Clays and Clay Minerals, Vol.

35, No, 6, 463-468, 1987,

QUANTITATIVE DETERMINATION OF CLINOPTILOLITE IN

SOILS BY A CATION-EXCHANGE CAPACITY METHOD

DOUGLAS W. MING 1 AND JOE B. DIXON

Department of Soil and Crop Sciences, Texas A&M University
College Station, Texas 77843

Abstract-A cation-exchange capacity (CEC) method based on ion-sieving properties was developed for
the quantitative determination of clinoptilolite in soils. In this method, both zeolitic and non-zeolitic
exchange sites in the soil sample are saturated with Na- . The CEC of the non-zeolitic exchange sites is
determined by replacing the Na- in these sites with tert-butylammonium ions. The tert-butylammonium
ion cannot be exchanged into the zeoli tic exchange sites because it is too large to pass through the channels
in the clinoptilolite structure, The sample is next washed with NH 4 0Ac to replace the Na+ in the zeolitic
exchange sites. The amount of soil zeolite is then estimated by comparing the CEC of zeoli tic exchange
sites to the total zeolite CEC (175 meq/l00 g for pure clinoptilolite). Prior to the CEC analyses, carbonates
and organic matter must be removed to minimize interference with the exchange process. A high cor-
relation (r2 = .96) was observed between the abundance of clinoptilolite estimated using the CEC method
and the abundance estimated by semiquantitative X-ray powder diffraction analysis.
The CEC procedure was used to quantify clinoptilolite in an Aridic Calciustoll soil from south Texas.
About 2-5% c1inoptilolite occurs in the A and B horizons, and concentrations progressively increase with
soil depth to as much as 20% in the CBk2 horizon.
Key Words-Cation-exchange capacity, Clinoptilolite, Quantitative mineralogy, Smectite, Soil, Tert-
butylammonium, Zeolite.

INTRODUCTION The zeolite of primary interest in this study is cli-

Few procedures deal with the direct quantitative de- noptilolite, which is widespread in soils derived from
termination of minerals in soils and sediments, pri- the Oligocene Catahoula Formation of southern Texas
marily due to the heterogeneity of the system and the (Ming and Dixon, 1986). Most of the clinoptilolite-
time required to conduct such analyses. Most quanti- bearing soils are Mollisols that contain calcite. To aid
tative mineralogy is accomplished by X-ray powder in determining the distribution and stability of the zeo-
diffraction (XRD) methods. XRD procedures are pro- lite in soils, a rapid, quantitative method of determin-
tracted if the analysis of each soil separate (i.e., sand, ing the amount of clinoptilolite in un fractionated soils
silt, clay fractions) must be made to minimize the ef- was developed.
fects of particle size on crystal orientation. Also, it
becomes difficult to establish an accurate estimate of THEORY
the mineral in question in the whole soil sample. Thus, Zeolites are crystalline, hydrated aluminosilicates of
a procedure that quantifies a mineral directly on a alkali and alkaline earth cations that possess a three-
whole-soil basis would vastly improve the accuracy of dimensional structure (i.e., tektosilicates). The nega-
the estimate and probably save time. tive charge created where AP+ replaces Si 4 + in the struc-
The occurrence of natural zeolites in soils is not well tural tetrahedra is counterbalanced by cations (e.g., Na+,
known and has only recently gained the attention of K+, and Cal+, Mg2+). These charge sites are located in
soil scientists. Therefore, very little has been done to large structural channels and cavities throughout the
quantify these minerals in soils. Of the more than 40 structure and will be referred to as zeolitic exchange
natural zeolite species, clinoptilolite, [(Na,K)6_2xCaxl' sites throughout this paper. Small ions and molecules
(AI 6 Si 300 n ), 24H 2 0, seems to be the most abundant can pass through these channels, but large ions and
zeolite in soils and sediments (Ming and Mumpton, molecules are excluded. This ion selectivity, based on
1987). Clinoptilolite has been reported in slightly acid size, is known as ion sieving. Zeolites have high cation-
to strongly alkaline soils (Ming and Dixon, 1986; Speirs exchange capacities (CEC) (100-300 meq/ 100 g), de-
etal., 1984; Jacob, 1984; Graham and Southard, 1983; pending on the amount of AP+ that replaces Si 4 + in the
Fanning et aI., 1983; Southard and Kolesar, 1978; As- structure. The procedure for quantifying clinoptilolite
vadurov et aI., 1978; Travnikova et a/., 1973; Gor- has been developed on the basis of the ion-sieving
bunov and Bobrovitskiy, 1973). properties and high CEC of this zeolite.
In clinoptilolite, 10- and 8-ring channels parallel the
I Present address: Mail Code SN 12, NASA Johnson Space c-axis of the structure and have free dimensions of
Center, Houston. Texas 77058. 4.4 x 7.2 A and 4.1 x 4.7 A, respectively. A third 8-
Copyright·j: 1987, The Clay Minerals Society 463
464 Ming and Dixon Clays and Clay Minerals

