we hereafter refer to this method as the Nelson method.
The where wb is the mass of the sample after being equilibrated at constant
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
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
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

 than 1% in all cases, regardless of whether the mineral was quartz,
kaolinite, illite, or Ca- or Mg-saturated montmorillonite.
The initial measurement of the Mg-montmorillonite
resulted in a 2% error; this was also observed with the pure
(100%) Mg-montmorillonite sample. We observed that pure
Mg-montmorillonite did not recover its original mass when
placed back in the desiccator after oven drying. We attributed
this discrepancy to hysteretic behavior of the clay or, in other
words, to the fact that the amount of water in the clay at a
fixed RH differs depending on whether the equilibrium mass
at the fixed humidity was reached in a saturating or desatu-
rating environment. It is well known that soils are hysteretic;
however, at low water contents we expected this to be neg-
ligible. Neglecting the hysteretic behavior in the case of the
Mg-montmorillonite, however, resulted in a measurable error
in the gypsum determination. The RH in the laboratory is
subject to variations. At the time of this particular experiment
shown in Fig. 3, the RH of the laboratory was 60%; as a con-
sequence, the clays dehydrated through a drying process when
placed in the desiccator (41% RH) before oven drying, while
following removal from the oven the clays rehydrated through
a wetting process in the desiccator. To overcome this problem
of initially dehydrating to 41% RH and then rehydrating to
41% RH after removal from the oven, we placed the sample in
a desiccator at a RH of 65% after removal from the oven for
6 h to reproduce the laboratory conditions at the beginning
of the experiment and until its mass had increased beyond its
initial starting mass. We then returned the sample to the des-
iccator with the 41% RH, allowing the sample to dehydrate.
The sample was then allowed to equilibrate for 2 d, after which
time we found that the mass had returned to a value similar to
the initial mass, resulting in an estimation error for the gypsum
content of <1%.
If hysteretic behavior is suspected in the samples and the
RH of the laboratory at the time of the experiment is higher
than the one chosen for the desiccator, we recommend an ad-
ditional step in which the samples, after removal from the oven,
are equilibrated to a RH similar to the value of the atmosphere
before being placed in the desiccator at 41% RH. If the RH
of the laboratory is lower than that of the desiccator (41%),
no additional step is needed since the samples will equilibrate
along the same portion of the wetting curve before and after
oven drying.
The soil samples used in this study were analyzed by
preparing a saturation paste and the extract was analyzed for
basic chemical composition. Table 1 shows the electrical con-
ductivity values (ECe) for the saturation extracts; the values
are consistent with the presence of gypsum. The ECe values
were between 2 and 2.5 dS m−1, indicating that the water was
saturated with gypsum but also indicating that no significant
amount of another, more soluble salt was present. No signifi-
cant amount of total C, organic or inorganic, was detected.
The pH values were <8, consistent with the very small amounts
of bicarbonates identified in the saturation extracts. X-ray
analysis of the mineral phase confirmed the presence of gyp-
sum as the main component of all the soils; in the top layers
(MT, SR1T, and SR2T) quartz was found in different quanti-
ties, and small amounts of calcite were present in the SR1 soil.
The soil samples were typically mixtures of gypsum and quartz
408
sand, with gypsum compositions ranging from zero to 100%
gypsum. Table 2 shows a semiquantitative analysis of the min-
eral composition of the soils in this study determined by x-ray
and compared with our new method. The results indicate that
the quantity of gypsum determined by the x-ray method differs
from the value determined using our new method. This is not
unexpected and reasonably typical of semiquantitative analysis
using x-ray diffraction.
