F ~
Bioresource Technology 43 (1993) 27-33
N A T U R A L ZEOLITES A N D SEPIOLITE AS A M M O N I U M A N D
A M M O N I A A D S O R B E N T MATERIALS
M. E Bernal & J. M. Lopez-Real
Department of Biochemistry and Biological Sciences, Wye College, University of London, Wye,Ashford, Kent TN25 5.411, UK
(Received l0 February 1992; revised version received 5 March 1992; accepted 7 March 1992)
Abstract
Zeofite clinoptilolite is a natural mineral with ion-
exchange and gas-adsorption properties. Ammonium-
and ammonia-adsorption processes were studied in the
zeolite cfinoptilolite and zeolite-like sepiolite minerals.
Maximum adsorption capacities of both ammonium
and ammonia were determined by fitting the experi-
mental results of the adsorption isotherm to Langmuir
and first-order models. Ammonium-adsorption capaci-
ties of the zeolites were from 8"149 to 15"169 mg N g- i;
up to 16~3 times higher than that of sepiolite. Ammo-
nium-adsorption capacity increased with the surface
charge density of the material, due to the readily avail-
able exchange sites in the surface.
Ammonia-adsorption capacities of the zeolites were
between 6"255 and 14"155 mg N g-i. Because of its large
surface area, sepiolite had a capacity of ammonia
adsorption three times higher than that of the ammo-
nium ion. The complexity of the ammonia-adsorption
process meant that no individual characteristics of the
materials influenced directly the adsorption capacity.
However, ammonia adsorption was enhanced on the
ammonium adsorption in zeolites with relatively low
surface charge density.
Key words: Adsorption isotherm, ammonia, ammo-
nium, Langmuir equation, sepiolite, zeolite clinopti-
lolite.
INTRODUCTION
The applications of natural zeolites include pollution
control, energy conservation, agriculture and aqua-
culture, mining and metallurgy (Mumpton, 1981). All
the applications of natural zeolites make use of one or
more of their physical and chemical properties: ion-
exchange, adsorption and related molecular sieve
properties, dehydration and rehydration, and siliceous
composition. About 39 naturally occurring zeolite
species have been subjected to study.
Bioresource Technology 0960-8524/92/S05.00 1992
Elsevier Science Publishers Ltd, England. Printed in Great
Britain
27
The ion-exchange capacity is basically a function of
the degree of substitution of aluminium for silicon in
the framework structure. The greater the substitution,
the greater the charge deficiency, and the greater the
number of cations required for electrical neutrality. In
practice, however, the ion-exchange depends on other
factors, notably the nature of the cation species (size,
charge, etc.), the temperature, the concentration of the
cation species in solution and the structural charac-
teristics of the zeolite. The cation-exchange equili-
brium between a zeolite and a solution is usually
depicted by an ion-exchange isotherm. Clinop-
tilolite is one of the commenest natural zeolites.
The small amount of aluminium substitution for
silicon in the framework (Si:AI>4) results in
a relatively low ion-exchange capacity. Its cation
selectivity has been reported as: C s > R b >
N H 4 > Ba > Sr > Na > Ca > Fe > AI > Mg > Li (Ames,
1960) and Pb > NH4 > Cu, Cd > Zn, Co > Ni > Hg
(Blanchard et aL, 1984).
Its characteristics in cation-exchange capacity and
cation selectivity have led to its frequent use in waste-
water treatments, mostly for waters with high levels of
ammonium (Hagiwara & Uchida, 1978; Murphy et al.,
1978; Baumann et aL, 1981; Liberti et aL, 1981; Tara-
sevich, 1988); in agriculture and aquaculture (Barba-
rick & Pirela, 1984); and in radioactive-wastewater
treatments (Mercer & Ames, 1978).
Crystalline zeolites are unique adsorbent materials
due to their large central cavities and entry channels.
Most of the surface area is found within the zeolite
structure and represents the inner surface of dehy-
drated channels and cavities. Molecules having dia-
meters small enough to pass through the channels are
readily adsorbed in the dehydrated channels and
central cavities. The unique geometries contained in
zeolitic channels and cavities create selective sorption
properties. Zeolites are active drying agents (Flaningen
& Mumpton, 1981; Dyer, 1988), they have been used
for reducing the odour due to ammonia in agricultural
wastes (Miner, 1984) and in livestock buildings (Koelli-
ker et al., 1980). Due to their channel sizes, they also
have molecular-sieve properties, and they can be used
in the purification of gases (Hayhurst, 1978) and in
catalysis (Chi etal., 1978).
28 M. P. Bernal, J. M. Lopez-Real

