Strontium isotope constraints on solute sources and mixing dynamics in a large

impoundment, South-Central USA

Li Sun
a
, Matthew I. Leybourne
b,
, Nathan R. Miller
c
, Roger E. Denison
a
a
Department of Geosciences, University of Texas at Dallas, Richardson, Texas 75083, USA
b
GNS Science, Lower Hutt, New Zealand
c
Department of Geological Sciences, University of Texas, Austin, Texas, USA
a b s t r a c t a r t i c l e i n f o
Article history:
Received 22 September 2010
Received in revised form 12 April 2011
Accepted 15 April 2011
Available online 28 April 2011
Editor: J. Fein
Keywords:
Lake water geochemistry
Metalimnion
Red River
Washita River
Upper Red River Basin
Sr isotopes
Strontium concentration and isotope composition (
87
Sr/
86
Sr) are important proxies for tracing solute and
suspended load origins in surface water systems, but have not been widely applied to lakes. We determined
these proxies, in addition to major ion compositions, in waters collected from Lake Texoma, a large crescent-
shaped (concave-west) impoundment on the border of Texas and Oklahoma that marks the downstream
culmination of the Upper Red River Basin (URRB), and its major inuent rivers. These rivers enter the lake at
its southerly and northerly arms and have distinctly different salinities and discharges, respectively: the more
saline Red River (mean total dissolved solids, TDS=2930 mg/L; 1290 mg/L weighted for discharge,
Gainesville gauging station) and the fresher Washita River (TDS=634 mg/L; 376 mg/L weighted for
discharge, Dickson gauging station). These two inuent river systems combine to mix in the deepest (main)
part of the lake. The URRB involves a heterogeneous mix of bedrock geologies, notably high solubility Permian
marine evaporites (gypsum, halite) and carbonates, and riverine solute load and composition can vary
accordingly with regional precipitation. Most river and lake waters show an strong positive correlation
between
87
Sr/
86
Sr and 1/Sr. Red River system waters have variable
87
Sr/
86
Sr values, ranging from 0.7076 to
0.7097 (n=34), whereas the Washita River system appears to be less isotopically variable, with
87
Sr/
86
Sr
values ranging from 0.7082 to 0.7087 (n=16). Lake Texoma
87
Sr/
86
Sr varies spatially between 0.7087 and
0.7092, reecting mixing of the two input rivers. Variations in Sr isotope composition, Ca/Na and Sr/Ca of river
and lake waters are consistent with the majority of the solute load being derived from dissolution of Permian
marine chemical sediments, dominantly halite with lesser gypsum. Waters with Sr isotope composition more
radiogenic than Permian seawater reect the contribution of Permian and Pennsylvanian siliciclastic
sediments in the case of the Red River watershed, and Precambrian granite in the Washita River watershed. In
the main lake water column, Sr concentrations and ltered
87
Sr/
86
Sr increase substantially with depth during
summer stratication (from0.7087 to 0.7091), likely reecting desorption of Sr fromsuspended solid surfaces
and breakdown of oxyhydroxides below the metalimnion. The differences in
87
Sr/
86
Sr between ltered and
unltered aliquots suggest that Sr associated with the suspended load (calcite) is either less radiogenic than
the dissolved load or more radiogenic than surface waters but only released to the dissolved pool under
deeper reducing conditions below the metalimnion. Either possibility has important implications for Sr
cycling in binary mixing models and paleolake reconstruction from Sr isotopes.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The concentration and isotopic composition of aqueous Sr (Sr and
87
Sr/
86
Sr) have been used as lithochemical proxies to characterize
sources of dissolved solutes, the geochemistry of surface water
groundwater interactions, and mixing dynamics in rivers, groundwa-
ters, and estuaries (Palmer and Edmond, 1989; Krishnaswami et al.,
1992; Ngrel et al., 1993; Ngrel and Dupr, 1993; Andersson et al.,
1994; Abrerg, 1995; Ngrel et al., 1997; Ngrel and Grosbois, 1999;
Aubert et al., 2002; Ojiambo et al., 2003; Xu and Marcantonio, 2004;
Xu and Marcantonio, 2007). However, relatively few studies have
utilized Sr isotopes to understand water sources, mixing and
stratication in lakes and impoundments (Stein et al., 1997; Nakanao
et al., 2005; Eckardt et al., 2008; Jin et al., 2010).
Watershed studies demonstrate the utility of Sr isotope systematics
for: (1) understanding the inuence of silicate and carbonate weath-
ering on the solute budget of rivers and watersheds (Clow et al., 1997;
Jacobson et al., 2002; Bickle et al., 2005; White et al., 2005; Pett-Ridge
et al., 2009; Musgrove et al., 2010; Souza et al., 2010), in addition to
(2) identifying sources and uxes of solutes for management of urban
Chemical Geology 285 (2011) 203214
Corresponding author.
E-mail address: m.leybourne@gns.cri.nz (M.I. Leybourne).
0009-2541/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2011.04.010
Contents lists available at ScienceDirect
Chemical Geology
j our nal homepage: www. el sevi er. com/ l ocat e/ chemgeo
water quality (Nakano et al., 2008; Hosono et al., 2010). The Sr isotope
composition of the silicate end-member is typically more radiogenic
than the carbonate end-member, so that in some systems, Sr isotopes
can be a powerful tool for determining relative proportions of silicate
and carbonate weathering. Although most large river systems are
dominated by silicate and marine carbonate end-members, sulfate and
chloride evaporite weathering also inuence a smaller number of
systems (Gaillardet et al., 1999). Different correlation patterns between
river discharge andSr isotope compositions have beenreported(Palmer
and Edmond, 1989; Abrerg, 1995; Clowet al., 1997). In some studies, an
inverse relationship between discharge and
87
Sr/
86
Sr value in stream
water has been observed, whereas in others a positive correlation
between discharge and
87
Sr/
86
Sr value is observed for large catchments
covering multiple lithologies, and in a small catchment draining granitic
rocks (Palmer and Edmond, 1989; Krishnaswami et al., 1992; Abrerg,
1995; Clow et al., 1997; Aubert et al., 2002).
The great utility of Sr isotopes in tracing solute sources and water
mixing is that the
87
Sr/
86
Sr value is unaffected by low-temperature
surface processes. Note however, that recent work on
88
Sr/
86
Sr values
has suggested that these may be fractionated by weathering and
pedogenesis (Halicz et al., 2008). Solutes in rivers and lakes generally
reect their lithological sources, which typically have signicantly
different Sr concentrations and
87
Sr/
86
Sr compositions in marine
chemical sediments compared to siliciclastic sediments and igneous
rocks. Marine chemical sediments typically have less radiogenic
87
Sr/
86
Sr values relative to siliciclastic rocks, which provides the proxy
power of Sr isotopes. Although diagenesis and surface processes may
alter primary
87
Sr/
86
Sr compositions of watershed lithologies,
differences between primary seawater compositions (carbonates/
evaporites0.708) and radiogenic old continental crust (siliciclas-
tics0.712 or greater) are so large that initial solutes (and suspended
loads) are unlikely to vary signicantly fromtheir primary lithological
origins (Burke et al., 1982; Denison et al., 1994; Denison et al., 1998;
Kirkland et al., 2000). Differences in strontiumisotope ratios between
dissolvedandsuspendedloads canoccur inenvironments where FeMn
oxyhydroxides formor dissolve (Anderssonet al., 1994). Inriver waters,
differences of
87
Sr/
86
Sr have been observed between particulates and
dissolved load (Ngrel et al., 1993; Semhi et al., 2000). However,
whether there are differences in the Sr isotope composition between
suspended load and dissolved load in lakes is still unclear.
Herein, we report results of a systematic 3-year study of the Sr
isotope composition of Lake Texoma, a large impoundment on the
border between Texas and Oklahoma (South-Central United States).
