Determination of Gypsum Content in Dryland Soils

Exploiting the Gypsum–Bassanite Phase Change

I. Lebron* The presence of gypsum in soil, even in small amounts, is relevant from the genetic, taxonomic, and
Univ. of the West Indies applied points of view. Moreover, those soils having gypsum as the main component, for example
Dep. of Food Production gypseous soils, host a number of rare and endangered organisms. Determining gypsum content
St. Augustine in soils is crucial to understanding their behavior; however, current methods of determination
Trinidad and Tobago are cumbersome or imprecise. This study was conducted to develop an accurate new method
to determine soil gypsum content by reducing the inaccuracies or poor assumptions in previous
J. Herrero methods. We determined gypsum content in samples using quartz sand and clay minerals mixed
Estación Experimental de Aula Dei with gypsum reagent powder to 0 and approximately 2, 5, and 50% gypsum content; we also
CSIC studied seven gypseous soil samples. Gypsum (CaSO4⋅2H2O), after heating at 105°C, dehydrates,
PO Box 13034 losing the two water molecules of the gypsum crystal cell and becoming mostly anhydrite
50059 Zaragoza, Spain (CaSO4). Anhydrite is very hygroscopic, absorbing atmospheric water very quickly; this process
has been found to occur even in desiccators where the relative humidity (RH) is between 12 and
D.A. Robinson 20% depending on the desiccant. Anhydrite rehydrates under laboratory conditions to bassanite
Univ. of the West Indies
(CaSO4⋅0.5H2O), which is stable at RH values <100%. We propose exploiting this difference in
Dep. of Food Production
mass between gypsum and bassanite to quantify the gypsum content of soils. We found that by
St. Augustine
equilibrating the soils at constant RH, e.g., 40%, before and after heating the samples, the clay
Trinidad and Tobago
water content is constant, eliminating a major error with other thermogravimetric methods. This
simple, yet effective method determined gypsum content to within 1% in all the mineralogies
studied, whereas other oven-based methods overestimated gypsum content by as much as 36% in
a pure Ca-montmorillonite sample.

Abbreviations: ECe, electrical conductivity of a saturation extract; RH, relative humidity.

ypsum is a major component of soils in many arid and
semiarid areas of the world. It has been estimated that
more than 100 million ha of the world’s soils are classified as
Gypsisols or soils containing >5% gypsum (FAO, 1990; Verheye
and Boyadgiev, 1997). It has been found that Gypsisols are im-
portant as a refuge for rare, vulnerable, and endangered species
like bryophytes and lichens. About 20% of the total bryophyte
and lichen flora are rare or endemic species that live exclusively
or almost exclusively on gypsiferous substrates (Guerra et al.,
1995). These habitats are ranked among the most threatened
ecosystems worldwide, and are considered a priority conserva-
tion concern (Belnap et al., 2001; Mota et al., 2003).
There are a number of methods in the literature to quan-
tify the gypsum content of soils. In general, these methods can
be classified into three groups: wet chemical methods, thermo-
gravimetric methods, and x-ray techniques. The wet chemical
methods are time consuming and have intrinsic problems; they
Soil Sci. Soc. Am. J. 73:403-411
doi:10.2136/sssaj2008.0001
Received 1 Jan. 2008.
*Corresponding author (inma_lebron@yahoo.com).
© Soil Science Society of America
677 S. Segoe Rd. Madison WI 53711 USA
All rights reserved. No part of this periodical may be reproduced or
transmitted in any form or by any means, electronic or mechanical,
including photocopying, recording, or any information storage and
retrieval system, without permission in writing from the publisher.
Permission for printing and for reprinting the material contained
herein has been obtained by the publisher.
PEDOLOGY
are based on dissolution of gypsum from the soil, selective pre-
cipitation of the gypsum by adding acetone, and dissolution
of the reprecipitated gypsum with water. The solution can be
analyzed by measuring electrical conductivity (EC), since there
is a correlation between the amount of dissolved salts and EC
(U.S. Salinity Laboratory Staff, 1954), or by analyzing SO42−
(Loeppert and Suarez, 1996) or Ca2+ (van Reeuwijk, 1987).
There are variations depending on the method used, but since
we cannot be certain that either SO42− or Ca2+ came exclusive-
ly from gypsum, especially in arid soils, and the exchangeable
cations in the clay complex may add or remove Ca from the
solution, error is unavoidable.
X-ray diffraction is good as a qualitative method for deter-
mining the presence or absence of gypsum (Khan and Webster,
1968). It is relatively easy to obtain measurements, provided one
has access to the expensive apparatus. Quantitative determina-
tion is cumbersome and time consuming, however, and be-
comes especially difficult in mixed-mineralogy soils. Therefore,
a number of researchers have suggested measuring the water
loss from gypsum as a simple, rapid, and cost-effective way of
determining soil gypsum content.
Thermogravimetric methods have been considered for
a long time as a semiquantitative approach; in Loeppert and
Suarez (1996), the method of Nelson et al. (1978) was rec-
ommended as a precursor to the wet chemical method to
determine the dilution needed to dissolve all the gypsum in
the sample. This method is based on the difference between
the masses of a sample equilibrated for 48 h in a desiccator
with silica gel and after drying in an oven at 105°C for 24 h;

