deep
Yangbajing reservoir with the highest boron concentration up to
165.4 mg/L. A previous study made by Zhang et al. (1982) reveals that
the geothermal springs in Tibet can be divided into two groups in
Fig. 3. Bivariate plot of boron versus EC, Cl, Na, K, Li, and As of all water samples.
15
terms of boron concentration with a critical value of 10 mg/L, and 70%
of the geothermal systems in Tibet fall into the boron-rich type. Accord-
ing to the classification of Zhang et al., the geothermal waters from both
Yangbajing and Yangyi belong to this type.
4.2. Boron isotopes
4.2.1. Yangbajing
The δ11B values of the Zangbo River waters and cold groundwaters at
Yangbajing range from −7.3 to −10.6‰ and −2.6 to −4.8‰ respec-
tively. In contrast, the geothermal waters have much higher boron
concentrations but more depleted boron isotopic composition (Fig. 5).
The geothermal waters from Yangbajing have quite similar δ11B values
(between −11.4 and −12.8‰), indicating once again that the shallow
and deep reservoirs are within the same hydrothermal system. More-
over, the boron concentrations and isotopic ratios of the shallow geo-
thermal waters are intermediate between the deep geothermal waters
and the cold groundwaters (Fig. 5), demonstrating that the former
might be a mixing product of the latter. Vengosh et al. (1994a, 1994b)
and Barth (1998) proposed a binary mixing model for calculating
the boron concentration (Eq. (1)) and δ11B value (Eq. (2)) of a mixed
solution:
Bmix ¼ Ba  F þ Bb  ð1−FÞ ð1Þ
16 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22

Table 3
Spearman's correlation coefficients of all water samples.a

B T pH EC Ca Mg Na K HCO3 SO4 Cl CO3 F Sr Li As

B 1.00
T 0.83 1.00
pH 1.00
EC 0.96 0.94 1.00
Ca −0.43 −0.44 −0.41 1.00
Mg −0.47 −0.50 −0.46 0.84 1.00
Na 0.93 0.95 0.99 −0.40 −0.47 1.00
K 0.98 0.76 0.92 −0.40 −0.44 0.89 1.00
HCO3 0.67 0.81 0.80 0.85 0.69 1.00
SO4 0.45 0.77 0.69 0.74 0.41 0.75 1.00
Cl 0.98 0.75 0.89 −0.43 −0.47 0.84 0.96 0.56 1.00
CO3 0.56 0.46 0.50 0.53 0.80 1.00
F 0.87 0.93 0.96 −0.46 −0.42 0.96 0.83 0.74 0.80 0.76 0.68 1.00
Sr 0.49 0.65 0.66 0.71 0.50 0.89 0.77 0.39 0.62 1.00
Li 0.91 0.88 0.97 −0.43 −0.42 0.96 0.901 0.76 0.74 0.82 0.56 0.97 0.64 1.00
As 0.99 0.84 0.97 −0.41 −0.45 0.94 0.97 0.69 0.450 0.96 0.36 0.89 0.52 0.93 1.00
a
Correlation coefficients significant at the 0.01 level are given.

