LINNAEUS-PALME ACADEMIC EXCHANGE

PROGRAMME

Chemical Processes and

Evolution of Groundwater
SHORT COURSE

Department of Geology
University of Dhaka
17-20 April, 2011

Prosun Bhattacharya
Professor

KTH-International Groundwater Arsenic Research Group

Department of Land and Water Resources Engineering
Royal Institute of Technology (KTH)
Part 3 SE-100 44 Stockholm
SWEDEN
1

1
 Contents

• Geochemical modeling

z What is Geochemical Modeling?

z Considerations in geochemical modeling
z Purpose
z Approaches
z Types
yp of models
z Forward modeling
z Inverse modeling
z Applications of modeling

What is Geochemical Modeling?

Technique for quantitatively evaluation of

groundwater chemical processes in groundwater
system for deducing operative chemical and
microbial processes from groundwater
chemistry is termed as geochemical modelling.

2
Considerations in Geochemical Modeling

• Hydrological Considerations
• Mineralogical Considerations
• Thermodynamic Considerations

Purpose of geochemical modeling

• The purpose of geochemical modeling is

primarily to deduce and quantify the
chemical (and biological) processes that
modify groundwater chemistry in a
hydrogeological system.

• There are several pre-requisites for inverse

geochemical modeling of evolving chemistry
in hydrologic systems. The first of them is
the knowledge of flow pattern. When we
study geochemical evolution in a
hydrogeological system, the sampling points
should be hydraulically connected. This
means that flow model has to be solved
before geochemical model.

3
 Geochemical sampling based on flow
system

Recharge zone

Lake
A D
C B

River

200

100

Approaches for geochemical modeling

• There are two principle approaches to
geochemical modeling:

• chemical equilibrium
• chemical kinetics

• The equilibrium approach is the most common,

and assumes very fast (instantaneous)
reactions compared to groundwater residence
time.

• The kinetic approach includes time factor, but

data about reaction rates of As-minerals
oxidation are still very limited. There are
however some exceptions.

4
Approaches for geochemical modeling
• Exceptions are special environments
like mine tailings with the oxidation of
pyrite.
py

• In general, we focus mostly on

equilibrium models, but applications of
some kinetic models are also applied
during the evaluation of contaminated
groundwater.

Types of Modeling

• Equillibrium models can be divided into:

• Forward (reaction path models), e.g.,

MINTEQA2 (Allison et al., 1993), PHREEQC
(Parkhurst, 1995) and PHREEQC-2 (Parkhurst
and Appelo, 1999).

• Inverse models, e.g., NETPATH (Plummer et

al., 1994) and inverse modeling module of
PHREEQC.

10

5
 Forward and inverse modeling

• In forward modeling, a priori prediction of

water chemistry are made based on assumed
geochemical processes and thermodynamic
constraints. In other words, these models
start with equations and parameters and run
forward (in time or space) to produce
variables.

• In inverse modeling, the available

hydrologic and groundwater chemistry data
are used to deduce the operative geochemical
processes in hydrologic system. In other
words, this model starts with the variables
and operate in the inverse direction to derive
the parameters.

11

Forward modeling

• A prerequisite of forward modeling is calculation of

speciation
speciation.

• Speciation represents calculation of the equilibrium

distribution of mass among complexes and redox
couples. The speciation module also calculates saturation
indices of a water sample with respect to different
minerals.

• Saturation index (SI) is defined as:

SI = log(IAP/Ksp)
where IAP is ion activity product and
Ksp is the solubility product for a given temperature.

12

6
 Forward modeling
• This means that when IAP = Ksp

When SI = 0 and water is at thermodynamic

equilibrium
ilib i with
ith respectt to
t the
th mineral.
i l

When SI > 0, water is supersaturated with respect to

the mineral and this mineral should precipitate.

On the other hand, if SI < 0, water is undersaturated

with respect to the mineral and this mineral should
dissolve.

• However, there is no information about the rate of the

reaction or even if it has proceeded or will proceed.
• Most reactions never reach equilibrium and reactants are
gradually transformed to products (for example, the
oxidation of organic matter by dissolved O2).

13

Forward modeling

• Speciation calculations are complicated by

uncertainty about values of thermodynamic
constants for mineral phases because pure
minerals are rather the exception than the rule.
• Equilibrium constants for solid solutions may
differ significantly from values in databases of
geochemical programs.
• Another problem is related to the complexation
of As and other species with organic matter. Only
few programs like WHAM (Tipping, 1994)
consider the effect of organic complexation.