SSSAJ: Volume 73: Number 2 • March–April 2009 403

 we hereafter refer to this method as the Nelson method. The
Nelson method is simple and relatively accurate when the soil
is sandy or has clays with low surface area and low cation ex-
change capacity. In the presence of illite or smectite, however,
this method may overestimate the gypsum content because
the silica gel, or desiccant, is unable to remove all the water
from the clays; this water when subsequently lost at 105°C is
then incorrectly interpreted as gypsum. Elprince and Turjoman
(1983) developed an infrared dehydration method, but it also
overestimates the gypsum content in the presence of some clay
minerals. Artieda et al. (2006) refined the water loss method
for determining gypsum in soils by estimating the gypsum con-
tent from the loss of water in the soil sample between 70 and
90°C. This requires reaching thermal equilibrium and constant
mass, with the samples at both 70 and 90°C; consequently, the
method requires multiple weighing of the samples. To reach a
constant mass in each weighing will depend on the oven type,
the number of samples, and the relative humidity. As indicated
by Artieda et al. (2006), the refined method seems unsuitable
for smectitic soils, and gypsum percentages <2% cannot be
determined. In this study, we developed a thermogravimetric
method that overcomes the sources of error of the previous
methods and that provides gypsum content to within 1%.
MATERIALS AND METHODS
Bassanite Method
The following steps describe the method that we developed:
1. Weigh, using a four-decimal balance, the sample
containers (wt).
2. Weigh at least 1 g of gypsum reagent into a sample container
to act as a control and place soil samples in the other
weighed containers.
3. If the samples contain expandable clays, the RH at which the
samples are equilibrated in the laboratory should be measured
at this time; this value can be used to correct for hysteretic
behavior if needed (see below).
4. Equilibrate the samples in a desiccator at a fixed RH similar to
the humidity of the laboratory (for example, using K2CO3
for a RH of ?41%,). Equilibration is achieved when the
weight of the samples is constant; we suggest that most
samples are equilibrated fully within 48 h. Choosing a RH
for the desiccator similar to that of the laboratory shortens
the equilibration time and also minimizes changes in the
sample mass while weighing.
5. Remove the containers from the desiccator one at a time and
accurately weigh the containers with the gypsum (wgb) and
the soil samples (wb). Having weighed all the samples, place
them in an oven at 105°C for 24 h.
6. Remove the samples from the oven and put them back in the
desiccator to reequilibrate at the fixed humidity (?41%) until
a constant mass is achieved (48 h). If the RH of the laboratory
in Step 3 was higher than the desiccator humidity (41%)
and the samples contain expandable clays, then they should
be allowed to rehydrate to this higher humidity (e.g., 60%)
before placing in the desiccator at 41% so that the samples
dehydrate following the same initial drying curve as in Step 4.
7. Reweigh the gypsum sample (wga) and the soil samples (wa)
after reequilibration. The gypsum content in the soil sample
is calculated according to
⎛ wb − wa ⎞⎟ ⎛100 ⎞⎟
Gypsum% = ⎜⎜ 100 ⎜⎜ ⎟ [1]
⎜⎝ wb − wt ⎠⎟⎟ ⎜⎝ wg ⎠⎟⎟
404
where wb is the mass of the sample after being equilibrated at constant
RH before oven drying, wa is the mass of the sample after oven drying
and after being reequilibrated at constant RH, wt is the mass of the
tin or container where the sample is held, and wg is calculated as
⎛ wgb − wga ⎞⎟
wg = ⎜⎜ ⎟100 [2]
⎝⎜ wgb − wt ⎠⎟⎟
where wgb is the weight of the gypsum reagent sample after equili-
brating at 41% RH before oven drying, wga is the mass of the same
sample after oven drying and after being reequilibrated in the desicca-
tor, and wt is the mass of the container.
Equilibrating the samples at the same RH before and after oven
drying is critical for the accuracy of the method. We placed a RH
sensor inside the desiccator to guide us concerning the equilibration
times; the use of an RH sensor is highly recommended. The RH sen-
sor should be in such a position that it can be read without open-
ing the desiccator. The RH sensor is placed in the desiccator before
putting the samples in and closing it; the reading by the RH sensor
should stabilize in about 1 h. After the samples are added to the desic-
cator, the RH will change as the samples equilibrate. When the read-
ing on the RH sensor is the same as before introducing the samples
in the desiccator and remains constant for a few hours, the samples
are equilibrated.
Some researchers, instead of using Eq. [2], have assumed a
gypsum water loss based on a “recovery factor” (Nelson et al., 1978;
Artieda et al., 2006) but we recommend the use of a pure gypsum
sample as a reference each time the samples are run. The use of a ref-
erence avoids experimental discrepancy due to the oven temperature,
which will vary depending on the number of samples being processed;
in this way the gypsum reagent sample acts as a control to correct for
this experimental variability.
If the soil contained no gypsum or hydrated salts, the mass of
the sample would be the same before and after oven drying since it is
equilibrated at the same RH before and after oven drying. Only the
presence of gypsum decreases the mass after oven drying and reequili-
bration due to the formation of bassanite. This difference is used to
determine the quantity of gypsum when compared with a standard
sample of crystalline gypsum subjected to the same procedure.
Special care should be taken when the presence of hydrated salt
minerals like mirabilite (Na2SO4⋅10 H2O), epsomite (MgSO4⋅7H2O),
or soda (Na2CO3⋅7 H2O) are suspected; these minerals are found
in evaporite systems like the Great Salt Lake Basin and the Aral Sea
(Eswaran and Zi-Tong, 1991). Many of these minerals are unstable,
irreversibly losing hydration water molecules at or above room tem-
perature if the relative humidity is low. If salts are suspected, we rec-
ommend measuring the electrical conductivity of the saturation ex-
tract (ECe). The presence of more soluble salts than gypsum will be
evident if the ECe is >2.5 dS m−1. If soluble salts are present, the ECe
will be much higher than 2.5 dS m−1. One of the advantages of hy-
drated salts is that they are highly soluble, while gypsum is not. These
salts could be removed by washing with deionized water and tracking
the mass balance; however, these systems were not the focus of this
study and the method should be investigated further to determine the
best approach to handling such samples.
Clay and Soil Samples
