Introduction to Water Chemistry

What is Geochemistry?
• The study of behavior, and distribution of
elements in natural environments
• Examples
– Natural Waters
– Mine Drainages
– Effects of Nuclear Waste Disposal
– Coal Bed Methane Discharge Waters
– Chemical Spills and Discharges
 Connections
• A lot of geochemistry is based upon a few
concepts
• These concepts appear in many different
systems
• Understanding the concept will allow one to
see the connection for the next system
 Key Concepts
• Water is a good solvent
– ionic compounds
• Weak acids
– Carbonate, sulfate, cyanide, phenols
• Role of pH
• Influence of Redox
 Key Concepts
• Distribution of species in solution
influences the concentrations in that
solution
– weak acids
– complexation in solution
• Equilibrium, Mass Limited or Kinetically
Controlled system
– Complexation in solution and surface
complexation
– Thermodynamics
 Key Concepts

• Processes that Control Fate of Metals

– Mineral precipitation and dissolution
• pH and redox effects
– Adsorption
• presence of other solid phases
– Coprecipitation
• Modeling can be applied to predict
behavior of metals
 Geochemical Processes
• Reactions in solutions
– Acid/base reactions
– Complexation
– Redox reactions
• Reactions between solutions and solids
– Precipitation/dissolution
– Adsorption/desorption
– Coprecipitation
– Redox reactions
What is in a Water Sample?

Ca2+ H+ CaOH+
CaCO3O CO3-
H2O
CaHCO + OH-
3

HCO3- H2CO3
 Water is Unique
• Hydrogen bonding produces large dipole
moment
– without hydrogen bonding mp -100°C, bp -80°C
• Large liquid range - elevated melting and
boiling points
• High heat capacity, heat of fusion and heat
of evaporation
• High surface tension
 Polar Nature of Water
• Polarity provides means to dissolve ionic
substances
– charged ions or complexes mainly
– inorganic substances or organic salts
• Nonpolar substances less soluble
– hydrocarbons not polar
– Oil and water do not mix
 Concentrations of Different Solutions in
Terrestrial Waters in the USA Displayed
in a Frequency Plot

from Appelo and Postma, 1994

 Waters
• Major cations
– Ca2+, Mg2+, Na+, K+, protons (H+) and NH4+
• Major anions
– SO42-, Cl-, HCO3-, F-, and NO3-
• Trace metals
• Fe, Al, U, Cu, Pb, Zn, Cd, As
 Concentration Units
• Laboratories report concentrations in
weight/weight or weight/volume units
– mg/kg or mg/L  parts per million (ppm)
– µg/kg or µg/L  parts per billion (ppb)
• 1 part per billion is equal to a 1 second
vacation in 31.7 years
 Moles and Equivalents
• Geochemists commonly use molar (mol/L)
or molal (mol/kg) concentrations
– Ca2+ at 400 mg/L = 1x10-2 moles/L
– (400 mg/L)/(40grams/mole X 1000grams/mg)

• For charged species, equivalents are used

– Ca2+ at 400 mg/L = 2x10-2 equivalents/L
– (400 mg/L X 2 eq/mole)/(40grams/mole X 1000grams/mg)
 Terminology
Concentration:

}
Milligrams Per Liter (mg/L)

Parts Per Million (ppm)

}
Moles Per Liter (Molarity) (mol/L) or m

Moles Per Kilogram (Molality) (mol/kg)

Millimoles Per Liter (mmol/L)

Equivalents Per Million or Milliequivalents (epm)

Major Elements:


Cations  Ca 2 , Mg 2 , Na  , K  , NH 4


Anions  HCO3 , CO32 , SO42 , Cl  , F  , NO3 

Carbonate Alkalinity
Trace Elements:
< 1 mg/L Generally
Fe, Al, Mn, Everything Else
 Electroneutrality
• Solutions are electrically neutral
– positive ions must equal negative ions
• charge balance
– provides method to check major ion analyses
• data validation
 Terminology
Charge balance:
epm CATIONS  epm ANIONS
 100  5% 
epm CATIONS  epm ANIONS
or
epm CATIONS  epm ANIONS
 100  10% 
epm CATIONS  epm ANIONS  2
Activity (effective concentration):
The product of the measured concentration (mi) and a correction factor called the
“activity coefficient” (yi)
ai  mi yi
AS m1  0, a1  m1

-Log [ H+], negative log of hydrogen ion activity pH of 8.5 means hydrogen ion
activity = 10-8.5 mols / L

