Environ Geochem Health

DOI 10.1007/s10653-007-9105-1

ORIGINAL RESEARCH

Chemical and colloidal analyses of natural seep water

collected from the exploratory studies facility inside Yucca
Mountain, Nevada, USA
James V. Cizdziel Æ Caixia Guo Æ
Spencer M. Steinberg Æ Zhongbo Yu Æ
Karen H. Johannesson

Received: 2 January 2007 / Accepted: 3 April 2007

Springer Science+Business Media B.V. 2007

Abstract Yucca Mountain is being considered as a
geological repository for the USA’s spent nuclear fuel
and high-level nuclear waste. Numerous groundwater
seeps appeared during March 2005 within the explor-
atory studies facility (ESF), a tunnel excavated in the
mountain. Because of the relevance to radionuclide
transport and unsaturated zone-modeling studies, we
analyzed the seep samples for major anions and
cations, rare earth elements, and colloids. Major ion
species and elemental concentrations in seep samples
reflect interaction of the water with the volcanic rock
and secondary calcites. Elemental fractograms from
flow-injection field-flow fractionation ICP–MS scans
detected Br, Ca, Cl, Cu, Fe, I, Mg, Si, Sr, W, and U at
void fractions, suggesting they may be present in the
form of dissolved anions. Colloids approximately
10 nm in hydrodynamic diameter, possibly calcite,
were also present in the seepage samples. Geochem-
ical calculations indicate, however, these may be an
artifact (not present in the groundwater) which arose
because of loss of CO2 during sample collection and
storage.
Keywords Colloids
Field-flow fractionation

Groundwater
ICP–MS
Rare earth elements

Seepage
Yucca Mountain

J. V. Cizdziel (&)
C. Guo

Harry Reid Center for Environmental Studies, University
of Nevada – Las Vegas, 4505 Maryland Parkway, Las
Vegas, NV 89154-4009, USA
e-mail: cizdziej@unlv.nevada.edu
S. M. Steinberg
Department of Chemistry, University of Nevada – Las
Vegas, 4505 Maryland Parkway, Las Vegas, NV 89154-
4003, USA
Z. Yu
Department of Geoscience, University of Nevada – Las
Vegas, 4505 Maryland Parkway, Las Vegas, NV 89154-
4010, USA
K. H. Johannesson
Department of Earth and Environmental Sciences, The
University of Texas at Arlington, 500 Yates St., 19049,
Arlington, TX 76019-0019, USA
Introduction
Yucca Mountain, located in Nye County, Nevada, has
been selected by the USA as a potential repository for
the nation’s spent nuclear fuel and high-level nuclear
waste (Fig. 1). The Department of Energy has been
given the task of evaluating the suitability of the site
for long-term geological storage of the waste and has
conducted or funded numerous studies to that end
(Moridis et al. 2003; Campbell et al. 2003; Dyer
2002). An overview of the Yucca Mountain project
and links to other site characterization studies can be
found on the internet at http://www.ocrwm.doe.gov/
ym_repository/index.shtml. The exploratory studies
facility (ESF) is an approximately 8-km-long tunnel

123

Fig. 1 Map showing the
location of Yucca
Mountain. Source: US
Department of Energy,
Yucca Mountain project
excavated into Yucca Mountain to enable scientists to
collect samples and conduct in-situ studies within the
mountain.
During March 2005 water began to drip (seep)
from the tunnel walls near the entrance to the south
portal of the ESF. The locations of the seepages were
fairly deep (*40–80 m below the surface), albeit not
as deep as the proposed repository (*300 m). The
cause of the seep was presumed to be related to
relatively high levels of precipitation during the
winter of 2004/2005. Approximately 300 mm (11.8
in) of rainfall was recorded at a nearby precipitation-
monitoring station (#412) during the period 10/1/04–
02/28/05; this was well above the previous ten-year
average of 92 mm (3.6 in) for the same period
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Environ Geochem Health
(A. Brandt, personal communication). Whereas the
increased precipitation may have initiated the event,
it was not clear whether the infiltration was inducing
seepage of older water or if there was rapid and direct
transport of the recharge, or both. In any case, the
event stands out for its intensity with substantial
flows at several locations at rates up to
125 mL h min 1 (Sanchez 2005).
The occurrence of this natural seepage inside the
ESF is, perhaps, not surprising, because they were
located in a zone of highly fractured and faulted
volcanic tuff with the potential to transmit recharge
water from the surface. A generalized map showing
the geology of Yucca Mountain and its surroundings
is presented in Fig. 2. Because of uncertainty in the
Environ Geochem Health
Fig. 2 Generalized
geological map of Yucca
Mountain showing rock
types and key faults in
relation to the exploratory
studies facility. Source: US
Department of Energy,
Yucca Mountain project
natural movement of water in the mountain, a key
element for assessment of the performance of the
geological repository, the seeping water was col-
lected and submitted for extensive chemical analysis.
The seepage was a rare opportunity to evaluate the
chemical constituents of water that has percolated
through a portion of the mountain. We analyzed the
samples for major cations and anions, rare earth
elements (REEs), and association of elements with
colloids.
Colloids are of interest because they are regarded
as a potential carrier of radionuclides in groundwater
and colloid transport may result in rapid migration of
radionuclides through geological repositories (Puls
et al. 1992; Novikov et al. 2006). Despite this, few
published studies have characterized colloids in
groundwater at Yucca Mountain and adjacent areas
including the Nevada test site (NTS). Colloids in
Nevada springs have been reported to be composed
primarily of amorphous silica (Kingston and Whit-
beck 1991). Silica in Southern Nevada groundwater
exists not as stable inorganic colloids but rather as
low-molecular-weight species (Steinberg et al. 2000).
Previous investigations concluded that substantial
concentrations of colloidal materials can persist in
southern Nevada groundwater under some conditions
(Steinberg et al. 2000). More recently, natural
colloids generated from zeolitized tuff from the
123

