GEOS 4430/5310 Lecture Notes:

Groundwater Chemistry
Dr. T. Brikowski

Fall 2012

Vers. 1.33, Printed: December 3, 2012

Introduction

1
 What use is Groundwater Geochemistry?
Example applications of low-temperature aqueous
geochemistry:

Simpson-Arbuckle Aquifer a potential new source of water

for Oklahoma city. See USGS Factsheet1
how good is this water for drinking
how much can be taken out safely (i.e. where does water
come from)
significance of nearby saline and sulfurous wells? (can this
water be avoided?)

Southern Nevada Region Groundwater System a contaminant

1
http://www.owrb.ok.gov/studies/groundwater/arbuckle_simpson/pdf/
ArbuckleSimpsonFactSheet2008.pdf
2
 risk (Nevada Test Site)? A source of water for thirsty Las
Vegas2??
can shallow contaminated water reach the currently-clean
deep aquifers?

CO2flooding A common secondary recovery method in

petroleum reservoirs. Why CO2, will it accidentally reduce
porosity? Examples include DOE-20093, Shiraki and Dunn
[2000]

2
http://www.latimes.com/news/nationworld/nation/
la-na-radiation-nevada13-2009nov13,0,3038881.story?track=rss
3
http://www.netl.doe.gov/technologies/oil-gas/publications/EP/small_
CO2_eor_primer.pdf
3
 Basic Principles: Measurement
concentration generally specified as milligrams mg L , this is
essentially equivalent to ppm (except in saline waters, where
>
TDS 7000 mg L )

thermodynamic measures [Sec. 9.2, Fetter, 2001]:

molality: one mole of solute per 1000 gm of solvent is a 1
molal solution
molarity: one mole of solute per liter of solvent is a 1
molar solution

comparative chemical behavior: millequivalents:

concentration of ionic species in mg
L , multiplied by ionic
charge, and divided by molecular (formula) weight
4
 a quantitative measure for comparing the chemical
behavior of dissolved species

5
 Reactions

Reversible reactions reach equilibrium easily. Typically

equilibrium is assumed in hydrochemistry, therefore
reversibility is implied

dissociation: most common type, separation of molecules

into individual ions (e.g. NaCl)

solvent (water) can directly participate in reaction (e.g.

carbonation reactions)

oxidation-reduction: exchange of electrons between ions, e.g.

electrons appear in the reaction equation, and one or more
cations change atomic charge
6
 Equilibrium Constant (Law of Mass Action)

an equilibrium constant can be expressed for an arbitrary

reaction as
cC + dD * ) xX + yY
[X]x[Y]y
K = c d
(1)
[C] [D]
where [X] is the molal concentration of X for an ideal
solution, and is the chemical activity a of X for non-ideal
solutions

a = m, where m is the molal concentration

activity coefficient can be calculated using the Debye-

Huckel equation [Eqn. 10-17, Fetter, 2001] if the ionic
7
 <
strength I of the solution is known [Eqn. 10-16, for TDS
5000 mg
L Fetter, 2001]

K values are tabulated at standard T & P (STP), can be

determined under other conditions using the expression
o
 
Gr
K = exp
RT

where Gor is the Gibbs Free-Energy change of the reaction

at STP

solubility product:
equivalent to the equilibrium constant for dissolution of
a mildly-soluble salt, e.g. NaCl * ) Na+ + Cl (at
8
 equilibrium):

[Na][Cl]
Keq =
[NaCl]
= [Na][Cl] Ksp

because [NaCl] 1, in reality the solubility product is

equivalent to the equilibrium constant at equilibrium

ion activity product

Kiap is the numerator of the equilibrium constant (1)
when Kiap > Keq , the salt is supersaturated and will
precipitate (ignoring kinetic effects)

common-ion effect 9
 is simply that when multiple sources for an ion exist, less
of at least one of those sources will dissolve than if it was
the only source
for this reason, quantitative calculations involving
groundwater chemistry must consider all dissolved and
solid species