Table I. Selected chemical and physical characteristics of the Aridic Calciustoll soil locality.
CaCO , Sand Coarse silt Fine and medium silt Clay
Depth eq. (2.0--0.05 mm) (O.05-D.02 mm) (O.02-D.002 mm) «0.002 mm)
Horizon (em) (%) (%) (%) (%) (%)

A 0-25 9 47 16 7 30
Bk1 25-38 17 34 14 16 36
Bk2 38-66 24 40 26 23 II
BCk 66-89 24 31 21 18 30
CBkl 89-1 04 24 46 18 20 16
CBk2 104-137 19 49 14 18 19
Soil constituents expressed as weight percentage of soil.

ring-channel system parallels the a-axis and has free exchange sites and is preferred over Na+ by the zeolite
dimensions of 4.0 x 5.5 A. Small hydrated cations so it readily replaces Na+ (Ames, 1960). The Na+-NH4 +
(e.g., Na+, Ca2 ~, K+) can easily enter the channels of exchange reaction in the system is expressed as follows:
clinoptilolite and compete for exchange sites; however,
2 NH4 T+ (CH 3hCNH 3-clay + Na-zeolite
large organic cations (e.g., tetramethylammonium and
= NaT + (CH3)3CNH3 + + NH4-clay + NH 4-zeolite.
tert-butylammonium ions) are excluded from the
(3)
channel system by ion sieving (Barrer et al., 1967).
Thus, all of the exchange sites of both the zeolite and MATERIALS AND METHODS
non-zeolite minerals may be saturated with Na+, the
A soil pedon known to contain as much as 20%
Na+in non-zeolitic exchange sites may then be replaced
clinoptilolite was selected for this study. This Aridic
by tert-butylammonium ions, and the zeolite CEC may
Calciustoll (Houla series) was derived from the zeoli tic
be determined by replacing the Na- in the zeoli tic ex-
tuffaceous sediments of the Catahou1a Formation in
change sites with NH4 +. These three steps and the re-
eastern Webb County, Texas. Morphological descrip-
actions involved are explained below.
tions for the Houla soil were reported by Ming (1985).
Step 1. Initially, all exchange sites in the soil are sat- Particle-size data and calcium carbonate equivalent
urated with Na\ which readily enters the zeoli tic chan- values of a typical Houla soil are presented in Table
nels. Clinoptilolite shows a selectivity for certain cat- 1. Air-died samples from each horizon were passed
ions (Ames, 1960), but this problem can be corrected through a 2-mm mesh sieve and treated with 1 N
by determining the Na-CEC of the clinoptilolite. Smec- NaOAc buffered to pH 5, 30% H2 0 2 , and dithionite-
tite-clinoptilolite-feldspar-quartz-calcite mineral as- citrate-bicarbonate to remove free carbonates, organic
semblages dominate the soils derived from the Cata- matter, and free iron oxides, respectively (Jackson,
houla Formation in southern Texas, so most of the 1974) . Samples of the soil horizons were size fraction-
non-zeolitic exchange capacity will be contributed by ated by conventional sieving and sedimentation meth-
smectite. The smectite exchange sites should readily ods (Jackson, 1974). All soil samples (i.e., soil separates
saturate with NaT. The overall reaction for step 1 is and un fractionated, chemically dispersed soil) were
therefore: freeze-dried and placed in a desiccator containing
Drierite for storage free from atmospheric H 20.
2 Na+ + X 'h -clay + X'h-zeolite
= Na-clay + Na-zeolite + X2+, (1)
Zeolite estimation by X-ray powder diffraction
where X = Ca 2+, Mg2+, etc.
Mixtures containing known amounts of sand (2.0-
Step 2. Na+ is replaced from non-zeolitic exchange sites 0.05 mm) and silt (0.05-0.002 mm), approximating
(i.e., smectitic exchange sites) by tert-butylammonium the soil ma trices, were prepared using a highly crys-
ions; the Na+, however, will remain at the zeoli tic ex- talline clinoptilolite purified from the CBk2 horizon of
change sites. Exchange ofNa+ bythe large organic mol- the soil described above (Ming and Dixon, 1987a) and
ecule On non-zeolitic sites is faci litated by heating the varying amounts of quartz and feldspar. A uniform
sample at 60°C during the exchange reaction. The Na- weight percentage of crystalline Al 2 0 3 was added to
replacement by tert-butylammonium ions can be ex- each of the standard mixtures and unknowns as an
pressed as follows: internal standard. Standards and unknowns were thor-
oughly mixed by wet grinding in acetone. Powdered
(CH3)3CNH3 + + Na-clay + Na-zeolite
samples were then pressed into a depression on a glass
= Na+ + (CH 3h CNH 3-clay + Na-zeolite. (2)
slide for X-ray powder diffraction (XRD) analysis. A
Step 3. The final step involves the replacement of the scan rate of 11z°28/ min was utilized to record the 9.01-
Na+ from the zeolitic exchange sites by NH4 The +. A peak (020) of ciinoptilolite and the 2.55-A peak (104)
NH4 +ion is small enough to gain access to the zeoli tic of Al z0 3. Regression equations were calculated (r 2 =
Vol. 35, No.6, 1987 Quantitative determination of clinoptilolite in soils 465