14

7
 Forward modeling
• Forward (reaction path) models are used for prediction of water
chemistry evolution.

• In this case the starting water chemistry is defined and an attempt

is made to model water evolution by dissolution and precipitation of
mineral phases and gases etc.

• The output of the program has the following form:

Initial water + Reacting phases =

Predicted water + Product phases

• During each small step the program transfers a limited amount of

mass from reactant to products. Then the code calculates mass
distribution among the products and calculates saturation indices.
Pre-determined phases, to which the water sample is
supersaturated, are allowed to precipitate.

• Both MINTEQA2 and PHREEQC used for forward modeling.

15

Forward modeling

• Both MINTEQA2 and PHREEQC used for forward modeling,

also include surface complexation modeling (SCM) with
p
several options.

• Unlike the application of adsorption isotherms, which are

applicable only under relatively constant pH and water
chemistry conditions, the approach is far more universal.

• Surface charge of adsorbents like hydrous ferric oxide (HFO)

changes with increasing pH of water from positive values at
l
low pH
H towards
t d negative
ti values
l att high
hi h pH.
H

• The pH value at which the bulk surface charge changes from

positive to negative is called the zero point of charge (pHZPC).

16

8
 Forward modeling

The overall adsorption constant is:

Kads = Kint x exp(-ΔZ.Ψ F/R.T)

• where Kint is the intrinsic adsorption constant representing a

chemical component of adsorption
• the expression in brackets called the electrostatic (also
coulombic or Boltzman) term accounts for the electrostatic
component
p of adsorption
p
• ΔZ is the change in surface charge due to adsorption,
• Ψ is the surface potential,
• R is the universal gas constant,
• T is temperature.

17

Forward modeling

• Values of Kint constants were determined for

adsorption on HFO by Dzombak and Morel (1990)
and are implemented in the diffuse double layer
model (DDLM), which is a module of the
MINTEQA2 and PHREEQC programs.
• Other possible approaches are:
• constant capacitance
p model ((CCM),
),
• basic Stern model (BSM), and
• triple layer model (TLM)

18

9
 Forward modeling

• The DDLM requires as input the following

parameters:
• concentration of adsorbent Mv (g/L),
• surface area of adsorbent SA (m2/g), and
• number of adsorption sites (mol/mol of
HFO).

• For surface complexation modeling, the

information about concentration of an adsorbent
such as Fe(III) hydroxide can be, for example,
obtained by sequential extraction of the solid
phase in contact with water.

19

Forward modeling

• When the data are not available, the amount of

precipitated Fe can be estimated from the
decreasing dissolved Fe concentration
downgradient.

• Surface complexation modeling can also include a

competition for adsorption sites with other ions.

20

10
 Inverse modeling
• Through inverse modeling, it is possible to determine the
possible reactions between 2 or more sampling points.
• One of the pre
pre-requisites
requisites is the knowledge on the solid
phase composition in the aquifers.
• This type of modeling is based on a mass-balance
approach and does not have thermodynamic constraints.
• Inverse modeling in is generally used to verify, if certain
reactions for the release of various contaminant species
of As release and immobilization are possible.
• Mass balance for As and As related species such as SO4
i performed
is f d using
i hydraulically
h d li ll connected
t d samples.
l
• Data on mineralogical composition of the solid phase are
essential because they have to be entered together with
water chemistry.

21

Inverse modeling
• Inverse or mass balance models are based on mass
balance calculations for solid phase and dissolved species
(sometimes also isotopes) in a geochemical system.
• The input comprises water samples from two or more
h d
hydraulically
li ll connected
t d sampling
li points
i t and
d the
th
composition of the solid phase between these points.
• The output has the form of

Initial water + Reacting phases

= Final water + Product phases

• However, there are no thermodynamic constraints in the

program, which can also suggest thermodynamically
impossible reactions.
• Thus, the code NETPATH based on mass balance
calculations is combined with the WATEQ4F program
(Plummer et al., 1976) and with mineralogical analysis to
determine mineral phases, which can dissolve or
precipitate (Glynn and Brown, 1996).
22

11
 Inverse modeling
• The mineral database in NETPATH (Plummer et
al., 1994) does not include all elements viz. As.

• However, inverse modeling module of

PHREEQC-2 (Parkhurst and Appelo, 1999)
makes it possible to define new elements and
mineral phases.