Lake Texoma is unusual in that two rivers of highly contrasting
salinities provide its main inows. This inowdichotomy results from
differing upstream bedrock lithologies and degrees of chemical
weathering, and these unique solute end-members thus provide an
excellent opportunity to use Sr isotopes to characterize the Lake
Texoma geochemical system in terms of temporal and spatial solute
mixing behavior. In addition to geologic variations in headwater
reaches, Lake Texoma chemistry is seasonally affected by summer
stratication and bottom anoxia. In this dynamic lake system, we
surveyed Sr concentrations and
87
Sr/
86
Sr for the two inuent rivers,
the lake, and its outow water to establish the relative inuences of
catchment weathering, hydrology andsummer anoxia on Sr chemistry
and isotopic composition. In order to determine differences between
total load and dissolved load in Lake Texoma waters, we measured
87
Sr/
86
Sr for both ltered and unltered samples. The two main
questions addressed in this paper are: (1) what are the sources of Sr in
the lake and its major inuent rivers, and (2) what are the major
temporal and spatial controls of
87
Sr/
86
Sr in Lake Texoma waters?
2. Geological setting
Lake Texoma is a large crescent-shaped (concave-west) impound-
ment on the border of Texas and Oklahoma that marks the
downstream culmination of the Upper Red River Basin (URRB).
Constructed in 1943 for ood control, power generation, conserva-
tion, and recreation, it is Texas' third largest impoundment (360 km
2
)
with a drainage area of 15,336 km
2
(Fig. 1). The deepest part of the
main lake is up to 35 m in summer and the mean depth of the whole
lake is 9.3 m. Inows to the lake are mainly from two rivers, the Red
River and the Washita River. Headwaters of both rivers within the
URRB share similar bedrock lithologies, including Mississippian and
Pennsylvanian siliciclastics and Permian evaporites, but the Washita
River uniquely intersects siliceous igneous rocks of the Wichita
Mountains closer to Lake Texoma. URRB bedrock in lowest reaches of
the Red River and Lake Texoma region is mainly upper Cretaceous
limestone (Fig. 1). The Red River ows into Lake Texoma from the
west along the TexasOklahoma border, whereas the Washita River
enters the lake from the northwest in south-central Oklahoma. Lake
bottom waters are released from Denison Dam (at the SE end of the
lake) to the lower Red River, and ultimately to the lower Mississippi
River.
The Red River constitutes about 60% of the inow to Lake Texoma
and is the dominant source of dissolved solids (Table 1). The
headwaters of the Red River system begin as springs at the base of
the Llano Estacado, the southernmost (W. Texas) portion of the High
Plains. The River crosses Permian marine chemical sediments
(gypsum, anhydrite and carbonates, with halite in the subsurface)
as well as paralic and terrestrial siliclastic rocks (Permian and
Pennsylvanian shales, siltstones, redbeds) and Cretaceous sandstone,
limestone and shale, and Cenozoic terrestrial sediments. The Washita
River also originates in the Texas Panhandle, but ows through south-
central Oklahoma before entering Lake Texoma from the north.
Although chemical sedimentary rocks are abundant in headwater
reaches of both rivers (Fig. 1), Washita River waters entering Lake
Texoma are typically fresher than the Red River (Red River:
TDS=2930 mg/L; 1290 mg/L weighted for discharge, Gainesville
gauging station; Washita River: TDS=634 mg/L; 376 mg/L weighted
for discharge, Dickson gauging station). Weighting for discharge
adjusts the salinity based on inverse relationship between discharge
and TDS, and is calculated as:
TDS
discharge weighted
=

n
i
discharge
i
TDS
i

discharge
:
Lake Texoma, like many other reservoirs in the southern and
western United States, undergoes thermal stratication in summer
and becomes almost completely mixed during the winter (Leifeste
et al., 1971; Sun et al., submitted for publication-b). Limnologically,
the lake also possesses strong horizontal chemical concentration
gradients (salinity, major and trace ions) with higher variability in the
more riverine areas compared to deeper areas of the main lake near
the Denison Dam (Work and Gophen, 1999; Sun et al., submitted for
publication-b).
3. Sampling and analytical methods
Samples were collected at several stations around Lake Texoma
(19982005), the URRB (19982005; Fig. 1), and from multiple
stations in Lake Texoma (20032005; Fig. 2). For Lake Texoma
samples, depth, temperature, dissolved oxygen (DO), oxidation
reduction potential (ORP) and pH were measured in situ using a
Hydrolab Quanta-multiprobe before sampling to ensure depth-
representative samples were obtained. The number of samples taken
from each station, varied from 1 to 8 samples, depending on station
water depth and vertical prole of physical and chemical parameters.
Lake water was collected using a depth discrete (Niskin-type) water
sampler and transferred to high-density polyethylene (HDPE) bottles,
which were rinsed three times with sample prior to collection. Both
204 L. Sun et al. / Chemical Geology 285 (2011) 203214
ltered and unltered samples for each location were collected for
cation analyses. For ltered samples, 250 mL volumes were passed
through 0.45 m Millipore Sterivex membrane lters. Cation samples
were acidied to pHb2 with 70% ultrapure HNO
3
. For the Red River
system, we collected samples for Sr isotope analysis from the main
stem of the Red River in the headwaters in West Texas (Pease and
Wichita rivers), fromseveral tributaries of the Red River inWest Texas,
and from the USGS gauging station at Gainesville, the last station
before the RedRiver enters Lake Texoma (Fig. 1). The largest number of
samples was collected from the USGS gauging station at Gainesville
(n=26) over the period 1998 to 2004. These URRB samples (and
samples collected below Denison Dam and the Washita River during
this period) were collected without ltration in pre-cleaned bottles
and stored in a cooler after collectionin the eld before refrigeration in
the lab.
Water samples for aqueous geochemical studies are typically ltered
using either 0.45 mor 0.2 mlters. Filteredanalyte concentrations are
then commonly considered as the dissolved load, whereas the
suspended load is considered the difference between ltered and
unlteredaliquots. However, theselter poresizes andthe classication
of b0.45 m as the dissolved load are only operationally dened (Hall
et al., 1996); the b0.45 m portion contains not only dissolved species,
but also ne colloidal material. To determine the truly dissolved portion
requires the use of ultraltration (Degueldre et al., 1996; Zanker et al.,
2002) or centrifugation (Leybourne et al., 2000) to 0.005 m or less.
With the caveat that 0.45 m lters do not represent truly dissolved
species, we measuredthe Sr isotope compositionof Lake Texoma waters
in ltered (b0.45 m) and, in a subset of samples, unltered aliquots.
Strontium and major ion concentrations were analyzed by
Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES;
Perkin Elmer Optima 3300 DV), ion chromatography (Dionex DX600),
and end-point titration (alkalinity). Complete analytical details are
provided in Sun et al. (submitted for publication-b).
Two methods using two different thermal ionization mass
spectrometers (TIMS) were used to determine
87
Sr/
86
Sr values. For
the rst method, 5 mL of 0.5M Na
2
CO
3
was added to 50 mL unltered
aliquots to precipitate CaCO
3
and SrCO
3
. Subsequently, samples were
centrifuged and the supernatant decanted. The remaining solids were
dried and dissolved in 0.5 mL of 3N HNO
3
. Strontium was separated
using a strontiumspecic resin and collected with deionized (Milli-Q)
water. Sr solutions were dried and solid samples were dissolved in
0.5 mL 3N HNO
3
, loaded onto etched Ta laments, and dried. The
Fig. 1. Geologic map of Lake Texoma and the Upper Red River basin (modied after King and Beikman, 1974) showing locations of water samples throughout the basin. Single sample
locations are shown with corresponding
87
Sr/
86
Sr values. Multi-sampled locations are indicated by site names listed on Table 3. The rectangular box outlines the Lake Texoma area.
