LEARNING OBJECTIVES

Review and learn general guidelines for

developing effecting sampling programs.
Practice how to interpret based on
geochemical data analysis.

CHEMICAL CHARACTERISTICS - 3

pH

pH (Hydrogen Ion Activity) affects aqueous complexation,

mineral solubility, adsorption properties, gas solubility, &
biochemical reactions.
9.5
A sample of GW ~
Effect of CO2 gas pressure
9
originally in equilibrium
on groundwater PH
with calcite at PCO2 = 0.1
8.5
atm
8
allowed to equilibrate
7.5
with atmosphere (PCO2 =
7
0.0003 atm)
Large change in pH
6.5
(pH 6.5 8.4) would
6
have a major effect on
-4.5
-3.5
-2.5
-1.5
the solubility of
Log PCO2
minerals.

-0.5

pH

The pH of water determines the solubility (amount that can

dissolved in the water) and biological availability (amount
that can be utilized by aquatic life)
14
of chemical constituents such as
bleach
13
nutrients (phosphorus, nitrogen,
12
ammonia
and carbon) and heavy metals
11
(lead, copper, cadmium, etc.).

beer
vinegar
lemon juice

10
9
8
7
6
5
4
3
2
1

sea water
distilled water
pure rain
most fish species die

CHEMICAL CHARACTERISTICS - 4

Alkalinity to determine the dissolved inorganic carbon concentration

(CO2(aq), H2CO3, HCO3- , CO32-) of a water sample
Hardness to measure the soap-consuming capacity & scale-forming tendency
of the water (Ca2+ + Mg2+)

Conductivity
measure of electrical
current (S/cm)
Because the electrical
current is transported
by the ions in solution,
the conductivity
increases as the
concentration of ions
increases.
Conductivity estimates
the amount of total
dissolved solids (TDS).

Conductivity

TDS

Divide Lake

10

4.6

Lake Superior

97

63

Lake Tahoe

92

64

Grindstone Lake

95

65

Ice Lake

110

79

Lake Independence

316

213

Lake Mead

850

640

Atlantic Ocean

43,000

35,000

Great Salt Lake

158,000

230,000

CHEMICAL CHARACTERISTICS - 5

TDS (Total Dissoloved Solids) - TDS meter

This meter works by measuring the electrical conductivity of the
water. Conductivity increases as the amounts of salts and other
dissolved solids increase in the water. Conductivity and TDS are
two different but related tests. One can be calculated from the
other by multiplying or dividing by a certain fixed number.
TDS (mg/L) = 0.55 to 0.7 x conductivity of sample ( S/cm)

CHEMICAL CHARACTERISTICS - 5

Redox = Oxidation + Reduction

Oxidation : substance loses or donates electrons (e -)
Reduction : substance gains or accepts electrons (e -)
Redox reactions can be thought of as reactions involving transfer of
oxygen.
1
2Fe 3 H2O 2Fe 2 O 2 2H
2
In solution chemistry it is generally more convenient to consider
redox reactions as electron transfers.

Fe3 e Fe 2

The redox potential is a measure of the affinity of a substance for

electrons.
Unit in volts - a transfer of electrons is an electrical current.

1
2
p
0
.
5
9
2
H
0
E
h
E
1lo
g
a

G
(lo
g
K
r)

REDOX POTENTIALS (Eh)

Redox Potential can be measured

using Redox tester on site.

Redox Potential (Eh) by the Nernst equation:

RT (at 25C & 1 atm pressure)

where E0 = standard0 potential
Eh

lnK
R = gas constant (kcal/(molK) sp
nF
T = temperature (kelvins)
F = Faraday constant (23.1 kcal/V)
n = number of electrons
Ksp = solubility product

2
.3
0R
T

S
P

Eh-pH DIAGRAM

1.4
1.2
1.0
Eh (volts)

0.8

O2

Eh
=

H 2O

1 .2

2-

0.6
0.2
0.0

H 2O

H2

Eh

-0.4
-0.6

Natual water
=-

0.0

-0.8
0

9pH

Water
is stable

0.4

-0.2

0.0
5

pH

59p
H
10

12

14

This diagram shows the

stability limits of water at
25C and 1 bar.
At conditions above the top
dashed line, water is
oxidized to O2; at conditions
below the bottom dashed
line, water is reduced to H2.
No natural water can persist
outside these stability limits
for any length of time.
Water in nature is usually
between pH 4 and pH 9.