NTS were examined in column experiments (Um and
Papelis 2002), and the transport of radioactive
colloids under ambient conditions from the potential
repository horizon to the water table was simulated
(Moridis et al. 2003). Both of these studies indicated
that the most important factors affecting colloid
transport are geochemical conditions and site hydrol-
ogy, including the presence of faults and fractures.
In this paper we report results from analysis of the
seepage by ion chromatography, inductively coupled
plasma mass spectrometry (ICP–MS), and flow
injection field flow fractionation (FIFFF) ICP–MS.
Information of this type is useful for characterization
of the site and geochemical modeling of infiltration of
the unsaturated zone.
Experimental
Sample collection, field measurements and
storage
The seepages were located near the entrance to the
south ramp of the tunnel in the general area between
76 + 00 and 75 + 00 (ESF designation) approximately
40–80 m below the surface. For perspective, the
depth at which it is proposed to bury the nuclear
waste containers is *300 m. Seep water was
collected by personnel of the United States Geolog-
ical Survey (USGS) and Sandia National Laboratory
(SNL). Seepage locations and field measurements are
presented in Table 1. In brief, drips were fed into
plastic (LDPE) or amber glass bottles by use of a
large plastic funnel. Conductivity and pH were
measured in the field when the volume collected
was sufficient to enable analysis using an Ultrameter
(Myron L Company, Carlsbad, CA, USA). Samples
were stored (untreated and unfiltered) in a refrigerator
until shipping or delivery to the laboratory. Samples
for rare earth element analyses were acidified to 1%
HNO3 before analysis.
Major anions and cations
Anions and cations were determined by ion chroma-
tography using a conductivity detector (Dionex
Models ICS-2000 and ICS-2500, and Chromeleon
Software Version 6.50; Dionex, Sunnyvale, CA,
USA). Samples were filtered through a 0.45 mm
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Environ Geochem Health
syringe filter and typically analyzed within 48 h of
collection. Standards were purchased from Spex
Certiprep (Metuchen, NJ, USA). Quality-assurance
measures included an initial calibration check,
continuing calibration checks, spikes, and sample
duplicates (10% frequency). Calibration check crite-
ria were recovery 90–110%; precision ±15% relative
percent difference; and spike recovery 85–115%. All
sample runs met these conditions.
Rare earth elements
Rare earth elements (REEs) were measured by use of
a VG Elemental, now Thermo Electron Corporation,
magnetic sector ICP–MS (Axiom). The instrument
was operated in low-resolution (*420) mode using a
standard concentric nebulizer (pumped at
*1 mL min 1) with a cyclonic spray chamber
followed in series with a bead-impact spray chamber.
A multi-element standard was used for calibration
(SPEX CertiPrep; Metuchen, NJ, USA) and separate
QC standards were purchased from High Purity
Standards (Charleston, SC, USA). Ultra pure nitric
acid was purchased from Sea Star (Sidney, BC,
Canada). DI water (18.2 MX cm 1) was used to
prepare all solutions. Sensitivity, stability, and oxides
were optimized before analysis. Typical sensitivity
was *1 · 106 counts per second (cps) for a 1 ng g 1
solution of In. Pt was used as internal standard. The
method detection limits ranged from 27–169 pg kg 1
(ppq). Two reference waters (PPREE1 and SCREE1
from the USGS) were analyzed with the samples and
recoveries ranged from 93–107%. The precision
(RSD) of the analysis varied as a function of
concentration: at ng L 1 concentrations it was
approximately 3% or better and at pg L 1 concen-
trations it was better than 10%.
Colloids
On-channel sample preconcentration flow-injection
field-flow fractionation–inductively coupled plasma—
mass spectrometry (FIFFF–ICP–MS) was used to
examine element-size distributions of two seepage
water samples (#1034575 and #1034582) from the
ESF. The principle of FIFFF has been described in
detail elsewhere (Giddings 1984; Siripinyanond and
Barnes 1999). Briefly, species are fractionated on the
basis of molecular weight. A small volume of sample is
Environ Geochem Health