Table 2. Cation-exchange capacities (CEC) determined for exchangeable Na+ was removed by adding 30 ml of 0.5
mixtures of a purified clinoptilolite and a standard smectite. N tert-butylammonium chloride, (CH3)3CNH3Cl, and
CEC (meq!l 00 g)' heating the suspension at 60°C for 24 hr to enhance
Mixtures' Na-TBA Na"-NH4- Total the exchange of Na+ by (CH3)3CNH3 +. Following the
heating process, samples were washed two more times
100% Cp 10 165 175
75% Cp + 25% S 23 124 147 with 0.5 N (CH3)3CNH3CL Tert-butylammonium
50%Cp + 50% S 38 79 117 chloride washings were decanted into 100-ml volu-
25% Cp + 75% S 53 40 93 metric flasks and saved for analysis of the Na+ con-
100% S 67 0 67 tributed by the non-zeolitic CEC. Excess (CH 3hCNH 3Cl
I Cp = c!inoptilolite; S = smectite. Clinoptilolite purified
was removed by washing the sample once with ethanol
from soil pedon developed on Catahoula Formation. Smec- (95%). Na- on zeolitic exchange sites was removed by
tite = montmorillonite, Texas. washing the sample three times with 1.0 N NH 4 0Ac.
2 Na+-TBA = Na' replaced by tert-butylammonium (TBA);
The NH 40Ac washings were decanted into I OO-ml vol-
Na+-NH. = Na+ replaced by NH 4 -; Total = sum of Na+-
umetric flasks and saved for analysis of the Na+ from
TBA and Na+-NH4+.
the zeoli tic CEC. Samples were analyzed in duplicate
and dispersed by ultrasonification during each washing
.99 for both fractions) and used to estimate the per- step. Na~ was determined with a Perkin-Elmer 603
centages of zeolite from the XRD peak-height ratios atomic adsorption spectrophotometer. The Na-CECs
of the zeolite to the Al 2 0 3 internal standard for un- for the zeoli tic and non-zeolitic phases are expressed
known samples. as meq/l 00 g based on the freeze-dried weight of the
Clay standards were prepared from < 2-J.Lm clinop- samples.
tilolite (purified from the soil and ground to size) and Standards were prepared to test the CEC procedure
Mg-montmorillonite (SMt5, Source Clays Repository by preparing mixtures composed of 100, 75, 50, 25,
of The Clay Minerals Society). Clay samples (Mg-sat- and 0 wt. % clinoptilolite that had been purified pre-
urated) from the soil and the standard mixtures were viously from the CBk2 horizon (Ming and Dixon,
mixed with acetone and smeared on glass slides. A scan 1987a) and corresponding smectite (montmorillonite
speed of th020/min was used to record the 14-15-A from Gonzales, Texas) quantities of 0, 25, 50, 75, and
peak of smectite and the 9.01-A peak ofclinoptilolite. 100%, respectively. The CEC procedure described
A regression equation (r2 = .99) was then derived by above was duplicated for 0.25 g of each standard mix-