Comparison of our proposed method with the widely used
Nelson method (Nelson et al., 1978; Nelson, 1982) was achieved
using soil samples and mixtures of different clays with a gypsum
SSSAJ: Volume 73: Number 2 • March–April 2009
reagent. Samples of Silver Hill il- Table 1. Chemical composition, pH, and electrical conductivity (EC) of the extracts from the
soils used in this study.
lite from Montana (IMt-1) and
Ca-montmorillonite from Cheto, Saturation extract chemical composition
Soil Depth Symbol pH EC
AZ (SAz-1) were obtained from the Ca2+ Mg2+ Na+ K+ SO42− Cl− NO3−
Clay Mineral Society’s Source Clay cm dS m −1 ———————mmolc L−1————————
Repository. We also used Wyoming 0–4 MT 7.6 2.56 33.2 1.73 0.96 0.51 31.6 0.77 0.14
bentonite (Aqua Technologies of Moab 4–10 MB 7.2 2.55 32.4 1.47 0.54 0.35 30.2 0.38 0.09
Wyoming, Casper), kaolinite from 0–4 SR1T 7.5 2.49 31.2 1.22 1.67 0.22 28.1 1.23 0.23
the Lamar pit (Bath, SC), and quartz SR1 4–12 SR1M 7.7 2.38 34.8 2.10 0.53 0.51 29.6 0.94 0.38
sand (Norco, CA). Reagent-grade, 12–20 SR1B 7.8 2.33 28.9 0.84 0.50 0.19 26.7 0.26 0.10
?200-μm gypsum was used as the 0–1 SR2T 7.5 2.09 31.5 4.82 1.61 0.39 33.3 0.88 0.32
control (Thomas Baker, Mumbai, SR2 1–10 SR2B 7.5 2.51 28.3 1.05 0.95 0.19 27.1 0.74 0.37
India). The SAz-1 montmorillonite Sandy soil 0–4 Sandy 7.7 0.5 9.1 1.0 1.14 0.00 7.3 0.70 0.32
was saturated with either Ca or Mg to
produce monosaturated clay samples cator with drierite. We prepared a second desiccator with a saturated
(Goldberg and Glaubig, 1987). Mixtures were prepared containing a solution of K2CO3; the RH determined by the sensor was 41 ± 3%.
mineral/gypsum air-dry ratio of ?0, 2, 5, and 50% gypsum content The advantage of using a solution of K2CO3 is that the equilibrium RH
by mass. In the case of the Ca- and Mg-saturated montmorillonite, is constant across a wide range of temperatures (Greenspan, 1977) and
only the 0, 5, and 50% gypsum content samples were prepared due to was also close to the RH in the laboratory. In this way, abrupt changes
the small quantities of the monosaturated clays available. in the RH were minimized when opening and closing the desiccator.
We collected three gypseous soils for this study. We use the term The soils and mixtures of clay minerals with gypsum were placed
gypseous, which implies that the soils are composed of gypsum and have in the desiccator with drierite with the RH sensor inside so that we
the characteristics of gypsum, rather than the term gypsiferous, which could read the RH inside the desiccator without opening it. We mea-
merely acknowledges any presence of gypsum (Gove, 1993). The sured the mass of the samples once a day for 5 d and monitored the
gypseous soils were collected from the Colorado Plateau. The first was RH inside the desiccator every day. We found that the mass of the
from Moab, UT (38°34′15.24″ N, 109°33′52.94″ W). The gypseous samples and the RH inside the desiccator was constant after 48 h,
soil occurs as an outcrop that is not mapped independently by the soil but we continued taking readings of weight and RH up to 5 d to
survey and occurs in the Thoroughfare fine sandy loam series (coarse- make sure no further changes occurred. Different sets of samples were
loamy, mixed, superactive, calcareous, mesic Typic Torrifluvents) in placed in the desiccator with K2CO3; we weighed the samples and
the map unit of the Canyonlands Area. The other two soils were monitored the RH inside the desiccator also for 5 d; we found con-
from the San Rafael Swell: San Rafael 1 (SR1, 39°3′28.74785″ N, stant mass and RH after 48 h. We then put all the samples in the
110°54′3.33300″ W) from the Robroost–Mussentuchit association oven at 105°C for 24 h. The samples that had been in the drierite
and San Rafael 2 (SR2, 39°2′31.78168″ N, 110°54′43.18264″ W) were weighed immediately after removal from the oven; the samples
from the Goblin–Gypsum Land–Mussentuchit complex; both had previously equilibrated with K2CO3 were put back in to the desicca-
gypsum as a parent material (Soil Survey Staff, 2008). The Moab soil tor with the K2CO3 and equilibrated for another 48 h. After 48 h, we
had two very contrasting colored layers in the soil profile; we took weighed the samples and calculated the gypsum percentage according
samples from each layer, 0 to 4 cm (Moab top, MT) and 4 to 12 cm to the Nelson method and the method proposed in this study.
(Moab bottom, MB). The first soil from San Rafael (SR1) was located Desiccators do not prevent rehydration of the samples; the amount
in the lower part of a valley; we sampled three depths with different of time the sample spends in the desiccator, and the initial temperature
colorations in the profile at 0 to 4, 4 to 12, and 12 to 20 cm (SR1T, at which the sample was heated affect the amount of rehydration of the
SR1M, and SR1B, respectively); the second sample (SR2) was on the samples. To quantify the amount of water taken up by our samples in
top of a plateau and the profile was very homogeneous except for the desiccator, we took soil samples (in triplicate) and one sample of
the top 1 cm (SR2T and SR2B). For comparison, we also collected gypsum reagent and heated them at 50°C in a convection oven for 24 h.
a sandy soil from the Moab area with no gypsum (Sandy), the total We weighed the samples directly from the oven, placed the samples in
number of soil samples tested came to eight. After sieving the
Table 2. Semiquantitative analysis of the mineralogy of the soils used
samples through a 2-mm screen, we prepared a saturation paste
in this study using x-ray diffraction. Calculated percentage of gypsum
for each of the soils and the saturation extract was analyzed based on weight loss at 105°C using the Nelson et al. (1978) method
for major cations and anions, electrical conductivity, and pH and the bassanite method.
(Table 1). We also sieved portions from each of the samples
X-ray diffraction Gypsum content
through a 500-μm sieve and analyzed the mineralogical compo- Soil
Gypsum Quartz Calcite Bassanite method Nelson method
sition of our soils using x-ray diffraction (Siemens P4, Siemens
——————————— % ———————————
USA, New York City), Table 2. Semiquantitative analysis
MT 40 60 49 52
was performed using the software package X’Pert HighScore
MB 100 97 98
(PANalytical, Almelo, the Netherlands).
SR1T 40 50 10 26 30
We prepared a desiccator by placing drierite (W.A. SR1M 64 27 9 75 76
Hammond Drierite Co., Xenia, OH) in an oven at 150°C SR1B 100 trace 92 91
for 3 h and transferring it to the desiccator to cool down. The SR2T 80 20 69 71
RH inside the desiccator was measured using an RH sensor SR2B 100 94 96
(Thermo-Fisher, Waltham, MA); the RH was 12% in the desic- Sandy 100 0.1 4