  n o
11 11 11
δ Bmix ¼ Ba  δ Ba  F =Bmix þ Bb  δ Bb  ð1−FÞ =Bmix
where Ba, Bb and Bmix and δ11Ba, δ11Bb and δ11Bmix are the boron concen-
trations and the δ11B values of endmembers a and b as well as their
mixing product, respectively. F represents the mixing ratio of the
endmember a. With two water samples collected from the deep
Yangbajing reservoir (δ11B = −11.4‰, B = 165.4 mg/L) and the shal-
low cold groundwater system (YBC-4: δ11B = −2.6‰, B = 0.3 mg/L)
as endmembers, a mixing curve can be easily drawn on the plot of
δ11B value vs. boron concentration (Fig. 6a). The shallow geothermal
water samples are plotted closely around the mixing line (Fig. 6a).
Although the boron concentration of the deep geothermal water
is much higher than those of the shallow geothermal waters and the
cold groundwater, the difference of δ11B value among them is relatively
small. The δ11B values of the shallow geothermal waters are actually
little affected by the mixing of local cold groundwater in view of its
quite low boron concentration.
4.2.2. Yangyi
The Luolang River waters are characterized by low boron concentra-
tions but high δ11B values (−1.0 to −3.9‰) as well (Fig. 7), just like the
situation for the Zangbo River at Yangbajing. The boron isotopic values
of the Yangyi geothermal waters are between −5.0 and −9.7‰, higher
than those of the Yangbajing geothermal waters. In addition, there is a
plausibly linear relationship between the Luolang River waters and
geothermal waters, demonstrating a boron contamination of river
waters caused by the discharge of geothermal waters (Fig. 6b).
There are two main dissolved species for boron: B(OH)3 and B(OH)− 4 usually have δ11B values similar to those of the reservoir host rocks,
whose relative abundance is pH dependent (Barth, 1998; Chao et al.,
2011; Dotsika et al., 2010; Wolska and Bryjak, 2013). The ionization
process of boric acid can be expressed as below:
− þ
BðOHÞ3 þ H2 O ¼ BðOHÞ4 þH :
At pH b7, B(OH)3 prevails in geothermal water, whereas at pH N10,
the dominant species of boron in geothermal water is B(OH)− 4 (Fig. 8).
11
B is preferably enriched in B(OH)3, while 10B is usually more abundant
in B(OH)− 4 . The isotope-exchange reaction between the two major
boron species is as follows:
10 11 − 11 10 −
BðOHÞ3 þ BðOHÞ4 ¼ BðOHÞ3 þ BðOHÞ4 :
The pH values of the geothermal waters from both Yangbajing and
Yangyi are less than 10, implying that B(OH)3 dominates in them. More-
over, the pH values of the Yangbajing geothermal waters are generally
lower than those of the Yangyi geothermal waters (Table 2), which is
ð2Þ possibly one of the factors responsible for their different δ11B values
(Fig. 9a and b). Nevertheless, the difference of lithology between the
reservoirs host rocks within two hydrothermal systems should still be
the primary reason inducing their δ11B differences. Finally, it is interest-
ing that the δ11B values of the Yangyi geothermal spring samples (with
mean value of − 5.2‰) are generally higher than those of the Yangyi
geothermal well water samples (with mean value of − 7.6‰), which
may result from their different discharge ways.
4.3. Origin of boron
At both Yangbajing and Yangyi, the major recharge source for the
geothermal waters is meteoric water. However, due to their very low
boron concentrations, either cold groundwater or local precipitation
and snow-melting water (see Table 2) should not be the main source
for boron in the geothermal waters.
The boron isotopic values of the geothermal waters from Yangbajing
and Yangyi are from −11.4 to −12.0‰ and from −5.0 to −9.7‰, re-
spectively, much lower than those of seawater (δ11B: 39‰) and marine
boron (δ11B: − 12 to 58‰). Moreover, the B/Cl molar ratios of the
Yangbajing and Yangyi geothermal waters range from 0.45 to 0.51 and
0.78 to 0.81 respectively, which are significantly higher than that of sea-
water (B/Cl: 8.1 × 10− 4). So there is no enclosed paleo-seawater
existing below Yangbajing and Yangyi that contributes to the formation
of geothermal water.
Boron can be easily released from different types of rocks during
water–rock interactions. It was reported that the geothermal waters
suggesting that the leaching of boron from boron-bearing minerals in
reservoir is the primary process affecting the boron concentration in
geothermal water (Leeman et al., 1992; Musashi et al., 1988; Palmer
and Sturchio, 1990). The rocks hosting the Yangbajing hydrothermal
system are granite and granitic mylonite, whereas the Yangyi system
is hosted by biotite granite and biotite granite porphyry (Table 1). The
δ11B values for both Yangbajing and Yangyi geothermal waters fall into
the scope of those for igneous rocks (−17‰ to −2‰), which indicates
that the interactions between geothermal waters and host rocks beneath
Yangbajing and Yangyi are definitely the controlling factor for their
boron concentrations. Tourmaline is the most abundant boron-bearing
mineral in the crust and exists in a variety of igneous rocks (Xiao et al.,
2013b). Previous studies suggested that different types of tourmalines
occur in the geothermal fields of Tibet, including Yangbajing and Yangyi
(Liao et al., 2006; Shen and Yao, 2000; Xia et al., 2011). Jiang et al. (1999)
reported that the δ11B values of tourmalines in the Sullivan Pb–Zn–Ag
deposit range from − 11 to 22.9‰, the lower limit of which is close
to those of the geothermal waters investigated in this study. Thus, we
 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22 17