Adsorption on crystalline zeolites is usually charac-
terized by Langmuir-type isotherms (Flannigen &
Mumpton, 1981), assuming that the surface upon
which the sorbed molecule sits is of uniform energy
(Dyer, 1988). When the aim is to obtain the maximum
adsorption to compare with other adsorbents, Lang-
muir, Freundlich and first-order kinetics equations are
generally used (Weber et al., 1983; Hunt & Adamsen,
1985; Witter & Kirchmann, 1988).
In this work the ammonium- and ammonia-adsorp-
tion process in zeolite clinoptilolite and in sepiolite
minerals was studied, with the aim of determining their
maximum adsorption capacity. The influence of the
physical and chemical properties of the materials upon
the ammonium- and ammonia-adsorption is also dis-
cussed.
METHODS
Four clinoptilolite zeolites and one sepiolite were used.
Zeolite 1 (ZI) was from S.P. Health & Hygiene Pro-
ducts, and the other three zeolites (Z2, Z3 and Z4)
were provided by Teage Mineral Products. Their main
differences were in cation-exchange capacity, surface
area, and density. The sepiolite sample was from Orera
in Zaragoza (Spain), provided by MYTA. Sepiolite is a
magnesium silicate with low aluminium content. Its
structure includes internal channels which provide
zeolitic properties (Zelazny & Calhoun, 1977).
Although its cation-exchange capacity is lower than
those in zeolites, it has a great surface area which
generates a high adsorption capacity.
Analytical methods
All samples were ground to < 2 mm. Their chemical
analyses are listed in Table 1. The pH values were
determined in 1:5 water and 1N KCI suspensions.
Electrical conductivity was measured in 1:5 water
extract. Water-holding capacity was determined at 1/3
atmosphere in a pressure cell apparatus (Klute, 1986).
A simplified ethylene glycol monoethyl ether proce-
dure was used for determining the specific surface area
(Cihacek & Bremner, 1979). Porosity was calculated
from bulk and particle density values, previously deter-
mined by core method (Blake & Hartge, 1986a) and
pycnometer method (Blake & Hartge, 1986b) respect-
ively. Total nitrogen was determined by a Kjeldahl
method (Bremner, 1965). Ammonium nitrogen was
extracted with 2N KCI, and determined colorimetri-
cally by a salicylate method (Krom, 1980). The ammo-
nium acetate saturation procedure was used for
determining the cation-exchange capacity (Chapman,
1965). Exchangeable cations were analysed from the
ammonium acetate extract; Na and K by flame photo-
metry and Ca and Mg by means of atomic absorption
spectrometry.
Ammonium-adsorption isotherm
Samples of zeolite and sepiolite were extracted with
different solutions of NH4CI + NaCI (total 0-2~) in a
ratio 1:10 g:ml. Isonormal solutions were used in
order to maintain a constant ionic strength in the
sample-solution mixtures. The initial NH4CI concen-
tration in the extracting solution was from 0"001 to
0"160M. Amounts of ammonium adsorbed by the
samples were calculated from the reduction of ammo-
nium in the solution after shaking for 2 h, and centrifu-
gation. A separate study of the ammonium adsorption
by the zeolite against time showed that the ammonium
adsorption was practically complete after 1 h of shak-
ing (Table 2). Significant differences were observed
after 5 h of shaking.
Ammonia-adsorption isotherm
Each dry material (5 g) was placed on a watch glass in a
closed container of known volume (between 10 and 11

Table 1. Characteristics of the materials

Z1 Z2 Z3 Z4 S
pH (H20) 8-15 8.05 7.78 6'79 7"68
pH (KCI) 6'80 6"90 6"65 5"75 7"45
WHC (%) 133"53 132"01 128-89 168"74 170"56
Surface area (m2 g- 1) 175 172 193 214 297
Bulk density (g cm-3) 0.982 0.796 0.858 0.561 0.684
Particle density (g cm- 3) 2,378 2.395 2.353 2.287 2.555
Porosity (%) 58"7 66.77 63.54 75.46 73.22
CEC (me kg- t) 930.29 1016.36 1396.16 1501-30 175.40
SCD" (/~e m- 2) 5.32 5.91 7.23 7.02 0.59
NH4-N (mg kg- l) 107 5 5 72 17
Exchangeable cations
Na (me kg- t) 161.7 161.8 198.5 285-8 1"00
K (me kg- l) 101-4 93.2 539.9 258.0 4.10
Ca (me kg- t) 654.8 630"5 306.6 687.0 69"8
Mg (me kg- ~) 41.6 47.7 10.7 100.7 127.0
aSurface charge density.
Z -- zeolite.
S = sepiolite.
 A m m o n i u m and ammonia in zeofites 29