Table 1 Sample information for ESF seepage

Sample ID ESF Coordinates Field dataa

Conductivity (mS cm 1) Total dissolved solids (mg g 1) pH

01014188 76 + 01 559 363 7.3

01014189 75 + 95 633 414 7.3
01014191 76 + 00 635 415 7.4
01014193 75 + 94 673 439 7.3
01014194 76 + 01 579 376 7.3
01015594 76 + 01 558 364 7.8
01015595 75 + 95 659 431 7.7
01015596 76 + 00 586 381 7.7
01015597 75 + 94 677 444 7.7
01015599 75 + 95 627 408 7.5
01034568 76 + 00.5 594 338 7.6
01034569 76 + 00 871 577 7.8
01034570 75 + 95 628 411 7.8
01034571 75 + 94 754 496 7.7
01034573 76 + 00 NA NA NA
01034574 76 + 00 882 580 6.9
01034575 75 + 97 583 380 7.5
01034576 75 + 94 645 419 7.6
01034578 75 + 75 NA NA NA
01034579 76 + 01 NA NA NA
01034580 76 + 00 NA NA NA
01034581 75 + 95 959 629 7.9
01034582 75 + 94 791 513 7.6
01034583 75 + 94 691 449 7.8
01034584 75 + 75 NA NA NA
01034585 75 + 94 723 481 7.6
01034586 75 + 75 2633 1897 7.7
01034587 75 + 94 723 485 7.7
01036762 76 + 00 597 388 7.4
01036763 75 + 94 736 481 7.6
01036764 75 + 95 616 402 7.6
01036765 75 + 89 1121 747 7.7
01036766 75 + 95 691 447 7.6
01036767 75 + 95 674 438 7.5
01036768 75 + 94 695 454 7.5
01036769 75 + 75 654 436 7.7
01036774 75 + 95 693 457 7.7
01036775 75 + 94 693 457 7.7
01036776 75 + 95 674 438 7.7
01036777 75 + 94 733 478 7.8
01036778 75 + 75 NA NA NA
Mean (all) 750 495 7.6
SD (all) 348 257 0.2

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Table 1 continued
Sample ID ESF Coordinates Field dataa
Conductivity (mS cm 1)
Meanb 681
SDb 92
Min 558
Max 2633
NA = Insufficient sample for analysis
a
Data from reference (Sanchez 2005); samples collected during March and April 2005
b
Samples 001034586 and 001036765 were removed because of possible evaporative loses
injected into a carrier liquid which traverses a channel
within a plastic, usually polycarbonate, flow cell. An
external flow field perpendicular to the separation axis
causes analytes to separate and migrate to an accumu-
lation wall. The cross flow retards movement of sample
particles and provides the fractionation among particle
sizes, as a result of from their diffusion coefficients.
The separated particles elute from the FFF system and
are introduced into the ICP–MS where they are
dissociated and converted to ions before detection.
Plots of intensity against time of the ICP–MS data
(called fractograms) yield a void peak, which may
contain low molecular weight species, followed by
colloidal peaks (if colloids are present in the sample).
In this study an FIFFF system (Model PN-1021-
FO, Postnova Analytik, Germany) equipped with a
1 kDa molecular weight cut-off and a regenerated
cellulose acetate membrane (Postnova) was used. The
FIFFF channel was 27.7 cm long, 2.0 cm wide, and
254 mm thick. A 30 mmol L 1 TRIS buffer (pH 7.5)
was used as a carrier liquid throughout this study.
During sample loading and focusing an HPLC pump
(Model PN 2101, Postnova Analytik, Germany) was
used to control the forward flow at 0.24 mL min 1
and another HPLC pump of the same model was used
to regulate the focus flow at 3 mL min 1. In the
elution step the channel flow was set at 1 mL min 1
and the cross flow rate was regulated at 2 mL min 1.
The UV detector (UV-2000 Spectra System) was set
at 254 nm to monitor light attenuation of separated
colloidal particles. An ICP–MS (Sciex/Elan 6000,
PerkinElmer Instruments, Shelton, CT, USA) was
used as an element detector after the UV absorption
detector. Owing to the similarity of the FIFFF
channel flow and ICP–MS sampling flow rates
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Environ Geochem Health
Total dissolved solids (mg g 1) pH
445 7.6
64 0.2
338 6.9
1897 7.9
typically used for analysis, the ICP–MS cross-flow
nebulizer was connected directly to the UV detector
outlet with a 35-cm length of poly(tetrafluoroethyl-
ene) tubing (PTFE, 0.58 mm i.d.). The FIFFF–ICP–
MS operating conditions are summarized in Table 2.
Poly(styrene sulfonate) standards of different molec-
ular weights were used for FIFFF channel calibration.
The element signals were not quantified (total
concentrations were not determined) because specific
concentrations were not of interest at the time.
For the seepage samples, Br, Ca, Cl, Cu, Fe, I, Mg,
Si, Sr, U, and W were monitored because they gave
significant signal intensities in preliminary investiga-
tion of element concentrations using semi-quantitative
analysis mode. To improve the detection of organic/
inorganic colloidal materials and their associating
elements, 5.0-mL water samples were introduced into
the FIFFF channel instead of the 20-mL injection
volume normally used in FIFFF separation using on-
channel preconcentration mode. The FIFFF on-chan-
nel preconcentration-size separation consists of two
steps:
1 sample loading/focusing and relaxation; and
2 elution.
The sample was loaded through the rear end of the
channel with a flow ratio of 1:12.5 between the
fo r w ar d ( 0. 2 4 m L m i n 1 ) a n d b a c k w a r d
(3 mL min 1) focusing flows. When the entire
sample volume was loaded and focused in the FIFFF
channel, the forward and backward flow pumps were
disengaged while the cross flow stream was intro-
duced. As with the regular injection mode, the
channel pump flow was then started to elute and
separate different size components.
Environ Geochem Health