• F
Furthermore,
th uncertainty
t i t in
i analytical
l ti l d
data
t can
be accounted for and a range of concentration
values may be entered instead of fixed
concentration values.

23

Inverse modeling
• Standard flow/transport packages like Visual MODFLOW
which includes transport program MT3D, can simulate
flow and transport p in 3-D,, but their ggeochemical
capabilities are limited.
• They include adsorption isotherms like linear adsorption
isotherm Kd and first order decay.
• The Kd value is generally determined from batch or
column experiments, when ground water in contact with
solid phase from the investigated aquifer is spiked with
the contaminant species in question viz. As.
• The slope of the straight line in a graph of equilibrium
adsorbed concentration S vs. dissolved concentration C is
based on a batch experiment determines the Kd value,
which is used to calculate the retardation coefficient R
(Fetter, 1999).

24

12
 Inverse modeling

v w Lw ⎛ρ ⎞
R= = = 1 + ⎜ b ⎟.K d
v c Lc ⎝ n ⎠

• where vw and vc indicate the velocity of ground water

flow and contaminant transport,
• Lw and Lc are distances of ground water flow and
contaminant transport,
• ρb is the bulk density of the solid phase, and
• n is porosity.
• Other adsorption isotherms like Freundlich and Langmuir
isotherms are also available, and the retardation factor R
based on these isotherms can be calculated as a
derivative of the relation S = f(C) according to C, and
substitution for Kd into the equation for R (Fetter, 1999).

25

Applications of geochemical modeling

• Geochemical modeling applications of As behavior are
presented here with selected case studies.
• Most of the typical applications including forward modeling
with
ith surface
f complexation,
l ti i
inverse modeling,
d li and
d transport
t t
modeling using both the reactive transport code and an
approach based on adsorption isotherms.

Forward modeling

• Prediction of As behavior requires a combination of forward

models with speciation and surface complexation
capabilities Speciation calculation can be used to indicate if
capabilities.
some As minerals can precipitate.
• However, As minerals like scorodite are not common, and
determination of the saturation index for As sulphide
minerals like orpiment is based on complicated sampling
and determination of dissolved reduced S species.

26

13
Applications of geochemical modeling
• Another application includes determination of
saturation indexes for minerals, which could be
sinks for dissolved Fe.
• In Bangladesh and West Bengal, India, the
correlation between dissolved Fe and As is poor in
some cases.
• Precipitation of Fe(II) iron minerals like siderite,
FeCO3, and vivianite, Fe3(PO4)2.8H2O, was
suggested to explain the lack of correlation by
S
Sracekk ett al.
l (2000);
(2000) Nickson
Ni k ett al.
l (2000) and d
Bhattacharya et al. (2002b).
• Saturation indices for both Fe(II) minerals were
consistently positive.

27

Applications of geochemical modeling

• Evaporation of recharge water and irrigation water
can be modeled with PHREEQC to determine, if
evaporation enrichment can explain high
concentrations
t ti off As.
A
• During evaporation, constraints can be put on
some minerals and mineral phases like Fe(OH)3
can be precipitated.
• The same code can be used to calculate the
resulting concentration of As after mixing of
surface water and ground water at a seepage
face
face.
• Mixing ratios can be determined by hydraulic
methods (application of seepage-meters or
piezometers, ground water flow modeling) or by
application of mixing equation for a conservative
tracer (Cl- etc.).
28

14
 Applications of geochemical modeling

• When the concentration of As decreases, but the

As mass remains the same, then this is the effect
of dilution and no geochemical processes have to
be considered.
• When dilution cannot explain attenuation of As,
other processes like adsorption on Fe(III) oxide
and hydroxides has to be considered.
• For example, adsorption of As on Fe(III) oxide
and oxyhydroxide was found to be the principal
sink
i k for
f As A in
i acid
id mine
i d i
drainage i
impacted
t d site
it off
Nevada (Webster et al., 1994).
• The process can be modeled using surface
complexation approach.

