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Pyrite Oxidation, Carbonate Weathering, and Gypsum Formation in a Drained

Potential Acid Sulfate Soil

Article in Soil Science Society of America Journal · July 1993

DOI: 10.2136/sssaj1993.03615995005700040015x

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 Published July, 1993
Pyrite Oxidation, Carbonate Weathering, and Gypsum Formation
in a Drained Potential Acid Sulfate Soil
C. J. Ritsema* and J. E. Groenenberg
ABSTRACT
To quantify the rate of pyrite oxidation, weathering of carbonates
and the formation of gypsum in a potential acid sulfate soil exposed
to drainage, a column experiment was executed for 175 d. During the
experiment, 24 g of FeS2, of the originally present 1327 g, oxidized
within 70 d. Weathering of carbonates prevented acidification; an
estimated 21 g of CaCO, and 17 g of CaMg(CO3)2 dissolved simul-
taneously within the first 70 d. Rising Ca2+ and SO2; concentrations
initiated gypsum precipitation from around Day 70 until the end of
the experiment. A numerical model was used to simulate the experi-
mental results. Estimated and simulated quantities of pyrite oxidation
and carbonate weathering, and measured and simulated soil solution
concentrations appeared to agree well. Model simulations indicate the
formation of 63 g CaSO4 between Days 70 and 175 in the upper 60
cm of the soil profile.
P YRITE (FES2)-CONTAINING SEDIMENTS Can be found
in several parts of the world, ranging from trop-
ical to temperate regions (Kawalec, 1973). In general,
these sediments have been formed in coastal areas
influenced by tides. As long as these sediments remain
waterlogged, the presence of pyrite does not constitute
any danger to the environment.
When they are drained, however, for instance in the
case of tidal land being reclaimed for agricultural pur-
poses, various soil physical and chemical processes
are initiated. First, the water table will drop below the
soil surface, enabling air to enter the soil profile. Sub-
sequently, O2 will start to oxidize pyrite, which pro-
duces a significant amount of H2SO4:
4FeS 2(s) 1502(g)
2 14H220
-» 4Fe(OH)3(s) + 16H(+aq) [1]
The rate at which pyrite oxidizes depends on the O2
concentration in the soil. Several authors (McKibben
and Barnes, 1986; Mathews and Robins, 1974) pos-
tulated rate laws to describe the oxidation process of
pyrite by dissolved O2. In pyritic soils, O2 concentra-
tions at a specific depth depend on O2 diffusion and
consumption. Oxygen consumption mainly occurs by
decomposition of organic matter and oxidation of pyr-
ite. The extent to which pyrite oxidizes under natural
conditions in soils has not been studied so far.
Whether the production of acid (Eq. [1]) actually
results in a drop in pH depends mainly on the avail-
ability of carbonates such as calcite (CaCO3) and do-
lomite [CaMg(CO3)2], which can neutralize acidity
according to the following reactions:
CaC03(s) 2H(+aq) H20 + C02(g)[2]