comparing the peak area of the zeolite to that of the ture. Based on the CEC values obtained from the stan-
smectite. Peak areas were estimated with a Lasico mod- dard mixtures (see Table 2), the following equation was
el 40 planimeter. A Philips X-ray diffractometer with developed to quantify the zeolite as a weight percent-
monochromatic CuKa radiation was used for XRD age:
analysis.
% clinoptilolite = [CEC (Na+ - NH4+)/165] x 100
Preparation of tert-butylammonium chloride
RESULTS AND DISCUSSION
Tert-butylammonium chloride for this study was
synthesized by a procedure analogous to that employed Quantification of standards
by Ruehlicke and Kohler (1981) for preparing n-al- It is important initially to establish the Na-exchange
kylammonium chlorides. Starting materials for the capacity of the clinoptilolite indigenous to the soil be-
synthesis of the tert-butylammonium chloride were fore obtaining quantitative CEC values that accurately
equal volumes of tert-butylamine (98%) and ethanol reflect the amount of that zeolite in samples of that
(95%). The only variation from Ruehlicke and Kohler's soil. Clinoptilolite in natural environments may have
procedure was to freeze dry the crystalline powder after several cations on the exchange sites, however, the
synthesis, thereby removing any excess acetone, eth- dominant cations are Na+, K+, and Ca2 +. Clinoptilolite
anol, or water. exhibits cation selectivity; e.g., Ca2+ is easily replaced
by NaT, but K - in the zeolite is replaced with difficulty
Clinoptilolite estimation by CEC procedures by either Ca 2 + or Na~ (Ames, 1960). The degree ofNa-
For this study, 2.5, 1.0, 1.0, 0.5, and 0.1 g of freeze- saturation on the zeoli tic exchange sites in step 1 of
dried, chemically treated whole soil and sand-, coarse the procedure described above (see Eq. (I» depends
silt-, fine and medium silt-, and clay-size fractions of on the original amount of K + on the zeolitic exchange
the soil, respectively, were added to 40-ml centrifuge sites. Therefore, to avoid problems caused by cation
tubes. Samples were then washed four times with 1 N selectivity, the CEC (Na+ - NH4 +) was determined for
NaOAc buffered to pH 5 to ensure complete Na-sat- the clinoptilolite that had been separated from the soil.
uration of exchange sites. Excess Na+ (interstitial) was NH 4 +, like K+, is highly selective on the zeolitic ex-
removed by one washing with distilled deionized H 20 change sites and readily replaces Na+.
and three washings with ethanol (95%). Non-zeolitic For this stUdy, the measured CEC (Na+ - NH4 +) of
466 Ming and Dixon Clays and Clay Minerals