29

Applications of geochemical modeling

for investigations on arsenic
Example Approach
1 Forward with SCM1
2 Forward with SCM
3 Forward with SCM
4 Forward with SCM
5 Forward with 1-D
transport and SCM
6 Inverse
7 Inverse and forward
with SCM
8 Inverse
9 Isotherms based on
SCM (Freundlich,
Langmuir) and
transport
1
SCM – Surface Complexation Modeling
Solid phase As data Program Objectives of References
modeling
Sequential extraction PHREEQC Determine the role of Welch and Lico,
Lico 1998
adsorption and potential As
sources/sinks
XRF, oxalate extraction, batch MINTEQA2, Determine factors controlling Lumsdon et al., 2001
experiments ECOSAT As distribution
Electron microprobe analysis MINTEQA2 Determine factors controlling Davis et al. 1994
(EMPA) As distribution
Batch experiments Models based on Determine the impact of Gao and Mucci, 2001
CCM, BSM and competitive adsorption
TLM
Sequential extraction PHREEQC Release of As along flow path Parkhurst, 1995
Transmission electron NETPATH Mass balance for potential As Schreiber et al., 2000
microscopy (TEM), X-ray source
absorption spectroscopy
(XAS)
Scanning electron microscopy NETPATH and Identification of geochemical Carillo-Chavez et al.,
(SEM)/energy dispersive MINTEQA2 processes 2000
spectroscopy (EDS), partial
sequential extraction
Partial sequential extraction PHREEQC Water chemistry evolution Armienta et al., 2001
Sequential extraction ECOSAT, Mobility of As “hot spots” DPHE/BGS, 2000
(oxalate step) MODFLOW/MT
3D

30

15
 Geochemical modeling using PHREEQC: Input data
1 du004 Puntia, Rajshahi 25.5m du004 c5
916. 1033. 9901 .0000 .9000 .0000 .0000 .0000 .0000 .0000
TEMP = 24.700000
PH = 6.870000
EH(0) = -.153000
DOC = .900000
DOX = .000000
CORALK = 0
FLG = MG/L
DENS = 1.000000
PRNT = 0
PUNCH = 1
EHOPT(1) = 0 Use measured Eh to calculate Fe species distribution
EHOPT(2) = 0 Use measured Eh to calculate Mn species other than +2
EHOPT(3) = 0 Use measured Eh to calculate Cu +1 species
EHOPT(4) = 0 Use measured Eh to calculate As species distribution
EHOPT(5) = 0 Use measured Eh to calculate Se species distribution
EHOPT(6) = 0 Use measured Eh to calculate Ion Activity Products
EHOPT(7) = 0 Use measured Eh to calculate atmospheric pO2
EHOPT(8) = 0 Use measured Eh to calculate H2S from SO4
EHOPT(9) = 0 Use measured Eh to calculate U species distribution
EMPOX = 0
ITDS = 1033.000000
COND = 916.000000
SIGMDO = .000000
SIGMEH = .000000
SIGMPH = .000000

Species Index No Input Concentration

--------------------------------------------
Ca : 0 : 188.00000000
Mg : 1 : 44.00000000
Na : 2 : 28.40000000
K : 3 : 1.93000000
1 93000000
Cl : 4 : 255.00000000
SO4 : 5 : 36.97000000
HCO3 : 6 : 473.10000000
Fe total : 16 : 5.22000000
H2S aq : 13 : .00000000
CO3 : 17 : .00000000
SiO2 tot : 34 : 30.60000000
NH4 : 38 : .00000000
B tot : 86 : .00000000
PO4 : 44 : .64400000
Al : 50 : .07300000
F : 61 : .00000000
NO3 : 84 : .00000000
Mn : 109 : .70500000
As total : 249 : .03750000
As3 tot : 261 : .01698000
As5 tot : 262 : .02050000

31

Geochemical modeling using PHREEQC: Recalculated data

1 du004 Puntia, Rajshahi 25.5m du004 c5 Date = 10/13/99 13:05
916. 1033. 9901 .0000 .9000 .0000 .0000 .0000 .0000 .0000
DOX = .0000 DOC = .9 INPUT TDS = 1033.0
Anal Cond = 916.0 Calc Cond = 1482.2 Activity H2S calc from SO4 and pe = 7.84E-12
Anal EPMCAT = 14.5219 Anal EPMAN = 15.7531 Percent difference in input cation/anion balance = -8.1335
Calc EPMCAT = 13.8902 Calc EPMAN = 15.1177 Percent difference in calc cation/anion balance = -8.4632
Total Ionic Strength (T.I.S.) from input data = .02216
Effective Ionic Strength (E.I.S.) from speciation = .02090