DLO Winand Staring Centre for Integrated Land, Soil and Water
Research (SC-DLO), P.O. Box 125, 6700 AC Wageningen, the
Netherlands. Received 26 Mar. 1992. * Corresponding author.
Published in Soil Sci. Soc. Am. J. 57:968-976 (1993).
968
CaMg(C03)2(s) 4H<+aq)
2H20 + 2C02(g) [3]
The presence of carbonate and its beneficial effect on
retarding acidification in (potential) acid sulfate soils
has been reported by several authors (Van Beers, 1962;
Pons, 1963; Harmsen, 1964; Van der Sluijs, 1970;
Van Breemen, 1973; Brinkman and Pons, 1973; Van
der Kevie, 1973; Van Darn and Pons, 1973), whereas
others mentioned the positive effect of regular addi-
tions of lime on acid sulfate soils (Bloomfield, 1973;
Dent, 1986). The presence of carbonates in soils is
more or less dependent on climatic conditions that
affect leaching intensity. According to Pons and Van
Breemen (1982), significant amounts of carbonates
are uncommon in the humid tropical regions, in con-
trast to the more temperate zones where carbonates
are often found in lowland areas.
The dissolution of carbonates is a rate-limited process
(Plummer et al., 1979; Rickard and Sjoberg, 1983;
Busenberg and Plummer, 1982; Herman and White,
1985). It appears that calcite is more easily weather-
able than dolomite (Winchell, 1951). Recently, Van
Breemen and Protz (1988) showed that mean annual
rates of CaCO3 removal from a variety of soils ap-
peared to be relatively constant through time and in
the range expected for equilibrium with calcite. How-
ever, from the method used by Van Breemen and Protz
(1988), it cannot be concluded that carbonate weath-
ering is an instantaneous process. The rate at which
carbonates dissolve in drained potential acid sulfate
soils to neutralize the rapid acid production arising
from pyrite oxidation has not been previously studied.
Furthermore, it has been found that gypsum is
sometimes formed in oxidizing acid sulfate soils (Mie-
dema et al., 1974; Van Breemen, 1973, 1976; Van
Dam and Pons, 1973; Westerveld and Van Hoist, 1973;
Dent, 1986). The Ca required to form gypsum can
originate either from carbonates or other Ca-bearing
minerals, or from dissolved and adsorbed Ca2+ (Van
Breemen, 1973). In the Dutch polder clays, Ca in-
volved in the formation of gypsum mainly originates
from available carbonates:
CaC03(s) + 2H(-aq) H,O
CaSO4-2H2O(s) + CO:2(g) [4]
It is generally assumed that the presence of gypsum
in soils under humid conditions is often seasonal (Van
Breemen, 1973). Due to its high solubility, gypsum
easily dissolves during the wet seasons and tends to
persist during the dry season. Until now, due to lack
of knowledge, no attempts have been made to estimate
and simulate the rates of carbonate weathering and
Abbreviations: ICP, inductively coupled plasma atomic emission
spectrophotometer; HPLC, high performance liquid chromato-
graph; TIC, total inorganic carbon analyzer.
 RITSEMA & GROENENBERG: TRANSFORMATIONS IN A POTENTIAL ACID SULFATE SOIL 969
0 -