Table 2 FIFFF–ICP–MS operating conditions

Flow FFF Model PN-1021-FO

FFF channel dimensions (cm) 27.7 long · 2.0 wide · 0.02 cm thick
1
Carrier liquid 30 mmol L TRIS (buffered at pH 7.5)
1
Channel flow rate (mL min ) 1.0
Cross flow rate (mL min 1) 2.0
Equilibration time (min) 2.0
Membrane 1 kDa MWCO poly(regenerated cellulose)acetate
ICP–MS Elan 6000
Rf generator frequency (MHz) 40
Rf forward power (W) 1,000
Torch Fassel type
Torch injector Ceramic alumina
Spray chamber Ryton Scott double pass
Nebulizer Gem-tip cross flow
Nebulizer gas flow rate (L min 1) 0.95
1
Auxiliary gas flow rate (L min ) 1.2
Outer gas flow rate (L min 1) 15
Resolution 1 ± 0.1 at 10% peak maximum
Scanning mode Peak hop transient signal
Measurement per peak 1
Dwell time (ms) 200
25 26 29 35 48 57 65 79 88 127 184 238
Isotopes monitored (m/z) Mg, Mg, Si, Cl, Ca, Fe, Cu, Br, Sr, I, W, U

Results and discussion
Field measurements and major anions and cations
Results for typical water-quality measurements are
given in Table 1. From the field data (Sanchez 2005)
Subsequent loss of CO2 from the groundwater during
seepage into the tunnel, and possibly during sample
collection and storage, has implications for colloid
formation (see the section Colloid formation).
Anion (F , Cl SO24 , Br , NO3 ) and cation (Na+,
K , Mg2+, Ca2+) data are provided in Table 3. Five
+

it is evident that the seepage samples are fairly
uniform with regard to pH and conductivity. The
water was relatively warm (temperature range 16.4
and 26.18C), near neutral (mean pH 7.6 ± 0.2), with a
moderate to high salt content (mean conductivity
750 ± 348 mS cm 1 ; total dissolved solids
495 ± 257 mg g 1) and some acid-neutralizing
capacity (alkalinity range from 39–194 mg L 1).
The pH of the seepage samples was, on average,
7.6 ± 0.2, which is usually less than that of
groundwater collected from the deeper saturated
zone from nearby wells of the Nye County early
warning drilling program. Introduction of CO2 from
microorganisms, or some other source in the near
surface environment, would tend to reduce the pH
and contribute toward dissolution of secondary
calcite deposited in the fractures of the vadose zone.
samples (#01034575, #01034578, #01034580,
#01034584, and #01034586) contained relatively
high concentrations of cations, possibly because of
of evaporative losses in the field. Summary statistics
are provided with and without these sample data
(Table 3). For the anions, sulfate was usually present
at the highest concentration, followed by chloride,
nitrate, fluoride, and bromide. Although alkalinity
was not measured in the samples listed in Table 3,
HCO3 concentrations for a group of 35 other seepage
samples collected at the same general location and
time averaged 123 ± 31 mg L 1 (1r) and ranged from
59 to 213 mg L 1 (Sanchez 2005).
For the cations, calcium tended to be highest
followed by sodium, magnesium, and potassium. The
concentrations of anions in the seepage were generally
higher than those found for nearby groundwater. For

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Table 3 Concentrations of major anions and cations in EFS seepage

Sample ID Anions (mg g 1) Cations(mg g 1)

