Professional Documents
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Groundwater Chemistry
Dr. T. Brikowski
Fall 2012
1
What use is Groundwater Geochemistry?
Example applications of low-temperature aqueous
geochemistry:
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 )
5
Reactions
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
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)
) H + + HCO
H2CO3 * 3, K = 106.4
HCO
3
*
) H +
+ CO2
3 , K = 1010.3
12
Water Autoionization
13
pH vs. T
14
pH of Common Solutions
CO2
3 stable only in highly basic water, so alkalinity is
essentially [HCO
3 ] [Table 9.5, Fetter, 2001]
16
Oxidation potential (Eh)
e+2} + 4H+ *
O2 + |4F{z e+3} + 2H2O
) |4F{z (2)
Reduced Oxidized
) 4FeIII + 2H2OII
O02 + 4FeII + 4H+ *
O2 + 4H+ + 4e *
) 2H2O
) 4F e+3 + 4e
4Fe+2 *
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
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)
24
Major Ion Chemistry
25
Water Analyses
collection methods important, see USGS manual [USGS,
1998]
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
30
Piper Diagram Example
31
Carbonate Equilibrium
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)
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
35
Ion exchange
36
Cross-Section, Central Oklahoma Aquifer
39
Flow Path Determination
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
45
Elizabeth City Location Map
Figure 13: Location of plume and permeable Fe wall, Elizabeth City, NJ. Hydraulic gradient is directly toward river,
46
Design of Elizabeth City Fe Wall
48
Bioremediation
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
55
Process of Isotopic Fractionation
56
Isotopic Fractionation Trends
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
Bibliography
60
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61
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