Table 3. Comparison of clinoptilolite content determined by X-ray powder diffraction (XRD) and cation-exchange capacity
(CEC) methods in soil separates.
Clinoptiioiite content (%)
Sand Coarse silt Fine and medium silt Clay
(2.0-0.05 mm) (0.05-D.02 mm) (0.02-D.002 mm) «0,002 mm)
Horizon CEC XRD CEC XRD CEC XRD CEC XRD

A 1 0 2 3 (1) 20 29 (8) 1 2 (1)

Bkl 1 0 2 4 (2) 9 17 (6) I I (1)
Bk2 2 3 (1) 4 7 (4) 6 12 (6) 1 2 (I)
BCk 6 10 (4) 8 14 (3) 21 38 (4) 1 2 (I)
CBkl 12 14 (6) 24 33 (8) 28 33 (5) 2 4 (1)
CBk2 12 16 (5) 24 30 (9) 45 47 (8) 2 3 (1)

Numbers in parenthesis represent a 95% confidence interval (n = 4) for semiquantitative XRD data only. CEC quantitative
numbers are average of 2 determinations (n = 2).

the soil clinoptilolite was about 175 meq/100 g, slightly Alexiades and Jackson (1965) because the CEC of the
lower than the theoretical CEC of clinoptilolite of200- zeolite is extremely large. In developing this zeolite
220 meq/100 g (Ming and Mumpton, 1987). Ca 2 + and quantification procedure, the only mineral other than
Na+ account for more than 95% of the cations on the clinoptilolite contributing to the CEC of the soil is
zeoli tic exchange sites in the soil (Ming and Dixon, assumed to be smectite. Vermiculite was excluded be-
1986). Ca2+ is the dominant cation on the exchange cause it rarely occurs with clinoptilolite and was not
sites, reflecting high concentrations of Ca 2 + in the soil found with the zeolite in the present study.
solution due to the calcareous nature of these soils. It
is unlikely that the lower CEC measured for clinoptil- Quantification of soil clinoptilolite
olite isolated from the soil is due to cation selectivity. Initial attempts at determining the amount of cli-
The ion-sieving properties of clinoptilolite are illus- noptilolite in whole soils by the CEC procedure failed.
trated by its exchange of Na" by NH4 + but not by Apparently, calcite in the soil (see Table I) dissolved
(CH3)3CNH3 + (Table 2). The amount of Na~ replaced in the (CH 3hCNH 3Cl solution, and released Ca 2 + re-
by (CH3)3CNH3 + for the monomineralic clinoptilolite placed Na+ at the zeolitic exchange sites. Calcite, there-
standard was 10 meq/l 00 g, indicating that a few of fore, was dissolved prior to the CEC procedure by 1
the charged sites of clinoptilolite are accessible to the N NaOAc buffered to pH 5.
large organic ion or that a small amount of undetected Organic matter and free iron oxides were also re-
smectite was present in the purified standard. Most of moved from the soil to enhance particle-size fraction-
this charge probably arises from external surface sites ation. Destroying the organic matter also eliminated
(i.e., non-channel sites) and half-cage sites, which are any cation-exchange capacity that it might have con-
zeolitic exchange sites near the aperture of a channel tributed; however, the CEC procedure will probably
where the (CH3)3CNH3+ has partial access to remove quantify the'amount of zeolite even in the presence of
the Na+ from that site. The particle size of the zeolite organic matter because most of the Na+ on charged
may have an effect on the amount of charge contributed sites of the organic matter will be replaced by
by half-cage and external surface sites, but this effect (CH 3 hCNH 3~. Chemical treatments caused no struc-
was not detected for the clinoptilolite used in the pres- tural change or damage to clinoptilolite (Ming and Dix-
ent study. Although the charge apparently contributed on, 1987a) and, in fact, aided its identification in soils
by external surface and half-cage sites was low, a cor- and sediments by XRD analysis. The only major effect
rection factor was used to determine the amount of of the chemical treatments was a change in the type of
zeolite (see Eq. (4». The zeolite CEC corrected for ex- cation on zeolitic exchange sites.
ternal surface and half-cage sites was 165 meq/l00 g A comparison of clinoptilolite determinations in soil
(i.e., (175 meq/100 g) - (10 meq/lOO g». The correc- separates by XRD and the CEC procedure is presented
tion permitted a more accurate calculation of the in Table 3. The results show similar trends in zeolite
amount of clinoptilolite in the standards (r2 = .99). concentrations with depth for both methods. A high
Actual zeolite percentages of 0, 25, 50, 75, and 100 correlation exists between the two procedures (r2 =
were calculated to be 0, 24, 48, 75, and 100, respec- .96).
tively, by inserting the CEC measured in step 3 of the The amount of clinoptilolite in whole soils can be
procedure into Eq. (4). estimated from XRD analysis by summing the zeolite
In a soil system containing as much as 20% of cli- fraction for each soil separate; however, particle-size
noptilolite in the clay fraction, smectite cannot be distribution (PSD) data are required. A primary ob-
quantified using the conventional CEC procedure of jective for developing this CEC procedure is to elim-
Vol. 35, No.6, 1987 Quantitative determination of clinoptilolite in soils 467