SSSAJ: Volume 73: Number 2 • March–April 2009 405

 Table 3. Water loss of the soil samples measured directly from the oven and after leav- was achieved after 2 h but we continued the
ing the samples in the desiccator with anhydrite (12% relative humdity) for 3 h. We experiment for a total of 7 d to make sure there
used fresh samples for each temperature.
was no more water uptake.
Measurement Weight loss We measured the water potential of
Soil
condition 50°C 70°C 105°C 200°C kaolinite, illite, Wyoming bentonite, and Ca-
——————— % ————–— and Mg-montmorillonite using a WP4-T
no desiccator 0.48 ± 0.03 0.67 ± 0.02 10.41 ± 0.21 12.99 ± 0.35 Dew-point Potentiometer (Decagon Devices,
MT
desiccator 0.22 ± 0.03 0.48 ± 0.05 9.53 ± 0.28 9.94 ± 1.05 Pullman, WA). The potentiometer measures
no desiccator 1.16 ± 0.31 1.84 ± 0.54 19.80 ± 0.05 20.80 ± 0.04 the combined effect of matric and osmotic
MB
desiccator 0.03 ± 0.06 0.00 ± 0.10 17.79 ± 1.30 18.18 ± 1.09 potentials; in samples with low salt contents,
no desiccator 0.57 ± 0.04 0.76 ± 0.02 5.97 ± 0.11 8.48 ± 0.66 the potential measured is considered to re-
SR1T
desiccator 0.33 ± 0.07 0.58 ± 0.02 5.32 ± 0.13 5.87 ± 0.49 flect the matric potential only. Clays were
no desiccator 0.61 ± 0.09 0.63 ± 0.08 15.16 ± 0.03 18.94 ± 0.36 equilibrated with different water contents
SR1M
desiccator 0.00 ± 0.05 0.13 ± 0.03 13.66 ± 0.14 14.60 ± 1.22 overnight; the potential was measured using
no desiccator 0.42 ± 0.08 0.65 ± 0.05 18.12 ± 0.04 20.55 ± 1.65 the WP4-T in a constant-temperature room
SR1B
desiccator 0.00 ± 0.11 0.11 ± 0.04 16.54 ± 0.62 16.94 ± 1.59 at 22°C. The salt content in the clay samples
no desiccator 0.36 ± 0.03 0.66 ± 0.11 14.05 ± 0.15 17.18 ± 0.49 was negligible and we therefore assumed that
SR2T
desiccator 0.17 ± 0.07 0.40 ± 0.03 12.87 ± 0.29 14.10 ± 0.53 the measurement reflected the matric poten-
no desiccator 0.77 ± 0.17 1.10 ± 0.29 19.03 ± 0.02 19.91 ± 0.13 tial. The final water content was measured by
SR2B
desiccator 0.03 ± 0.04 0.00 ± 0.03 18.03 ± 0.74 18.38 ± 0.95 oven drying at 105°C, and matric potential
no desiccator 0.04 ± 0.01 0.0 ± 5 0.00 0.10 ± 0.03 0.37 ± 0.06 was transformed to RH.
Sandy
desiccator 0.02 ± 0.01 0.02 ± 0.00 0.02 ± 0.01 0.01 ± 0.00

Gypsum
no desiccator 0.51 ± 0.03 2.39 ± 1.58 19.75 ± 0.15
desiccator 0.04 ± 0.02 1.43 ± 1.71 18.82 ± 0.34
the desiccator with drierite, and allowed them to cool down for 3 h. We
weighed the soil samples again and returned them to the desiccator and
reweighed the samples after 2 d. We repeated the procedure with fresh
samples each time and heated at 70, 105, or 200°C. We used a styro-
foam block as a thermal insulator for weighing to avoid errors in the
measurements or damage to the scale (data shown in Table 3).
We repeated the heating process at 50, 70, 105, and 200°C with
a new batch of soil samples, weighing the samples before and after
oven drying, but this time the samples were left open to the laboratory
atmosphere at 37% relative humidity and 21°C. The mass increase of
the samples was registered every 10 min for the first hour and then at
every hour and every 3 and 12 h until constant mass. Constant mass
Fig. 1. Water content relative to oven dryness for different clay
minerals at different relative humidities. The water content for
gypsum and bassanite is shown as ×.
20.91 ± 0.10 RESULTS AND DISCUSSION
19.75 ± 0.64 Figure 1 presents the gravimetric
water content of the mineral samples as a
function of RH. In effect, this diagram demonstrates the water
release characteristic of the clay minerals as a function of RH.
This diagram illustrates the flaw in the assumption that by plac-
ing the samples in a desiccator with a RH of 12 or 20%, the clay
minerals will lose all their absorbed water and that any further
water loss on oven drying is due exclusively to gypsum. The
apparent success in previous work was because Na-bentonite
was used as a standard (Nelson et al., 1978), which loses almost
all of its adsorbed water at 20% RH. Figure 1 shows, however,
that Ca- and Mg-saturated montmorillonites both have >10%
gravimetric water content remaining at a RH of 20%; even
at 12% RH, the water contents are >7%. Figure 1 shows that
not only the mineralogy but also the dominant cation present
in our soils is very important, especially Ca-montmorillonite,
which is common in semiarid ecosystems. Water loss on oven
drying will be a combination of water from the clay as well as
from the gypsum. This could potentially result in large errors
in the estimation of the gypsum content, depending on the
clay percentage in the sample.
The gravimetric water content of gypsum and bassanite
are also presented in Fig. 1, they follow almost straight lines
across the wide humidity range shown. When gypsum is heat-
ed at 105°C, its water of crystallization is removed; subsequent
rehydration in the laboratory results in the formation of bas-
sanite at relative humidities below saturation (100% RH). As
bassanite has only 0.5 of a water molecule per unit cell, there is
a loss of 1.5 water molecules between the gypsum and bassan-
ite phases, representing a 15.68% reduction in mass compared
with gypsum. In our experiments, we found that we could re-
cover the original gypsum from the bassanite phase only by
physically wetting the sample.
Rehydration curves for four different gypsum reagent
samples, following gypsum removal from the oven at 105°C,
are presented in Fig. 2. The graph shows that, left in the labora-

