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5. GROUNDWATER GEOCHEMISTRY

As part of this study, the chemistry of groundwater in the El Toro Planning Area was
evaluated to help provide a general understanding of groundwater occurrence and
movement, and to assist with assessment of the quality and quantity of available
groundwater resources in the study area. This evaluation included the following tasks:

Compilation and evaluation of available groundwater chemical data on file for wells in
the El Toro Planning Area.
Sampling of groundwater at select wells and analysis for major ion chemistry, stable
isotopes, and other groundwater quality indicators including arsenic and nitrate

Available groundwater chemistry data were evaluated to help identify general water
quality trends and the nature of their distributions within the study area. Groundwater
sampling was conducted to evaluate water quality trends or influences more specifically
(e.g. by geologic formation).


5.1 Groundwater Sampling and Analysis

One of the objectives of groundwater sampling was to evaluate potential hydraulic
communication between geologic formations and the degree of mixing between aquifers.
In order to evaluate groundwater mixing, groundwater chemistry was compared between
samples collected from different geologic formations. Many wells in the El Toro
Planning Area are screened across two or more different geologic formations, but wells
that appeared to be screened in a single formation (or in two adjacent formations for
mixing evaluation) were targeted for sampling and chemical analyses for this study.
Available information, including screen interval and formation--as determined from
drillers logs, cross-sections, geologic mapping, and other available data--was used to
select wells for sampling.

Water samples were collected from a total of 25 wells and analyzed by the Monterey
County Health Department Consolidated Chemistry Laboratory using the following
methods:
Major anions: calcium, magnesium, sodium, and potassium by SM3111B
Major cations: chloride and sulfate by EPA Method 300 and total alkalinity by
SM2320B
Arsenic and cadmium by EPA 200.8
Nitrate by EPA method 300
Conductivity by EPA 120.1
pH by EPA 150.1



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In addition, samples for stable isotope analyses were sent to Zymax Laboratories in San
Luis Obispo, California, and analyzed for isotopes of oxygen (
16
O/
18
O) and
deuterium/hydrogen (
2
H/
1
H). Figure 5-1 shows the locations of wells sampled for this
study.

Laboratory reports of chemical analyses of water samples collected from wells for this
study are confidential and therefore and not included with this report, but have been
provided to MCWRA as a supplementary confidential attachment.

Major ion chemistry and selected stable isotopes were analyzed and evaluated using
various graphical techniques to characterize the groundwater in different geologic units
and examine possible mixing of groundwater between geologic units.


5.2 Major Ion Chemistry and Water Quality

Major cations and anions were characterized in each sampling location and a summary of
the resulting signatures are presented on the Piper and trilinear diagrams shown as
Figures 5-2 and 5-3 and the Stiff diagrams shown as Figure 5-4 and 5-5. The general
signatures of groundwater compositions can be summarized in terms of their dominant
cation and anion. In the El Toro Planning Area, samples are classified as intermediate-
composition, in that they do not exhibit both a dominant cation and anion. As shown in
Figure 5-3, there is some variability in composition between lithologic units, and samples
from individual formations are generally clustered together.

In some natural systems, water types may include sodium-sulfate and sodium-chloride
groundwaters, which are generally described as high TDS formation waters. These
groundwaters typically exhibit TDS concentrations in the several thousands of mg/l. The
lack of these groundwaters but presence of moderate to high TDS concentrations in the
study area suggests that formation waters in the marine formations have been diluted
through groundwater extraction and recharge. The uniformity of TDS values in our
samples suggests a substantial hydraulic interconnectivity between lithologic units, as
also suggested by groundwater elevations throughout the El Toro Planning Area.

While it is useful to group groundwater signatures with respect to the dominant cation
and anion, groundwater signatures can also be grouped by the presence or absence of
sulfate. Within the study area, all bedrock units contain some sulfate, likely originating
from the marine formations. Significant sulfate reduction has not occurred. The
Quaternary continental deposits (QTc), which consist of Plio-Pleistocene alluvium, have
the lowest sulfate (Figure 5-2 and 5-3), consistent with derivation from non-marine units.
Samples from the marine Tsm formation generally have higher sulfate concentrations.



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However, some QTc samples contain significant sulfate, suggesting mixing with waters
with higher sulfate content.

The relative composition of groundwater signatures noted above suggests a relatively
simple groundwater-geochemical system in the El Toro Planning Area. The lack of
compositional and TDS variability exhibited by groundwater samples supports some
level of mixing between bedrock units. However, samples from each formation have a
relatively narrow range of chemical compositions, suggesting that mixing is limited.

5.3 Chemical Impacts to Groundwater

In addition to evaluating individual samples, the overall groundwater chemistry of
lithologic units was evaluated using past results and periodic water quality data available
from MCEHD and DHS files. All wells evaluated as part of this study were assigned to a
formation or group of formations based on available data including drillers logs and
cross-sections prepared for this study. Each well was grouped by formation, and the most
recent available water quality data for each well were used in our evaluation.