Table 2. Influence of the extraction time in the ammonium-adsorption isotherm

Extraction time (h)

1 2 3 5 7

NH 4 adsorbed 0.761 b 0.769b 0.781 b 0.840a 0.854a

(mg N/g zeolite)
Analysis of variance
Source DF Sum of square Mean square F

Treatments 4 0.014 83 0.003 71 102"407"**

Residual 5 1.8 x 10 -4 3"62 x 10 -5
Total 9 0-015 01

***Results are significant at the probability level of 0.001. Numbers followed by the same letter are not statistically different at
the probability level of 0"01 according to the DMRT test.

litres) over 48 h with a constant atmosphere of ammo- 7"-" 4.0

~t0
nia. Ammonia concentration in the container was Z
3.5
0"17-15"70 mg N litre -1. The constant atmosphere ~ 3.o
was obtained by several additions of 100 ml of 5N v 2.5
NaOH to a predetermined amount of NH4CI during 2.o
the incubation time. Ammonia adsorbed by the mate- ~ 1.s
rials was determined by KCI extractions, acidified with 1.0
HCi (pH 4) to prevent any ammonia loss during the
-* 0.5
analysis. The Kjeldahl-N method was compared to KCI
I I i I I I I
extracts in one zeolite; the results indicated that all 0.0 0 1 2 3 4 5 6 7
ammonia adsorbed in the zeolite was KCl-extractable Extraction times

(data not shown).
Statistical analyses
Results from both ammonia- and ammonium-adsorp-
tion isotherms were fitted to Langmuir and first-order
kinetic models by non-linear least squares, using SAS
procedures (SAS Institute, 1985). Analysis of variance
and Duncan's multiple range test (DMRT) were used
to compare data obtained from different treatments.
RESULTS AND DISCUSSION
Influence of the zeolite particle size in the ammonium
adsorption
Two different particle sizes of zeolite 1 were tested in
the adsorption of ammonium. One of them was less
than 0.5 mm, and another between 2"0 and 0"5 mm. Six
sequential extractions with a 0"01M NH4CI+0"09M
NaCI solution were carried out (extraction ratio 1:10 g
ml-~). After each individual equilibrium was reached
no statistical differences in the amount of ammonium
adsorbed were observed between the two sizes tested
(Fig. 1 ). The particle sizes used did not have any effect
on the amount of NH4-N adsorbed in the zeolite. This
is logical since, according to Flaningen and Mumpton
( 1981 ), the external surface of the particle accounts for
only about 1% of the total surface area of the zeolite.
For this reason, zeolite and sepiolite samples used in
the following experiments were ground to < 2 mm
only.
Fig. I. |nfluence of the panicle size of the zeolite in the
ammonium adsorption by sequential extractions with
solution NH4CI 0-01N+NaC! 0"09N (O, size <0"5 mm; A,
0"5 < size < 2 mm).
Ammonium-adsorption isotherm
Figure 2 represents the experimental results in the
adsorption isotherm of ammonium, and the curve fitt-
ing for the four zeolites and the sepiolite.
The basic Langmuir equation is usually written in
the form:
n = MbC/( 1 + bC)
where n is the amount adsorbed per unit of adsorbent,
M is the maximum adsorption, b is a constant, and C is
the equilibrium solution concentration.
The first-order function is also an asymptotic growth
curve, and it can be written as:
n= M ( 1 - e -k,)
where n, M and C represent the same factors as in the
Langmuir model, and k is the first-order model con-
stant.
Linearity of the Langmuir model (i.e. C/n plotted
versus C) was not used, because plottingJ~ C) versus C
decreases data variability and always provides a statis-
tically significant correlation coefficient (Harter, 1984).
As Table 3 shows, the Langmuir model fitted the
experimental results better than the first-order model.
30 M. P. Bernal, J. M. Lopez-Real

