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)

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 characteristics of the zeolite. The cation-exchange equilibrium between a zeolite and a solution is usually
depicted by an ion-exchange isotherm. Clinoptilolite 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 wastewater treatments, mostly for waters with high levels of
ammonium (Hagiwara & Uchida, 1978; Murphy et al.,
1978; Baumann et aL, 1981; Liberti et aL, 1981; Tarasevich, 1988); in agriculture and aquaculture (Barbarick & 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 dehydrated channels and cavities. Molecules having diameters 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 (Koelliker 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).

Abstract

Zeofite clinoptilolite is a natural mineral with ionexchange and gas-adsorption properties. Ammoniumand 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 experimental results of the adsorption isotherm to Langmuir
and first-order models. Ammonium-adsorption capacities of the zeolites were from 8"149 to 15"169 mg N g- i;
up to 16~3 times higher than that of sepiolite. Ammonium-adsorption capacity increased with the surface
charge density of the material, due to the readily available 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 ammonium 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, ammonium, Langmuir equation, sepiolite, zeolite clinoptilolite.
INTRODUCTION
The applications of natural zeolites include pollution
control, energy conservation, agriculture and aquaculture, mining and metallurgy (Mumpton, 1981). All
the applications of natural zeolites make use of one or
more of their physical and chemical properties: ionexchange, 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

28

M. P. Bernal, J. M. Lopez-Real

Adsorption on crystalline zeolites is usually characterized 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, Langmuir, 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-adsorption 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 discussed.
METHODS

Four clinoptilolite zeolites and one sepiolite were used.

Zeolite 1 (ZI) was from S.P. Health & Hygiene Products, 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 procedure was used for determining the specific surface area
(Cihacek & Bremner, 1979). Porosity was calculated
from bulk and particle density values, previously determined by core method (Blake & Hartge, 1986a) and
pycnometer method (Blake & Hartge, 1986b) respectively. Total nitrogen was determined by a Kjeldahl
method (Bremner, 1965). Ammonium nitrogen was
extracted with 2N KCI, and determined colorimetrically by a salicylate method (Krom, 1980). The ammonium 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 photometry 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 concentration in the extracting solution was from 0"001 to
0"160M. Amounts of ammonium adsorbed by the
samples were calculated from the reduction of ammonium in the solution after shaking for 2 h, and centrifugation. A separate study of the ammonium adsorption
by the zeolite against time showed that the ammonium
adsorption was practically complete after 1 h of shaking (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

pH (H20)
pH (KCI)
WHC (%)
Surface area (m2 g- 1)
Bulk density (g cm-3)
Particle density (g cm- 3)
Porosity (%)
CEC (me kg- t)
SCD" (/~e m- 2)
NH4-N (mg kg- l)
Exchangeable cations
Na (me kg- t)
K (me kg- l)
Ca (me kg- t)
Mg (me kg- ~)
aSurface charge density.
Z -- zeolite.
S = sepiolite.

Z1

Z2

Z3

Z4

8-15
6'80
133"53
175
0.982
2,378
58"7
930.29
5.32
107

8.05
6"90
132"01
172
0.796
2.395
66.77
1016.36
5.91
5

7.78
6"65
128-89
193
0.858
2.353
63.54
1396.16
7.23
5

6'79
5"75
168"74
214
0.561
2.287
75.46
1501-30
7.02
72

7"68
7"45
170"56
297
0.684
2.555
73.22
175.40
0.59
17

161.8
93.2
630"5
47.7

198.5
539.9
306.6
10.7

285-8
258.0
687.0
100.7

1"00
4.10
69"8
127.0

161.7
101-4
654.8
41.6

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)

NH 4 adsorbed
(mg N/g zeolite)

0.761 b

0.769b

0.781 b

0.840a

0.854a

Analysis of variance
Source

DF

Sum of square

Mean square

Treatments
Residual
Total

4
5
9

0.014 83
1.8 x 10 -4
0-015 01

0.003 71
3"62 x 10 -5

102"407"**

***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 ammonia. Ammonia concentration in the container was
0"17-15"70 mg N litre -1. The constant atmosphere
was obtained by several additions of 100 ml of 5N
NaOH to a predetermined amount of NH4CI during
the incubation time. Ammonia adsorbed by the materials was determined by KCI extractions, acidified with
HCi (pH 4) to prevent any ammonia loss during the
analysis. The Kjeldahl-N method was compared to KCI
extracts in one zeolite; the results indicated that all
ammonia adsorbed in the zeolite was KCl-extractable
(data not shown).
Statistical analyses
Results from both ammonia- and ammonium-adsorption 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.