10
*V -\
20 - ^"\.

30 *\
.0. 40 N,
~-»
f »
Q
60
; / •
70 -
80

90 i i i i i
D 1 2 3 4 5 5 10 15 20 0 50 100 150 200 250 300
Pyrite content (weight %) Carbonate content (weight %) Total exchangeable cations (mmolc kg"1)
Fig. 1. Pyrite content, carbonate content, and exchangeable cations of the potential acid sulfate soil.

gypsum formation in a drained potential acid sulfate umn into the soil by an excavator, whereafter it was dug out.
soil. In the laboratory, the column was placed on a 20-cm-high sand
The primary objective of this study was to quantify and gravel bed with a drainage system. In the column, ten-
the degrees of pyrite oxidation, carbonate weathering, siometers, Pt electrodes, air chambers, and soil water extrac-
tion cups were installed at five depths to measure soil water
and gypsum formation. Therefore, an undisturbed po- tension and redox potentials, and to extract soil air for deter-
tential acid sulfate soil from the Netherlands was drained mining its O2 content, and soil water for analyzing its chemical
in a column experiment and monitored during 175 d.
A secondary objective was to assess the ability of a
numerical model (Bronswijk and Groenenberg, 1993; -2.5cm
Van Wijk et al., 1993) to simulate the experimental
results. Observed and simulated results on ion con-
centrations in soil water and rates of pyrite oxidation,
carbonate weathering, and gypsum formation were
compared.
MATERIALS AND METHODS
Soil l/L
The potential acid sulfate soil sample was taken from the
lower section (between 65- and 165-cm depth) of a Typic Sul-
faquept (Soil Survey Staff, 1990) or Thionic Fluvisol (Food -25.0cm
and Agriculture Organization, 1989), near the village of
Nieuwkoop, the Netherlands. This soil mainly consists of il-
lite, quartz, feldspars, pyrite, calcite, and dolomite. The pyrite
content, determined by the HF-HC1 method (Breeuwsma et
al., 1985: besides pyrite, all other Fe-containing compounds
are dissolved in a mixture of concentrated HF and HC1 1:1; in
the remaining residue, the pyrite content is determined by mea-
suring the Fe content after destruction at 1073 K) and by x-
ray diffraction analysis, appeared to be low in the upper 10
cm, increasing up to 3% by weight with depth (Fig. 1). The
carbonate content, measured by the Scheibler method (Collins,
1906), is low in the upper 20 cm and extremely high in the -82.5cm
lower part of the profile (Fig. 1). X-ray diffractograms (of soil
samples <2 mm) showed that both calcite and dolomite are
present in the lower section of the profile (Fig. 2). At a depth
of 25 cm, in the transition zone between reduced and oxidized
conditions, calcite has almost disappeared, but dolomite is still
present (Fig. 2). In the oxidized thin upper layer at 2.5-cm
depth, neither dolomite nor calcite could be detected (Fig. 2).
More than 80% of the cation-exchange complex, determined
by the unbuffered BaCl2 method based on the method devel-
oped by Gillman (1979),
2+
is
+
occupied by Ca2*; the remainder
is occupied by Mg , Na , and K* (Fig. 1) (Ritsema et al., I I I
1992). O
T-
i— •**" CO
CM CM CM
CM<OO>
8 8
CM CMCVJ CM 3««
odd
Column Experiment d (nm)
The potential acid sulfate soil was sampled (in duplicate) in Fig. 2. X-ray diffractograms from the potential acid sulfate
the field by carefully pushing a 1-m-long and 0.3-m-wide col- soil column at 2-, 25.0-, and 82.5-cm depths.
970 SOIL SCI. SOC. AM. J., VOL. 57, JULY-AUGUST 1993
composition, respectively. The soil material that was removed
from the column when installing the instruments was used to
determine initial pyrite and carbonate contents, the exchange-
able cations at the exchange complex, and the ammonium ox-
alate extractable Fe and Al content.
At the start of the experiment, the soil column was (gravity)
drained, and during the 175 d of the experiment the bare soil
was only exposed to evaporation. During the experiment, soil
water was extracted regularly to determine its acidity (pH),
and3 ionic concentrations (Na*,2 K>, Ca2*, Mg2*, Fe2*, Mn2*,