406 SSSAJ: Volume 73: Number 2 • March–April 2009

tory (RH 20–30%) to rehydrate, the samples took 1.5 to 2 h
to increase their mass to the point at which bassanite is formed,
and they then stopped gaining any further mass. The samples,
one at a time, were taken from the oven and weighed imme-
diately; an average weight loss of 20.6% was determined. We
also observed the rapid rehydration in the first minutes after
the samples were removed from the oven, which may indicate
that the samples lost the full two water molecules (20.91%).
The transfer time between removal from the oven and measure-
ment on the balance may have been sufficient for the samples
to rehydrate a little, and thus values <20.91% are often record-
ed. The Nelson method also indicated that gypsum loses the
two water molecules when heated for 24 h at 105°C but an
experimental recovery factor of 19.42 was used rather than the
theoretical value of 20.91.
We show the four rehydrating samples in Fig. 2 instead
of averaging and providing an error, as we interpret that the Fig. 2. Water uptake with time for four different samples of different
weights from the same gypsum reagent. The samples had previously
physical differences between the rehydration of the samples is been in an oven at 105°C for 24 h. Water uptake is expressed relative
due to differences in diffusion rates that may occur for a num- to the original weight of the CaSO4⋅2H2O.
ber of reasons. The differences among samples demonstrate
that rehydration in gypsum is a kinetic process and that diffu- sanite with 15.68% less water. Avoiding measurement of the
sion rates play an important role in how fast the samples take sample while the anhydrite is still hydrating to form bassanite
up water. The mass of sample for the gypsum reagent varied eliminates the second source of inaccuracy. The sample is only
from sample to sample: Sample 1, 1.83 g; Sample 2, 1.30 g; measured once bassanite has formed and the sample is in stable
Sample 3, 1.75 g; and Sample 4, 1.18 g. As we observe in Fig. equilibrium with the RH. The accuracy of the method is there-
2, Samples 2 and 4 had faster water uptake than Samples 1 and fore largely determined by our ability to accurately equilibrate
3. Our interpretation of this is that the greater mass used in the sample at a fixed RH and measure its mass.
Samples 1 and 3 resulted in the water having to diffuse through
a greater quantity of gypsum sample to fully rehydrate the an- Gypsum Determination in Mixtures of Clay and
hydrite in the mass to bassanite. Samples 2 and 4, with thinner Gypsum and Soil Samples
masses, rehydrated faster. The results for the range of clay mineral samples mixed with
Once the samples reached equilibrium, they all settled gypsum are presented in Fig. 3. In this sensitivity plot, the quantity
at the same water content, which we found to average 5.52% of gypsum predicted by our new method was subtracted from the
less at 22% RH than the original weight before oven drying. known quantity of gypsum in the mixture. The figure illustrates
Bassanite (CaSO4⋅0.5H2O) contains 5.23% water; the 0.3% that the gypsum content was predicted to an accuracy of better
discrepancy between the amounts of water found in our ex-
perimental data and the theoretical water content for bassanite
is probably due to absorbed water on the crystal surfaces of
the powdery gypsum reagent. Table 3 shows that the gypsum
reagent lost 0.5% of its mass in the oven when heated at 50°C,
which we attribute to surface-absorbed water.
Figure 2 also shows the difficulty in obtaining reproduc-
ible water loss with gypsum when it is weighed within the first
1.5 h after the samples are removed from the oven. First of all,
the fastest change in mass occurs in the first 2 min, but at any
time 1 to 2% difference between samples can be obtained, even
with the gypsum reagent, where the crystal size was uniform for
all the samples. In natural soil samples with inhomogeneous
crystal size and different crystal morphologies, we expect the
kinetics of rehydration to be more complex and it becomes
critical to ensure that the sample is in equilibrium before re-
cording the mass.
The method for gypsum determination that we present
here eliminates two important sources of inaccuracy. The first Fig. 3. Differences between real gypsum content and gypsum
one is the contribution of water from the clays, since the soil calculated using the bassanite method. The samples were mixtures of
sample is equilibrated at a specific humidity before and after gypsum reagent and different clay minerals. All weights are related
to 41% relative humidity (RH). Drying and wetting curves in Mg-
oven drying. Therefore, in the absence of evaporitic salts, the montmorillonite showed different water contents at the same RH. To
only recorded reduction in mass of the sample is due to the overcome hysteresis, we exposed the clay to 60% humidity after oven
water lost as gypsum dehydrates and rehydrates to form bas- drying and before drying it down to 41% RH in the desiccator.