-I" " 8
T f (b)
z Z

,= 3 0~ 4

,~ 2
e~
2
ZI 1 Z
I

Z 0 I z 0 I I I I I I I

200 400 600 800 1000 1200 0 200 400 600 800 1000 1200 1400 1600

Equilibriurti cone. ( l i i g N 1-1) Equilibrium COILC. ( I n g N 1-1)

,,--, -'" 10
10
I (o) I (4)
z 8 z 8
E
6 6

o. 4 4

z 2 Z 2
I I
i
z 0 I I I I I I I
Z 0 I I I I I I I

200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400
-l
Equilibriutn uollt:. ( l l l ~ N l ) Equilibrium cone. (ntg N I-l)

1.4
I (e)
Z. 1.2
f
~ 1.o
'~ 0.8

~ 0.6

~ 0.4

L 0.2

Z 0.0 I I I I I

0 200 400 600 800 I000

Equilibrium conc. (mg N 1-1)

Fig. 2. Experimental results (o) and Langmuir curve fitting ( - - ) of the ammonium adsorption isotherm in zeolite 1, 2, 3, 4
and sepiolite (a, b, c, d and e, respectively).

Although, according to the values of R 2 all the equa- The maximum adsorption of NH4-N was between
tions were significant at the 0.001 probability level in 8.149 and 15.169 mg N g-l for zeolite, and 1.470 mg
both models, the lowest values of the standard error of N g- l for sepiolite. Although sepiolite had the greatest
estimate were obtained with the Langmuir equation. In surface area its capacity to adsorb ammonium was very
the first-order model the maximum adsorption was low, relating to its cation-exchange capacity. Zeolite
underestimated by 19"27- 31%. was up to 10.3 times more effective in NH4-N adsorp-
The maximum ammonium adsorptions calculated tion than sepiolite. The different adsorption capacity of
by the Langmuir model were 62"57, 74"61, 77"61, these minerals was related to both their cation-
61-12 and 59"86% of the cation-exchange capacity in exchange capacity and surface area. The surface-
zeolites 1, 2, 3, 4 and sepiolite, respectively, with an charge density (CEC/surface area) was correlated with
average value of 67" 15%. Therefore, only a fraction of the ammonium adsorption capacity, and the regression
the exchange sites were accessible to the ammonium equation was significant at the 0.01 probability level:
ion. In a previous paper Witter and Kirchmann (1989)
calculated ammonium-adsorption capactiy by Lang- N,d~,= 1"892 SCD - 0"212; r-- 0"971
muir and first-order models, but the values obtained by
the Langmuir model were only 10% greater than those where N,a s is the ammonia adsorption capacity (mg N
predicted by the first-order model. In that zeolite g-1) and SCD is the surface-charge density (/~e m-Z).
79"5% of the exchange sites were available for the Ammonium-adsorption capacity in-
ammonium adsorption. creased with the surface-charge density of the zeolite,
 Ammonium and ammonia in zeolites 31

Table 3. Parameter values, coefficients of determination and standard error of estimate for ammonium-adsorption isotherm

Material" Langmuir model First-order model

Nm~ b R2 SE Nm~ k R2 SE

ZI 8"149 0"024 0"998*** 0"1745 6"132 0"0027 0"997*** 0"2125

Z2 10"616 0"0014 0"998*** 0"2121 7"682 0"001 7 0"998*** 0"228 7
Z3 15"169 0"001 1 0"997*** 0"3135 10"467 0"0014 0"996*** 0"3376
Z4 12"847 0"0017 0"997*** 0"4770 9"581 0"0019 0"991"** 0"5290
S 1"470 0"0039 0"992*** 0"0903 1"187 0"0039 0"989*** 0"1019

Nm. , = Maximum adsorption of ammonium in the material (mg N g- ').

b-- Langmuir model constant (litres mg- i N).
k = First-order model constant (litres mg- ~N).
R -~-- Coefficient of determination.
SE-- Standard error of estimate.
*** Results are significant at the probability level of 0.001.