Al *, C1-, HOV, and SO - ) using ICP, HPLC and TIC
techniques. Ion activities and saturation indices were calcu-
lated using the chemical equilibrium program WATEQX (Van
Gaans, 1989). A value of 0 for the saturation index indicates
equilibrium between the ion activity product and the solubility
product of the mineral concerned. The solubility products used
in WATEQX to calculate the calcite, dolomite, and gypsum
saturation indices2 were
4 640 2
1Q-8-475, IQ-17-000 (Van Gaans, 1989)
and 10- - mol L,- (Lindsay, 1979), respectively.
The ion concentrations were used to estimate the degree of
pyrite oxidation and carbonate weathering in various soil layers
during the experiment. Therefore, measured pressure heads
were needed, together with the initially determined dry bulk
densities and water retention curves (see Agency for Agricul-
tural Research and Development, 1992), in order to calculate
total water contents for each layer on the days soil water was
extracted. Measured SO2- , Ca2*, and Mg2* 2concentrations
could then easily be transformed into total SO .- , Ca2*, and
Mg2* amounts per soil layer. The estimated degrees of pyrite
oxidation and carbonate weathering were compared with sim-
ulated ones (see below).
MODEL DESCRIPTION
The model SMASS (Simulation Model for Acid Sulfate Soils)
(Bronswijk and Groenenberg, 1993; Van Wijk et al., 1993) is
a one-dimensional, numerical model that dynamically simu-
lates the transport of water, O2, and solutes, together with
chemical processes such as pyrite oxidation, weathering of
minerals, and cation-exchange reactions in the unsaturated as
well as in the saturated zone. The model has a modular struc-
ture consisting of four submodels, computing water transport,
solute transport, O2 transport and pyrite oxidation, and chem-
ical processes. In the computation procedure, the soil profile
is divided into compartments of equal or variable size. The
model operates on a daily basis and output for each soil com-
partment relates to all terms of the water balance, O2 concen-
trations, concentrations of cations and anions in soil water and
drainage water, remaining pyrite contents, and the amount of
adsorbed cations and minerals or precipitates. The principles
of the SMASS model will be briefly outlined here.
The water transport submodel is based on the SWATRE
model (Feddes et al., 1978; Belmans et al., 1983). The
SWATRE model calculates one-dimensional vertical transient
water flow in soils. The input consists of the measured water
retention and hydraulic functions, and time-dependent input
describing the top and bottom boundary conditions during the
experiment. The output of the water transport submodel yields
the water fluxes between the various compartments and the
soil water contents.
The fluxes are used in the solute transport submodel to cal-
culate transport of solutes between the adjacent soil compart-
ments.
The principles of the O2 transport and pyrite oxidation sub-
model have been outlined by Bronswijk et al. (1993). In the
model, it is assumed that pyrite in natural soils with pH ~ 3
and3 higher is mainly oxidized by O2. Neglecting oxidation by
Fe * is justifiable because, above pH 3, Fe3* has 3
a low sol-
ubility. Furthermore, oxidation of pyrite by Fe * in natural
soils will be inhibited by complexation of Fe3* by organic
substances, as was found by Pichtel et al. (1989) for sewage
sludge. Finally, in the3
case of pyrite oxidation by Fe3*, the
concentration of Fe * must be sustained by the oxidation of
Fe2* by O2, and thus O2 is still the driving force for pyrite
oxidation.
In the model approach, two main processes were distin-
guished: vertical diffusion of gaseous O2 through air-filled ma-
cropores and lateral diffusion of dissolved O2 from macropores
into the saturated soil matrix. The two processes interact at the
walls of the macropores where gaseous O2 dissolves into the
soil solution matrix. The equilibrium between gaseous and dis-
solved O2 at the walls of the macropores is described by Hen-