SSSAJ: Volume 73: Number 2 • March–April 2009 407

from the oven, begins hydrating rapidly. The time it
takes to weigh all the samples will affect the percent-
age of water determined to be present in the samples.
Those measured soonest will have the lowest water con-
tent; those measured last, the highest.
A general step with all the previous methods is
to cool the samples in the desiccator before weigh-
ing. The concept is that the desiccant in the desiccator
will prevent rehydration of the sample while it cools.
The more common desiccants are silica gel and dri-
erite; drierite is anhydrite (dehydrated gypsum) with
an indicator that changes color when the anhydrite is
not able to absorb more water. Typically the humid-
ity achieved with drierite is 12%, as we found with
our desiccator, and 20% for silica gel. We performed a
simple experiment in which we compared the weight
loss of our soil samples when weighed immediately af-
ter removal from the oven, and the weight of the same
samples after they had been allowed to cool in the des-
iccator with drierite (anhydrite) as a desiccant for 3 h
or 2 d, or subsequently left open to the atmosphere in
Fig. 4. Water loss of three soil samples with close to 100% gypsum and a sample
the laboratory. Drierite (anhydrite) was chosen in this of gypsum reagent after being heated at different temperatures; all samples were
experiment because it is the most common desiccant in triplicate, standard errors are shown. The weights were measured immediately
found in many laboratories. Table 3 shows the weight after oven drying or after being in a desiccator with drierite for 3 h, 2 d, or left
loss percentage after oven drying the soil samples for open for 7 d under laboratory conditions.
24 h at 50, 70, 105, and 200°C, with and without sit-
ting in a desiccator for 3 h. All the samples showed the highest high surface areas. Figure 6 shows the main peak from the x-ray
weight loss when the sample was measured directly from the diffractograms for MB, SR1B, and SR2B; we observe a general
oven without waiting for it to cool in the desiccator. All the broadening for the MB and SR1B samples compared with the
gypsiferous samples gained water in the desiccator while wait- SR2B sample. This indicates differences in either the crystallin-
ing to cool down; the higher the gypsum content of the sample, ity or the crystal size among the three soils. Although our ob-
the higher the discrepancy in mass lost between the oven-dry served differences can be explained by the quantities used, the
mass and the mass after cooling in the desiccator. The results crystallinity and particle size differed and may lead to a further
for the soils with almost 100% gypsum are shown graphically avenue of research on water uptake by gypsiferous soils. When
in Fig. 4 with the water uptake in the desiccator after 2 d and the samples were left in the open atmosphere for 7 d, the final
left open to the atmosphere. The figures reinforce the results water uptake was very similar for all the samples (Fig. 4).
presented in Table 3 and clearly show that values for the recov-
ery factors can differ by several percentage points depending Comparison with the Nelson Method
on whether the sample mass was determined immediately fol- One of the more popular methods used in the soils lit-
lowing removal from the oven or after allowing it to cool in the erature to calculate the amount of gypsum in soils, especially
laboratory atmosphere. When the sample was left to rehydrate in pedology and soil survey, is that proposed by Nelson et al.
in the laboratory, the samples showed a maximum water up- (1978) or modifications of the same concept (Artieda et al.,
take at about 2 h that did not increase any further in the 7-d 2006). We followed the Nelson method and compared the re-
experiment. The increase in mass for the soils was 5.9 ± 0.17 sults with our new method. We calculated the gypsum con-
and 5.6 ± 0.15% for the reagent samples, consistent with the tent of our clay–gypsum mixtures and our soils. Based on the
bassanite phase. The standard errors of the measurements were amount of water retained by each of the clays at 12% humidity,
generally smaller than the symbols used in the graph. we could estimate for each clay mineral the error in the de-
We also observed that the water gained was not equal for termination of the gypsum content using the Nelson method
the three soil samples. After being heated at 200°C, MB gained (Table 4). The results clearly indicate that the error is most sub-
more water in the desiccator than the SR2B and gypsum re- stantial in the divalent cation saturated montmorillonite clays.
agent samples. This is consistent with the previous finding il- In the Nelson method, Na-bentonite was considered, where
lustrated in Fig. 2 that the samples with a greater amount of the error is much smaller. In semiarid environments, however,
soil sample rehydrated more slowly because of the retardation Ca-saturated montmorillonite is much more prevalent, and
of water diffusing through the mass of soil (SR2B and the gyp- thus these data identify a serious flaw in the Nelson method.
sum reagent). In addition, these differences are also consistent This is highlighted in Fig. 7A and 7B, where the y axis is ex-
with smaller particle size crystals in the MB and SR1B samples. tended in Fig. 7B, showing the large errors for the Ca- and Mg-
The scanning electron micrograph in Fig. 5 for MB indicates saturated clay samples, overestimating the gypsum content by
that the natural arrangement of the gypsum crystals in the soil up to 30%. The type of cation present on the exchange com-
has a very intricate, anisotropic, platy pattern that could lead to plex plays an important role in how much, and how strongly,

SSSAJ: Volume 73: Number 2 • March–April 2009 409

Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 14350661, 1994, 6, Downloaded from https://acsess.onlinelibrary.wiley.com/doi/10.2136/sssaj1994.03615995005800060006x by University of Queensland Library, Wiley Online Library on [01/03/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
BERIGARI & AL-ANY: GYPSUM DETERMINATION BY CONVERSION TO SODIUM SULFATE 1625

Table 1. Selected depths and properties of the Typic Gypsiorthids.

Particle-size analysis
Sample pH Electrical Organic Equivalent
no. Depth Sand sat Clay (water) conductivity C CaCO3 Gypsum
cm % dSm-' eke-
6 6
1

1.1 0-15 26 40 34 7.7 2.20 6.3 222 52.4

1.2 15-45 33 37 30 7.9 2.21 1.3 72.5 698
2.1 0-15 34 30 36 7.8 2.20 4.8 75.0 391
2.2 15-60 36 38 26 7.6 2.32 2.0 72.5 124
3.1 0-30 29 43 28 7.7 2.42 7.9 209 188
3.2 30-45 29 40 31 7.8 2.36 6.0 195 341
3.3 45-60 27 29 44 7.7 2.60 5.0 172 492