F Cl SO4 2 Br No3 Na+ K+ Mg2+ Ca2+

01014188 2.70 47.1 103 0.54 27.60 26.80 3.34 12.9 59.1
01014189 3.03 52.4 111 0.56 32.90 31.20 3.62 13.5 74.5
01014191 3.28 44.0 105 0.54 33.40 37.70 3.99 11.9 68.6
01014193 2.69 64.9 128 0.59 30.30 25.60 2.95 13.8 84.8
01014194 2.96 49.0 107 0.55 29.10 27.50 3.7 15.0 60.1
01015594 3.03 50.8 109 0.58 31.90 27.50 3.7 15.0 60.1
01015595 3.07 53.1 116 0.55 33.70 30.60 3.78 12.8 65.1
01015596 3.14 41.3 98 0.54 30.90 30.30 3.89 11.8 76.3
01015597 2.68 63.9 127 0.57 30.20 35.40 3.92 10.4 66.2
01015599 2.97 52.1 113 0.57 32.80 30.10 3.55 11.8 74.3
01034568 3.12 50.7 118 0.29 31.00 25.90 3.55 15.7 64.4
01034569 4.27 73.0 157 0.41 51.40 41.60 5.26 21 103.9
01034570 3.65 54.1 115 0.31 35.60 30.40 3.72 15.3 76.6
01034571 3.09 74.0 151 0.40 35.70 28.80 3.18 13.8 98.1
01034573 3.69 52.4 124 0.29 35.10 281 9.42 134 5124
01034574 3.78 90.7 170 0.54 53.90 33.60 5.31 17.4 107
01034575 3.32 40.9 109 0.24 31.50 31.40 3.26 10.4 65.0
01034576 3.02 61.3 133 0.34 33.70 28.10 4.04 11.6 71.8
01034578 2.77 171 286 0.65 44.60 1005 230 58.5 296
01034579 3.12 54.7 122 0.30 34.30 27.90 3.85 13.7 71.1
01034580 3.83 64.8 139 0.37 43.00 1790 219 71.6 283
01034581 4.79 100 193 0.21 56.10 49.20 6.81 21.8 106
01034582 4.06 79.3 169 0.15 35.40 30.70 3.45 15.6 94.4
01034583 3.75 67.4 151 0.16 33.70 35.30 3.42 14.2 85.7
01034584 4.37 181 NA 0.28 NA NA NA NA NA
01034585 3.09 88.7 176 0.18 40.00 33.00 3.66 17.3 100
01034586 5.39 491 655 1.25 129 119 20.6 64.3 374
01034587 2.75 79.5 153 0.17 36.20 31.80 3.32 15.0 98.5
01036762 3.39 72.0 134 0.68 36.00 41.90 5.57 16.7 63.4
01036763 3.27 77.4 157 0.62 36.20 29.70 3.12 14.9 101.2
01036764 3.17 53.9 117 0.57 33.60 30.30 3.17 13.6 78.7
01036765 4.26 137.7 240 0.95 76.00 69.10 8.61 23.7 136.4
01036766 3.32 58.0 121 0.45 37.70 29.60 3.91 14.8 84.8
01036767 3.42 59.4 126 0.46 38.90 34.50 4.07 15.2 87.7
01036768 3.06 70.0 135 0.45 34.70 29.40 3.05 149 96.4
01036769 3.86 198.6 319 0.67 62.00 NA NA NA NA
01036774 3.34 58.4 122 0.45 37.70 37.70 4.34 15.4 86.5
01036775 2.97 71.9 141 0.44 35.30 29.20 3.11 15.3 101
01036776 3.44 60.5 128 0.44 39.60 29.70 4.18 15.9 90.7
01036777 3.01 71.1 141 0.46 34.80 29.20 3.23 14.8 99.7
01036778 2.99 149 255 0.57 46.40 43.70 6.96 23.2 173
Summary statistics:
Mean(all) 3.39 86.1 159 0.47 40.60 112 15.9 22.0 234

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Table 3 continued
Sample ID Anions (mg g 1) Cations(mg g 1)

F Cl SO4 2 Br No3 Na+ K+ Mg2+ Ca2+

SD(all) 0.59 75.0 94 0.21 17.30 319 49.2 23.0 807

Meana 3.30 71.4 144 0.46 38.10 33.30 4.07 15.1 86.6
SDa 0.48 31.9 46 0.17 10.10 8.20 1.24 3.2 23.1
Min 2.68 40.9 98 0.15 27.60 25.60 2.95 10.4 59.1
Max 5.39 491 655 1.25 129.00 1790 230 134 5124
MDL (mg g 1) 0.043 0.11 0.057 0.014 0.12 0.140 0.026 0.0096 0.063
NA = insufficient sample for analysis; MDL = method detection limit
a
Samples 001034575, 001034578, 001034580, 001034584, and 001034586 were not included because of possible evaporative losses