ry's law. In the O2 transport and pyrite oxidation submodel,
air-filled porosity is calculated as the complement of the soil
water contents, which has been calculated in the water trans-
port model. In SMASS, the gaseous O2 concentration profile
in the air-filled pores is calculated by (Christensen et al., 1986):
3
where C a(x) is the concentration of O2 in air-filled pores (m
O2 m- 3 air), £> (e
s g ) is the diffusion coefficient of O 2 in air-
filled pores (m2 d-1), x 3is distance
3
(m), a1 is the O2 consump-
tion rate in the soil (m O2 m- soil d" ), and eg is the air-
filled porosity. The relation between diffusion coefficient Ds,
and air content, eg, is described in the model by:
[6]
where Ds is the diffusion coefficient of O2 in the atmosphere
(m2 d-1), F is an empirical tortuosity factor (dimensionless),
and D0 is the O2 diffusion coefficient in air (m2 d"1). To solve
differential Eq. [5], a must be quantified. In the model, O2 is
consumed by two processes inside the soil matrix: decompo-
sition of organic matter and oxidation of pyrite (Eq. [1]). Ac-
cording to Bronswijk et al. (1993) the steady-state diffusion
equation for the aerobic part of the soil matrix can be written
as:
d2Cw(*) 0.311262xFeS2
+ Q [7]
' dc2
where Dw is the diffusion coefficient of O2 in the soil aggregate
(m2 d~'), Cw is the concentration of dissolved O2 (kg m-3),3
and Q is the O2 consumption rate by organic matter (kg m~
d-1). The first part of the right-hand side of this equation
expresses the disappearance of pyrite crystals by oxidation and
is derived by combining the equal-diameter reduction model
(Swartzendruber and Barber, 1965) with the McKibben and
Barnes rate law for pyrite oxidation (McKibben and Barnes,
1986). Solving this equation with appropriate boundary con-
ditions yields expressions for the steady-state O2 concentration
profile in the aerobic part of the soil matrix, for the radius of
the (an)aerobic zone, and for the total mass O2 consumption
per volume of soil. The steady-state pyrite O2 consumption is
then expressed by the difference between the total O2 con-
sumption and the (constant) O2 consumption by organic matter.
Next, the amount of oxidized pyrite can be computed, together
with the produced quantities of Fe3*, H*, and SO2.- . Because
the O2 consumption rate depends on the O2 concentration and,
conversely, the O2 concentration on the O2 consumption rate,
an iterative procedure has been applied in the O2 transport
submodel to solve Eq. [7].
In the chemical submodel, changes in solution concentra-
tion, changes in adsorbed amounts, and changes in amounts
of minerals and precipitates as a result of cation exchange and
precipitation-dissolution reactions are calculated. Because ca-
tion exchange and precipitation-dissolution reactions are re-
 RITSEMA & GROENENBERG: TRANSFORMATIONS IN A POTENTIAL ACID SULFATE SOIL
Table 1. Some input parameters for the SMASS model and
their values as used in this study.
Parameter Value
Diffusion coefficient of gaseous O2 in air 0.21 x 10-4m2s-'
(25 °C)
Diffusion coefficient of dissolved O2 1.10 x 10- 5 m 2 d-'
in saturated soil matrix
Average diameter of structural elements 0.08-0.24 m
Dry bulk density 1.0 g cm-3
Cation-exchange capacity 200 mmol,- kg-'
Cation-exchange coefficients
Na+-Ca2+2+ 0.55
K+-Ca
2+ 2+ 9.2
Mg -Ca 1.0
Rate constants for precipitation-dis-
solution reactions
CaC03 1.6 x 10-
CaMg(C03)2 1.0 x 10-
lated to ion activities, ion association is considered as well.
For each time step, for each compartment, total amounts for
each chemical component in solution and at the exchange com-
plex are calculated from the amounts at the previous time step,
the amounts released into the soil solution due to the oxidation
of pyrite, and the net amounts transported to or from that
compartment. From these total amounts, new concentrations,
adsorbed amounts, and new amounts of minerals and precip-
itates are calculated.
Ion association and cation exchange are modeled as equilib-
rium processes, while precipitation-dissolution of minerals and