0 7 14
Acid Neutral Alkaline
 Charge Balance
• Solutions are electrically neutral
• Charge balance calculation provides
method check analytical results for major
ions
– anything missing?
• Equivalence concentrations

(ANIONS - CATIONS)
CHARGE BALANCE  X100
(ANIONS  CATIONS)
 Relation of Water Chemistry and
Charge Balance to Lithology
(Adapted from Hem, 1989)

16

14

12
Shale
Millimoles per Liter
Milliequivalents or

10

8 Limestone
Sandstone Granite
6 Basalt

Na + K Mg Ca
SO4 CO3 + HCO3 Cl + F + NO3 SiO2
Ionic Balance Berkeley Pit, Montana
Pit Lake at 100 m Depth
Typical Major Ions Only
(from Davis and Ashenberg, 1989)

CONCENTRATION MILLIEQUIVALENTS PER LITER

m g/L (CATIONS) (ANIONS)
Ca 506 25.2
Mg 272 22.4
Na 73 3.2
K 25 0.6
NH 0 0.0
3
HCO 0 0.0
3
Cl 20 0.6
SO 7060 147.0
4
NO 0 0.0
3
F 0 0.0

SUM OF CATIONS 51.4

SUM OF ANIONS 147.6
CHARGE DIFFERENCE -48.3%
Ionic Balance Berkeley Pit, Montana Pit
Lake at 100 m Depth
Major Ions Plus Trace Elements

CONCENTRATION MILLIEQUIVALENT PER LITER

mg/L (CATIONS) (ANIONS)

Ca 506 25.2
Mg 272 22.4
Na 73 3.2
K 25 0.6
Fe 1040 46.6
Al 206 22.9
Cu 218 6.9
Mn 162 7.4
Zn 496 15.2
HCO3 0 0.0
Cl 20 0.6
SO4 7060 147.0

Sum of Cations 150.3

Sum of Anions 147.0
Charge Difference 0.92%
Equivalents Exercise
 Exercise
• Calculate the molar concentrations and then equivalents
for the following concentrations reported as mg/L
– Ca 28
– Mg 12
– Na 50
– K 10
– Alkalinity 105 (as CaCO3)
– SO4 75
– Cl 60
 Reliability of Water Analysis

Concentration Conc/FW
Parameter FW Charge meq/L Sums
mg/L mmol/L
Ca 2+ 42.5 40 1.06 2.00 2.13
Mg2+ 3.2 24.3 0.13 2.00 0.26
Na + 13.7 22.99 0.60 1.00 0.60
K+ 1.18 39 0.03 1.00 0.03 3.01

HCO3- 79.9 61 1.31 -1.00 -1.31

SO42- 39 96 0.41 -2.00 -0.81
NO3- 1.3 62 0.02 -1.00 -0.02
Cl - 31.2 35.454 0.88 -1.00 -0.88 -3.02
 Reliability of Water Analysis
EN = (3.01+-3.03)/(3.01--3.03)*100 = -0.3%
 Exercise
Concentration Conc/FW
Parameter FW Charge meq/L Sums
mg/L mmol/L
Ca 2+ 28 40.8 0.69 2.00 1.37
Mg2+ 12 24.31 0.49 2.00 0.99
Na + 50 22.99 2.17 1.00 2.17
K+ 10 39.1 0.26 1.00 0.26 4.79

Alkalinity 105 50 2.10 -1.00 -2.10

SO42- 75 96 0.78 -2.00 -1.56
Cl - 60 35.454 1.69 -1.00 -1.69 -5.35
 pH as a Master Variable

• Bookkeeping method for protons (H+)

• pH = - log (H+), activity of hydrogen ion
• p functions for large changes in concentration
• At 25°C
– pH> 7.0 basic, pH = 7.0 neutral, pH< 7.0 acidic
• Natural water pH values range 1.9 to 11.78
– Iron Mountain, California pH values of -3
• Most waters pH values around 6.0 to 8.5
 Importance of pH
• Key variable in carbonate system
• Affects mineral solubility reactions
• Affects metal speciation and adsorption
• Affects changes on clays
• Affects microbiological activity
• Affects rates of many reactions
 Alkalinity
• Important concept
• Acid neutralizing capacity in a water
• Amount of acid needed to lower pH to 4.3
• Mainly measures CO32- and HCO3-
concentrations
• Reported as mg/L as CaCO3
 Distribution of Species in
Carbonate System
0.0012
H2 CO3 HCO3- CO32-