Eh-pH DIAGRAM
1.2
1.0
0.8

Eh (volts)

0.6

[O
C
2] =
Min onta
1a
ew
ct w
tm
at e
r, R ith a
t
ain
, St mosp
r
h

Bo
gw

0.4
0.2
0.0
-0.2
-0.4
-0.6

ate
r,

Iso
wa lated
te

eux
eni
c

eam
e
s, O re
ce a
ns

Gro
und

wa
ter

rlog fro
ma
g
ma
rine ed, o
tmo
r
g
[O
bas
ani
sph
c
2] =
i
n
10 -83.1 s, or -rich ere
atm ganic-r soils,
ich
brin
es.
pH

This diagram
shows for the
Eh-pH range of
common
geological
environments

Eh-pH DIAGRAM

1.4
1.2

Eh (volts)

1.0 Fe 3+O
H2
0.8

0.6
0.4
0.2

Fe 2+

0.0

H 2O

Fe(OH)3(s)

-0.2
-0.4
-0.6
-0.8
0

Fe(
OH
)

Water is stable
2

pH

10

12

14

Eh-Ph diagram can be

used to show the fields of
stability for both solid and
dissolved ionic species.
Iron Fe will be mobile only
under the Eh-pH
conditions where Fe2+ and
Fe3+ are stable in the
diagram. This will occur
either under strongly
acidic conditions at any
Eh, or under reducing
conditions under more
normal pH conditions.

CHEMICAL CHARACTERISTICS - 6

Dissolved Oxygen (DO) the only gas routinely measured in

water samples (mg/L).
Dissolved oxygen refers to the volume of oxygen that is contained
in water. Oxygen enters the water by photosynthesis of aquatic
biota and by the transfer of oxygen across the air-water interface.
The amount of DO depends on the water temperature, salinity,
and pressure.
When performing the dissolved oxygen test, only grab samples
should be used, and the analysis should be performed
immediately. Therefore, this is a field test that should be
performed on site.
As dissolved oxygen levels in water drop below 5.0 mg/L, aquatic
life is put under stress. The lower the concentration, the greater
the stress.

Death Valley Springs

Geochemical Investigation

AREA INFORMATION

Researchers suggest that ground water in the Yucca Mountain

area is hydraulically connected to the Lower Carbonate Aquifer.

Discharge from the major springs in Death Valley may be faultcontrolled.

The objective of this geochemical study of spring waters was to

to determine the source of these waters.

Geology in the study is highly variable and complex. Although

it is possible to readily map the surface geology of the area, our
knowledge of the subsurface geology beneath the alluvial basin
is based upon a limited number of boreholes.

Most of the springs

are located near the
top of the recharge
system.
The very high HCO3
conc and very low
conc of Na, Cl, SO4, &
Mg indicate a very
young ground water
source.

Two springs differ

from the other
springs - they are
localized
intermittent seeps.

These springs have

very similar chemical
compositions - high
conc of Na & K and
intermediate conc of
HCO3, SO4, & Cl.
This indicate water
discharging from
these springs has
followed long travel
paths.

#2, #4, & #5 springs

have similar chemical
compositions, but are
not geographically near
each other. These
springs can be
described as a mixed
bag of sources, based
on the wide range of
chemical compositions.

These springs are

totally dominated by
evaporation
processes, with high
conc of NaCl.

The composition of
#7 is similar to other
mountain springs,
which suggest this
is a fault controlled
spring source.

SEWAGE DISPOSAL SYSTEMS

Barker Reservoir, Nederland, CO

Residence
Surface Water Sample Site
Ground Water Sample Site

AREA INFORMATION

Barker Reservoir is a mountain reservoir adjacent to Nederland,

that supplies 40 percent of the drinking water for the city of
Boulder.
The study area is primarily Precambrian igneous and
metamorphic rock, except for Quaternary alluvium and
colluvium in streambeds and drainages that lead to the reservoir.
Ground water that discharges into Barker Reservoir flows
beneath residential developments on the north and south sides of
the reservoir.
Homes on both sides of the reservoir use individual sewage
disposal systems for disposal of domestic wastewater.
USGS & City of Boulder conducted this study to evaluate
whether sewage disposal systems affect the quality of ground
water entering Barker Reservoir or its tributaries.

Boron (B) is a good indicator of sewage disposal system effects on ground

water because (1) natural background concentrations are generally low
relative to sewage disposal effluent, (2) B does not undergo biological
removal during treatment, and (3) B is not significantly sorbed in the
subsurface.
B conc. typically range from less than10 g/L to 40 g/L.
Elevated B conc. can indicate human influence (non-chlorine bleaches and
fruit)

(g/L)

Dissolved boron concentrations in ground water and surface water

ACID MINE DRAINAGE

AREA INFORMATION

The study area is located in rural southern Stark

Ohio in the Bear Creek Run Watershed.