10
 pH
pH is the negative logarithm of [H+] ion concentration (really
H3O)

a neutral solution has equivalent [H+] and [OH], i.e. the

concentrations are controlled by water dissociation (Fig. 1)

since equilibrium constants vary considerably with T, so does

the neutral pH (at 0C neutral pH is 7.5, at 25C it is 7.0,
Fig. 2)

should be measured when water sample is collected, since it

can change after a few minutes of atmospheric contact

acids are proton donors to the aqueous solution. Strong11

 acids tend to completely dissociate, weak acids generally
dissociate partially. E.g. dissociation of carbonic acid [eqn.
9.21A-B, Fetter, 2001]

) H + + HCO
H2CO3 * 3, K = 106.4
HCO
3
*
) H +
+ CO2
3 , K = 1010.3

pH is important because it controls/indicates the distribution

of many species. E.g. the three-component system C-H-O
contains seven species H+, OH, H2CO3, HCO 3 , CO 2
3 ,
CO2, H2O. Given the concentration of the components and
the pH, the concentrations of the species can be determined.

12
 Water Autoionization

Figure 1: Autoionization reaction of water.

13
 pH vs. T

Figure 2: Variation of pH vs. temperature.

14
 pH of Common Solutions

Figure 3: pH of common solutions (after Purves et al., Life:

The Science of Biology, 4th Edition).
15
 Alkalinity

ability of solution to neutralize acid (i.e. to react with H +)

generally reported as meq of bicarbonate (HCO

3) +
carbonate (CO2
3 )

CO2
3 stable only in highly basic water, so alkalinity is
essentially [HCO
3 ] [Table 9.5, Fetter, 2001]

in common usage also a measure of the tendency to form

carbonate scale

16
 Oxidation potential (Eh)

in effect Eh is the negative log10 of [e]

field-measured ORP is essentially (Eh 200mV ) (e.g. see

YSI manual4)

oxidation refers to the removal of electrons from an

atom, increasing its oxidation number (the net charge of
a compound), reduction is the addition of an electron

redox pairs generally control (buffer) conditions, e.g. Fe+2

Fe+3 in near-surface oxygenated waters (Fig. 5)
4
http://www.ysi.com/media/pdfs/T608-Measuring-ORP-on-YSI-6-Series-Sondes-Ti
pdf
17
 in nature such redox reactions are invariably mediated by
bacteria, which use the reactions as an energy source

difficult to obtain accurate value in the field, since any

contact with O2 dramatically changes Eh

often analyzed using Eh-Ph diagram, for determining stability

of redox pairs (e.g. iron)

e+2} + 4H+ *
O2 + |4F{z e+3} + 2H2O
) |4F{z (2)
Reduced Oxidized

) 4FeIII + 2H2OII
O02 + 4FeII + 4H+ *

every redox reaction can be expressed as a pair of half-18

 reactions, e.g. (2) can be expressed as:

O2 + 4H+ + 4e *
) 2H2O
) 4F e+3 + 4e
4Fe+2 *

important in many remediation schemes (e.g. air sparging

can clog local aquifer with iron oxide precipitates)

presence of organic compounds leads to reducing conditions

by consumption of oxygen e.g. carbohydrate breakdown
[section 12.5, Domenico and Schwartz, 1998]

O2(g) + CH2O *
) CO2(g) + H2O (3)

19
 Redox in Batteries

Figure 4: Redox in a crude battery. Shown is an early battery called the Daniell Cell (for a true battery the two

beakers are connected by a salt bridge, allowing ions to flow between them, and avoiding explosive H2 gas formation). Zinc is

oxidized at the anode, donating an electron e as it dissolves. Cu2+

aq accepts electrons (is reduced), plating onto the cathode.

The total reaction is Zn(s) + Cu2+ Zn2+ + Cu(s) .