Fig. 5. Boron concentrations and δ11B values of water samples from the Yangbajing
geothermal field.

4.4. Processes affecting boron isotope fractionation within the

hydrothermal systems

As mentioned earlier, the δ11B values of the Yangbajing geothermal

samples are very close to each other (ranging from −11.4 to −12.3‰),

Fig. 4. Dendrogram from hierarchical cluster analysis of all water samples (group A: sam-
ples with boron concentrations b4 mg/L, group B: samples with B concentrations between
38.5 and 67.9 mg/L, group C: deep geothermal well sample with boron concentration of
165.4 mg/L).

speculate that tourmaline in granitic rocks is the primary source of boron

for the Yangbajing and Yangyi geothermal waters.
Furthermore, the existence of a magmatic heat source at Yangbajing
and Yangyi has been verified by a series of geophysical studies and geo-
chemical studies (Chen et al., 1996; Guo et al., 2009; Nelson et al., 1996).
Arnorsson and Andresdottir (1995) suggested that the elevated boron
concentration in high-temperature geothermal waters with magma
as heat source can be expected to originate from degassing magma
chamber. It was found that there exist hydrides of boron (e.g. B2H6) in
volcanic gases (Arnorsson, 1983), which also supports the notion that
boron in geothermal water may come from magma degassing. Hence,
it is considered that parts of boron in the Yangbajing and Yangyi geo-
thermal waters are probably of magmatic source. However, due to the
Fig. 6. (a) δ11B value versus boron concentration of the Yangbajing samples collected in
lack of boron isotopic values for magmatic waters, it is impossible to different times. The mixing line was plotted based on a mixing calculation using deep
make a quantitative evaluation for the contribution of magmatic geothermal water and local cold groundwater as two endmembers. (b) δ11B value versus
boron to that in geothermal water by use of B isotopic data. boron concentration of the Yangyi samples.
18 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22

Fig. 7. Boron concentrations and δ11B values of water samples from the Yangyi geothermal
field.

denoting that there was only slight boron isotope fractionation

upon the secondary processes occurring during the geothermal fluid
upflow (e.g. boiling and mixing). Previous studies indicated that there
are four main factors possibly inducing boron isotopic fractionation,
including separation between water and vapor phases, water–rock
interaction, CO2 degassing and exploitation.

4.4.1. Separation between water and vapor phases

Xiao et al. (2007) found that 11B can be enriched in the vapor phase
during seawater evaporation. Leeman et al. (1992) studied the boron
isotopic fractionation between coexisting vapor and liquid in natural
geothermal systems, and considered that in low-temperature hydro-
thermal systems, the boron isotopic fractionation is non-negligible.
For the Yangbajing geothermal system, the steam ratios of geothermal
well discharges range from 10.7% to 18% (Guo et al., 2007), and
therefore boron isotope fractionation may occur due to the water–
vapor separation during sampling. A plot of boron isotopic value vs.
steam ratio was drawn (Fig. 10), which clearly shows that the δ11B
value decreases with the increase of steam ratio, indicative of the
occurrence of boron isotope fractionation during water–vapor separa- Fig. 9. Plot of δ11B versus pH value of geothermal water from the Yangbajing geothermal
tion. 11B is more enriched in B(OH)3 than 10B, and B(OH)3 is more vola- field (a) and the Yangyi geothermal field (b).
tile than B(OH)− 4 . Thus, during the processes of water–vapor separation,
11
B existing as the form of B(OH)3 enters the vapor preferentially,
resulting in that 10B becomes abundant in solution. According to
Kasemann et al. (2004), the boron isotopic fractionation between
vapor and liquid during boiling cannot change 11B value markedly at