Sato
Input Sigma Fe3/Fe2 Sigma NO3/NO2 Sigma NO3/NH4 Sigma SO4/S= Sigma S/S= Sigma H2O2/O2 Sigma H2O/O2
Sigma
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Eh - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
-
-.153 .000 -.153 .000 9.900 .000 9.900 .000 9.900 .000 9.900 .000 9.900 .000 9.900
.000

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - pe - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
-
-2.589 .000 -2.589 .000 100.000 .000 100.000 .000 100.000 .000 100.000 .000 100.000 .000 100.000
.000

As5/As3 Sigma As3/As Sigma Se6/Se4 Sigma Se4/Se Sigma Se/Se= Sigma U6/U4 Sigma Sigma
Sigma
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Eh - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
-
.003 .000 -.297 .000 9.900 .000 9.900 .000 9.900 .000 9.900

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - pe - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
-
.049 .000 -5.028 .000 100.000 .000 100.000 .000 100.000 .000 100.000

32

16
Geochemical modeling using PHREEQC: Saturation Index

Phase Log IAP/KT Log IAP Sigma(A) Log KT Sigma(T)

39 Adularia .673 -19.923 -20.596
40 Albite -.502 -18.523 -18.021
140 Al(OH)3 (a) -.676 10.144 10.820
50 Alunite -.803 -2.166 -1.363
42 Analcime -2.518 -15.233 -12.714
17 Anhydrite -2.044 -6.403 -4.360
21 Aragonite .087 -8.247 -8.334 .020
497 Arsenolite -23.764 -26.576 -2.812
472 Basaluminite .326 23.026 22.700
19 Brucite -6.123 10.737 16.860
12 Calcite .231 -8.247 -8.478 .020
97 Chalcedony .264 -3.291 -3.555
20 Chrysotile -6.606 25.631 32.237
99 Cristobalite .300 -3.291 -3.591
154 Diaspore 3.247 10.144 6.897
11 Dolomite (d) -.371 -16.902 -16.532
401 Dolomite (c) .181 -16.902 -17.083
340 Epsomite -4.670 -6.812 -2.142
112 Ferrihydrite -4.339 .552 4.891
51 Gibbsite (c) 2.017 10.144 8.127 .200
110 Goethite 1.553 .553 -1.000 .800
18 Gypsum -1.823 -6.403 -4.581
64 Halite -6.757 -5.175 1.581
47 Halloysite 1.179 13.706 12.527
205 Jarosite K -21.753 -30.939 -9.187 1.100
46 Kaolinite 6.245 13.706 7.461
128 Laumontite 3.868 -27.121 -30.989
10 Magnesite -.631 -8.655 -8.024
189 Manganite -12.633 12.707 25.340
141 Prehnite -.981 -12.684 -11.703
183 Pyrolusite -24.440 16.988 41.428
101 Quartz .694 -3.291 -3.985
190 Rhodochrs(d) -.577 -10.967 -10.390
492 Scorodite -11.523 -31.772 -20.249
153 Sepiolite(d) -7.057 11.603 18.660
36 Sepiolite(c) -4.165 11.603 15.768
9 Siderite (d) .356 -10.094 -10.450
395 SiO2 (a) -.576 -3.291 -2.714
146 Strengite -5.141 -31.540 -26.399 33
106 Vivianite -.290 -36.290 -36.000

Geochemical modeling using PHREEQC: Aqueous Species

1 du001 Mokamtala, Bogra 24m du001 a5
Effective
T pH TDS ppm Ionic Str pO2 Atm ppm O2 Atm pCO2 Atm ppm CO2 Atm log pCO2 CO2 Tot Ncrb Alk
aH2O
30.20 6.530 617.2 .00998 6.48E-65 2.07E-60 8.63E-02 3.80E+03 -1.064 7.31E-03 1.03E-05
.9997