10 -"" 12
(a) / ' =D
Z 8

6
+ ~ + + .....
++
z I0

~ 4

2
Z 0 I '" I I I I I I I Z 0 I I I 1 I I I I

2 4 6 8 10 12 14 16 2 4 6 8 10 12 14 16
Equilibriuln cone. (rag N l -t) Equilibrium c o n e . (rag N l - t )

7 .'-" 10
(c) , (d)

f.
I

Z 6
5

4 ~ 6

3 ~ 4
2
Z Z 2
i 1 I
e~

Z 0 i i i , , i i Z 0 I I I I I I

2 4 6 8 10 12 14 2 4 6 8 10 12
Equilibrium c.ozlc. ( r a g N l -L) Equilibrium c o n e . ( r a g N l -L)

5
7 (e)
Z 4

Z 0 I I i I I

0 1 2 3 4 5

Equilibrium cone. (rag N l-t)

Fig. 3. Experimental results (0), Langmuir ( ) and first-order (----) curve fitting of the ammonia-adsorption isotherm in
zeolite 1, 2, 3, 4 and sepiolite (a, b, c, d and e, respectively).
32 M. P. Bernal, J. M. Lopez-Real
due to the readily available exchange sites for this ion
on the surface,
Ammonia-adsorption isotherm
Experimental results of the ammonia-adsorption iso-
therm were also fitted to Langmuir and first-order
models. Figure 3 shows the experimental results and
the curve-fitting.
The zeolite samples were not wetted before expo-
sure to the ammonia atmosphere, in order to avoid any
possible blocking of the internal channels by water
adsorption. According to Hayhurst (1978), in the zeo-
lite phillipsite, when both ammonia and water were
present, the adsorption rate and capacity were both
reduced from that found for pure ammonia adsorption.
This effect would be expected in clinoptilolite, because
of its higher kinetic pore diameter compared to phillip-
site (Hayhurst, 1978).
The experimental results obtained fitted to both
Langmuir and first-order models. As with the ammo-
nium-adsorption isotherm, coefficients of determina-
tion in the Langmuir model were also higher than those
of the first-order model (Table 4), and the standard
error of estimate was always lower in the Langmuir
model. For these reasons, the Langrnuir model more
accurately described the adsorption process. Maximum
adsorptions of ammonia calculated by the first-order
model were 9.74-19.7% lower than the values found
with the Langmuir equation.
The maximum adsorption of ammonia in zeolite was
between 6.255 and 14.155 mg N g - k Sepiolite also
adsorbed less NH3-N than the zeolites (4"55 mg N g-~).
Nevertheless, its capacity for ammonia adsorption was
three times higher than that for the ammonium ion.
The large surface area of the sepiolite resulted in a
great increase in the nitrogen adsorption as ammonia
gas, with respect to the ammonium-ion form. Increases
in ammonia adsorption in contrast to ammonium were
also observed in zeolites 1 and 2 (24 and 33.3%,
respectively), while decreases occurred in zeolites 3
and 4 (58.8 and 34.9%, respectively).
To be able to understand this it is necessary to take
into account the different processes associated with the
Table 4. Parameter values, eoefficients of determination and standard error ofestimate
Material ~ Langmuir model
Nm~ b R2
Z1 10.103 0-5529 0"993*** 0.6323
Z2 14"155 0.266 1 0-994*** 0.7878
Z3 6"255 1"3718 0.993*** 0.4663
Z4 8"365 1"519 7 0.993*** 0.653 3
S 4"552 1-7068 0"996*** 0.2729
Nm~ = Maximum adsorption of ammonia in the material (mg N g- l).
b = Langmuir model constant (litres mg- l N).
k= First-order model constant (litres mg- t N).
R 2 Coefficient of determination.
~
SE-- Standard error of estimate.
***Results are significant at the probability level of 0.001.
adsorption of ammonia gas in these materials. The
adsorption processes include the following individual
reactions:
--ammonia diffusion into the atmosphere;
--intraparticular diffusion of ammonia in the gase-
ous phase;
-- adsorption of ammonia gas on the zeolite surface
(internal channels);
- - equilibrium between the ammonia gas and ammo-
nia in solution (due to the partial pressure of H 2 0
in the atmosphere, and the moisture content of
the solid phase);
- - intraparticular diffusion of ammonia in solution;