County

This area is an unglaciated part of Ohio with

relief of
up to 200 feet per 0.5 miles. Three
Pennsylvanian aged units
are present in the
area; the Conemaugh, Allegheny,
and Pottsville
Formations. These units consist of interbedded
coals, shales, and limestone including the Brookville Underclay which
acts as a major regional aquiclude, and occurs at the contact between
the Pottsville and the Allegheny Formations.

The area has been strip mined for coal and limestones for most of this
century and abandoned mine spoils occupy approximately 40% of
the drainage basin.

A
C
E
D

B
G

Areas occupied by strip mine

spoils (red)

SAMPLE DATA (conc. in mg/L)

Temp
pH
HCO3
CO3
Cl
SO4
PO4
N
Br
Na
K
Mg
Ca
Al
Mn
Fe
Si
TDS

A
12.0
7.46
876
0
1266.4
<10
0.15
0.26
11.50
890
8.5
6.21
20
0.13
0.01
0
3.4
2996

B
11.7
8.42
776
67
72.9
<10
0.75
0.18
1.20
340
3.0
0.36
0.8
0.13
0
0.01
3.3
1264

C
11.7
8.60
552
0
10.4
10.9
0.55
0.22
0.06
220
2.3
0.18
0.6
0.13
0
0.01
3.4
800

D
10.6
7.04
424
0
43.1
<10
0.10
0.31
0.60
140
7.2
7.43
22
0.13
0.03
0.02
3.1
645

E
11.5
7.55
512
0
32.5
<10
0.20
0.40
0.44
190
5.0
3.99
12
0.11
0.02
0.01
3.1
757

F
12.1
7.17
324
0
15.9
82.4
0.18
0.44
0.13
160
2.1
0.70
2
0.13
0.01
0.02
3.3
590

G
11.2
4.89
28
0
8.7
2069.9
0.10
0.26
0.04
20
5.6
223.50
443
5.40
46.1
46.7
ND
2890

CHLORIDE (Cl)

Does not substitute for other anions (no water-rock interaction)

conservative element
Used in mass balance calculations for mixing of water bodies.
Cl (mg/L)
Park

Park

32

River

15

Local Aquifer

39

Based on the water chemistry, the park water was a mixture

of aquifer and river water. What is the mixing ratio?

BROMINE (Br)

Bromine is widely distributed in nature, generally in low

concentrations in the form of bromine salts. The most common
forms of bromine are soluble salts found naturally in seawater,
salt lakes, inland seas, and brine wells such as those in
Michigan and Arkansas in the United States.

Seawater contains about 65 ppm bromide salts (much smaller

quantities than chloride).
Br is also a conservative ion (no water-rock interaction).
Br/Cl ratio is used to trace origins of salinity.
For ocean water, Br/Cl = 3.5 x 10-3
Groundwater flowing through aquifer with halite (NaCl)
Salt dissolution will lower Br/Cl as Cl increases.

NITRATE (N)

Some N in rainfall (dissolution of atmospheric N &

anthropogenic NOx emissions)

Also input from soil (especially where fertilisers are used or

near septic systems) Used to assess impacts of pollution
(effluent, fertilisers)
Tends to be conservative in most groundwater environments.
Aerobic condition, NO3 is stable and a conservative tracer.

Schoeller Diagram

50

A
B
C
D
E
F
G

45
40

meq/L

35
30
25
20
15
10
5
0
0

HCO3
1

Cl
2

SO4
3

Na
5

Mg
6

Ca
7

1200
G
Well Depth (elevation above sea
level)

1100
F

1000
900

800

E
C
B
A

700
600
0

500

1000
1500
2000
2500
Total Dissolved Solids (mg/L)

3000

3500

80

60 )+B
i

te(
CO
3

O4
e(S0
20

%meq/l
20
40

rb 40
on
ate
(H 20
20 CO
3)
40

ca

60

60

HCO3 +CO3

Chloride (Cl)
60

AN IONS

t
lfa
Su

80

A
80

Ca
rb
on
a

80

si u
m(
60
Mg
)

20

20

e(S
40

Su
lfa
t

g)
(M
iu m

Ma
gn
e

es
gn

40

60

O4
)+

Ma
a)+ 40
(C

20

Ch
lor
ide
(C
l)
80

K)
m(
siu 80

Na+K

ium0

80

C AT I O N S
20

lc
Ca

t as
Po0

40

80

60

Calcium (Ca)
60

)+
Na
40
m(
diu 40
So

80
20

Ca
20

Mg

SO 4

80

Cl