0.001
Concentration Moles/L

0.0008

0.0006

0.0004

0.0002

0
3.0 5.0 7.0 9.0 11.0 13.0
pH
 Acid Base Reactions
• pH is master variable
• Many reactions influenced by pH
• pH is a measure of the activity of the H +
ion
pH = - log (H+)

• Don’t confuse the activity of the proton

(pH) with H+ concentration (acidity)
 Acids and Bases
• Many species behave as acids (acids can
donate protons).
H2CO3° = H+ + HCO3- pKa = 6.35
HCO3- = H+ + CO32- pKa= 10.33
H2SO4 = H+ + HSO4- pKa = -3.0
HSO4- = H+ + SO42- pKa = 1.99
 ACIDS AND THEIR CONJUGATE BASES
Acid Base pKa
-
HCl° Cl ~-3
H2SO4° HSO4- ~-3
HNO3° NO3- ~0
- 2-
HSO4 SO4 1.99
-
H3PO4° H2PO4 2.15
3+ 2+
Fe(H2O)6 Fe(OH)(H2O)5 2.19
-
HF° F 3.18
Fe(OH)(H2O)52+ Fe(OH)(H2O)4+ 3.48
HCOOH° COOH- 3.75
CH3COOH° CH3COO- 4.76
Al(H2O)63+ Al(H2O)52+ 5
-
H2CO3° HCO3 6.35
H2S° HS- 7.03
- 2-
H2PO4 HPO4 7.2
-
HCN CN 9.23
NH4+ NH3° 9.24
H3BO3° H2BO3- 9.24
-
H4SiO4° H3SiO4 9.82
- 2-
HCO3 CO3 10.33
HPO42- PO43- 12.35
- 2-
H3SiO4 H2SiO4 13.1
H2O OH- 14
HS- S2 -
~18.5
+ n n+1
Ka = [H ][A ]/[HA ]
 Alkalinity Measurements
• Done by titration with H2SO4
• Definition proportional to amount of acid need to reach
endpoint
– not an absolute analysis
• Endpoint pH around 4.3
– if pH in solution is less than 4.3 initially, then alkalinity
is zero
• Different types of alkalinity
• Hydroxide, carbonate and bicarbonate most common
 Alkalinity and Carbonate System
• Usually alkalinity is used to calculate carbonate
and bicarbonate concentrations
• Under near neutral pH conditions

HCO3- (mg/L) = 1.22 * Alkalinity (mg/L as CaCO3)

• Errors possible
– if other weak acids or bases present, can overestimate
bicarbonate
 Alkalinity Titration
• Use kinetic methods to calculate pH as a
function of time in a carbonate solution
• Addition of acid from a drip system
• no solids in reactions
– buffering is solely from dissolved carbonate
• Do not have rate constants for reactions
– Assume the reactions are fast relative to acid
addition
 Buffering Capacity (ß)
ß = -dCA/dpH
• Measurement of solution’s ability to respond
to change in proton concentration
• Dissolved carbonate provides most buffering
capacity in natural solutions
• Other weak acids/bases (H3PO4) usually at low
concentrations
• Redox capacity (buffering) is similar
 Alkalinity Titration Using
PHREEQC
• Reactions in solution are instantaneous

• Merely use KINETICS keyword to add acid

• Allows verification of process because an alkalinity

titration curve is produced

• RATES keyword block requires five lines and only

two lines of BASIC

• Can expand to other acids and neutralizing compounds

 Alkalinity Titration - Kinetic

12

9
pH

0
0 50 100 150 200 250
Time in Seconds
 Chart 2
Distribution of Carbonate Species
- Kinetic Titration
0.005
H2CO3 -
HCO3 2-
CO3
0.004

0.003
Molalitity

0.002

0.001

0.000
2 4 6 8 10 12
pH
 Complexation Reactions
• Reactions between cation and anion or
neutral species
Mea+ + nLb- = MeLn(a -nb)
 Importance of Complexes
• Increase solubility of minerals
• May be the predominant form in solution
• Influence adsorption reactions
• Impact toxicity and bioavailability
 Hydroxyl Complexes
• Acids, such as Fe3+, can dissociate water and
form hydroxyl complexes
Fe3+ + H2O = Fe(OH) 2+ + H+
Fe3+ + 2H2O = Fe(OH)2+ + 2H+
Fe3+ + 3H2O = Fe(OH)30 + 3H+