example, the mean chloride and sulfate concentrations
for six different groundwater samples collected in
2005 from wells of the Nye County early warning
drilling program (NCEWDP) were 10 ± 4 and
55 ± 43 mg g 1, respectively, compared with 71 ± 32
and 144 ± 46 mg g 1 for the seepage samples. Sodium
and potassium tended to be higher in the groundwater
(mean 98 ± 51 and 11 ± 10 mg g 1, respectively) than
in the seepage water (33 ± 8 and 4 ± 1 mg g 1) whereas
calcium and magnesium were higher in the seepage
water (87 ± 23 and 15 ± 3 mg g 1, respectively) than in
the groundwater (16 ± 11 and 3 ± 3 mg g 1). These
differences probably reflect the different origins of the
two waters. The groundwater stems from a volcanic
aquifer, and although others have shown it contains a
small but detectable signature from the underlying
deep carbonate aquifer (Stetzenbach et al. 2001), most
of the chemical associations reflect interaction with
rock of volcanic origin. The seepage water, on the
other hand, is expected to be recently recharged water
that may have picked up an even greater carbonate
(calcium and magnesium) signature, because the
presence of caliche in the overlying soil. Indeed, soil
profiles at the surface above the ESF are indicative of
limited soil coverage, significant outcrop, and a
shallow carbonate horizon.
Rare earth elements
The seep samples, collected from the unsaturated
zone, contained relatively high concentrations of
REEs (Table 4) compared with nearby deeper and
presumably older groundwater. Concentrations ran-
ged from <1 ng kg 1 for Eu and Tm (in most
samples) to several hundred ng kg 1 for La, Ce, and
Nd. The high REE concentrations in the seepage are
not surprising, considering the most likely path for
water infiltrating through Yucca Mountain would be
through regions of relatively high permeability
sometimes associated with fissures and faults. Fault
gouge would have a high surface area and quickly
release labile REEs that are weakly adsorbed on the
surfaces.
Negative Ce and Eu anomalies were observed for
the chondrite-normalized REE patterns in the seep-
age (Fig. 3). The Eu anomaly is relatively common
in southern Nevada groundwater and reflects the
pattern observed for the volcanic rocks of the region
(Johannesson et al. 2000). Pinpointing the origin of
the negative Ce anomaly in groundwater samples
near Yucca Mountain is more complex. A negative
Ce anomaly is observed for the carbonate rocks of
the region, possibly reflecting the seawater from
which they precipitated (Johannesson et al. 2000).
The presence of this anomaly in relatively shallow
volcanic rock aquifers has caused researchers to
suggest upwelling of groundwater from deep car-
bonate aquifers into the more shallow alluvial
groundwater systems (Stetzenbach et al. 2001). The
characteristic negative Ce anomaly also can be
found in calcite deposits within the overlying
unsaturated volcanic rock (US DOE 1999). Given
that the seepage samples were collected well above
the groundwater table, a more likely explanation is
that water infiltrating through fissures containing
secondary calcites picked up the depleted Ce
signature. Finally, oxidation and removal of Ce
from solution as the water travels through the vadose
zone is another possibility that cannot be eliminated
(Leybourne et al. 2000). It is worth noting that

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Table 4 Rare earth element concentrations (ng kg 1) in Yucca Mountain seepage

Element Sample ID Mean S.D.

01034568 01034570 01034571 01034579 01034580

Y 51 33 250 68 130 110 88

La 71 33 270 100 160 130 93
Ce 53 41 330 73 300 160 140
Pr 15 7.7 66 23 41 31 23
Nd 53 28 230 81 150 110 82
Sm 11 5.5 51 17 31 23 18
Eu 0.6 0.5 1.5 0.4 2.2 1.0 0.8
Gd 12 6.0 55 17 33 25 20
Tb 1.6 0.9 7.4 2.1 4.3 3.3 2.7
Dy 8.6 5.1 42 12 25 19 15
Ho 2.7 1.9 12 3.8 7.6 5.6 4.1
Er 1.9 1.0 15 2.9 7.8 5.6 5.6
Tm 0.4 0.3 2.3 0.6 1.4 1.0 0.8
Yb 4.4 3.2 20 6.4 13 9.6 7.3
Lu 1.2 0.8 4.0 1.4 2.8 2.0 1.3
Th 23 12 76 39 50 40 25
Sample 01034579 is an average of field duplicates

Fig. 3 Rare earth element 1e-3

concentrations in seepage (a)
from the exploratory studies
Seep Waters/Chondrite

facility normalized to
chondrite (a) and local
volcanic rock (b). The
1e-4
chondrite normalizing
values are those of Hanson
(1980), whereas the NTS
volcanic rock normalizing
factor is the mean value for
each rare earth element for 1e-5
six different felsic volcanic
rocks collected from the
Nevada test site and present
in Table 2 of Johannesson (b)
Seep Water/NTS Volcanic Rock

et al. (2000). The numbers

provided in the legend are 1e-2
for individual sample
identification. The mean is
for the five samples listed