Considerations for the Determination of Gypsum
Content in Soils
Data reported in the literature show that, when heated
at 105°C, the gypsum crystal loses between 13 and 19% of its
mass (Artieda et al., 2006) instead of the 20.91% correspond-
ing to the two water molecules. There are some discrepancies
in the literature as to when exactly gypsum loses the two water
molecules; as mentioned above, the Nelson method is based
on total water loss at 105°C when heated for 24 h, but Lide
(1993) reported that total loss occurs at 163°C. The difference
between the two temperatures can be reconciled if we consider
that dehydration of gypsum is a kinetic process (Molony and
Ridge, 1968; Fatu, 2001; Robertson and Bish, 2007). Most of
the gypsum dehydration studies in the literature used Raman
infrared spectroscopy (Razouk et al., 1960; Putnis et al., 1990;
Sarma et al., 1998; Prasad et al., 2001; Chio et al., 2004), neu-
tron diffraction data (Atoji and Rundle, 1958), or x-ray dif-
fraction (Molony and Ridge, 1968; Cole and Lancucki, 1974),
but to follow the release of the water molecules from the crystal,
they have used fast heating devices (5 or 10 K min−1) (Prasad et
al., 2001; Chio et al., 2004; Sarma et al., 1998). Consequently
the temperature at which they found total loss of water is
around 163°C, since fast heating does not allow time for the
water to diffuse through the crystal.
In addition, the RH is also important. During oven drying,
the RH is generally close to 100% but when the RH is altered,
dehydration is affected. Robertson and Bish (2007) reported
total dehydration of gypsum after 5.6 h when the sample was
heated at 85°C in 17.6% RH, but it took 50 h to lose the
water at the same temperature with the RH at 47%. This may
have important environmental implications for mineral phase
changes in natural samples in arid regions where soil surface
temperatures may reach in excess of 70°C with RH values as
low as 10 to 15%.
The soils literature provides a spectrum of possible water
loss percentages, besides the theoretical 20.91%, when gypsum
is oven dried. As a consequence, the gypsum literature has ad-
opted the term recovery factor, defined in Burns et al. (2002),
to account for the discrepancy between the experimental water
loss at 105°C and the total theoretical water loss (20.91%). In
reality, the recovery factor is a practical solution to overcome
the fact that 105°C is an arbitrary temperature and we do not
know exactly how much gypsum water is lost at this tempera-
ture, especially because initial RH values change from labo-
ratory to laboratory. The fact that different researchers have
found such different numbers for the recovery factor, however,
also suggests inconsistencies in laboratory procedures.
In our view, this inconsistency is due to the handling of
the samples after they are removed from the oven and the use
of desiccators. As shown in Fig. 2, the anhydrite, once removed
SSSAJ: Volume 73: Number 2 • March–April 2009
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


Fig. 5. (A) Scanning electron micrograph of the crystalline gypsum
in the Moab soil using a back-scatter detector, and (B) detail of the
gypsum crystals.
water is retained at the clay surfaces. At 12% RH, the humid-
ity in the desiccator with drierite resulted in the Ca- and Mg-
montmorillonite having 10% water content. When multiplied
by a recovery factor, this translates into an error of 38 to 52%,
depending on the recovery factor used (19–14%).
The results from the Nelson method are also presented in
Table 2 for the soils and can be compared to our new bassanite
method. The values using the Nelson method are similar to the
Fig. 6. X-ray diffractogram for the Moab soil, the 12- to 20-cm SR1
soil sample, and the 1- to 10-cm SR2 soil sample.
410
Table 4. Percentage of water, related to the oven-dry state,
remaining in clays at 12% relative humidity (RH). Loss of
water while performing the Nelson et al. (1978) method
translates to erroneous gypsum content.
Water content at Error in gypsum content
Clay
12% RH using Nelson method
———————— % ————————
Kaolinite 0.44 ± 0.04 2.28 ± 0.23
Illite 0.7 ± 0.26 3.61 ± 1.36
Na-bentonite 0.84 ± 0.40 4.33 ± 2.04
Sand 0.12 ± 0.09 0.6 ± 0.46
Ca-montmorillonite 6.24 ± 0.38 32.13 ± 1.98
Mg-montmorillonite 7.3 ± 1.07 37.61 ± 5.52
ones calculated with our method but consistently higher. The
mineralogy for these soils was predominantly quartz sand and
silt, and consequently not much water was retained; however,
we observe that the change in mass for the sandy soil was sig-
nificant enough to estimate a 4% gypsum content using the
Nelson method. The chemical analysis in Table 1 confirms the
absence of gypsum in the sample. As a result, the new method
exploiting the bassanite stability is an appreciable improvement
Fig. 7. (A) Differences between the real gypsum content and the
gypsum content calculated using the Nelson et al. (1978) method and
the bassanite method. The samples were mixtures of gypsum reagent
and different clay minerals. All values are related to oven-dry weight;
and (B) the effect of the saturating clay cation on the differences
between gypsum contents calculated using the Nelson method and
the real gypsum content.