(aq) (aq)
20
 Redox Ladder

Figure 5: Redox pairs vs. Eh, most oxidizing environment on

the top, electron donor on the right, acceptor on the left. After
NIEH Meeting Report5.
21
 Eh-pH Diagram

Figure 6: Eh-pH diagram, showing effect on the solubility of

metal ions (Fe), after [Fig. 9.4, Fetter, 2001].
22
 A Civil Action: Woburn PCE

a famous lethal groundwater chemical plume court case,

memorialized in the movie, jury blamed the most innocent
party

see Woburn Spreadsheet Model Homework6

see also animation of best model results7

6
http://www.utdallas.edu/~brikowi/Teaching/Hydrogeology/Homework/
woburn_spreadsheet_model.pdf
7
http://serc.carleton.edu/files/woburn/resources/tce_animation.avi
23
 Dissolved oxygen (DO)

critical for redox reactions and biological processes

in last decade became standard to measure DO, wasnt done

much before that

easily measured with a specific probe, useful indicator of Eh

can remain in groundwater far from recharge sites

24
Major Ion Chemistry

25
 Water Analyses
collection methods important, see USGS manual [USGS,
1998]

generally reported in concentrations of actual ions, some (like

SiO2, nitrate NO3) are lumped together, and/or reported as
oxides

Analytic methods standardized for EPA and environmental

applications in general [USGS, 1979, WEF, 1998]

check error in analysis by performing charge balance (sum

of cations and anions expressed as milli-equivalents). This
sometimes fails, e.g. for strongly colored fluids which may
contain organic complexes)
26
 Graphical Analysis

Stiff Diagram Fetter [Fig. 9.10, 2001] or Parkhurst et al.

[Fig. 11, 1996], Fig. 7
plot most common milli-equivalent cations on one side of
a line, most common anions on the other
intended to give distinctive geometric pattern, allowing
mapping of groundwater bodies/facies
Typically plot Cations on left: Na+K, Ca, Mg, Fe; right
side anions: Cl, HCO 3 , SO 4 , CO 2
3
try free software from TWDB8

Piper diagram
8
http://www.twdb.state.tx.us/publications/reports/GroundWaterReports/
Open-File/Open-File_01-001.htm
27
 plot natural groupings on two trilinear diagrams (one for
cations, one for anions), the combination of these two
plots is made by projecting these onto the quadrilateral
diagram above (Fig. 8)
classification of the water chemistry is based on the sum
of cation and anion classifications Fetter [Fig. 9.9, 2001]
evolution of waters along flow path is often revealed by
these diagrams [e.g. Floridan aquifer, p 377-9, Fetter,
2001], or water sources (e.g. Floridan aquifer9)
try free GW-Chart software10 from USGS

activity-activity plots
usually used in modeling studies, or determination of
9
http://sofia.usgs.gov/publications/wri/02-4050/distsources.html
10
http://water.usgs.gov/nrp/gwsoftware/GW_Chart/GW_Chart.html
28
 mineral reaction effects
plot chemical activity (often ratios) of two ions in the fluid
and superimpose mineral stability fields [Fig. 2 Parkhurst,
1995]

29
 Stiff Diagram Example

Figure 7: Stiff diagram example, after [Fig. 9.10, Fetter, 2001].

30
 Piper Diagram Example

Figure 8: Piper diagram example, after [Fig. 9.8, Fetter, 2001].

31
 Carbonate Equilibrium

most common reaction series in groundwater (any water in

contact with atmosphere equilibrates with CO2: rainwater
reaching equilibrium with atmospheric CO2 acquires acidic
pH 5.7; sufficient to dissolve limestone/dolomite)

Important reactions
solution of CO2

H2O + CO2 *
) H2CO3 (4)
aH2CO3
KCO2 =
PCO2
where PCO2 is the partial pressure of CO2 (equivalent
32
 to its activity, essentially mole fraction times total gas
pressure)
dissolution (hydrolysis) of calcite. The following reactions
are equivalent, for modeling the first equation would be
used
) Ca2+ + CO2
CaCO3 * 3

) Ca2+ + HCO
CaCO3 + H2O * 3 + OH

) Ca2+(aq) + 2 HCO3(aq)
CaCO3 + CO2 + H2O *

dissociation of bicarbonate

HCO
3
*
) H +
+ CO2
3 (5)
33
 dissociation of carbonic acid

) H + + HCO
H2CO3 * 3 (6)

all of (4) (6) are strongly influenced by pH (e.g. Fig. 9)

(4), (5), (6) control fluid pH for fluids in contact with the
atmosphere

since atmospheric reservoir of CO2 is enormous, fluid is

buffered with respect to PCO2

34
 Carbonate Species vs. pH
o
Dissolved Inorganic Carbon Species at 20 C
1

- 2-
0.8 H2CO3 HCO3 CO3
Fraction of Species Present

0.6

0.4

0.2

0
2 4 6 8 10 12 14
pH

Figure 9: Carbonate species vs pH.