I Species Anal ppm Calc ppm Anal Molal Calc Molal % of Total Activity Act Coeff -Log Act
50 Al 3 .134000
134000 .000024
000024 4
4.969E-06
969E 06 8
8.816E-10
816E 10 .02
02 3
3.459E-10
459E 10 .3924
3924 9
9.461
461
52 Al(OH)2 1 .045 7.448E-07 14.99 6.713E-07 .9013 6.173
181 Al(OH)3 0 .038 4.837E-07 9.73 4.848E-07 1.0023 6.314
53 Al(OH)4 -1 .353 3.715E-06 74.76 3.348E-06 .9013 5.475
261 As3 tot 0 .017 2.324E-07
250 H3AsO3aq 0 .029 2.318E-07 67.52 2.323E-07 1.0023 6.634
262 As5 tot 0 .008300 1.109E-07
257 HAsO4 -2 .007012 5.015E-08 14.61 3.309E-08 .6598 7.480
256 H2AsO4 -1 .008547 6.070E-08 17.68 5.470E-08 .9013 7.262
0 Ca 2 47.400 44.846 1.183E-03 1.120E-03 94.63 7.489E-04 .6687 3.126
29 CaHCO3 1 4.730 4.682E-05 3.96 4.220E-05 .9013 4.375
31 CaSO4 aq 0 1.833 1.347E-05 1.14 1.350E-05 1.0023 4.870
4 Cl -1 86.161 86.119 2.432E-03 2.431E-03 99.97 2.187E-03 .8997 2.660
6 HCO3 -1 289.500 277.405 4.747E-03 4.550E-03 62.29 4.115E-03 .9045 2.386
85 H2CO3 aq 0 159.537 2.574E-03 35.24 2.580E-03 1.0024 2.588
16 Fe total 2 22.700 4.067E-04
7 Fe 2 16.911 3.030E-04 74.51 2.000E-04 .6598 3.699
309 FeHCO3 1 10.661 9.130E-05 22.45 8.229E-05 .9013 4.085
63 H 1 .000326 3.233E-07 .00 2.951E-07 .9128 6.530
3 K 1 22.400 22.381 5.732E-04 5.728E-04 99.93 5.154E-04 .8997 3.288
1 Mg 2 18.800 17.807 7.738E-04 7.330E-04 94.73 4.934E-04 .6731 3.307
21 MgHCO3 1 2.306 2.705E-05 3.50 2.438E-05 .9013 4.613
22 MgSO4 aq 0 1.364 1.134E-05 1.47 1.137E-05 1.0023 4.944
109 Mn 2 .824 .622 1.501E-05 1.134E-05 75.53 7.479E-06 .6598 5.126
311 MnCO3 aq 0 .049 4.276E-07 2.85 4.285E-07 1.0023 6.368
119 MnHCO3 1 .353 3.044E-06 20.28 2.743E-06 .9013 5.562
2 Na 1 69.000 68.811 3.003E-03 2.996E-03 99.75 2.703E-03 .9023 2.568
26 OH -1 .000938 5.522E-08 .00 4.976E-08 .9013 7.303
44 PO4 -3 3.414000 .000002 3.597E-05 1.720E-11 .00 6.750E-12 .3924 11.171
46 HPO4 -2 .580 6.047E-06 16.81 3.990E-06 .6598 5.399
47 H2PO4 -1 1.982 2.045E-05 56.85 1.843E-05 .9013 4.734
34 SiO2 tot 0 41.500 6.911E-04
23 H4SiO4aq 0 66.330 6.907E-04 99.93 6.922E-04 1.0023 3.160
5 SO4 -2 15.310 12.426 1.595E-04 1.295E-04 81.18 8.617E-05 .6656 4.065

34

17
Geochemical modeling using PHREEQC: Aqueous Species
1 du001 Mokamtala, Bogra 24m du001 a5
Effective
T pH TDS ppm Ionic Str pO2 Atm ppm O2 Atm pCO2 Atm ppm CO2 Atm log pCO2 CO2 Tot Ncrb Alk
aH2O
30.20 6.530 617.2 .00998 6.48E-65 2.07E-60 8.63E-02 3.80E+03 -1.064 7.31E-03 1.03E-05
.9997