precipitates is modeled as a kinetic process. The equations
describing these different processes are solved simultaneously.
Precipitation-dissolution is modeled for Fe(OH)3, CaCO3 (cal-
cite), CaMg(CO3)2 (dolomite), and CaSO4 (gypsum). It has
been assumed that the dissolution-precipitation rate of these
minerals and precipitates is proportional to the difference be-
tween the activity product (Q,) and its particular solubility product
(Kj) (e.g,. see Kachanoski et al., 1992). The rate expression
is formulated as follows:
= K(Q, - KJp/B [8]
where Bt is the amount of precipitate i (kg m~ 3 ), K is a rate
constant, p is the bulk density of the solid phase (kg m~ 3 ),
and 0 is the volumetric water content. This differential equa-
tion can be approximated with final differences, and the change
in the amount precipitated can be calculated according to:
Afl, = , - K,)p/6 [9]
with Q, the activity product at the end of the time step. In the
model simulation, the rate constants for Fe(OH)3 and CaSO4
were set very high to simulate instantaneous equilibrium with
these minerals. Cation exchange is modeled according to the
Gaines-Thomas expression (see Bolt, 1967).
A list of important (time-independent) system parameters
needed as input for the O2 transport and pyrite oxidation sub-
model and the chemical submodel are given in Table 1, to-
gether with their values as used in this study.
RESULTS AND DISCUSSION
Pyrite Oxidation
Figure 3 shows the CaSO4 saturation indices at several
depths during the experiment. Between Days 70 and 100,
CaSO4 equilibrium was reached at all depths except 85
cm (Fig. 3). This means that, before Day 70, SOJ- pro-
duced by the oxidation of pyrite was released into the
971
-10
aDa
55 -15
-20
-25
_L _L _!
-30
20 40 60 80 100 120
Time (d)
Fig. 3. Gypsum saturation index at various depths during the
column experiment.
soil solution without simultaneously precipitating as gyp-
sum.
However, SO4~ may have been immobilized by other
processes during these first 70 d of the experiment. First,
the pH measured during the experiment was near neutral
and therefore too high to allow jarosite to be formed.
Second, sulfate may also be adsorbed by various Fe and
Al oxides and hydrous oxides, which has been assumed
the primary mechanism for SO4~ retention in a variety
of soils (Parfitt and Smart, 1978; Johnson and Todd,
1983; Singh, 1984; Harrison et al., 1989). Mean am-
monium oxalate extractable Fe and Al at the start of the
experiment equaled 59 and 18 mmol kg-1, respectively.
Using the reported SOI" adsorption capacity of 0.6 mmol
SO|- g-1 Fe(OH)3 (Parfitt and Smart, 1978), together
with the mean oxalate-extractable Fe content of the stud-
ied soil, it was calculated that a total of 54 mmolc
SO|- could be adsorbed on Fe(OH)3 (Eq. [1]) within the
whole soil column. This calculation is an approximation,
as the size of the Fe(OH)3 surface area is unknown in
this study. This amount equals 7% of the total SO|~
quantity released into the soil soluuuj between the start
of the experiment and Day 70 (772 mmolc SO|- ). In
the calculation of the 54 mmolc SO|" , metic aspects
of SOI" sorption (Hodges and Johnson, I9o7) and com-
petition from other anions (Sposito, 1989) have not been
taken into account, so the actual percentage of SO4~
sorption can be even lower than 7%. However, on the
other hand, pyrite oxidation during the first 70 d of the
experiment will probably result in the formation of new
Fe precipitates, which increases the SO4~ sorption ca-
pacity. Calculation of the possible SO4~ sorption by Al
(hydr)oxides in the studied soil has been carried out by
using the regression equation between SO|- sorption and
the quantity of oxalate-extractable Al for Inceptisols re-
ported by Harrison et al. (1989), which resulted in a
negative SO|~ sorption of 0.2 mmol kg"1. From these
calculations, it may be concluded that during the exper-
imental period SO4~ sorption was of minor importance
972 SOIL SCI. SOC. AM. J., VOL. 57, JULY-AUGUST 1993