collected from the depths specified in Table 1. The samples (Table 2) was thoroughly mixed with 1.8-g samples of a
were air dried, ground, and passed through a 2-mm sieve. nongypsic soil in triplicate to give 10% soluble salt or 2.5%
The <2-mm fraction was ground further to pass through a of each sulfate salt as an extreme case. The soil-salt mixture
0.5-mm sieve for chemical analysis. The soil analysis data was shaken with 25 mL of 50% ethanol for 1.0 h on a
presented in Table 1 were determined according to convention- horizontal shaker. The supernatant solution was separated by
ally accepted methods (Page et al., 1982). Particle-size analysis centrifugation as described above and analyzed for SO^ turbi-
was obtained by the standard pipette method after removal of dimetrically. This provided a test of the extent of soluble
organic matter, gypsum, and carbonates (Day, 1965). sulfate removal from the soil samples by 50% ethanol compared
with that of the same sulfate salts in 50% ethanol but without
Proposed Method the soil sample.
Triplicate 2.0-g soil samples in 50-mL polycarbonate centri- Comparative Method
fuge tubes were washed once with 25-mL portions of 50%
ethanol to remove soluble sulfates while reducing the solubility Soil samples were extracted with water at different soil/
of gypsum..The bulk solution was centrifuged and the sediment water ratios (Nelson, 1982) and gypsum content was obtained
was suspended in 25 mL of the 0.50 M NaaCOs solution by by the Bower-Huss (1948) method and from SO4~ analysis
a 30-s Bonification to disturb formation of stable CaCO3(s) by turbidimetry (Greenberg et al., 1985).
coating on gypsum, thus enhancing its stoichiometric conver-
sion to water-soluble Na2SO4. The supernatant solution was Statistics
centrifuged at 1000 X g and 25° C, then filtered quantitatively
through Whatman no. 42 filter paper. This extraction procedure For statistical comparisons of the methods, the coefficient
was repeated until a negative test for sulfate with BaCk crystals of variation (CV) and analysis of variance of the means were
was obtained. Sulfate in the aqueous extract was measured by determined by Tukey's honestly significant difference tests
standard BaSO* gravimetry and turbidimetry after the necessary to compare the methods within each soil collection. Linear
dilutions and acidification were made to prevent precipitation regression analysis was used to depict the graphical relations
of BaCO3 and Ba3(PO4)2 (Greenberg et al., 1985). Also, the between the methods.
correction for sample color and turbidity was applied for
turbidimetric SO4~ measurement as described by Greenberg RESULTS AND DISCUSSION
et al. (1985). Gypsum content in the soil samples was obtained
from SOl~ analysis assuming that all the SOl~ in the extract The selected soils were classified as Typic Gypsior-
came from soil gypsum, CaSO4-2H2O: thids, which are the most common soils of the experiment
station. The soil samples were selected to cover a wide
gypsum (g)/soil (kg) = [SO?- (g)/soil (kg) (172/96.1)] [3]
range in gypsum content (52.4-698 g kg"1), CaC(>3
Known Addition of Gypsum equivalent (72.5-222 g kg"1), and other properties as
shown in Table 1.
The accuracy of the proposed method of gypsum extraction Soil samples were washed once with 50% ethanol to
from gypsic soils was determined by adding known quantities remove the soluble sulfates of common cations of arid-
(100 and 200 g gypsum kg~' soil) of a reference-grade gypsum zone soils (Na, Mg, K, and NRt) and possibly the
(100 ± 1 % purity) to the samples, then using the proposed organically bound SOij" prior to gypsum extraction. This
method of extraction and turbidimetric SOi~ analysis to com-
pute the relative quantity of gypsum recovered. was done to minimize the positive error, i.e., overestima-
tion of SOl" from nongypsic sources, and meanwhile
Correction Measures
Table 2. Solubilities of sulfate salts of common soil cations in 50%
Soils may contain nongypsic soluble sulfates of Mg, Na, ethanol, determined in our laboratory at 25°C.
K, and NYU but amounts seldom exceed 2% (Nelson, 1982). Single Equimolar Saturated
These soluble sulfates cause positive errors in gypsum determi- Salt salt additiont solution:):
nation from SO4~ analysis unless a correction is applied for « T -1
such SO4~ or it is removed selectively prior to gypsum extrac-
tion. (NH&SO, 95.5 10.0 40.6
Na2SO4 97.4 10.2 28.4
The solubility of each sulfate of the common soil cations K2S04 1.6 3.0 3.6
and an equimolar mixture (taking 10.0 g (NH4)2SO4 L~' solvent MgS04-6H2O 12.8 2 7.4 1.6
as the basis for calculations) in 50% ethanol was determined CaSO4-2H2O 1.0 x 10- 1.7 x 10-2 2.5 x 10-2
at 25° C. A 0.200-g soluble sulfate mixture, consisting of equal t Addition based on 10 g (NH^SO, L-> of 50% ethanol.
weights (50 mg) each of NH/, Na + , K + , and Mg2+ sulfate t Solution saturated with cosolutes simultaneously.
 14350661, 1994, 6, Downloaded from https://acsess.onlinelibrary.wiley.com/doi/10.2136/sssaj1994.03615995005800060006x by University of Queensland Library, Wiley Online Library on [01/03/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
1626 SOIL SCI. SOC. AM. J., VOL. 58, NOVEMBER-DECEMBER 1994

Table 3. Soil gypsum extraction by the proposed method and measurement by gravimetric (Method A) and turbidimetric SO2" (Method
B) analyses vs. water extraction and measurement by turbidimetric SOi" (Method C) and the Bower-Huss conductometric (Method
D) analyses. Values represent averages of three replications.
Sample no. Method A CV Method B CV Method C CV Method D CV HSDt
1 1
gkg- % gkg- % gkg- 1
% gkg- 1
% gkg- 1
1.1 52.4 2.4 47.9 2.9 45.0* 5.9 43.0* 5.9 5.4
1.2 698 1.5 705 1.6 557» 3.1 593* 3.7 42.0
2.1 391 5.1 385 2.0 355 4.0 295* 4.7 38.2
2.2 124 1.6 116 1.1 91.7* 6.6 105* 11.0 17.3
3.1 188 2.9 184 3.8 144* 4.8 139* 6.1 18.5
3.2 341 1.3 313 2.4 213* 8.2 217* 5.2 29.6
3.3 492 3.7 477 1.4 358* 4.0 326 5.3 56.4
* Significant (P = 0.05) compared with the standard method (A).
t Tukey's honestly significant difference (P = 0.05) to compare the results of four methods of gypsum determination within each soil sample.