Table 1
Total annual average discharge to Lake Texoma by the Red River and the Washita River
in six consecutive years fromUSGS real-time water data set (http://waterdata.usgs.gov/
nwis). Locations of USGS gage stations at Gainesville and Dickson are shown on Fig. 1.
Unit: m
3
/s.
Year Gainesville
(Red River)
Dickson
(Washita River)
Washita R. inow as a
% of the Red R. inow
1998 39,350 26,138 60%
1999 18,923 14,420 57%
2000 26,786 18,642 59%
2001 32,421 23,612 58%
2002 16,749 12,849 57%
2003 9643 8192 54%
2004 27,726 16,782 62%
Mean 24,514 17,234 58%
SD 10,090 6206 3%
205 L. Sun et al. / Chemical Geology 285 (2011) 203214
isotope ratios were measured on a second order, double focusing mass
spectrometer with a 60, 33.0 cm radius of curvature magnetic sector
and a 91

, 40.1 cm radius of curvature electric sector. Masses 85, 86,

87, and 88 were measured simultaneously in four faraday cups. The
87
Sr/
86
Sr values were normalized to
86
Sr/
88
Sr=0.1194. The isotope
ratios of the unknown samples were measured by comparison to NIST
standard SRM-987, normalized to a value of 0.710240.
For the second method, ltered and unltered Lake Texoma
samples containing ~3 g Sr were evaporated under HEPA-ltered air.
Unltered samples were shaken thoroughly before processing to
ensure the incorporation of both particulates and dissolved solutes in
dried solids. Dried samples were dissolved in 0.2 mL of 3N HNO
3
, and
then loaded into polypropylene columns containing 0.3 mL of Sr-
specic resin (Eichrom). After washing the resin column with 1.8 mL
3N HNO
3
, Sr was eluted with 1 mL of deionized (Milli-Q) water. Two
drops of 1N phosphoric acid were added to visualize the sample after
evaporation; again under ltered air. Samples were loaded onto Re
laments as tantalum oxide slurries, which promotes ionization, and
analyzed in static mode for Sr isotopes on a Finnigan MAT261 TIMS.
NIST SRM-987, analyzed every three samples, yielded an average
87
Sr/
86
Sr composition of 0.710297. Sample LS-LT0803 12, analyzed
twice over 4 months yielded
87
Sr/
86
Sr values of 0.70875621 and
0.70878923, respectively. After the rst group of tests on both TIMS,
differences in
87
Sr/
86
Sr value between ltered and unltered aliquots
of identical samples were observed. In order to rule out the possibility
of machine bias, two identical unltered aliquots (LS-LT0803 92)
were analyzed on both TIMS. The two instruments yielded
87
Sr/
86
Sr
values of 0.70874220 and 0.70874420, respectively, indicating no
systematic bias.
Descriptive statistics for strontium concentration and isotope data
were calculated and evaluated using the Minitab statistical analysis
programv. 14.1(Minitab, Inc., State College, PA). Correlationcoefcients
were also calculated using student and paired sample t-tests to
determine 95% (unless otherwise noted) signicance levels of differ-
ences between selected variables. Speciation and saturation indices (SI)
for the lake waters were calculated using PHREEQCi (Parkhurst and
Appelo, 1999), with pe controlled by measured Eh.
4. Results
4.1. Catchment geology and regional waters
Permian marine chemical sediments, including evaporites (gyp-
sum outcrops and halite in subcrop) and carbonates, dominate the
geology of the headwater regions for both the Red and Washita rivers.
Samples of gypsum analyzed in this study and elsewhere in the
watershed (Miller and Leybourne, 2002; Miller et al., in preparation)
(Table 2) are consistent with values for Permian seawater, with
87
Sr/
86
Sr of ~0.7079. Gypsumand carbonate fromSalt Flat, Texas, are more
radiogenic than Permian seawater, with
87
Sr/
86
Sr of ~0.7087. Closer to
Lake Texoma both of the main inuent rivers ow over Cretaceous
marine carbonate-dominated lithologies (Fig. 1). Although we did not
analyze Cretaceous carbonates in the catchment, seawater during this
time had a narrowrange of
87
Sr/
86
Sr (0.70700.7075), which brackets
the strontium isotope composition of major bedrocks in the catch-
ment area.
Based on data collected in the Wichita River watershed (Miller and
Leybourne, 2002; Leybourne et al., in preparation) and USGS gauging
stations, highest salinities in the Red River system occur in headwater
regions with some tributaries having salinities in excess of seawater
(e.g., South Fork Wichita River). For the samples reported here, TDS
ranges fromas high as 11,900 mg/L in the Prairie Dog Town Fork of the
Red River to as lowas 319 mg/L at the downstreamGainesville station
(Table 3). Salinities decrease along the Red and Washita rivers
towards Lake Texoma, with salinities variable as a function of
discharge. At the Gainesville gauging station, just above Lake Texoma
on the Red River, salinity variations as a function of discharge and
relative solute contributions from headwater tributaries follow a
power law: Ln[SpC] =0.289 Ln[m
3
/s] +9.2, r=0.69. During low
ow periods, salinity at the Gainesville station commonly exceeds
3000 mg/L. By contrast, at the Dickson gauging station on the Washita
River, river salinity is typically much lower than at Gainesville,
although salinity and discharge still follow a power law: Ln[SpC]=
0.182 Ln[m
3
/s] +7.5, r=0.51. The dampening effect on water
chemistry of Lake Texoma is evident for the Denison Dam gauging
station, where salinity decreases only slightlywithdischarge: Ln[SpC]=
0.030 Ln[m
3
/s] +7.5, r=0.28.
Table 2
87
Sr/
86
Sr ratios of carbonates and gypsum in the URRB.
Sample ID
87
Sr/
86
Sr Description
Carbonate SF-1C 0.708694 6 Salt at, surface carbonate
sand, Hudspeth Co. TX
SF-2C 0.708681 10 Salt at, core carbonate
SF-3C 0.708739 9 Salt at, core carbonate
SR-4C 0.708695 9 Salt at, core carbonate
Mean 0.708702 SD 0.000025
Gypsum SF-1G 0.708726 18 Salt at, surface gypsum sand
SF-2G 0.708740 13 Salt at, core gypsum
SF-3G 0.708664 10 Salt at, core gypsum
SR-4G 0.708690 9 Salt at, core gypsum
13173G 0.707919 17 White sands gypsum,
Dona Ana Co., NM
WS-1 0.707930 10 White sands NM gypsum
Mean 0.708445 SD 0.000404
Fig. 2. Lake Texoma map showing locations of sampling sites (020) and USACE
chloride zones the Main Lake (ML), the Red River zone (RRZ), and the Washita River
zone (WRZ) and two transition zones (RRTZ and WRTZ) (MC = mean chloride)
(Atkinson et al., 1996).
206 L. Sun et al. / Chemical Geology 285 (2011) 203214
Table 3
Sr concentration and
87
Sr/
86
Sr values in surface waters collected in Lake Texoma and the Upper Red River Basin from 1998 to 2004 (mostly unltered unless otherwise indicated).