Table 2. Estimated and simulated quantities of pyrite oxidation Table 3. Estimated and simulated quantities of carbonate
in the soil column during the first 70 d of the experiment. weathering in the soil column during the first 70 d of the
Initial Estimated Simulated
experiment.
FeS2 FeS2 FeS2 Initial Estimated Simulated Estimated Simulated
Depth content oxidation oxidation carbonate calcite calcite dolomite dolomite
————— g ————— Depth content weathering weathering weathering weathering
cm
cm _ r*ra-
0-10 9 3 3 g b »•"
10-35 289 11 11 0-10 53 2 1 1 2
35-55 - 437 7 7 10-35 350 4 5 6 6
55-75 335 3 3 35-55 2056 4 3 3 3
75-90 257 0 0 55-75 1982 2 2 1 1
Total 1327 24 24 75-90 1637 1 1 0 0
Total 6078 13 12 11 12

within the studied soil. Therefore, it was decided to ne-

glect the influence of SO*- sorption on the evaluation
of measured SO2- concentrations in the soil solution.
Measured SO2" concentrations were then used for a di-
rect estmation of the rate of pyrite oxidation.
At each depth, the measured SO2~ concentration until
Day 70 was used to calculate the total quantity of
SO2- released into the soil solution by that soil layer.
From these total SO^ ~ amounts, the total pyrite oxidation
could be estimated. These estimated amounts of pyrite
oxidation during the first 70 d are shown in Table 2, as
well as the amounts simulated by SMASS. Furthermore,
the pyrite contents measured at the beginning of the ex-
periment are given. It can be seen from Table 2 that
estimated and simulated amounts of pyrite oxidation agree
exceptionally well.
Carbonate Weathering
Not only is 864" mobilized by the oxidation of pyrite,
but H + is also released (Eq. [1]), which is neutralized
by the weathering of carbonates (Eq. [2] and [3]). Cal-
cium and Mg, dissolved between the beginning of the
experiment and Day 70, are released into the soil solu-
tion, and are assumed not to participate in adsorption
processes. This assumption is based on the fact that the
adsorption complex at the start of2+ the experiment was
almost completely occupied by Ca and +
partly+by Mg2+
(Fig. 1). However, a slight rise in Na and K concen-
trations was monitored during the first 70 d of the ex-
periment, indicating some exchange for Ca2+, Mg+2+, or
both. From the differences between the initial Na and
K + concentrations and those determined at Day 70, it
was calculated that in the whole soil column a total of
43 mmolc Na + and K + were released from the adsorption
complex. This is ~5% of the total increase in dissolved
Ca2+ and Mg2+ for the same period, which is assumed
neglegible here.
This gives the opportunity to estimate the quantity of
carbonate weathering in the same way as was done for
pyrite oxidation. The Mg2+ concentrations can be used
to estimate the amount of dolomite weathering. From the
total Ca2+ amount, the dolomite part is subtracted, and
the remaining Ca2+ amount represents the quantity orig-
inating from calcite weathering.
In Table 3, initial amounts of carbonate are given for
various soil layers, as well as the estimated and simu-
lated quantities of calcite and dolomite weathering, which
both agree well.
Figures 4 and 5 show the saturation indices for calcite
and dolomite during the experiment, which both indicate
continuous equilibrium in all layers below 5-cm depth.
Due to the initially lower calcite contents in the upper
part of the soil profile, dolomite weathering is relatively
more intensely here than 2+ in the lower part of the profile.
This results in lower Ca /Mg2+ ratios in the soil solu-
tion in the upper part of the soil (=4.5) compared with
those found in the lower part (=6.5).
Gypsum Formation
After Day 70, gypsum formation started. A direct es-
timation of the quantity of gypsum formed between Days
70 and 175 could not be made, because not enough water
could be extracted to analyze the complete chemical
composition at every depth. In Table 4, only the simu-
lated quantities of gypsum formed are summarized. Sim-
ulation results indicated that gypsum would be formed
to a depth of 60 cm. After the experiment, x-ray dif-
fraction analyses revealed the occurrence of gypsum in
soil samples from 5.0-, 12.5-, 25.0-, 35.0-, 45.0-, and
55.0-cm depth. Thin section analyses yielded similar re-
sults. Figure 6 shows an example of a large gypsum
crystal, which was formed during the experiment at a
depth of =25 cm.
J -4
Depth (cm)
• 5
• 25
A 45
O 65
A 85
-10
20 40 60 80 100 120
Time (d)
Fig. 4. Calcite saturation index at various depths during the
column experiment.
 RITSEMA & GROENENBERG: TRANSFORMATIONS IN A POTENTIAL ACID SULFATE SOIL 973

Table 4. Simulated quantities of gypsum formed in the soil

column between Days 70 and 175; at the beginning of the
experiment no gypsum was present.
Depth Simulated amount
cm g
0-10 18
-2 10-35 32
35-55 12
55-75 1
75-90 0
Total 63
^
CO