• Al3+ also produces hydroxyl complexes

 Distribution of Fe(III) - OH species

100.00

Fe3+ Fe(OH)2+

80.00 FeOH2+ Fe(OH)4-

Percent of Species

60.00

40.00

Fe(OH)3o

20.00

0.00
0 2 4 6 8 10 12
pH
Piper Diagram of Water Chemistry

1. Shows relative percentages of major ions

2. Allows generalized characterization of water type

3. Reveals spatial or temporal trends

 Stiff Diagrams
Cations, Milliequivalents Per Liter Cations, Milliequivalents Per Liter
10 8 6 4 2 2 4 6 8 10
Na + K Cl
Ca HCO3
Mg MW-291
SO4
Fe
CO3
Na + K Cl
Ca HCO3
Mg MW-630
SO4
Fe
CO3
Na + K Cl
Ca HCO3
Mg PW-1
SO4
Fe
Na + K CO3
Cl
Ca HCO3
Mg MW-161 SO4
Fe
CO3
Na + K Cl
Ca HCO3
Mg MW-292
SO4
Fe
CO3
 Exercise part 2
• Calculate the percentage equivalents for the
following concentrations reported as mg/L
– Ca 28
– Mg 12
– Na 50
– K 10
– Alkalinity 105 (as CaCO3)
– SO4 75
– Cl 60
 Exercise - part 2
Conc/FW Equivalent
Parameter Conc. FW Charge meq/L Sums
mmol/L %
Ca 2+ 28 40.8 0.69 2.00 1.37 28.7
Mg2+ 12 24.31 0.49 2.00 0.99 20.6
Na + 50 22.99 2.17 1.00 2.17 45.4
K+ 10 39.1 0.26 1.00 0.26 4.79 5.3

Alkalinity 105 50 2.10 -1.00 -2.10 39.2

SO42- 75 96 0.78 -2.00 -1.56 29.2
Cl - 60 35.454 1.69 -1.00 -1.69 -5.35 31.6
Use of Trilinear Diagrams of Monitoring Well
Data to Track Leachate
MW-B Ca 59
Mg 26
Na 75
MW-A Ca 24 K 25
Mg 12 Ca 28
Alk 185 MW-C
Na 45 Mg 12
SO4 190
K 6 Na 50
Cl 72
Alk 108 K 10
SO4 96 Alk 105
SO4 75
Cl 28
Cl 60

MW-D Ca 42
Mg 26
Na 50
K 7
Alk 155
SO4 126
ORE/WASTE STOCKPILE
Cl 41

e.g., SPENT ORE DETOXIFICATION PRODUCING Cl - AS BY-PRODUCT

Piper Diagram

C
D
B
A

D
B
A C
D
AC
B
 Fractionation in 18O During the
Hydrologic Cycle

-13‰ Vapor -15‰ Vapor -17‰ Vapor

-3‰ Rain -5‰ Rain

 18 0  0 0 00 from Siegenthaler, 1979

Stable Isotopes to Locate Source of
Water in Shaft

Possible Sources of water:

1. recharge from fracture system

2. recharge along bedding
3. pond
 d 2H and d 18O for Mine Inflows and Lake

-102

-112
Global Meteoric Water Line Lake Samples
d H (‰)

2 18
d H = 8d O + 10
-122
2

-132
Underground Samples

-142
-19 -18 -17 -16 -15 -14
18
d O (‰)
 Tracking ARD Sources with
Stable Sulfur Isotopes

Pyrite (FeS2)

34
S

Ev
ap
or
Also applicable: S
34

it
e
O, H, N, C

(C
SPy +
34
S
34

aS
CaSO4

O4
)
Use of Isotopes to Settle Disputes Regarding
Contamination of Water Supply

Nitrogen Isotopes
15N of explosives
and water upslope
will be different
than 15N of animal
waste
Use of Stable Isotopes to
Solve Water Disputes
 Fingerprinting Methods at the
Grasberg/EESS site Area
• Ca/Mg ratios
• Block Cave study at EESS
• Grasberg
 Ca/Mg Ratios
• Originally identified based upon Piper
Diagrams
• Believed to reflect changes caused by extent
of dolomitization
• Skarns highly variable with low
concentrations of Ca
• Possible relationship to depth (travel
distance) of ground water in EESS
 Ca/Mg Ratios
• Sequential Batch Tests performed on
numerous samples
• Gypsum responsible for high Ca
concentrations
• Other waters sources such as Poker Chip
also identified by low pH