Location Sample ID Collection
date
87
Sr/
86
Sr TDS
(mg/L)
Sr
(mg/L)
Ca
(mg/L)
Sr/Ca
(molar)
Ca/Na
(molar)
Discharge
(m
3
/s)
Upstream Red River Red River-24 07/07/99 0.707867 7 3730.00 6.73 591.47 0.0052 0.0758
Red River-18 02/20/99 0.708156 17 3870.00 4.09 331.05 0.0056 0.1387
Red River-19 02/20/99 0.707797 15 1550.00 4.59 463.23 0.0045 1.1203
Red River-20 02/20/99 0.707659 13 11900.00 10.86 779.05 0.0064 0.0940
Red River-21 02/20/99 0.707982 15 4250.00 3.22 232.18 0.0063 0.1810
Mean 0.707892 5060.00 5.90 479.40 0.0056 0.32196
SD 0.000188 3966.95 3.06 215.49 0.00079 0.44815
Red River tributaries Pease River 03/21/99 0.707610 17 10000.00 12.11 926.62 0.0060 0.1278
Wichita Falls 03/21/99 0.709654 17 2760.00 5.36 305.07 0.0080 0.1785 0.40
Wichita Falls 09/07/99 0.708967 12 2800.00 4.53 268.93 0.0077 0.1694 1.56
Wichita Falls 05/05/00 0.708373 8 2900.00 3.77 252.43 0.0068 0.1874 0.76
Mean 0.708651 4615 6.4425 438.26 0.00713 0.16578 0.96
SD 0.000869 3590.48 3.8337 326.31 0.00091 0.02636 0.57
Red River at Gainesville Red River-1 03/03/98 0.708400 14 1870.00 1.70 119.46 0.0065 0.1906 168.66
Red River-2 05/26/98 0.708322 14 2480.00 2.65 188.33 0.0064 0.1908 42.08
Red River-4 07/10/98 0.708694 9 2120.00 3.62 229.82 0.0072 0.1787 21.92
Red River-5 08/06/98 0.708772 10 2200.00 3.05 178.25 0.0078 0.1604 10.62
Red River-9 09/10/98 0.708538 17 2580.00 3.73 247.77 0.0069 0.2017 7.05
Red River-10 10/23/98 0.708611 8 2450.00 10.82
Red River-13 11/24/98 0.708382 14 2850.00 3.72 280.33 0.0061 0.1684 13.42
Red River-15 12/29/98 0.708369 16 2380.00 3.45 260.07 0.0061 0.1873 11.02
Red River-15 01/28/99 0.708356 7 2950.00 3.63 270.08 0.0061 0.1746 12.66
Red River-17 02/25/99 0.708365 15 3010.00 3.42 247.54 0.0063 0.1566 14.67
Red River-22 04/22/99 0.708963 15 1150.00 1.51 119.34 0.0058 0.2146 27.33
Red River-23 06/03/99 0.708390 8 732.00 1.10 101.99 0.0049 0.3010 200.43
Red River-25 10/12/99 0.708695 15 2430.00 3.30 215.29 0.0070 0.1578 7.53
Red River-27 01/13/00 0.708524 15 2390.00 2.54 185.69 0.0063 0.1639 11.30
Red River-29 02/03/00 0.708466 10 2920.00 3.31 246.15 0.0061 0.1744 9.74
Red River-30 02/17/00 0.708486 17 3180.00 3.61 263.17 0.0063 0.1582 6.77
Red River-33 09/17/00 0.708565 13 2890.00 3.93 265.26 0.0068 0.1750 2.69
Red River-35 11/10/00 0.709349 7 319.00 0.51 57.33 0.0041 0.3405 462.05
Red River-36 01/26/01 0.708855 18 1550.00 1.96 125.32 0.0071 0.1418 45.08
Red River-37 10/20/01 0.708903 16 1280.00 11.19
Red River-38 10/20/01 0.708893 14 1360.00 11.19
Red River-39 04/26/02 0.708578 11 1210.00 0.2453 53.01
Red River-40 11/19/02 0.708325 11 2920.00 14.10
Red River 41 04/10/03 0.708536 11 2920.00 9.17
Red River-42 11/06/03 0.708982 17 2170.00 4.33
Red River-44 11/11/04 0.709211 12 458.00 44.03
Mean 0.708636 2106.5 2.82 200.07 0.0063 0.1938 47.40
SD 0.000281 841.74 1.03 68.75 0.0008 0.0510 97.01
Red River below Denison Dam Red River-3 05/26/98 0.708688 15 952.00 1.44 120.86 0.0055 0.2995 13.22
Red River-6 08/06/98 0.708693 15 823.00 1.37 117.32 0.0053 0.3464 120.29
Red River-8 09/10/98 0.708668 12 761.00 1.37 116.84 0.0054 0.3472 64.48
Red River-11 10/23/98 0.708598 15 838.00 1.42 89.27 0.0073 0.2445 61.19
Red River-12 11/24/98 0.708603 13 1220.00 1.72 111.13 0.0071 0.1954 46.24
Red River-14 12/29/98 0.708497 11 870.00 1.48 101.18 0.0067 0.2678 57.94
Red River-14 01/28/99 0.708594 16 878.00 1.50 104.08 0.0066 0.2736 58.50
Red River-16 02/25/99 0.708620 16 922.00 1.64 120.30 0.0062 0.3036 57.14
Red River-26 01/13/00 0.708560 13 1070.00 1.51 108.27 0.0064 0.2591 75.97
Red River-28 02/03/00 0.708513 12 1090.00 1.54 116.35 0.0061 0.2796 60.91
Red River-31 04/02/00 0.708560 17 1040.00 1.57 121.13 0.0059 0.2955 160.16
Red River-32 04/04/00 0.708567 16 1060.00 194.90
Red River-34 09/17/00 0.708472 18 1010.00 1.65 127.99 0.0059 0.2546 7.45
Red River-43 10/18/04 0.708666 14 853.00 70.76
Red River-45 01/26/05 0.708639 7 813.00 159.08
Red River-46 02/16/05 0.708746 13 809.00 158.52
Mean 0.708605 938.06 1.52 112.89 0.0062 0.2806 85.43
SD 0.000762 129.93 0.11 10.70 0.00065 0.0424 55.70
Downstream Red River Red River-7 08/06/98 0.708673 18 740.00
Washita River at Davis Washita-1 03/03/98 0.708382 13 847.00 2.49 144.97 0.0079 1.0983
Washita-2 (ltered) 05/05/98 0.708600 18 565.00 1.51 93.08 0.0074 1.1113
Washita-12 04/22/99 0.708246 13 740.00 2.57 190.92 0.0062 1.7623
Washita-13 10/12/99 0.708456 16 935.00 2.49 182.50 0.0063 0.8866
Mean 0.708421 771.75 2.265 152.87 0.0070 1.21463
SD 0.000148 159.23 0.5047 44.583 0.00083 0.37937
Washita River at Chickasaw
Recreation Area
Pavilion Spring 09/17/00 0.711143 9 420.00 1.82 43.29 0.0193 0.3218
Vendome Well 09/17/00 0.711142 15
Washita River at Tishomingo Washita-3 05/26/98 0.708368 15 711.00 2.16 158.25 0.0063 1.3376 35.23
Washita-4 07/10/98 0.708514 10 800.00 2.27 138.21 0.0075 0.7398 10.42
Washita-5 08/06/98 0.708380 15 885.00 2.48 157.60 0.0072 0.7496 4.81
Washita-6 09/10/98 0.708431 17 810.00 2.36 151.16 0.0071 0.7089 2.69
Washita-7 10/23/98 0.708715 18 547.00 1.17 70.54 0.0076 0.7639 17.39
Washita-8 11/24/98 0.708189 16 920.00 3.03 215.51 0.0064 1.7506 17.19
(continued on next page)
207 L. Sun et al. / Chemical Geology 285 (2011) 203214
Waters collected fromRed River tributaries provide some measure
of the Sr ux and range of
87
Sr/
86
Sr associated with Red River input to
Lake Texoma. On the main stem of the upper Red River,
87
Sr/
86
Sr
varies between 0.7077 and 0.07082 (average=0.70790.0002,
n=5). These values are similar to Permian seawater. Four Upper
Red River tributary samples (one on the Pease River and three on the
Wichita River at Wichita Falls) have Sr isotope compositions
comparable to or more radiogenic than Permian seawater (
87
Sr/
86
Sr=0.70760.7097). A more comprehensive study of the Sr isotope
systematics of the Wichita River systemis in progress, but preliminary
data indicate that
87
Sr/
86
Sr values range from0.7074 to 0.7126 (Miller
and Leybourne, 2002; Miller et al., in preparation); the eastern
Wichita River near its conuence with the Red River (Wichita Falls) is
more radiogenic and typically less saline than its western headwaters.