Groundwater quality in the El Toro Planning Area is generally poor. Based on
compilation of groundwater chemistry data from MCEHD and DHS files and analyses of
samples collected from 25 wells for this study, primary maximum contaminant levels
(MCL) are exceeded in 33% (27 of 82) of wells with available data, and secondary MCLs
are exceeded in 78% (64 of 82) of wells. Figure 5-6 shows locations of all wells with
water chemistry data that were compiled for this study. The distribution of wells with
water quality data that does not meet regulatory drinking water standards is widespread in
the El Toro Planning Area.

Natural groundwaters in the El Toro Planning Area have intermediate to high total
dissolved solids (TDS) concentrations, commonly in the hundreds to thousands of mg/l.
In this study, all samples had conductivity values of 885 to 2530 micromho per
centimeter (mho/cm), corresponding to TDS values
3
of approximately 575 to 1650 mg/l.
All but one of the samples exceeded the drinking water secondary maximum contaminant
level (MCL) for conductivity. Based on EPA secondary drinking water guidelines, water
with TDS above 500 mg/l is not recommended for use as drinking water.

Figures 5-7 through 5-10 are plots that show the average and range of concentrations of
various chemical parameters for each formation. Dashed horizontal lines in these figures
represent primary or secondary MCLs for drinking water established by the California
Regional Water Quality Control Board (RWQCB). As shown in Figure 5-7, all
formations have conductance ranges above secondary water quality goals. Figure 5-8
shows ranges for chloride and sulfate, and as discussed previously most formations are
intermediate in composition.

3
Assuming an average conversion factor of TDS (mg/l) =0.65 EC mho/cm (e.g. Harter, 2003).



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Groundwater concentration ranges of iron and manganese are shown in Figures 5-9.
Nearly all available groundwater chemistry data have iron and manganese values that
exceed secondary MCL for drinking water. In addition, many water samples also have
concentrations of arsenic that exceed primary MCL for drinking water (10 g/l).
Concentration ranges for arsenic and cadmium are shown in Figure 5-10. On average,
the concentrations of arsenic in groundwater from wells screened in the QTc (Paso
Robles) and in the El Toro Primary Aquifer System (QTc +Tsm) exceed primary
MCLs. Available historical data for Ambler Park and Toro Water System show that
arsenic concentrations are well above the current MCL (Figure 3-5). Further
development of the El Toro Primary Aquifer System as a drinking water source will
require groundwater treatment for arsenic. Figure 5-10 shows that some samples of
Monterey Formation groundwater contained cadmium in excess of MCLs, but in general
cadmium does not appear to be a major concern like arsenic.

Transient chemical impacts by nitrate and coliform bacteria are a potential problem in
areas with dense concentrations of septic tanks and shallow wells. However, the
relatively densely developed portions of the Corral de Tierra and San Benancio subareas
have been connected to a sewer system for several years. The sewer system pipes waste
water along Hwy 68 out of the El Toro Planning area to the Salinas Valley near
Spreckels. Nitrate concentrations in samples collected during this study ranged from
non-detectable to 14 mg/l, significantly less than the primary MCL of 45 mg/l.


5.4 Stable Isotope Analysis

Isotopes are atoms of the same element that have differing numbers of neutrons. Stable
isotopes are those that do not undergo nuclear decay. For example, both hydrogen and
oxygen have two stable isotopes (
1
H and
2
H, and
16
O and
18
O, respectively). Natural
hydrologic processes including precipitation segregate these isotopes of hydrogen and
oxygen, which makes them ideal tracers of water. Stable isotope geochemistry can
provide insight into the origin and age of groundwater. In addition, analysis of stable
isotopes may provide information on the degree of mixing of isotopically light and heavy
waters, and provide support to mixing models.

As part of this study, a total of 22 groundwater wells were sampled and analyzed for
hydrogen and oxygen isotopic composition. Stable isotope data are normally reported as
values, with units of parts-per-thousand (or per mil) relative to a standard of known
composition. A negative value for a sample indicates that the sample has an isotopic
ratio lower than the standard. For example, a
2
H value of -49.2means that the
2
H/
1
H
ratio of the sample is 49.2 parts-per-thousand or 4.9% lower than the
2
H/
1
H ratio of the



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standard. values are compared on the basis of high versus low values or more/less
positive versus more/less negative values.

Figure 5-11 is a scatter plot of the
2
H versus
18
O for the El Toro wells sampled for this
study with the data grouped on the basis of screened geological units. This data was used
to estimate a possible local meteoric water line (LMWL; y =5.806x 8.6305, R
2
=0.83),
although no isotopic data from precipitation are available. A LMWL slope of 5.8 is
notably lower than both the global meteoric water line (GMWL) and U.S. national
MWL (both with slopes of approximately 8.1) but is not atypical of LMWLs found in the
western U.S. (Kendall and Coplen, 2001).