I Species Anal ppm Calc ppm Anal Molal Calc Molal % of Total Activity Act Coeff -Log Act
50 Al 3 .134000 .000024 4.969E-06 8.816E-10 .02 3.459E-10 .3924 9.461
52 Al(OH)2 1 .045 7.448E-07 14.99 6.713E-07 .9013 6.173
181 Al(OH)3 0 .038 4.837E-07 9.73 4.848E-07 1.0023 6.314
53 Al(OH)4 -1 .353 3.715E-06 74.76 3.348E-06 .9013 5.475
261 As3 tot 0 .017 2.324E-07
250 H3AsO3aq 0 .029 2.318E-07 67.52 2.323E-07 1.0023 6.634
262 As5 tot 0 .008300 1.109E-07
257 HAsO4 -2 .007012 5.015E-08 14.61 3.309E-08 .6598 7.480
256 H2AsO4 -1 .008547 6.070E-08 17.68 5.470E-08 .9013 7.262
0 Ca 2 47.400 44.846 1.183E-03 1.120E-03 94.63 7.489E-04 .6687 3.126
29 CaHCO3 1 4.730 4.682E-05 3.96 4.220E-05 .9013 4.375
31 CaSO4 aq 0 1.833 1.347E-05 1.14 1.350E-05 1.0023 4.870
4 Cl -1 86.161 86.119 2.432E-03 2.431E-03 99.97 2.187E-03 .8997 2.660
6 HCO3 -1 289.500 277.405 4.747E-03 4.550E-03 62.29 4.115E-03 .9045 2.386
85 H2CO3 aq 0 159.537 2.574E-03 35.24 2.580E-03 1.0024 2.588
16 Fe total 2 22.700 4.067E-04
7 Fe 2 16.911 3.030E-04 74.51 2.000E-04 .6598 3.699
309 FeHCO3 1 10.661 9.130E-05 22.45 8.229E-05 .9013 4.085
63 H 1 .000326 3.233E-07 .00 2.951E-07 .9128 6.530
3 K 1 22.400 22.381 5.732E-04 5.728E-04 99.93 5.154E-04 .8997 3.288
1 Mg 2 18.800 17.807 7.738E-04 7.330E-04 94.73 4.934E-04 .6731 3.307
21 MgHCO33 1 2
2.306
306 2 705 05
2.705E-05 3
3.50
50 2
2.438E-05
438 05 .9013
9013 4
4.613
613
22 MgSO4 aq 0 1.364 1.134E-05 1.47 1.137E-05 1.0023 4.944
109 Mn 2 .824 .622 1.501E-05 1.134E-05 75.53 7.479E-06 .6598 5.126
311 MnCO3 aq 0 .049 4.276E-07 2.85 4.285E-07 1.0023 6.368
119 MnHCO3 1 .353 3.044E-06 20.28 2.743E-06 .9013 5.562
2 Na 1 69.000 68.811 3.003E-03 2.996E-03 99.75 2.703E-03 .9023 2.568
26 OH -1 .000938 5.522E-08 .00 4.976E-08 .9013 7.303
44 PO4 -3 3.414000 .000002 3.597E-05 1.720E-11 .00 6.750E-12 .3924 11.171
46 HPO4 -2 .580 6.047E-06 16.81 3.990E-06 .6598 5.399
47 H2PO4 -1 1.982 2.045E-05 56.85 1.843E-05 .9013 4.734
34 SiO2 tot 0 41.500 6.911E-04
23 H4SiO4aq 0 66.330 6.907E-04 99.93 6.922E-04 1.0023 3.160
5 SO4 -2 15.310 12.426 1.595E-04 1.295E-04 81.18 8.617E-05 .6656 4.065

35

Geochemical modeling using PHREEQC: Aqueous Species

1 du001 Mokamtala, Bogra 24m du001 a5
Effective
T pH TDS ppm Ionic Str pO2 Atm ppm O2 Atm pCO2 Atm ppm CO2 Atm log pCO2 CO2 Tot Ncrb Alk
aH2O
30.20 6.530 617.2 .00998 6.48E-65 2.07E-60 8.63E-02 3.80E+03 -1.064 7.31E-03 1.03E-05
.9997