Table 4. Clinoptilolite content determined by X-ray powder noptilolite. Therefore, in developing this CEC quan-
diffraction (XRD) and cation-exchange capacity (CEq meth- tification procedure, only smectite and clinoptilolite
ods in carbonate-free and carbonate-containing soils.
were assumed to have charged sites. The presence of
Ciinoptilolile other charged materials (e.g., volcanic glass, opal-CT,
Clinoptilolite Clinoptilolite in carbonate-
Horizon by XRD' by CEC' containing 50i1s 3 vermiculite) may, however, introduce error into the
A 3 (1)4 procedure. Possibly, the large tert-butylammonium ion
3 3
Bkl 4 (1) 2 2 may not completely penetrate all of these non-zeolitic
Bk2 6 (3) 3 2 phases, thereby producing an overestimation of zeolite
BCk 13 (3) 9 7 abundance.
CBkl 19 (5) 15 II Each of the > 40 zeolites that occur in nature has a
CBk2 21 (5) 20 16
unique crystal structure, ion-sieving properties, cation
I Zeolite contents calculated from carbonate-free fractions selectivities, and cation-exchange capacity. The CEC
(Table 1) and zeolite contents for soil separates (Table 3). procedure reported here is strictly intended for quan-
2 Zeolite contents on carbonate-free soil determined by CEC
tifying clinoptilolite; the presence of another zeolite
procedure.
3 Zeolite percentages have been rounded to the nearest whole
will complicate the exchange reactions; however, cli-
number. noptilolite generally does not coexist with another zeo-
4 Numbers in parenthesis represent a 95% confidence in- lite in soils (Ming and Mumpton, 1986; Ming and Dix-
terval (n = 4) for semiquantitative XRD data only. CEC on, 1986c).
quantitative values are average of 2 determinations (n = 2).
CONCLUSIONS
inate the time-consuming particle-size fractionation In the last decade, zeolites have been found with
procedure and XRD analysis of each soil separate. Good increasing regularity in soils. Clinoptilolite, the most
agreement between the clinoptilolite content estimated abundant zeolite in soils and sediments, is one of the
by the CEC procedure and by XRD of the size fractions highest charged minerals occurring in soils and where
suggests that the particle size of c1inoptilolite had little it is present complicates the interpretation of soil CECs.
effect on the results of the CEC quantification proce- The CEC quantification procedure developed in this
dures (see Table 4). The size of the individual crystals study differentiates between the charge contributed by
of clinoptilolite in these soils is 2 to 20 /-Lm (Ming and clinoptilolite and that contributed by other charged
Dixon, 1986). Sand- and coarse silt-size zeolite par- materials, chiefly smectite. Because of clinoptilolite's
ticles consist of aggregates of individual crystals, agronomic importance (see Pond and Mumpton, 1984),
whereas, only fragments of crystals are in the clay frac- the abundance of this zeolite in soils should be deter-
tions. The clay-size fragments probably resulted from mined. The CEC procedure reported here will aid in
mechanical breaking. Therefore, zeolite crystals in the that determination .
soils examined are relatively uniform in size regardless
of the fraction in which they occur; therefore, particle- ACKNOWLEDGMENTS
size per se has little effect on the CEC quantification This research is a contribution from the Texas Ag-
procedure. ricultural Experiment Station as journal series number
About 2-5% clinoptilolite was found in the A and 21348 . We are indebted to L. L. Ames, L. R. Hossner,
B horizons of the soil used in the present study, and M. H. Hulbert, F. A. Mumpton, and R. A. Sheppard
concentrations progressively increased with depth to for their critical reviews of this manuscript.
as much as 20% in the CBk2 horizon (Table 4). The
underlying sediments or parent materials also con-
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