1e-3 01034568
01034570
01034571
01034579
01034580
Mean

1e-4
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

123
Environ Geochem Health
because negative Ce anomalies are not usually
observed for groundwater from perched felsic
volcanic-rocks from the Nevada test (Johannesson
et al. 2000) the seepage studied probably comes
from recent infiltration rather than older perched
water that was induced to flow.
Colloids
Results from the FIFFF–ICP–MS of seepage samples
1034575 and 1034582 are presented as elemental
fractograms in Figs. 4 and 5, respectively. These
results should be interpreted as follows. The total
time used for focusing and relaxation was 8 min.
Therefore, the first 8 min in the fractograms should
not be considered. The first large peak starts slightly
before 10 min, the time the void peak is expected.
Because the peak is significantly larger than that of
the blank, however, dissolved elements co-eluting
with the void fraction are probably a major compo-
nent. Because, during the focusing, the dissolved
elements should be filtered from the membrane and
should not be detected, their presence in the void
fractions suggests they are present in the anionic
form, and were retained in the FIFFF channel by
membrane repulsion (and hence were not 100% lost).
It is worth noting that although the FIFFF system may
preferentially measure dissolved anionic forms, it
does not preclude cationic forms from being present
in the sample. Nevertheless, because U is commonly
found as the cation UO2+ 2 in groundwater systems, we
modeled our data using MINEQL+ to determine the
dominant U species in our seepage samples. The
result was the anionic complex UO2(CO3)22 , which
is consistent with the observed fractograms. Also,
because of the large size of the first peak, which is
centered at approximately 11 min and extends to
approximately 13 min, colloids of approximately 2–
4 nm in hydrodynamic diameter cannot be ruled out.
One possible explanation of the large ‘‘dis-
solved’’ peak is that it arises as a result of micelles
created by the surfactant solution used during the
FFF separation. If the concentration of the surfac-
tants exceeded the critical micelle concentration, ion
pairs formed between the analytes and the micelles
may behave like higher-molecular-weight com-
pounds in the field flow instrument. The micelle
ion-pair effect has been used to remove small anions
from aqueous solution using micro or nano-
filtration, even when pore sizes in the membrane
correspond to 5–10 kda (Gecol et al. 2004). The
retention of low-molecular-weight species would be
enhanced if the resulting micelle was negatively
charged and repelled by the membrane.
The second feature of the fractograms is a slow
rise and fall in the baseline from approximately
20 to 40 min, suggesting that larger colloidal
materials were present. This region corresponds to
colloids of approximately 10–40 nm in hydrody-
namic diameter. Although the traces indicate some
colloidal material in this range, the bulk of the
signal is in the earlier peak representing material
that is either dissolved or of very low molecular
weight. Although greater sample preconcentration
would lead to clearer signals, because the sample
volume was limited, further analysis was not
performed. Interestingly, not all of the elements
monitored yielded the second peak. There was little,
if any, evidence of Si, U, W, Cu, and Fe colloids.
The lack of a clear Si signal is consistent with
previous work that found that Si does not tend to
form stable inorganic colloids in Southern Nevada
groundwater but instead occurs as low molecular
weight species (Steinberg et al. 2000). Mg, Sr, Cl, I,
and to a lesser extent Ca, and Br, were, in contrast,
detected in the late retention times. The halogen
anions peaked earlier than the metal cation
(*27 min compared with *35 min). Similar trends
between #01034575 and #01034582 samples were
observed for all the elements studied.
Summarizing the results from colloid analysis, Br,
Ca, Cl, Cu, Fe, I, Mg, Si, Sr, U, and W were detected
at void fractions, suggesting they were present as
dissolved anionic forms. Although a portion of the
elements listed above co-eluted with void, they also
appeared at slightly longer retention times, suggest-
ing that they may also be present as colloids of
approximately 2–3 nm hydrodynamic diameter. The
slow rise and fall of the baseline (>20 min) was real
and suggested that larger colloidal materials were
present. Halogen elements might also be present as
larger size colloids of approximately 10 nm in
hydrodynamic diameter.
Colloid formation
The pH of the samples, measured in the laboratory
after analysis for colloids, had increased by an average
123
 Environ Geochem Health

350000 1600000

Signal intensities (cps)

Signal intensities (cps)

Si29
300000 Cl35 1400000
Si30
Br79 1200000
250000 Ca48
I127
1000000
200000
800000
150000
600000
100000 400000
50000 200000
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Retention time (min) Retention time (min)

2500000

Signal intensities (cps)

70000
Signal intensities (cps)

Mg25
2000000 Mg26 60000 Fe57
Sr88
50000
1500000
40000
1000000 30000
20000
500000
10000
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Retention time (min) Retention time (min)

2500
Signal intensities (cps)

Cu65
2000 W184
U238
1500

1000

500

0
0 10 20 30 40 50
Retention time (min)

Fig. 4 Elemental fractograms of seepage sample #01034575

2000000
600000
Signal Intensities (cps)
Signal intensities (cps)