SSSAJ: Volume 73: Number 2 • March–April 2009
over prior methods and may help to reduce the likelihood of
the misclassification of soils.
CONCLUSIONS
We have developed an improved, simple, and accurate
method to determine gypsum content in soils. This method
considers the differences in water content between gypsum
and bassanite after the samples have been heated in an oven at
105°C. To achieve equilibrium with bassanite and to keep the
clay water content constant, we equilibrated the soil samples
at the same RH before and after oven drying the samples. The
use of the desiccator with a fixed RH after oven drying allowed
us to accomplish two objectives: to reach equilibrium with bas-
sanite, and to return the clays to the same water content as
before oven drying. Given Mg-saturated smectitic soils or soils
exhibiting possible hysteresis, we recommend a more involved
method requiring two equilibration steps after oven drying.
This extra step is to ensure that the sample always hydrates fol-
lowing the same portion of the wetting curve. By standardizing
the initial and final weights of our samples, we minimized the
major sources of error found with other weight loss methods.
Our new method, in the absence of hydrated salts, consistently
estimated the actual quantity of gypsum in the sample to better
than 1% regardless of the clay mineralogy present.
ACKNOWLEDGMENTS
We wish to express our thanks to colleagues at Stanford University,
Scott Fendorf and Rosemary Knight, for their help and support in
conducting this research, and to Scott Jones at Utah State Univ. J.
Herrero thanks the Spanish Government for the grants AGL2006-
01283/AGR and PR2007/0453.
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Reproduced with permission of the copyright owner. Further reproduction prohibited without permission.
 Published November, 1994
Gypsum Determination in Soils by Conversion to Water-Soluble Sodium Sulfate
M. S. Berigari* and F. M. S. Al-Any
ABSTRACT
Precise and accurate determination of gypsum in soils has been
difficult by the wet-chemical methods, based on its solubility in water.
In this work, 2-g samples of three Typic Gypsiorthids were washed
once with 25-mL portions of 50% (v/v) ethanol to selectively remove
nongypsic soluble sulfates. Soil gypsum was subsequently converted
to CaCO.i(s) and Na2SO4 by ultrasonic dispersion of the samples twice
with 25-mL increments of 0.5 M Na2CO3 solution. The SoV in the
supernatant solution was centrifuge separated and analyzed by the
standard gravimetric BaSO4 (A) and turbidimetric (B) methods to
obtain the gypsum content of the samples. The agreement between
the data of Methods A and B was excellent where the best-fitted
regression line coincided with the 1:1 line in a scattergram. Soil gypsum
was also extracted with water, then determined by turbidimetric
SO|" (C) and the Bower-Huss conductometric (D) methods for com-
parison. Statistical analyses of the data showed higher values (P =
0.05) of gypsum in soils obtained by the proposed method than by
water extraction even when the same method of SO|" analysis was
applied. The efficiency of the proposed method was 25 to 31 times
greater than that achieved by water. The proposed method of gypsum
extraction and its determination in soils from turbidimetric SO|~
analysis is simple, rapid, and quite accurate for soil taxonomy, land
reclamation, and other engineering purposes.
G YPSIFEROUS SOILS are widespread in arid and semi-
arid regions. Complete extraction and accurate
measurement of gypsum in soils are often needed for
taxonomic and land reclamation purposes. Numerous
methods are available that vary in accuracy, precision,
sensitivity and speed of analysis. Skarie et al. (1987)
pointed out limitations of physical and wet-chemical
methods being used for gypsum determination in soils.