35
 Ion exchange

important process in groundwater chemistry, especially where

clays prominent (e.g. many soils)

typically Ca exchanges for Na in the clay, naturally

softening the groundwater [e.g. Central Oklahoma aquifer,
Parkhurst et al., 1996] Figs. 1011

can be a problem in irrigation, eventually defloculating the

clays (destroying soil texture)

36
 Cross-Section, Central Oklahoma Aquifer

Figure 10: E-W cross-section through Central Oklahoma

Aquifer, after [Fig. 5, Parkhurst et al., 1996]. Henessy Group
contains abundant clays, providing ion exchange medium.
37
 Stiff Diagram, Central Oklahoma Aquifer

Figure 11: Stiff diagram, Central Oklahoma Aquifer, after [Fig.

11, Parkhurst et al., 1996]. Significant Ca-Na exchange is
visible along flow path (down vertical axis of diagram).
38
Applications of Major Ion
Chemistry

39
 Flow Path Determination

Nevada Test Site/Yucca Mountain, NV [Winograd and

Thordarson, 1975], [Case Study: Great Basin (p. 250-254),
Fetter, 2001]. Also Death Valley Springs Study11

Central Oklahoma Aquifer [Parkhurst et al., 1996]

covers central OK, from Oklahoma City eastward about 50
miles [Fig. 2, Parkhurst et al., 1996]
mostly composed of Permian red-bed aquifers (sandstone),
some Qal & Qt [Fig. 3, Parkhurst et al., 1996]
unconfined to East, confined to West by Hennesy Group
(clays)
11
http://hydrodynamics-group.net/yucca.html
40
 groundwater flow from W to E, most streams gain from
aquifer; 100-1000 ft. of freshwater above saline (thinnest
at aquifer edges)
Ca-Mg-HCO 3 waters in unconfined, Na-HCO
3 in confined
(ion exchange of originally atmospheric-influenced Ca-Mg-
HCO 3 recharge waters)
high DO, nitrates, 3H, indicating relatively rapid travel
time
Chemical reactions:
after recharge, soil CO2dissolves, allowing dolomite
dissolution, generating Ca-Mg-HCO 3 water. Usually
dolomite calcite saturated after short travel distance
[Parkhurst, 1995]
then Ca+Mg exchange for Na (natural softening) [Table
11, Parkhurst, 1995].
41
 flow path calculations based on this conceptual model
indicate 50 mile flow paths requiring 103105 years
core analysis supports the model, indicating much of the
soluble carbonate is gone from parts of the aquifer
mass-balance calculations also clarify the evolution of the
groundwater (e.g. probable early ET increased N, TDS)
[Fig. 119, Parkhurst et al., 1996], (Fig. 12)

42
Rock Reaction Model, Central Oklahoma Aquifer

Figure 12: Rock reaction model, Central Oklahoma Aquifer, after [Fig. 11, Parkhurst et al., 1996]. As Ca-water is

added, exchange capacity of rock is eventually exceeded at about 100 pore-volumes of water added. Note reduction in mobile

arsenic (As) by surface complexation.

43
 Remediation: Active Barriers

One option is to bury a passive, permeable medium that can

remove pollutants

Example, Elizabeth City, NC chromate plume EPA project

[Puls et al., 1996].

Remediated by permeable iron wall (grid) reducing the

chromate and precipitating it (Fig. 13)

Wall is 150 long, 24 ft high, positioned to intercept the Cr

plume, made up of Fe cylinders (trench filled with iron chips
became impermeable, this design is the second try, Fig. 14.44
 Barrier is effective at removing Cr, and most of the TCE (a
common poly-chlorinated solvent, Figs. 15

45
 Elizabeth City Location Map

Figure 13: Location of plume and permeable Fe wall, Elizabeth City, NJ. Hydraulic gradient is directly toward river,

contaminant is Cr-bearing TCE (solvent). After Puls et al. [Fig. 1, 1996].