I Species Anal ppm Calc ppm Anal Molal Calc Molal % of Total Activity Act Coeff -Log Act
50 All 3 .134000
134000 .000024
000024 4
4.969E-06
969 06 8
8.816E-10
816 10 .02
02 3
3.459E-10
459 10 .3924
3924 9
9.461
461
52 Al(OH)2 1 .045 7.448E-07 14.99 6.713E-07 .9013 6.173
181 Al(OH)3 0 .038 4.837E-07 9.73 4.848E-07 1.0023 6.314
53 Al(OH)4 -1 .353 3.715E-06 74.76 3.348E-06 .9013 5.475
261 As3 tot 0 .017 2.324E-07
250 H3AsO3aq 0 .029 2.318E-07 67.52 2.323E-07 1.0023 6.634
262 As5 tot 0 .008300 1.109E-07
257 HAsO4 -2 .007012 5.015E-08 14.61 3.309E-08 .6598 7.480
256 H2AsO4 -1 .008547 6.070E-08 17.68 5.470E-08 .9013 7.262
0 Ca 2 47.400 44.846 1.183E-03 1.120E-03 94.63 7.489E-04 .6687 3.126
29 CaHCO3 1 4.730 4.682E-05 3.96 4.220E-05 .9013 4.375
31 CaSO4 aq 0 1.833 1.347E-05 1.14 1.350E-05 1.0023 4.870
4 Cl -1 86.161 86.119 2.432E-03 2.431E-03 99.97 2.187E-03 .8997 2.660
6 HCO3 -1 289.500 277.405 4.747E-03 4.550E-03 62.29 4.115E-03 .9045 2.386
85 H2CO3 aq 0 159.537 2.574E-03 35.24 2.580E-03 1.0024 2.588
16 Fe total 2 22.700 4.067E-04
7 Fe 2 16.911 3.030E-04 74.51 2.000E-04 .6598 3.699
309 FeHCO3 1 10.661 9.130E-05 22.45 8.229E-05 .9013 4.085
63 H 1 .000326 3.233E-07 .00 2.951E-07 .9128 6.530
3 K 1 22.400 22.381 5.732E-04
5.732E 04 5.728E-04
5.728E 04 99.93 5.154E-04
5.154E 04 .8997 3.288
1 Mg 2 18.800 17.807 7.738E-04 7.330E-04 94.73 4.934E-04 .6731 3.307
21 MgHCO3 1 2.306 2.705E-05 3.50 2.438E-05 .9013 4.613
22 MgSO4 aq 0 1.364 1.134E-05 1.47 1.137E-05 1.0023 4.944
109 Mn 2 .824 .622 1.501E-05 1.134E-05 75.53 7.479E-06 .6598 5.126
311 MnCO3 aq 0 .049 4.276E-07 2.85 4.285E-07 1.0023 6.368
119 MnHCO3 1 .353 3.044E-06 20.28 2.743E-06 .9013 5.562
2 Na 1 69.000 68.811 3.003E-03 2.996E-03 99.75 2.703E-03 .9023 2.568
26 OH -1 .000938 5.522E-08 .00 4.976E-08 .9013 7.303
44 PO4 -3 3.414000 .000002 3.597E-05 1.720E-11 .00 6.750E-12 .3924 11.171
46 HPO4 -2 .580 6.047E-06 16.81 3.990E-06 .6598 5.399
47 H2PO4 -1 1.982 2.045E-05 56.85 1.843E-05 .9013 4.734
34 SiO2 tot 0 41.500 6.911E-04
23 H4SiO4aq 0 66.330 6.907E-04 99.93 6.922E-04 1.0023 3.160
5 SO4 -2 15.310 12.426 1.595E-04 1.295E-04 81.18 8.617E-05 .6656 4.065

36

18
Geochemical modelling using Visual MINTEQ
(current ver 3.0)

http://www2.lwr.kth.se/English/OurSoftware/vminteq/

37

Geochemical modelling using Visual

MINTEQ (current ver 3.0)
http://www2.lwr.kth.se/English/OurSoftware/vminteq/

Visual MINTEQ is a Windows version of MINTEQA2 ver 4.0,

released
l dbby th
the USEPA in
i 1999.
1999

MINTEQA2 is a chemical equilibrium model for the calculation

of metal speciation, solubility equilibria etc. for natural waters.

Development of the Windows version of MINTEQA2 is being

supported by the two Swedish research councils VR and
MISTRA and the program is distributed via Internet from free
of charge.
charge

Visual MINTEQ has been developed to make the powerful

features of MINTEQA2 more easily accessible for graduate and
post-graduate students in soil and water chemistry. Visual
MINTEQ has also been modernised to include new options for
adsorption modelling.
38

19
Visual MINTEQ (current ver 3.0): Salient uses
http://www2.lwr.kth.se/English/OurSoftware/vminteq/

Ion speciation using equilibrium constants from the MINTEQA2

database, which has been updated using the most recent NIST
d t tto contain
data t i > 3000 aqueous species i andd > 600 solids
lid
Solubility calculations involving solid phases .

Adsorption calculations with adsorption isotherms, five surface

complexation models (Diffuse Layer, Constant Capacitance,
Triple Layer, Basic Stern and Three Plane), with the 1-pK or 2-
pK formalisms, and with the CD-MUSIC concept.

Ion-exchange calculations and metal-humic complexation can

be simulated using the Gaussian DOM, the Stockholm Humic
Model, or the NICA-Donnan model.

Calculations with redox couples and gases (e.g. CO2)

Presentation of results from Visual MINTEQ runs on separate
output tables; export of results to Excel.
39

20