The data generally plot into a tight group, indicating that groundwater over the sampled
region likely originates from the same source, independent of lithlogic unit, and that
groundwater mixing between lithologic units may be ongoing. Two exceptions are the
wells in Upper Corral de Tierra Valley (Station IDs 25 and 76) which, unlike the other
wells included in the sampling, are primarily screened in the basal sandstone geological
unit. Samples from both of these wells had significantly lower values of
2
H and
18
O,
indicating that groundwater in the basal sandstone aquifer may be distinct from other
groundwater in the El Toro Planning Area. The lower
2
H and
18
O values suggest that
recharge to the basal sandstone is derived from a higher elevation. Recharge to the basal
sand aquifer likely occurs in areas of higher elevation on the flanks of Mt Toro above
Upper Corral de Tierra Valley.

5.5 Summary of groundwater geochemistry

Groundwater quality in the El Toro Planning Area is universally impaired by high
TDS, and locally impacted by specific constituents (i.e., arsenic)
General grouping of geochemical data by formation supports limited mixing of
groundwaters between lithologic units;
Groundwater from the El Toro Primary Aquifer System generally contains arsenic at
concentrations exceeding the primary drinking water standard of 10 (g/l) , so
additional utilization of this resource generally requires treatment.
Isotopic data suggest a relatively common recharge area; however, water produced
from the basal sand aquifer likely occurs from higher elevations such as the flanks of
Mt Toro above Upper Corral de Tierra Valley.


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107
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64
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34
125
Calera Creek
Watson Creek
Corral De Tierra
San Benancio Gulch
El Toro Creek
Well Locations Sampled for this Study
El Toro Groundwater Study
Monterey County, California
Figure
5-1
P:\GIS\ElToro\project\20070524mtg\WaterSampling.mxd
J une 2007
3,000 0 3,000 1,500 Feet

NOTES:
This figure was originally produced in color. Reproduction
in black and white may result in loss of information.
77

8 6

Laguna Seca
Area
Legend
Intermittent Stream
Parcel Boundary
!
Location and Station ID of Wells
with 2007 Groundwater Sample
Subarea Boundary
Legend
S
O
4

+

C
l
C
a

+

M
g
8
0
%
8
0
%
6
0
%
6
0
%
4
0
%
4
0
%
QTc
QTc + Tsm
Tsm
QTc + Tmd
4
%
2
0
%
2
0
%
J
J J
J
J
J
J
J
J
J
J
J
J
J
B B
B
B
J B
J
Tmd
Tmd + Tus
Tus
2
0
%
4
0
%
60%
6
0
%
80%
M
g
2
0
%
4
0
%
60%
6
0
%
80%
S
O
4
N
a

+

K
H
C
O
3

+

C
O
3
J
PRELIMINARY DRAFT
For Discussion Purposes
20%
2
0
%
40%
4
0
%
6
0
6
0
%
8
0
%
8
0
%
C
20%
2
0
%
40%
4
0
%
%
6
0
%
8
0
%
8
0
%
Cl
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
J
B
B
B
B
B
B
B
B
J
J
B
B
J
J
Ca Cl
Groundwater Chemistry
Piper Diagram
5-2
P:\GIS\ElToro\ppt\AqQAchem\final2003.ppt
Legend
2
0
%
80%
QTc
QTc + Tsm
Tsm
QTc + Tmd
4
0
%
60%
%
C
o
S
O
4 J
J
J
J
J
J
J
J
B
B
B
B
J
Tmd
Tmd + Tus
Tus
20%
40%
6
0
%
8
0
%
J
J
J
J
J
J
J
J
J
J
B
B
J
J
PRELIMINARY DRAFT
For Discussion Purposes
2
0
%
4
0
%
6
0
%
8
0
%
Cl
Groundwater Chemistry
Ternary Diagram
5-3
P:\GIS\ElToro\ppt\AqQAchem\final2003.ppt
Stiff Diagrams
Alluvium - Paso Robles (QTc)
and Santa Margarita (Tsm)
El Toro Groundwater Study
Monterey County, CA
Figure
5-4
P:\GIS\ElToro\AI\Stiff.ai
J une 2007
Mg SO
4
Ca HCO
3
+CO
3
Na +K Cl
Mg SO
4
Ca HCO
3
+CO
3
Na +K Cl
Cations Anions meq/kg
0 5 10 5 10
Cations Anions meq/kg
0 5 10 5 10
NOTES:
Each diagram represents a single groundwater sample collected as part of this study. Each sample was collected from
a different well. Diagrams are color-coded to match the formation of origin of the sample (based on well screen interval).
This figure was originally produced in color. Reproduction
in black and white may result in loss of information.
Aromas - Paso Robles (QTc) Aromas - Paso Robles + Santa Margarita (QTc + Tsm)
Aromas - Paso Robles + Santa Margarita (QTc + Tsm)
Santa Margarita (Tsm)
Stiff Diagrams
Monterey (Tm) and Basal Sand (Tus)
El Toro Groundwater Study
Monterey County, CA
Figure
5-5
P:\GIS\ElToro\AI\Stiff2.ai
J une 2007
Mg SO
4
Ca HCO
3
+CO
3
Na +K Cl
Mg SO
4
Ca HCO
3
+CO
3
Na +K Cl
Cations Anions meq/kg
0 5 10 5 10
Cations Anions meq/kg
0 5 10 5 10
NOTES:
Each diagram represents a single groundwater sample collected as part of this study. Each sample was collected from
a different well. Diagrams are color-coded to match the formation of origin of the sample (based on well screen interval).
This figure was originally produced in color. Reproduction
in black and white may result in loss of information.
Aromas - Paso Robles + Monterey Formation (QTc + Tmd)
Basal Sands (Tus)
Monterey Formation (Tmd, Tm) Monterey Formation + Basil Sands (Tmd + Tus)
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#*
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Calera Creek
Watson Creek
Corral De Tierra
San Benancio Gulch
El Toro Creek
Groundwater Chemistry Showing
Locations with MCL Exceedances
El Toro Groundwater Study
Monterey County, California
Figure
5-6
P:\GIS\ElToro\project\20070524mtg\GWChem.mxd
J une 2007
3,000 0 3,000 1,500 Feet