The Red River at Gainesville (above Lake Texoma) is variable in
terms of Sr isotope composition, salinity and discharge. Unltered
water samples have
87
Sr/
86
Sr values that uctuate through time be-
tween 0.7083 and 0.7093. Although there is no statistically signicant
relationship between Sr isotope composition and discharge, the Red
River at Gainesville is generally more radiogenic during periods of
increased discharge. For this station, Ca/Na
molar
values vary inversely
with discharge. The Ca/Na
molar
values, along with Sr isotope compo-
sition, are primarily controlled by bedrock lithology.
Washita River waters collected at Davis, Oklahoma (about 100 km
northwest of Lake Texoma), and Tishomingo, Oklahoma (proximal to
the Washita input; Fig.1) have
87
Sr/
86
Sr ranging from0.7082 to 0.7087
(n=15). The highest Washita River
87
Sr/
86
Sr values (0.7111, n=2)
were found in Pavilion Spring and Vendome Well, Oklahoma (about
70 km NNW of Lake Texoma) (Fig. 1).
OutowfromLake Texoma (i.e., the Red River belowDenisonDam)
has relatively uniform
87
Sr/
86
Sr close to 0.70868 (unltered, n=16;
Table 3); slightly less radiogenic than Lake Texoma (0.708818
0.000180, unltered, n=8; Table 4) (t =5.83, pb0.001).
River and lake samples show a general inverse relationship
between
87
Sr/
86
Sr and both Sr concentration and TDS (Fig. 3). River
waters above Lake Texoma, from the Red River at Gainesville and
Washita River at Tishomingo, exhibit negative correlations between
Sr concentrations and
87
Sr/
86
Sr values (r=0.54; and r=0.91,
respectively) (Fig. 3). TDS is also negatively correlated with
87
Sr/
86
Sr
values at Gainesville (r=0.712; n=18). However, samples from
the upper Red River main stem show much greater variation in Sr
concentration, with only subtle changes and least radiogenic
signatures in Sr isotopes (Fig. 3), except that there is an positive
trend for three samples from the Wichita River at Wichita Falls that
are characterized by more radiogenic
87
Sr/
86
Sr with increasing Sr
concentration (Table 3; Fig. 3).
Strontiumconcentrations decrease downstreaminthe URRBcatch-
ment area above, within, and below Lake Texoma. The highest mea-
sured Sr concentration of 12.1 mg/L was found for the Pease River, a
Red River tributary (500 km west of Lake Texoma). Sr concentrations
between 11 and 3 mg/L (average: 5.903.06, n=5) occur in the main
stemof the Red River west of Lake Texoma (Table 3). River Sr input just
above Lake Texoma averages 2.81.0 mg/L (n=18) for Gainesville
(Red River) and 2.30.5 mg/L (n=11) for Tishomingo (Washita
River). The Red River belowDenisonDamhas Sr concentrations within
a narrow range, 1.71.4 mg/L (average: 1.50.1 mg/L), reasonably
comparable to that in the lake (2003 average: 1.00.1, n=13;
Table 4).
Ca concentrations range from 43 to 927 mg/L in the Red River,
5586 mg/L in Lake Texoma, 43216 mg/L in the Washita River, and
89128 mg/L in the outowbelowthe Denison Damin the Red River.
Red River waters have Ca/Na
molar
values ranging from 0.09 to 0.35
(average=0.210.19), with one sample N1.0 (Fig. 4). Lake Texoma
water samples have broadly similar Ca/Na
molar
values, ranging from
0.18to 0.45 (average=0.260.06). By contrast, Washita River samples
exhibit more elevated Ca/Na
molar
values, typically N1 (average=1.13
0.42).
4.2. Lake Texoma
Sr concentrations vary both laterally and vertically within Lake
Texoma. Highest concentrations in the range of 0.72 to 1.32
Table 4
Sr and Ca concentrations and Sr isotope compositions of water samples from Lake Texoma (August 2003).
Sample ID Collection
date
Sample depth
(m)
pH Water column
depth (m)
Filtered
87
Sr/
86
Sr
Unltered
87
Sr/
86
Sr
Sr
(mg/L)
Ca
(mg/L)
Na
(mg/L)
Sr/Ca
(molar)
Ca/Na
(molar)
TDS
(mg/L)
LS-LT0803 12 08/09/03 4 8.23 12 0.708756 21 0.709023 27 1.185 84.6 266.0 0.006407 0.1824 1105.12
LS-LT0803 52 08/09/03 3 8.23 15 0.708747 21 1.06 79.6 206.0 0.006005 0.2216 939.49
LS-LT0803 54 08/06/03 15 7.27 15 0.708944 22 0.708733 17 1.100 83.0 217.0 0.006035 0.2194 990.90
LS-LT0803 72 08/06/03 6 8.07 22.5 0.708722 18 0.999 78.2 187.0 0.005765 0.2399 883.86
LS-LT0803 75 08/06/03 20 6.99 22.5 0.708740 18 0.708663 19 1.090 84.0 189.0 0.005908 0.2549 896.2
LS-LT0803 82 08/06/03 5 8.21 21 0.708871 20 1.040 78.6 200.0 0.005965 0.2254 930.12
LS-LT0803 92 08/06/03 6 8.06 28 0.708931 22 0.708744 20 1.010 80.7 192.0 0.005685 0.2411 905.66
LS-LT0803 93 08/06/03 15 7.66 28 0.708694 10 0.708699 18 0.986 80.7 185.0 0.005603 0.2502 893.06
LS-LT0803 94 08/06/03 18 7.39 28 0.708861 19 1.030 81.8 194.0 0.006067 0.2419 913.06
LS-LT0803 95 08/06/03 24 7.2 28 0.709106 18 0.708756 20 1.090 86.2 188.0 0.005731 0.263 913.87
LS-LT0803 96 08/06/03 27 7.12 28 0.708955 17 0.708752 14 1.080 86.1 185.0 0.005711 0.267 894.73
LS-LT0803 142 08/06/03 6 7.75 14 0.708998 24 0.930 75.0 133.0 0.005678 0.3235 746.09
LS-LT0803 162 08/08/03 1 7.73 1 0.709233 17 0.709173 18 0.775 54.8 71.8 0.006365 0.4378 457.98
Mean 7.69 0.708889 0.708818 1.029 79.5 185.7 0.005917 0.2591 882.32
SD 0.45 0.000162 0.00018 0.099 8.1 44.7 0.000258 0.0627 149.60
Table 3 (continued)
Location Sample ID Collection
date
87
Sr/
86
Sr TDS
(mg/L)
Sr
(mg/L)
Ca
(mg/L)
Sr/Ca
(molar)
Ca/Na
(molar)
Discharge
(m
3
/s)
Washita-9 12/29/98 0.708188 16 756.00 2.64 183.94 0.0066 1.5580 28.68
Washita-10 01/28/99 0.708342 14 764.00 2.33 188.61 0.0057 1.4251 15.35
Washita-11 02/25/99 0.708376 16 780.00 2.63 203.09 0.0059 1.5638 20.76
Washita-14 01/13/00 0.708559 16 762.00 1.75 132.23 0.0060 1.0424 12.83
Washita-15 02/03/00 0.708538 14 800.00 1.91 159.77 0.0055 1.1827 11.38
Mean 0.708418 775.91 2.25 159.90 0.0065 1.1657 16.11
SD 0.000158 96.10 0.50 39.58 0.0007 0.3862 9.57
Washita River at Tishomingo
208 L. Sun et al. / Chemical Geology 285 (2011) 203214
(average=1.060.12) occur near the inow of the Red River (site 1;
RRZ), whereas systematically lower concentrations are encountered
with increasing proximity to Washita River inow (site 16; WRZ,
Table 4). Within the deep main lake, Sr concentrations decrease
slightly with depth toward the metalimnion (i.e., 15 m at site 9) and
then increase again toward the lake bottom (Table 4, Fig. 5).