Fig. 8. The isotopic composition of boron species at different pHs (after Xiao et al., 2013a,
2013b). δ11BSW, δ11B3 and δ11B4 denote the boron isotopic compositions of seawater, Fig. 10. Plot of δ11B versus steam ratio of geothermal water from the Yangbajing geothermal
B(OH)3 and B(OH)− −
4 respectively; f3 and f4 are the fractions of B(OH)3 and B(OH)4 . field.
 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22 19

high-temperatures (N150 °C), the effect of boron isotopic fractionation

being generally below 3‰. This is in accordance with the fact that the
reservoir temperatures beneath Yangbajing are from 166 to 255 °C
(Guo et al., 2010), and the corresponding variation of boron isotope
values of geothermal water is no more than 0.9%.

4.4.2. Water–rock interactions

Although tourmalines in granitic rocks are the major source of boron
in the Yangbajing geothermal waters and the dissolution of tourmalines
is the primary factor controlling their boron isotopic compositions,
hydrothermal alteration was prevalent in the Yangbajing geothermal
field (Zhang, 1998) and may contribute to the variation of δ11B values
of geothermal water as well. In fact, boron can be easily adsorbed onto
those hydrothermally altered minerals, and the boron species depleted
in 11B (i.e. B(OH)−4 ) is usually preferably incorporated into them, lead-
ing to the enrichment of 11B in the liquid phase. For example, Palmer
and Sturchio (1990) found that the hot springs from Norris Geyser
Basin, Upper Geyser Basin and Calcite Springs area in the Yellowstone
National Park (USA) have δ11B values close to that of unaltered rhyolite
(− 5.2‰). In contrast, the geothermal waters from Mammoth Hot
Springs, Sheepeater, and Rainbow Springs of Yellowstone have δ11B
values which are different from that of hydrothermally altered rhyolite
(− 8‰), possibly indicating a boron isotopic equilibrium between
geothermal water and altered minerals. Similarly, in the Yangbajing
geothermal field, two samples YBJT-2 and YBJT-6 with higher δ11B
values than the deep geothermal water may undergo a process where
10
B is incorporated into secondary minerals. However, owing to the
unavailability of chemical analysis data and boron isotopic compositions
of hydrothermal alteration minerals at Yangbajing, more detailed
analysis of the contribution of hydrothermal alteration to variation of
boron isotopic ratios in geothermal water cannot be made here.

4.4.3. CO2 degassing

As the geothermal fluids move upward all the way to the surface, the
decrease of fluid pressure causes CO2 degassing, which in turn induces
the transformation of HCO− 2−
3 to CO3 .

− 2−
2HCO3 ¼ CO3 þ CO2 ðgÞ þ H2 O ð3Þ Fig. 11. Bivariate plot of δ11B versus HCO−
3 concentration of water samples from the
Yangbajing geothermal field (a) and the Yangyi geothermal field (b).