- - chemical equilibrium between ammonia and the
ammonium ion (NH 3 + H 2 0 ~ NH4 + O H - ); and
- - adsorption of the ammonium equilibrium form to
the exchange sites by cation exchange.
The complexity of the process means that no indi-
vidual characteristic of the materials has a direct influ-
ence on the maximum adsorption of ammonia.
However, a greater ratio of NHa/NH 3 adsorbed
occurred in zeolites with higher surface-charge density.
The ion-exchange process prevailed in materials with
high surface-charge density, diminishing the ammonia
adsorption. To increase the NH3-N adsorption in these
materials the protonation equilibrium,
NH3 + H 2 0 ~NH4 + O H - , should be directed to the
ammonium ion formation. In this case the acid pre-
treatment of the zeolite could stimulate the process,
owing to the presence of hydrogen ions (protons) on
the exchange sites. Prior to the actual ion-exchange
process, a protonation of ammonia occurs on the acid
exchange-sites. On the other hand, in materials with
relatively low surface-charge density, the adsorption
process is enhanced by gas adsorption in the internal
channels of the zeolitic structure. Thus, pH and base
saturation could also play an important role in the
predominance of ion-exchange or gas adsorption
processes.
Witter and Kirchmann (1989) found the ammo-
nium-adsorption capacity of zeolite clinoptilolite to be
more than 10 times greater than the ammonia adsorp-
for ammonia-adsorptionisotherm
First-order model
SE Nm~ k R2 SE
8"950 0.4197 0"984*** 0"9532
11-368 0.2586 0"990*** 0"9966
5"646 0-9643 0-983*** 0.7497
7.413 1"1891 0.984*** 0"965 5
3"913 1.3925 0-989*** 0"4327
 A m m o n i u m and ammonia in zeolites
tion. They concluded that the high pH avoided the
transformation of ammonia into ammonium, this being
the limiting factor, resulting in low ammonia adsorp-
tion for the high CEC value. However, the strong.
adsorption preference of ammonia gas over other gas
compounds by zeolites has been shown (Hayhurst,
1978). The reason for the low ammonia-adsorption
capacity found by Witter and Kirchmann (1989) could
be due to the procedure, in which zeolite was wetted
before exposure to the ammonia atmosphere. The
water molecules present in the zeolite could have
blocked the internal channels for the ammonia adsorp-
tion in the zeolite.
ACKNOWLEDGEMENTS
The authors wish to thank the Ministry of Education
and Science of Spain for the financial support awarded
to Dr M. P. Bernal; Dr R. Manly, Kingston Polytechnic,
for supplying some zeolite samples; Dr R. Ortiz, Uni-
versity of Murcia (Spain), for the identification of the
zeolite types by X-ray diffraction; also D. Haymes for
his comments on the manuscript.
REFERENCES
Ames, L. L. Jr. (1960). The cation sieve properties of clinop-
tilolite. Am. Mineral., 45,689-701.
Barbarick, K. A. & Pirela, H. J. (1984). Agronomic and
horticultural uses of zeolites: a review. In Zeo-agriculture.
Use of Natural Zeolites in Agriculture and Aquaculture,
eds W. G. Pond & E A. Mumpton. Westview Press,
Boulder, Colorado, pp. 93-104.
Baumann, E. R., Hopping, W. D. & Warner, E D. (1981).
Field evaluation of the treatability of type A zeolite in a
trickling filter plant. Water Res., 15, 889-901.
Blake, G. R. & Hartge, K. H. (1986a). Bulk density. In
Methods of Soil Analysis, Part 1, Agronomy 9 (2nd edn),
ed. A. Klute. American Society of Agronomy, Soil Science
Society of America, Madison, Wisconsin, pp. 363-75.
Blake, G. R. & Hartge, K. H. (1986b). Particle density. In
Methods of Soil Analysis, Part 1, Agronomy 9 (2nd edn),
ed. A. Klute. American Society of Agronomy, Soil Science
Society of America, Madison, Wisconsin, pp. 377-82.
Blanchard, G., Maunaye, M. & Martin, G. (1984). Removal
of heavy metals from waters by means of natural zeolites.
WaterRes., 18, 1501-7.
Bremner, J. M. (1965). Total nitrogen. In Methods of Soil
Analysis, Part 2, Agronomy 9, ed. C. A. Black. American