Overall,
87
Sr/
86
Sr values of ltered waters from Lake Texoma from
August 2003 range from0.70869410 (site 9 at 15 m) to 0.709233
17 (site 16 at 1 m) with a mean value at 0.708889162 (Table 4).
Regionally, Sr isotope compositions of Lake Texoma waters were most
radiogenic in the WRZ (August 2003) (Fig. 4). In the main lake area,
87
Sr/
86
Sr values vary with depth, temperature, pH, and DO (Fig. 5). For
example, at site 9 above Denison Dam, the least radiogenic sample was
found at 15 m (0.7087), whereas more radiogenic values occurred in
the surface and bottom waters (0.70880.7091; Fig. 5). Lake Texoma
waters become more radiogenic, and Sr contents decrease, away from
the Red River inow and toward the Washita River inow.
Several other geochemical indices (Ca, Ca/Na, and Sr/Ca) appear to
follow lateral and vertical Sr concentration and
87
Sr/
86
Sr variations
within Lake Texoma (Table 4, Fig. 4). For example Ca concentrations
(range: 55 to 86 mg/L) are greater toward the Red River input and
lower toward the Washita River input, and also increase with depth
(e.g., sites 7 and 9, Table 4). Ca/Na is generally higher toward Washita
River input (Table 4; Fig. 4C) and with depth (sites 7 and 9). Sr/Ca
variations within Lake Texoma appear to be somewhat more
complicated. Although they are generally higher toward Red River
input, locality 16 closest to Washita River inow has the second
highest Sr/Ca value and is a notable exception to this trend. In
addition, Sr/Ca seems to increase then decrease with depth near the
metalimnion, but the depth of maximum enrichment is shallower
than that for
87
Sr/
86
Sr described above (Table 4).
4.3. Sr isotope composition of ltered and unltered samples
Regionally, ltered Lake Texoma samples (n=8) generally have
more radiogenic
87
Sr/
86
Sr compositions compared to their unltered
companions, with two notable exceptions. One sample from the main
lake zone (LS-LT0308 93) has identical ltered and unltered values,
and one sample from the Red River zone (LS-LT0308 12) has a more
radiogenic unltered signature compared to its ltered aliquot
(0.70902327 vs. 0.70875621; paired sample t-test: all samples
n=8, t =1.56, P=0.164; without the two exceptions n=6, t =4.22;
P=0.008). Interestingly, compared to ltered samples from the main
lake zone that show vertical
87
Sr/
86
Sr variations relative to the
metalimnion, corresponding unltered samples have virtually iden-
tical
87
Sr/
86
Sr compositions (Site 9; Fig. 5).
Limited comparisons for riverine samples also demonstrate
87
Sr/
86
Sr variations between ltered and unltered samples. Specically,
one ltered sample collected from the Washita River at Davis is more
radiogenic (0.70860018) than three other unltered samples
(0.70824613 to 0.70845616).
4.4. Mineral saturation calculations
All Lake Texoma waters are undersaturated with respect to gypsum
(average SI
gypsum
=1.340.03) and halite (average SI
halite
=5.89
0.20). In contrast, many waters are saturated with respect to calcite (and
dolomite) (Fig. 5c). LakeTexomawaters donot showsignicant variation
in major ion chemistry and this is reected in the restricted range in
SI
calcite
, from1.04 to 0.58. Furthermore, there is no signicant regional
variation in calcite saturation within the lake (e.g., Red River arm versus
Washita arm and main lake). However, there is a clear distinction
between SI
calcite
and depth, pH, dissolved oxygen and Eh (e.g., DOshown
in Fig. 5). Waters below~12 mdepth are undersaturated throughout the
lakewithrespect tocalcite, withthedegreeof undersaturationincreasing
withdepth. Incontrast, waters above ~10 mare saturatedwithrespect to
calcite. In comparison, Leybourne et al. (in preparation) found that
essentially all surface waters in the Wichita River watershed and the
upper Red River are saturated with respect to calcite. Thus, the
hypolimnion (the lower or, in summer, the anoxic layer) is characterized
by calcite undersaturation, whereas the metalimnion and epilimnion are
characterized by calcite saturation.
A
B
C
Fig. 3. Plots relating Sr isotope composition of Lake Texoma waters and catchment
rivers to salinity/TDS and Sr concentration.
209 L. Sun et al. / Chemical Geology 285 (2011) 203214
5. Discussion
5.1. Solute sources and catchment control on the Sr isotope composition
of Lake Texoma
Surface water
87
Sr/
86
Sr has been used as a lithogeochemical proxy
to better understand the relative contributions of carbonate and
silicate weathering to the solute budget of rivers, lakes, and the ocean
(Semhi et al., 2000; Jacobson et al., 2002; Bickle et al., 2005).
Signicant volumes of highly soluble chemical marine strata (Permian
gypsum/anhydrite, sub-surface halite, Permian/Cretaceous carbon-
ate) within headwater regions of the URRB complicate a similar
assessment for Lake Texoma (Fig. 1) and its two main (Red/Washita)
inow systems.
Siliciclastic weathering
Gypsum weathering
G
y
p
s
u
m
w
e
a
th
e
rin
g
S
i
l
i
c
i
c
l
a
s
t
i
c

w
e
a
t
h
e
r
i
n
g
B
A
C
D
F
E
Fig. 4. Solute molar cation cross-plots showing probable mineralogical end-member associations. A)
87
Sr/
86
Sr vs. Ca/Na
molar
, B)
87
Sr/
86
Sr vs. Sr/Na
molar
, and C) Ca/Na
molar
vs. Sr/
Na
molar
. Shaded boxes on A, B, and represent the respective insets for D, E, and F. Also shown are data for large rivers of the world, from Gaillardet et al. (1999).
210 L. Sun et al. / Chemical Geology 285 (2011) 203214
Weathering related solute ux studies are also important for
understanding the secular evolution of seawater
87
Sr/
86
Sr relative to
variations in its major inputs non-radiogenic Sr derived from
hydrothermal alteration of seaoor and radiogenic Sr derived from
chemical weathering of old continental crust (Burke et al., 1982). For
example, Jacobson et al. (2002) used Sr isotopes and major ion
concentrations to show that Himalayan stream solutes derive mainly
(~76%) fromcarbonate dissolution. For Lake Texoma waters, it is more
difcult to constrain the relative contributions from silicate and
carbonate weathering, as the dissolution of evaporites play a major
role in composition of solute sources. This inuence of evaporite
dissolution on the URRB and Lake Texoma is evident by comparison
with the composition of major rivers elsewhere (Fig. 4) (Gaillardet
et al., 1999). Most of the world's large river systems primarily
represent mixing between carbonate and older silicate weathering
end-members in terms of Sr isotope compositions and major ion
ratios (Fig. 4). By contrast, both the Red and Washita rivers show the
strong inuence of evaporite dissolution; for the Red River, halite
dissolution is a major inuence, whereas for the Washita River,
gypsum dissolution is important (Fig. 4).