greatly reduce the solubility of gypsum (Matushevskiy, samples (Table 3). These differences are vividly seen in
1968) thus minimizing the negative error resulting from the scattergrams where the best-fit regression lines devi-
its loss with the solvent. The efficiency of this solvent ate from the 1:1 line as the gypsum content of soil
was verified by 100% recovery of 2.5% additions of samples increases (Fig. Ib and Ic). On the other hand,
each of Na, Mg, K, and NUt sulfate as mixtures with the agreement between the best-fit regression line and
nongypsic soil samples based on turbidimetric SO2." anal- the 1:1 line for Methods C vs. D is very good (Fig.
ysis. Also, the data of Table 2 show that gypsum solubility Id), indicating that the extraction procedure was the
in 50% ethanol is very low (1.0 x 10~2 to 2.5 x 10~2 g major cause for the deviations of Methods C and D from
L"1) depending on the composition of solution. Thus, the Methods A and B. Also, it is worth noting that Methods
negative error in gypsum determination in soils caused by C and D displayed lower precision given by CV ranges
its dissolution in 25 mL of this solvent per 2-g soil (3.1-8.2 and 3.7-11.0%, respectively; Table 3).
sample is not likely to exceed 0.62 mg or 0.031 %, which In general, the gypsum contents were higher when
is negligible. Moreover, treatment of soil samples with extracted by the proposed method (N^COs solution)
50% ethanol can retard biological transformation of whether SOl~ was measured by the standard gravimetric
SO?T, thus eliminating the error that may arise from this (A) or the turbidimetric (B) method. Moreover, the soil
source. gypsum extracted by the proposed method and by distilled
The Na2CO3 solution was selected to convert soil water (Nelson, 1982) was determined from SO2," by the
gypsum to soluble Na2SO4 and CaCC>3(s) for several same turbidimetric method (B and C) yet differences
reasons: (i) it and its reaction product NaaSC^ are very exist between the two sets of data (B vs. C, Table 3),
soluble in water, (ii) it is relatively inexpensive, and which should be ascribed largely to the variation between
(iii) soil treatment with its excess will saturate the ex- the two methods of gypsum extraction. This means that
change sites with Na + . This will allow good dispersion distilled water, which has been used routinely, is a weak
of the soil suspension with Bonification, which is effective extractant for gypsum (15 mM) where a very wide water/
for rapid dissolution of gypsum since the Ca2+ displaced soil ratio with numerous extractions were required for
from the exchanger and that derived from gypsum will improved gypsum extraction from soils high in gypsum
precipitate as CaCO3(s), leaving behind SO2." in solution
that can be separated and analyzed. 800 800
Ten y = 7.28 +1.00 X y=­6.03*0.79X
The values of gypsum content of the soil samples "£,600 r = 0.98 600 r = 0.98
obtained with the two methods of extraction and three CO
methods of determinations are listed in Table 3. Method S 400 400
A is used for comparison because it is the standard .£
a*
method for SO2." analysis. The agreement between the 2 200 200
values obtained with Methods A and B is excellent (r = 0
0.98). There were no significant differences at P = 0.05 I 200 400 600, 800 200 400 600 800
between the two sets of data by analysis of variance and Method A gkg" Method A gkg"'
also as shown by the best-fit regression line, which "iai
800 £00
y =­6.77* 1.00 X
coincides with the 1:1 line (Fig. la). Methods A and B "o. 600
' CTl
£600 r = 0.99
have about the same precision measured by CV range o
.(1.3-5.1 and 1.1-3.8%, respectively). The agreement •a A 00
o
between Methods A and B used here is closer than that
found in Chesnin and Yien (1950) for SO2." extraction 1200 1 200
from a sandy soil from Nebraska. Since the turbidimetric 0 0
method (B) of SO?r analysis is simple, rapid, and accu- 200 400 600 800 200 400 600 800
rate, we recommend it for gypsum determination in soils. Method A gkg'' Method C gkg"
The differences between the values of gypsum content Fig. 1. Comparison of the methods used for gypsum determination
obtained wiJi Methods A and C were significant (P = of the soil samples: (a) turbidimetric B vs. gravimetric A, (b)
0.05) for six out of seven soil samples, whereas with turbidimetric C vs. gravimetric A, (c) conductometric D vs. gravi-
Method D the differences were significant for all the metric A, and (d) conductometric D vs. turbidimetric C.
 14350661, 1994, 6, Downloaded from https://acsess.onlinelibrary.wiley.com/doi/10.2136/sssaj1994.03615995005800060006x by University of Queensland Library, Wiley Online Library on [01/03/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
BERIGARI & AL-ANY: GYPSUM DETERMINATION BY CONVERSION TO SODIUM SULFATE 1627

Table 4. Recovery of gypsum added to 2-g soil samples as extracted by the proposed method and obtained from turbidimetric SO3 ~ analysis.
Values represent averages of triplicates, unless otherwise specified.
Gypsum Gypsum
Present Present
Sample + G,t Found CV Recovery^ + G2t Found CV Recovery:):
———— g k g - > - 1
———— gkg- -
1.1 148 144 1.3 97.3 248 239 1.0 96.4
1.2 805 798 0.5 99.1 905 890 0.6 98.3
2.1 485 478 0.9 98.6 585 572 0.8 97.8
2.2 216 211 1.1 97.7 316 306 0.7 96.8
3.1 284 282 0.8 99.3 384 377 2.3 98.2
3.2 413 406 2.9 98.3 513 508 0.3 99.0
3.3 577 579 3.0 100 677 666 1.2 98.4
Mean (n = 7) 1.5 98.6 1.0 97.8
t Gi and Gi represent 100 and 200 g additions of gypsum kg"1 sofl sample, respectively.
t Percentage recovery is based on total gypsum found divided by [gypsum present (Table 3, Column 4) plus that added] x 100.

contents. These operations are laborious and time con- its determination from turbidimetric 864 analysis ap-
suming, as have been experienced by other investigators pears to be simple, rapid, accurate, and very efficient
(Lagerwerffetal., 1965; Nelson, 1982). relative to the methods where water is used as the ex-
Table 4 shows the data of gypsum recovery from two tractant.
levels of standard additions to various soil samples using
the proposed method of Na2COs extraction with turbidi- ACKNOWLEDGMENTS
metric SOi~ analysis. The recovery of gypsum ranged
between 96.4 and 100%, with an overall mean of 98.2%, We wish to thank Lila H. Ibrahim and Ahlam H. Al-Khafaji
which is very good considering the speed and simplicity for certain phases of laboratory work and F.J. Jack for the
of the extraction and measurement steps and the complex- graphical work.
ity of soil systems.
The efficiency of the proposed method of gypsum
extraction relative to that obtained by water is shown in
Table 5. With the proposed method, two equilibrations
at a solution/soil ratio of 25:2 were sufficient to extract
gypsum completely from four soil samples selected to
bracket the range of gypsum content (Tables 1 and 3).
However, extraction with water required a wider water/
soil ratio, 250:2, and a greater number of equilibrations
even for low levels of gypsum, such as 5% in the case
of Sample no. 1.1 (Table 3). The efficiency of gypsum
extraction for the proposed method relative to that by
water as defined by Eq. [4] ranged from 9 to 28.7 for
the first equilibration, increasing with the increase in
gypsum content. The efficiency of gypsum extraction
varied depending on the initial gypsum content of the
soil sample and the sequence of extraction. Mean values
of 25.0 to 30.7 with an overall average of 27.8 were
obtained with the proposed method (Table 5).
The proposed method of soil gypsum extraction and

Table 5. Number of equilibrations needed and efficiency of the

proposed method of gypsum extraction (25:2) relative to water
extraction (250:2) based on turbidimetric SO|~ analysis.
Extraction efficiencyt of
Equilibrations needed proposed method relative to
to extract all gypsum water extraction method
Sample Proposed Water 1st 2nd
no. method method extraction extraction Mean
1.1 2 3 9.0 52.4 30.7
1.2 2 4 28.7 30.0 29.4
2.1 2 4 20.8 31.6 26.2
2.2 2 3 9.5 40.5 25.0
Mean 17.0 38.6 27.8
t Efficiency =
Na2COrextracted gypsum , water/soil sample ratio
[4]
water-extracted gypsum Na2CO5 solution/soil sample ratio