The wet-chemical methods use water with or without
electrolytes to extract gypsum from soils followed by
analysis of SO2.- or Ca2+ in the extract. In each case a
correction is applied for nongypsic SO2." or Ca2+ for
more reliable computation of the extracted gypsum. How-
ever, gypsum determination from Ca2+ analysis was
criticized because the Ca2+ derived from gypsum dissolu-
tion is subject to loss on the soil exchange complex,
causing low recovery of gypsum from the samples (Skarie
et al., 1987). The SO2." is relatively free from such
problems and can be measured accurately in soil water
extracts by several methods (Johnson and Nishita, 1952;
Nelson, 1982; Greenberg et al., 1985; Skarie et al.,
1987). Precise and accurate determination of gypsum
in soils, however, is hindered mainly by incomplete
extraction of this mineral with water (Bower and Huss,
1948; Nelson et al., 1978) rather than by the accuracy
of SO2." or Ca2+ analysis. This may be true even when
the time-consuming trial and error method of Nelson
M.S. Berigari, 11449 S. St. Louis, Ave., Chicago, IL 60655; and F.M.S.
Al-Any, Talib M. Sa'id & Brothers Co., Jordan Square, Baghdad, Iraq.
Received 4 Dec. 1989. "Corresponding author.
Published in Soil Sci. Soc. Am. J. 58:1624-1627 (1994).
1624
(1982) is used to select a water/soil ratio that provides
a gypsum concentration of 5 mM.
In this study, nongypsic soluble sulfates were selec-
tively removed with 50% ethanol from soil samples,
causing essentially no loss in gypsum. Gypsum was
subsequently converted to water-soluble sulfates using
Na2COa plus Bonification and was determined from
SO2." analysis by two well-known methods. For compari-
son, gypsum was also extracted from the samples with
water and determined by the Bower-Huss (1948) method
and from turbidimetric SO2.- analysis of the extract.
THEORY
The problem of incomplete gypsum extraction from soils
by water is 5associated mainly with its low solubility, K^ =
2.44 X 10~ (Nakayama, 1971). The solubility of CaCO3(s)
in water is much lower, Ksp = 5.03 x 10'9 (Nakayama, 1971),
yet both
2
minerals can 3coexist when the activity ratio (SO2.")/
(CO ") > 4.85 x 10 based on the given Ksp(s). However,
through the common ion effect it should be possible to convert
all soil gypsum to CaCO3(s) in the presence of excess COi"
in soil solution as follows:
CaCO3 (s) = Ca2+ + CO2" [1]
2+ 9
Ksp = (Ca ) (CO?-) = 5.03 x 10- at25°C
CaSO4-2H2O(s) = Ca2+ + SO2,- + 2H2O
2+ 2 5
[2]
£sp = (Ca ) (SO -) = 2,44 x 10- at25°C
When a water-soluble carbonate salt such as Na2CO3 is
added in excess to the above system the (CO2") in solution
increases instantly causing a shift in Reaction [1] to the left,
thus reducing the (Ca 2 +) through CaCO2+3(s) precipitation until
its Ksf is attained. This reduction in (Ca ) will drive Reaction
[2] to the right, causing dissolution of gypsum. The net effect
is total conversion of gypsum Ca2+ to CaCO3(s), leaving behind
the SOi" in solution. Since the prevalent charge on soil colloids
of temperate regions is negative, the SO2." retention by soil
constituents can be negligible at soil pH > 6.0 (Kamprath et
al., 1956; Williams and Steinbergs, 1962) due to the prevalence
of anion exclusion phenomena in such systems (de Haan and
Bolt, 1963).
Theoretically one equilibration of a soil sample with an
excess quantity of Na2CO3 hi solution should suffice to convert
all the gypsum in the sample to2 an equivalent quantity of
CaCO3(s). This will leave the SO ." in solution, which can be
separated from the solid phase and analyzed by an appropriate
method. In actual practice, however, the extraction2 step should
be carried out at least twice to remove the SO .- from the
interstitial solution of the first equilibration; its recovery can
be hastened by sonification.
The efficiency of the proposed method of gypsum extraction
relative to that obtained by water can be calculated from the
quantity of gypsum extracted per unit weight of soil per unit
volume of the extract by each method.
MATERIALS AND METHODS
Samples from three Typic Gypsiorthid soils from Al-Door
Experimental Station (150 km north of Baghdad, Iraq) were
 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.