46
 Design of Elizabeth City Fe Wall

Figure 14: Design of permeable Fe wall, Elizabeth City, NJ,

after Puls et al. [Fig. 2, 1996].
47
 Chemical Changes With Time, Elizabeth City

Figure 15: Chemical changes with time, Elizabeth City, NJ,

after Puls et al. [Fig. 6, 1996]. Note immediate drop
in Cr to near zero, order-of-magnitude drop in TCE, and
seasonally-varying changes in Fe.

48
 Bioremediation

typically need to maintain nutrients (N, P), substrate (the

contaminant) and electron donor (O2)

provides natural attenuation of many petroleum-based

contaminants [Semprini et al., 1995, Weaver et al., Sept.
11-13, 1996]

e.g USGS study of degrading TCE plume12

EPA natural attenuation13 overview

12
http://pubs.usgs.gov/sir/2006/5030/images/fig03.png
13
http://www.clu-in.org/techfocus/default.focus/sec/Natural_
Attenuation/cat/Overview/
49
 natural attenuation in Macondo Well leak, Gulf of Mexico,
2010 (previously unknown bacteria save the Gulf, Fig. 16).
This interpretation controversial14.

14
http://dx.doi.org/10.1126/science.1199697
50
 Natural Attenuation, Macondo Well, 2010

Figure 16: Natural attenuation, Macondo Well blowout, Gulf of Mexico, 2010. FTIR shows development of petroleum

breakdown products (left), these are spatially-correlated with bacteria (right). From Hazen et al. [2010].

51
Isotope Hydrology

52
 Introduction to Isotope Hydrology
Very important for determining recharge setting of and
impacts of surficial processes on any water; can be used to
estimate travel time for many waters

53
 Light-Stable Isotopes
18
O D
Typically these are 16 O , H

usually expressed as a normalized ratio (relative to a

o
standard) in per-mil ( oo ). Increasing values mean enrichment
in the heavy isotope

lighter isotope partitions into gas phase. Evaporation leads

to increasing 18O and D at a slope of about 5:1 on a
18O D diagram [Fig. 12-12, Domenico and Schwartz,
1998], see Fig. 17

meteoric water line shows T-dependence of precipitation (low

T/high elev lower 18O D )
54
 various processes are indicated by scatter/mixing in samples
(Fig. 18)

local meteoric water lines can develop resulting from local

climate effects (usually rain shadows). These are invariably
more depleted than the world meteoric water line

examples: Claassen [1985], 18O & 14C indicate spring

waters recharged during last glacial maximum. See also
Fetter [Fig. 9.7, 2001]

55
 Process of Isotopic Fractionation

Figure 17: Isotopic fractionation processes in the water cycle.

56
 Isotopic Fractionation Trends

Figure 18: Isotopic fractionation trends, on 18O -D diagram,

after [Fig. 12.12, Domenico and Schwartz, 1998].
57
 Radiogenic isotopes

14
C
generated by cosmic radiation in the atmosphere, decays
with approximately 5000 yr half-life
14 13
can date groundwater using 12C , use 12C
C
C
ratio to correct
for isotopically dead carbon 12C input during subsurface
flow

3H (Tritium)
produced as fallout from atmospheric nuclear testing, 13
year half-life
3H in precipitation peaked around 196715, useful as
15
http://gwadi.org/sites/gwadi.org/files/diagram1.gif
58
 natural tracer of groundwater [Fig. 14.28, Domenico
and Schwartz, 1998]
most often used qualitatively to discern water recharged in
the last 40 years, and to make crude velocity estimate

36
Cl - also from fallout. Useful for waters up to 2 million years
old. Requires particle accelerator for analysis (expensive,
usually done at National Laboratories). Examples: Yucca
Mtn notes16, Scanlon [1991]

16
http://www.utdallas.edu/~brikowi/Teaching/Applied_Modeling/
GroundWater/LectureNotes/YuccaMtn/yuccaMtn.pdf
59
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60
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