1800000
Cl35
500000 1600000 Si29
Br79
1400000 Si30
400000 I127
1200000 Ca48
300000 1000000
800000
200000 600000
400000
100000
200000
0 0
0 10 20 30 40 50 0 10 20 30 40 50
Retention time (min) Retention time (min)

120000
2500000
Signal Intensities (cps)
Signal intensities (cps)

Mg25 Fe57
100000
2000000 Mg26
Sr88 80000
1500000
60000
1000000
40000
500000 20000

0 0
0 10 20 30 40 50 0 10 20 30 40 50
Retention time (min) Retention time (min)

3000
Signal Intensities (cps)

Cu65
2500
W184
2000 U238

1500

1000

500

0
0 10 20 30 40 50
Retention time (min)

Fig. 5 Elemental fractograms of seepage sample #01034582

123
Environ Geochem Health

of 0.5 pH units, to 8.2, compared with the earlier field
data. On the basis of these observations we used
equilibrium chemical modeling to evaluate a possible
mechanism for formation of a colloidal phase in these
samples. These calculations indicate that the loss of
CO2 from these samples during their collection and
storage could result in precipitation of carbonate (e.g.
calcite) or fluoride (e.g. fluorite) minerals (Fig. 6).
Calculations were performed using MINEQL+ Ver-
sion 4.5 (Environmental Research Software, Hallo-
well, ME, USA) and similar results were obtained
with Geochemist Work Bench (RockWare, Golden,
CO, USA). First, the apparent in-situ Pco2 for the seep
samples were calculated as follows. Alkalinity was
estimated to be the difference between the sum of
cations and sum of anions reported in Table 2
(converted to molarity). This estimated alkalinity
was used with the field-measured pH to calculate the
Pco2 of the solution on retrieval. Ionic strength was
estimated from Pco2, the ion concentrations mea-
sured, and the field pH. Equilibrium constants were
8.2
8.1
8.0
corrected for activity using the Davis equation, with
ionic strength estimated from the chemical analysis
and carbonate and bicarbonate ion concentrations
calculated with the measured pH and alkalinity and
estimated Pco2 (iterative process).
The estimated Pco2 and the estimated initial
alkalinity were used, with the ion composition
reported in Table 2, as a starting point to calculate
the saturation index (SI) for different potential
precipitates. The electroneutrality boundary condition
was used to calculate the initial pH of the solution
using the geochemical equilibrium code MINEQL+ or
Geochemist Work Bench. This calculated pH agreed
(± 0.1 pH units) with the field measurements indicat-
ing the initial estimation method was self-consistent
and reasonable. pH and SI for different minerals were
then calculated as a function of Pco2 for the samples
from the starting value down to the present average
Pco2 for the atmosphere. MINEQL+ calculations
indicated that loss of CO2 during storage would result
in the precipitation of calcite. The results for sample
#01034582 indicated that fluorite should also precip-
itate. Both calcium and halide peaks were observed in
1.2
the fractograms (Fig. 5). Consequently, although
1.0 colloids can be a potential carrier of radionuclides in
groundwater our result should be viewed with caution,
0.8
because the colloidal material may have formed on
SI(Calcite)

7.9
pH

0.6 equilibration with the atmosphere.

7.8
0.4
7.7

7.6 logPco2 vs pH 0.2 Conclusion

logPco2 vs SI

7.5 0.0
–3.6 –3.4 –3.2 –3.0 –2.8 –2.6 –2.4 The anion, cation, and trace element data obtained
Log Pco
2
from unusual samples of seepage collected in the
exploratory studies facility at Yucca Mountain and
8.1 1.05 presented here can serve to refine geochemical
End 1.00 models. Rare earth element patterns in the seepage
8.0
0.95 suggest oxidizing water interacting with rock of
Saturation Index

7.9 0.90 volcanic origin. A range of elements were found in

pH

0.85 the seepage, ostensibly present as dissolved anionic

7.8 0.80
forms. Fractograms show that halogen elements, in
0.75
particular, seem to be present as larger colloids.
7.7
log Pco2 vs pH
0.70
Geochemical calculations indicate the colloids found
log Pco2 vs SI (Calcite) Start
in the seepage samples may be an artifact, because
7.6 0.65
–3.6 –3.5 –3.4 –3.3 –3.2 –3.1 –3.0 –2.9 loss of CO2 during collection and storage.
Log Pco
2

Acknowledgements This work was funded, in part, by the

Fig. 6 Evolution of pH and calcite saturation index with log US Department of Energy through a cooperative agreement
Pco2. The upper graph is for Sample #01034575 and the lower with the Nevada System of Higher Education. The authors
graph is for sample #01034582 thank Julie Bertoia (Harry Reid Center, UNLV) for the cation

123

and anion analyses, and Atitaya Siripinyanond and Ramon
Barnes (University Research Institute for Analytical
Chemistry) for FIFFF–ICP–MS data and some interpretations.
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