To apportion the halite dissolution contribution to Lake Texoma,
an equivalent amount of Na to the concentration of Cl is assigned to
halite dissolution, and for SO
4
derived from gypsum/anhydrite
dissolution; an equivalent amount of Ca is apportioned (Jacobson
et al., 2002). The remaining Na (Na
silicate
) is then assumed to be
derived from silicate weathering, with Ca
silicate
calculated from whole
rock Ca/Na values (e.g., Jacobson et al., 2002). However, Lake Texoma
waters have Na/Cl
molar
indicating that essentially all of the Na and Cl is
derived by dissolution of halite (average Na/Cl
molar
=0.990.029).
There is an excess of SO
4
over Ca (average Ca/SO
4-molar
=0.82
0.047), whereas adding Mg (from epsomite dissolution) produces an
excess of (Ca+Mg)/SO
4
(average [Ca+Mg] / SO
4-molar
=1.37
0.067). Even if all of the DIC in the upper 10 m of Lake Texoma
comes from carbonate dissolution, at most 35% of the dissolved load
can be accounted for by congruent carbonate dissolution, and
removing the mole equivalent of Ca and Mg results in (Ca+Mg)/
SO
4-molar
closer to unity (average [Ca+Mg] / SO
4-molar
=1.15
0.048). These calculations are consistent with variation in the Sr
isotope compositions of Lake Texoma and its inuent rivers (Fig. 4), as
most water samples are located closer to the halite than to other two
end members with respect to Ca/Na
molar
and
87
Sr/
86
Sr (Fig. 4). The
variations in Sr/Ca
molar
, Ca/Na
molar
and
87
Sr/
86
Sr, thus, indicate that
weathering in the headwater catchments to Lake Texoma is
dominated by dissolution of halite and gypsum with Sr isotope
compositions consistent with Permian seawater (reected in the
upper Red River main stem and Pease River samples; Fig. 4), and
weathering of clastic sedimentary rocks with substantially more
radiogenic Sr isotope compositions. More radiogenic Sr derived by
silicate weathering is indicated by the sample from Chickasaw, which
is locally inuenced by chemical weathering of Precambrian granit-
oids, and the samples from the Wichita River at Wichita Falls (Fig. 4)
that ow through Paleozoic (Carboniferous) paralic siliciclastics.
Thus, Lake Texoma solutes and Sr isotope signatures are dominated
by chemical and clastic sediments in the headwater catchments; the
extensive Cretaceous carbonates closer to Lake Texoma have a minor
inuence. However, the decrease in salinity from the headwater
regions from near seawater to values ~1000 mg/L is a function of
runoff and base-ow dilution of the Red and Washita river systems as
they ow eastwards to Lake Texoma. Mixing calculations for the
different lithology end-members indicate that N95% dilution of higher
salinity headwater streams has little inuence on the Sr/Ca
molar
, Ca/
Na
molar
and Sr isotope composition of the mix.
The average
87
Sr/
86
Sr values for all samples in the catchment area
is signicantly lower (0.0003 or 300 ppm less) than that of Lake
Texoma (average=0.7086 vs. 0.7089) and modern seawater (
87
Sr/
86
Sr=0.7092) (DePaolo and Ingram, 1985). However, as shown by
the decrease in salinity with increasing discharge and the Sr isotope
composition over time for the Gainesville gauging station, the Sr
isotope composition of Lake Texoma reects the dampening effects of
the lake on the chemistry of the rivers entering the lake. Our more
limited time series data for the Washita River suggests that
87
Sr/
86
Sr
compositions are less variable compared to Red River input. However,
-1.2
-0.9
-0.6
-0.3
0.0
0.3
0.6
8 6 4 2 0
S
I
c
a
l
c
i
t
e
Main lake
Washita River arm
Red River arm
Dissolved oxygen (DO)
pH
Sr concentrations
87
Sr/
86
Sr filtered
87
Sr/
86
Sr unfiltered
0.7086 0.7088 0.7090 0.7092
87
Sr/
86
Sr
Sr (mg/L) DO (mg/L)
DO (mg/L)
0
4
8
12
16
20
24
28
D
e
p
t
h

(
m
)
0.95 1.00 1.05 1.10 1.15
7.00 7.50 8.00 8.50
pH
Epilimnion
Hypolimnion
Metalimnion
0 2 4 6 8
A B C
Fig. 5. Comparison of
87
Sr/
86
Sr values between ltered and unltered samples collected at Site 9 in Lake Texoma in August 2003 (a) in the background of vertical variations of pHand
dissolved oxygen (DO) proles (b). Filtered samples had higher
87
Sr/
86
Sr than their paired unltered samples except Sample 93. Also shown in the gure are three layers of water
stratication, epilimnion (upper or oxic layer), metalimnion (middle or transitional layer), and hypolimnion (lower or anoxic layer). This stratication normally appears in summer
seasons in Lake Texoma fromearly June to late September. c) Plot showing the relationship between the saturation index of calcite (SI
calcite
) and dissolved oxygen. The data suggest a
major change in calcite saturation at the chemocline, where waters become reducing and pH decreases; namely, waters above and below the chemocline are respectively saturated
and unsaturated with respect to calcite.
211 L. Sun et al. / Chemical Geology 285 (2011) 203214
at the time the samples from the Washita River arm of Lake Texoma
were collected, the Washita River was anomalously radiogenic, likely
reecting rainfall in the lower portion of the Washita River watershed,
with subsequent baseow to the river and runoff more inuenced by
chemical weathering of the granitic rocks.
5.2. Sr isotopes in Lake Texoma waters
The negative correlation between
87
Sr/
86
Sr values and Sr concen-
trations, (similarly documented by (Semhi et al., 2000), can be
explained by variable solubilities of catchment lithologies. Higher
riverine Sr concentrations with lower
87
Sr/
86
Sr compositions are
related to greater dissolution of soluble chemical sediments compared
to less soluble igneous and clastic sedimentary rocks, contributing
more radiogenic Sr. As shown above, the chemical sediment end-
member appears to be dominated by dissolution of gypsumand halite
evaporites, with comparatively minor inuence from the extensive
carbonate lithologies in the Red River and Washita River catchments.
In the study of erosion sources in the Congo Basin by major element
and strontium isotope ratios (Ngrel et al., 1993), suspended and
dissolved loads from the seven main tributaries were compared with
respect to their
87
Sr/
86
Sr values. These Congo Basin results show that
87
Sr/
86
Sr values of the suspended load are 0.01 higher than that of the
dissolved load. The reason is that the suspended loads originate from
weathering of old igneous rocks that bear a higher
87
Sr/
86
Sr ratio
because of
87
Rb decay. In another study, the suspended load was also
found to be higher than the dissolved load due to occurrences of
minerals enriched with Rb associated with particulates during a ood
event in the Garonne River and its tributaries in SWFrance (Semhi et al.,
2000). Similarly, suspended sediment (N0.2 m) in the Mississippi and
Atchafalaya rivers at the Gulf of Mexico is more radiogenic than the
dissolved load (Xu and Marcantonio, 2004; Xu and Marcantonio, 2007).
In our study, for the sample LS-LT0803 12, collected at the station
closest to where the Red River enters Lake Texoma (Fig. 2), the
unltered aliquot has a more radiogenic
87
Sr/
86
Sr value than the ltered
aliquot. Here, the suspended sediment is more radiogenic than the
dissolved load because the suspended sediment in the Red River is
dominated by low solubility silicates from Permian and Pennsylvanian
(Fig. 1) redbeds in the headwater regions and sediments derived by
runoff during rainfall events more proximal to the lake.
In the central deep portion of Lake Texoma, the b0.45 m ltered
aliquots are more radiogenic than the unltered aliquots (Fig. 5).