Society of Agronomy, Madison, Wisconsin, pp. 1149-78.
Cihacek, L. J. & Bremner, J. M. (1979). A simplified ethylene
glycol monoethyl ether procedure for assessment of soil
surface area. SoilSci. Soc. Am. J., 43, 821-2.
Chapman, H. D. (1965). Cation-exchange capacity. In
Methods of Soil Analysis, Part 2, Agronomy 9, ed. C. A.
Black. American Society of Agronomy, Madison, Wiscon-
sin, pp. 891-901.
Chi, C. W., Lee, H. & Vaughan, D. E. W. (1978). Evaluation
of natural ferrierite as a claus tail-gas catalyst. In Natural
33
Zeolites. Occurrence, Properties and Use, eds L. B. Sand &
F. A. Mumpton. Pergamon Press, Oxford, pp. 495-502.
Dyer, A. (1988). An Introduction to Zeolite Molecular Sieves.
John Wiley & Sons, Bath, Avon.
Fianingen, E. M. & Mumpton, E A. (1981). Commercial
properties of natural zeolites. Rev. MineraL, 4, 165-75.
Hagiwara, Z. & Uchida, M. (1978). Ion-exchange reactions
of processed zeolite and its application to the removal of
ammonia-nitrogen in wastes. In Natural Zeolites. Occur-
rence, Properties and Use, eds L. B. Sand & E A. Mump-
ton. Pergamon Press, Oxford, pp. 463-70.
Harter, R. D. (1984). Curve-fit errors in Langmuir adsorp-
tion maxima. SoilSci. Soc. Am. J., 48, 749-52.
Hayhurst, D. T. (1978). The potential use of natural zeolites
for ammonia removal during coal-gasification. In Natural
Zeolites. Occurrence, Properties and Use, eds L. B. Sand &
E A. Mumpton. Pergamon Press, Oxford, pp. 503-8.
Hunt, H. W. & Adamsen, E J. (1985). Empirical representa-
tion of ammonium adsorption in two soils. Soil Sci., 139,
205-10.
Klute, A. (1986). Water retention: laboratory methods. In
Methods of Soil Analysis, Part 1, Agronomy 9 (2nd edn),
ed. A. Klute. American Society of Agronomy, Soil Science
Society of America, Madison, Wisconsin, pp. 635-62.
Koelliker, J. K., Miner, J. R., Hellickson, M. L. & Nakaue, H.
S. (1980). A zeolite packed air scrubber to improve
poultry house environments. Trans. ASAE, 157-75.
Krom, M. D. (1980). Spectrophotometric determination of
ammonia: a study of a modified Berthelot reaction using
salicylate and dichloroisocyanurate. The Analyst, 105,
301-16.
Liberti, L., Boari, G., Petruzzelli, D. & Passino, R. (1981).
Nutrient removal and recovery from wastewater by ion
exchange. WaterRes., 15, 337-42.
Mercer, B. W. & Ames, L. L. (1978). Zeolite ion exchange in
radioactive and municipal wastewater treatment. In
Natural Zeolites. Occurrence, Properties and Use, eds L. B.
Sand & E A. Mumpton. Pergamon Press, Oxford, pp.
451-62.
Miner, J. R. (1984). Use of natural zeolites in the treatment of
animal wastes. In Zeo-agriculture: Use of Natural Zeolites
in Agriculture and Aquaculture, eds. W. G. Pond & F. A.
Mumpton. Westview Press, Boulder, Colorado, pp.
257-62.
Mumpton, F. A. (1981). Utilization of natural zeolites. Rev.
Mineral., 4, 177-204.
Murphy, C. O., Hrycyk, O. & Gleason, W. T. (1978). Natural
zeolites: Novel uses and regeneration in wastewater treat-
ment. In Natural Zeolites. Occurrence, Properties and Use,
eds L. B. Sand & F. A. Mumpton. Pergamon Press,
Oxford, pp. 474-8.
Statistical Analysis System (SAS) Institute Inc. (1985). User's
Guide: Statistics, Cary, Raleigh, North Carolina, USA.
Tarasevich, Y. I. (1988). Natural zeolites in water treatment
processes. Soy. J. Water Chem. Tech., 10, 22-32.
Weber, M. A., Barbaric, K. A. & Westfall, D. G. (1983).
Ammonium adsorption by a zeolite in a static and a
dynamic system. J. Environ. QuaL, 12, 549-52.
Witter, E. & Kirchmann, H. (1989). Peat, zeolite and basalt
as adsorbents of ammoniacal nitrogen during manure
decomposition. Plant and Soil, 115, 43-52.
Zelazny, L. W. & Calhoun, E G. (1977). Palygorskite (atta-
pulgite), sepiolite, talc, pyrophyllite, and zeolites. In
Minerals in Soil Environments, eds J. B. Dixon & S. B.
Weed. Soil Science Society of America, Madison, Wiscon-
sin, pp. 435-71.