As revealed by the plot of δ11B value vs. HCO− 3 concentration

(Fig. 11), the δ11B values of the Yangbajing geothermal samples do
not change evidently with the variation of their HCO− 3 concentrations.
The δ11B values of the Yangyi geothermal waters, however, show a
general decrease with the increase of HCO− 3 concentrations.
The CO2 degassing from geothermal fluid and subsequent conver-
sion of HCO− 3 to CO3
2−
should occur commonly below Yangyi, as con-
firmed by the fact that travertine prevails in and around the Yangyi
geothermal fields. The saturation indices of the Yangyi geothermal
waters with regard to common carbonate minerals such as calcite,
domomite and strontianite, calculated by use of geochemical code
PHREEQC, also indicate the precipitation of these minerals (Guo et al.,
2009). The precipitated carbonate minerals can adsorb boron from the
liquid phase, and cause boron isotope fractionation. In the plot of δ11B
value vs. Sr concentration (Fig. 12), the δ11B values of the geothermal
waters change in a similar way with variation of Sr concentration, just
as we have discussed for the δ11B value vs. HCO− 3 concentration plot.
It implies that the precipitation of SrCO3 was accompanied by the
incorporation of boron, inducing the change of boron isotopic ratios of
geothermal water. This speculation is also in accordance with what is
shown by the plot of δ11B value vs. SI-strontianite (Fig. 13). Besides
the precipitation of carbonate minerals, CO2 degassing can also cause
the increase of pH values of the geothermal waters. As discussed earlier,
the pH variation-induced conversion of B(OH)3 to B(OH)− 4 results in the
preferential adsorption of 10B-rich B(OH)− 4 onto solid phase, elevating
the δ11B values of the geothermal waters.
4.4.4. Geothermal fluid exploitation
Before the first Yangbajing geothermal power plant was built
(in 1981), there were 54 hot springs and a hot water lake with an area
of 7350 m2 in the south area of the Yangbajing geothermal field
(Li et al., 2003). However, after the geothermal power plant was put
into use, almost all of the primary hydrothermal manifestations disap-
peared. In recent years, under the effect of long-term intensive exploita-
tion of geothermal water, 21 wells drilled into the shallow reservoir
were abandoned due to the decrease of water-vapor production as
well. Moreover, according to Japanese scientists (Japan International
Collaboration Agency and Tibet Electric Power Company, 2006), the
concentrations of chloride in the geothermal water from Well ZK4001
are 946 and 1020 mg/L in January and August of 2005 respectively,
both of which are different from the analytical result of this study
(1073 mg/L). In a word, the chemical parameters of the geothermal wa-
ters in the Yangbajing hydrothermal system have been dynamically
changing due to the geothermal exploitation for electricity generation,
affecting the boron isotopic fractionation process as well. Lv et al.
(2012) have made a series of investigations in the Yangbajing geother-
mal field, and noticed that the boron isotopic fractionation in 1995 was
greater than in 2005. Based on the boron isotopic compositions of the
Yangbajing geothermal waters presented by Lv et al. and in this study,
a diagram of δ11B value variation over sampling time was plotted
(Fig. 14). Fig. 14 shows that the δ11B values of the Yangbajing
20 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22
Fig. 12. Bivariate plot of δ11B versus Sr concentration of water samples from the
Yangbajing geothermal field (a) and the Yangyi geothermal field (b).
geothermal waters changed little before 2001, but decreased evidently
after 2001 due to the exploration of geothermal fluids to a larger degree.
Hence, the exploitation of geothermal fluids is another factor related to
the change of boron isotopic values of geothermal water.
Fig. 13. Plot of δ11B values versus the saturation indices of the Yangyi geothermal water
samples with regard to strontianite.
Fig. 14. Variation of δ11B values of the Yangbajing geothermal waters in different sampling
times.
4.5. Boron and boron isotope compositions in the Zangbo River
Boron is very sensitive to human activities at some cases (Wolska
and Bryjak, 2013), and therefore has been widely used as a tracer
for evaluating anthropogenic inputs of boron to groundwater and sur-
face water systems (Chetelat et al., 2009). Moreover, boron isotopic
composition is a powerful tool for identifying contamination sources
and discriminating domestic or industrial effluent-derived boron from
agricultural practice-derived boron (Chetelat and Gaillardet, 2005). In
the Yangbajing geothermal field, there is no artificial recharge for the