-6 to decrease from around Days 70 to 100. This can be

explained by a relative increase in Mg2+ adsorption at
the cation-exchange complex, since in the model simu-
lations from that moment all further dissolved Ca2+ pre-
cipitated as gypsum. As a consequence, only Mg2+,
dissolved by continuing dolomite weathering, remained
-10 to exchange for the univalent ions Na + and K + (Fig. 1).
20 40 60 80 100 120 The measured Mg2+ concentrations are simulated well
Time (d) by SMASS (Fig. 7).
Fig. 5. Dolomite saturation inaex ai various depths during the
column experiment.
CONCLUSIONS
The experimental results with the drained Nieuwkoop
Ion Concentrations potential acid sulfate soil, and the simulations carried
out with SMASS, make it clear that:
In addition to the comparison between estimated and 1. In 70 d, 24 g (0.038% w/w) of pyrite was oxidized
simulated rates of pyrite oxidation and carbonate weath- in a drained potential acid sulfate soil that origi-
ering, a comparison can be made between measured and nally contained 1327 g (2.086% w/w) of pyrite. It
simulated ion concentrations. would take at least 10.6 yr (1327/24)(70/365), with
In Figure
2+
7, measured and simulated SOI" , Ca2+, similar drainage conditions as applied during the
and Mg concentrations are shown for several depths. experiment, to oxidize all the avialable pyrite within
Owing to O2 entering the soil system, pyrite starts to this soil column. Probably, this 10.6 yr is an under-
oxidize, which results in an immediate production of estimation because, due to the possible formation
SO2- (Eq. [1]). In Figure 7 it can be seen that measured of oxidation products around individual pyrite
SO2~ concentrations increased rapidly from around 0 to crystals, pyrite oxidation may decrease in time.
35 mmolc L~' within 70 to 100 d of drainage, after which 2. Instantaneous weathering of carbonates neutralized
the increase was retarded due to gypsum formation. In the acid produced; an estimated 21 g (0.033% w/
the computer simulations, gypsum formation is assumed w) of calcite and 18 g (0.028% w/w) of dolomite
to be an instantaneous process,2 which resulted in an ab-
rupt ending of the rise in SO " concentrations between
Days 70 and 100. It seems that measured 804" concen-
trations were higher than computed ones in the second
part of the experiment. Based on these observations (Fig.
7), it may be concluded that a kinetic description of the
gypsum precipitation process would probably yield better
results in model simulations.
Parallel to the production of SO2.- , a proportional
amount of H + is produced by the oxidation of pyrite (Eq.
[1]). However, the pH at the various depths remained
stable, i.e., around 7.5, during the entire experiment.
All the acid produced was buffered effectively, due to
the dissolution of carbonates, which resulted in a steep
rise in Ca2+ concentrations (Fig. 7). From around Day
70 to 100, the increase in measured Ca2+ concentration
slowed due to gypsum formation. After Day 100, sim-
ulated Ca2+ concentrations tended to be lower than mea-
sured ones (as was found for SO2- also), which probably
was caused by the use of an instantaneous gypsum pre-
cipitation process in the model simulations.
Fig. 6. Old pyrite framboids and crystallites (circle) originating
In addition to Ca2+, the concentration of Mg2+ also from the Nieuwkoop potential acid sulpahte soil, and a large,
rose during the experiment, due to2+ dolomite weathering. partly cracked gypsum crystal (dashed outline), which was
However, the computed rise in Mg concentrations started formed during the column experiment.
974 SOIL SCI. SOC. AM. J., VOL. 57, JULY-AUGUST 1993

Calcium Magnesium
50 r -5cm 25 -5cm

40 20

_u 30 Jo 15
o o
_E E
+ 20
"a
O

10

50 r -25cm 50 r- -25cm 25 r- -25cm

40 40 20

_o 30 _0 30 _
o o o
. E E

CO
20 10
O

10 10

50 r -45cm 50 r- -45cm 25 f- -45cm

40 40 20

_o 30 _u 30 _o 15
o
E E_
20 10
co
O

10 10

0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100120140160

Time(d) Time (d) Time (d)
2 2+ 2+
Fig. 7. Measured (point) and simulated (line) SO ^ , Ca , and Mg concentrations at 5-, 2S-, and 45-cm depths in the soil
profile.

dissolved during the first 70 d. During 10.6 yr of
continuous oxidation, a maximum of 1160 g of
calcite and 995 g of dolomite would be expected
to dissolve.
3. Gypsum formation started around Day 70; accord-
ing to model simulations, approximately 63 g
(0.099% w/w) of gypsum formed in the soil col-
umn between Days 70 and 175 to a depth of 60
cm. In 10.6 yr under similar conditions, a maxi-
mum of 2321 g of gypsum would be formed within
this soil.
4. Simulated (SMASS) and estimated quantities of
pyrite oxidation and carbonate weathering, and
measured and simulated ion concentrations corre-
sponded well.
ACKNOWLEDGMENTS
This research was carried out as part of the project Research
on Acid Sulfate Soils in the Humid Tropics, which is a col-
laborative Dutch-Indonesian research project, by LAWOO (Land
and Water Research Group, the Netherlands), and AARD
(Agency for Agricultural Research and Development, Indo-
 RITSEMA & GROENENBERG: TRANSFORMATIONS IN A POTENTIAL ACID SULFATE SOIL 975

nesia). This research is sponsored by the Directorate General

for International Cooperation (DGIS), the Netherlands.
 976 SOIL SCI. SOC. AM. J., VOL. 57, JULY-AUGUST 1993

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