Legend
#*
Historical Groundwater Sample
!
Groundwater Sampled for this Study (2007)
! Result Exceeds Secondary MCL
!
Result Exceeds Primary MCL
Intermittent Stream
Subarea Boundary
Parcel Boundary

NOTES:
This figure was originally produced in color.Reproduction
in black and white may result in loss of information.

8 6

Laguna Seca
Area
Conductance (TDS)
by Formation
5-7
P:\GIS\ElToro\ppt\200706report\Conductance.ppt
Conductance
700
1100
1500
1900
2300
2700
Q
t
c
Q
t
c
+
T
m
d
Q
t
c
+
T
s
m
T
m
d
T
m
d
-
T
u
s
T
s
m
T
u
s
Formation
M
i
c
r
o
S
i
e
m
e
n
s

p
e
r

c
e
n
t
i
m
e
t
e
r
MCL
Chloride Concentrations
0
100
200
300
400
500
Q
T
c
Q
T
c
+
T
m
d
Q
T
c
+
T
s
m
T
m
d
T
m
d
-
T
u
s
T
s
m
T
u
s
Formation
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
g
/
L
)
Sulfate Concentrations
0
100
200
300
400
500
600
Q
T
c
Q
T
c
+
T
m
d
Q
T
c
+
T
s
m
T
m
d
T
m
d
-
T
u
s
T
s
m
T
u
s
Formation
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
g
/
L
)
Chloride and Sulfate
by Formation
5-8
P:\GIS\ElToro\ppt\200706report\Chloride & Sulfate by Formation.ppt
MCL
MCL
Manganese and Iron
by Formation
5-9
P:\GIS\ElToro\ppt\200706report\Fig5-9 Manganese & Iron by Formation.ppt
Manganese Concentrations
0
100
200
300
400
500
600
700
800
Q
t
c
Q
t
c
+
T
m
d
Q
t
c
+
T
s
m
T
m
d
T
m
d
-
T
u
s
T
s
m
T
u
s
Formation
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
g
/
L
)
Iron Concentrations
0
2000
4000
6000
8000
10000
Q
t
c
Q
t
c
+
T
m
d
Q
t
c
+
T
s
m
T
m
d
T
m
d
-
T
u
s
T
s
m
T
u
s
Formation
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
g
/
L
)
MCL
MCL
Arsenic and Cadmium
by Formation
5-10
P:\GIS\ElToro\ppt\200706report\Arsenic & Cadmium by Formation.ppt
MCL
MCL
Groundwater Stable Isotope Data
El Toro Groundwater Study
Monterey County, CA
Figure
5-11
P:\GIS\ElToro\AI\StableIsotopevv.ai
J une 2007
-60
-55
-50
-45
-40
-35
-30
-9 -8.5 -8 -7.5 -7 -6.5 -6 -5.5 -5

18
O

2
H
Qtc
Qtc - Tsm
Tsm
Qtc - Tmd
Tmd
Tmd - Tus
Tus
451 Corral de Teirra
Station ID 76
431 Corral de Tierra
Station ID 25
Global Meteoric Water Line

2
H =8 *
18
O +10
Local Meteoric Water Line

2
H =5.806 *
18
O +8.6305