reservoirs. However, the geothermal wastewaters generated by the
Yangbajing geothermal power plants, as an artificial input source of
boron, are directly discharged into the Zangbo River, elevating the con-
centrations of boron in the river waters and changing their δ11B values.
The boron concentration and δ11B value of YBJS1, collected from the up-
stream of the Zangbo River, are 0.1 mg/L and −7.3‰ respectively, quite
different from those samples collected in the downstream that had
been affected by the geothermal wastewater drainage. For example,
the sample YBJS3 collected near the geothermal wastewater drainage
exit has a boron concentration and δ11B value of 3.9 mg/L and −8.8‰,
respectively.
The boron concentration and δ11B value of the Zangbo River water
vary along its flow direction (Fig. 3). From the sampling location of
YBJS3 to that of YBJS12, the boron concentration of river water declines
sharply, which is probably due to the self-purification of the Zangbo
River, especially adsorption of boron in river water onto riverbed
sediment. However, from YBJS12 to YBJS14, the boron concentration
shows an increase. During our field investigation, we noticed that a
stream with high boron concentration (represented by sample YBJM-
7) merged into the Zangbo River, and the sample YBJS14 was just
collected very near their intersection. Thus, the boron concentration of
YBJS14 may be affected by the recharge of this boron-enriched stream.
From YBJS14 to YBJS15, the boron concentration decreases again.
Nevertheless, from YBJS3 to YBJS12, YBJS14 and YBJS15, the δ11B
value became more and more negative. Moreover, the δ11B values of
the Zangbo river waters downstream of the geothermal wastewater
drainage exit are between those of the upstream river waters and the
geothermal wastewaters (Fig. 5), indicating a mixing process. Besides
the mixing, adsorption/desorption should also be responsible for the
variation in boron isotope composition of the Zangbo River water.
During the adsorption of boron by riverbed sediment, 10B is preferably
incorporated into the solid phase, which leads to the enrichment of
11
B in the aqueous phase. The reverse holds true upon boron desorption
from riverbed sediment. The 11B in the Zangbo River waters became
 J. Yuan et al. / Journal of Geochemical Exploration 140 (2014) 11–22
more depleted from the geothermal wastewater drainage exit to the
downstream, indicating that desorption plays an important role in the
boron isotope fractionation of the Zangbo river system.
5. Conclusions
At Yangbajing and Yangyi, the boron concentrations are low and the
δ11B values are high in cold groundwaters and surface waters, while
geothermal waters have higher boron concentrations and lower δ11B
values. Although the boron concentrations of the Yangbajing and Yangyi
geothermal waters are comparable, the δ11B values of the geothermal
waters from Yangyi are higher than those from Yangbajing. Moreover,
the Yangbajing geothermal samples display quite close δ11B values
ranging from −11.4 to −12.8‰, indicating that the shallow and deep
reservoirs beneath Yangbajing are essentially within the same hydro-
thermal system. The dissolution of tourmaline-rich granitic rocks
dominantly controls the boron concentrations and δ11B values of the
Yangbajing and Yangyi geothermal waters. However, the boron isotope
ratios of geothermal water samples investigated in this study were also
affected by various secondary processes occurring in the reservoirs,
such as geothermal water–vapor separation and CO2 degassing.
Due to the drainage of geothermal wastewater by the Yangbajing
geothermal power plants, the boron concentration and δ11B value of
the Zangbo River water downstream of the wastewater drainage exit
are between the local background values of river water and those of
geothermal wastewater. The adsorption/desorption of boron onto/
from riverbed sediment are the major geochemical processes responsi-
ble for the variations of boron concentration and δ11B value of River
water along the flow direction. This study reveals that boron concentra-
tion and δ11B value are useful indicators for recognizing the origin of
boron in geothermal water and tracing the sources for aqueous environ-
ment contamination.
Acknowledgments
This study was financially supported by the National Natural Science
Foundation of China (No. 41120124003 and 40702041), the Fundamen-
tal Research Fund for National Universities, China University of
Geosciences (Wuhan) (Nos. CUG120505 and CUG120113), the Minis-
try of Education of China (111 project, No. B08030) and the Research
Fund of Bureau of Science and Technology of Qinghai Province (No.
2013-G-Q08A).
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