Filtered and unltered samples (although different) generally show
similar trends in
87
Sr/
86
Sr proles, but show the greatest divergence
in the waters of the hypolimnion. That both proles become less
radiogenic and approach comparable
87
Sr/
86
Sr values in the meta-
limnion might suggest that this interval may represent the maximum
dissolution of marine chemical particulates carrying low
87
Sr/
86
Sr, or
that surface and bottom waters are effectively decoupled in terms of
Sr isotope equilibrium (as possibly indicated by lower Sr in the
metalimnion). Furthermore, that the proles then become substan-
tially more radiogenic than even their surface values indicates an
increased proportion of radiogenic Sr released to the dissolved phase
within the hypolimnion, or that bottom waters reect a time-
dependent equilibrium mixing process that does not necessarily
reect surface water chemistry i.e., depending on relative inputs from
the two inuent rivers and the development and maintenance of
summer stratication and whole water column mixing in the fall and
winter. Some of this effect might be explained by the release of acidic
species (such as HS
-
and organic acids) associated with organic matter
decomposition in the hypolimnion or early diagenesis of lake
sediments. River waters collected below Denison Dam have consis-
tently lower
87
Sr/
86
Sr values than Lake Texoma waters (Fig. 4),
consistent with the lower
87
Sr/
86
Sr values in the unltered hypolim-
nion lake waters, given that Denison dam is bottom released.
Watershed geology of the URRB above Lake Texoma can be divided
into two groups; 1) marine chemical sediments, with Sr isotope
compositions that reect seawater at the time they were deposited,
and 2) igneous rocks and siliciclastic sedimentary rocks with more
radiogenic isotope signatures than the marine sediments. The rst
group includes Permian evaporites (gypsum/anhydrite and halite)
and Permian and Cretaceous carbonates. All of these chemical
sediments have Sr isotope compositions in the range 0.70700.7080.
However, of these, only less soluble carbonates (limestone and
dolostone) are likely to persist as suspended particulates in the inow
fromRed and Washita rivers. Survivability of carbonate particulates is
particularly favored by high carbonate saturation indices (as indicated
earlier for the Wichita River sub-watershed of the Red River
(Leybourne et al., in preparation). The surface waters of Lake Texoma
(i.e., above the metalimnion) are also saturated with respect to calcite
and dolomite (Fig. 5).
Differences in dissolved Fe and Mn concentrations in Lake Texoma
suggest that Fe- and Mn-oxyhydroxides are present in the surface
waters of the main lake during summer, but are dissolved in the
metalimnion (Sun et al., submitted for publication-a). Strontium
associated with particulate oxyhydroxides will be returned to the
dissolved pool below the chemocline, resulting in an increase in
dissolved Sr concentrations below the metalimnion, as observed for
site 9 in the main lake (Fig. 5). Thus, if Sr associated with these phases
is more radiogenic than Sr associated with suspended carbonate
minerals, this would account for the differences in isotope ratio
between the suspended and dissolved pools for the deep waters in
Lake Texoma. Note, however, that calcite is typically slightly
undersaturated in these deeper waters, so the dissolution of these
suspended carbonates cannot be discounted. Supporting evidence for
the role of suspended calcite and oxyhydroxides comes from a recent
study of the Sr isotope composition of the suspended and dissolved
load of the Mississippi River at the Gulf of Mexico (Xu and
Marcantonio, 2004). This study demonstrated, via sequential extrac-
tion experiments, that suspended calcite was less radiogenic than the
dissolved load, and that suspended Fe oxyhydroxides were slightly
more radiogenic than calcite. It may also be that highly radiogenic
particulates are preferentially adsorbed on Fe and Mn oxyhydroxides,
clays, or OM, and are released to the dissolved pool when they settle
below the redoxocline (due to reduction and possibly also dissolution
by organic acids). The fact that the sample collected from the
metalimnion shows essentially no difference between the dissolved
and suspended pools may indicate that calcite has been partially
dissolved in this layer (Fig. 5; Table 4). However, the Sr concentration
is lowest in this sample for this site. For the sample collected in the
epilimnion, the fact that the dissolved load is more radiogenic than
the suspended load may be due to atmospheric loading (meteoric
runoff) of more radiogenic Sr. Alternatively, there may be Sr
associated with organic matter that is introduced into the surface
waters by runoff.
5.3. Implications for paleolimnological studies
Our data from Lake Texoma shows signicant lateral and vertical
geochemical and isotopic variations. The total variation in
87
Sr/
86
Sr
values for Lake Texoma is around 0.0007 (Fig. 4). Although its inuent
rivers have much larger
87
Sr/
86
Sr ranges tied to differential weath-
ering of different catchment rocks and downstream mixing, some of
the regional and temporal isotopic variability is preserved, in addition
vertically variations associated with development of chemical
stratication in the summer. These ndings have important implica-
tions for studies that rely on recent or fossil lake sediments to
interpret changes in regional hydrology, limnology and climate. For
example, Li et al. (2008) investigated sediment from the Salton Sea in
order to understand changes in river inputs over the last 20,000 years.
The total variation in
87
Sr/
86
Sr recorded in the Salton Sea sediments
212 L. Sun et al. / Chemical Geology 285 (2011) 203214
was around0.0002 (Li et al., 2008), well withinthe variationobservedin
Lake Texoma waters. Similarly, a recent study of carbonate deposited by
a lake in the Eocene in central Utah found total
87
Sr/
86
Sr variations
similar to those in Lake Texoma (Gierlowski-Kordesch et al., 2008).
Although this study of paleolake conditions showed systematic
variations in
87
Sr/
86
Sr with stratigraphic height, our work on Lake
Texoma suggests that such data needs to be interpreted in light of
potentially signicant variations owing to seasonal stratication.
Conclusions
1. Sr concentrations and isotope compositions were determined
spatially within Lake Texoma and its two major input rivers (Red
and Washita). Water samples with higher Sr concentrations tend to
have lower
87
Sr/
86
Sr, and this pattern is observed in the gross
mixing pattern for Lake Texoma. Specically, lake waters become
more radiogenic, and Sr contents decrease, away from the Red
River inow and toward the Washita River inow. These
lithochemical proxy results concur with earlier studies (Miller
and Leybourne, 2002; Leybourne et al., in preparation) that Sr
cycling in the URRB surface waters primarily involves three-
component mixing between halite, gypsum/carbonate, and alumi-
nosilicates, of which evaporites exert the greatest control on solute
load chemistry.
2. Differences in
87
Sr/
86
Sr between ltered and unltered aliquots of
the upper Lake Texoma water column, in addition to saturation
considerations, suggest that the suspended load of surface waters
may include an appreciable marine carbonate component (with
non radiogenic
87
Sr/
86
Sr), which dissolves at and immediately
below the metalimnion.
3. Below the metalimnion, dissolved (ltered) Sr increases with
depth and
87
Sr/
86
Sr becomes more radiogenic. Explanations for this
behavior may be related to: (1) euxinia, organic decomposition
and/or early diagenesis of lake sediments below the metalimnion/
redoxocline, during which radiogenic Sr associated with low
solubility aluminosilicate detritus is released to the dissolved
pool, or (2) that surface waters are out-of-phase with deeper
waters due to a time-dependent (seasonal stratication?) equilib-
riummixing process i.e., depending on relative inputs fromthe two
inuent rivers and the development and maintenance of summer
stratication and whole water column mixing in the fall and
winter. This vertical solute-load phenomenon and its explanation
have important implications for Sr cycling in Lake Texoma, which
may also be important for solute studies of other lake systems.
Acknowledgments
The authors thank Adam Franklin, Cornel Olariu, Jamil Sader,
Willie Manton, Katherine Robertson, and Trey Hargrove for their help
with eld and lab work and Neil Basu for help with the Sr isotope
analyses. This program was supported by NSF grant 0224551 (MIL)
and a Geological Society of America Student Research Grant (LS).
Journal editors Bourdon and Fein and two anonymous reviewers are
thanked for comments that greatly improved the manuscript.
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