7"-" 4.0
~t0
3.5
Z
~ 3.o
v 2.5
2.o
~ 1.s
1.0
-*

0.5

0.0

3
Extraction

times

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 fitting 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 constant.
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 statistically significant correlation coefficient (Harter, 1984).
As Table 3 shows, the Langmuir model fitted the
experimental results better than the first-order model.

M. P. Bernal, J. M. Lopez-Real

30
T

-I" "

(b)

,=

,~

0~

e~

ZI

400

600

Equilibriurti

200

,,--,

10

800

cone.

1000

1200

200

400

600

800

Equilibrium

( l i i g N 1-1)

-'"

(o)

10

1000

1200

1400

1600

COILC. ( I n g N 1-1)

(4)

E
6

o.

200

400

600

Equilibriutn

800

1000

1200

1400

uollt:. ( l l l ~ N l

1.4

Z.

-l

Z
I

600

800

1000

1200

1400

cone.

(ntg N I-l)

(e)

1.2

'~

0.8

0.6

0.4

0.2
0.0
0

200

400

600

800

I000

Equilibrium

Fig. 2.

400

Equilibrium

~ 1.o

200

conc.

(mg

N 1-1)

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 equations were significant at the 0.001 probability level in
both models, the lowest values of the standard error of
estimate were obtained with the Langmuir equation. In
the first-order model the maximum adsorption was
underestimated by 19"27- 31%.
The maximum ammonium adsorptions calculated
by the Langmuir model were 62"57, 74"61, 77"61,
61-12 and 59"86% of the cation-exchange capacity in
zeolites 1, 2, 3, 4 and sepiolite, respectively, with an
average value of 67" 15%. Therefore, only a fraction of
the exchange sites were accessible to the ammonium
ion. In a previous paper Witter and Kirchmann (1989)
calculated ammonium-adsorption capactiy by Langmuir and first-order models, but the values obtained by
the Langmuir model were only 10% greater than those
predicted by the first-order model. In that zeolite
79"5% of the exchange sites were available for the
ammonium adsorption.

The maximum adsorption of NH4-N was between

8.149 and 15.169 mg N g-l for zeolite, and 1.470 mg
N g- l for sepiolite. Although sepiolite had the greatest
surface area its capacity to adsorb ammonium was very
low, relating to its cation-exchange capacity. Zeolite
was up to 10.3 times more effective in NH4-N adsorption than sepiolite. The different adsorption capacity of
these minerals was related to both their cationexchange capacity and surface area. The surfacecharge density (CEC/surface area) was correlated with
the ammonium adsorption capacity, and the regression
equation was significant at the 0.01 probability level:
N,d~,= 1"892 SCD - 0"212;

r-- 0"971

where N,a s is the ammonia adsorption capacity (mg N

g-1) and SCD is the surface-charge density (/~e m-Z).
Ammonium-adsorption
capacity
increased 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

ZI
Z2
Z3
Z4
S

First-order model

Nm~

R2

SE

Nm~

R2

SE

8"149
10"616
15"169
12"847
1"470

0"024
0"0014
0"001 1
0"0017
0"0039

0"998***
0"998***
0"997***
0"997***
0"992***

0"1745
0"2121
0"3135
0"4770
0"0903

6"132
7"682
10"467
9"581
1"187

0"0027
0"001 7
0"0014
0"0019
0"0039

0"997***
0"998***
0"996***
0"991"**
0"989***

0"2125
0"228 7
0"3376
0"5290
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

-""
(a)

~ + +

12

' =D

++

.....

I0

2
Z

'" I

10

12

14

16

10

12

14

16

Equilibriuln cone. (rag N l -t)

.'-"
,

10

Equilibrium

(c)

6
5

c o n e . (rag N l - t )

(d)

f.

2
Z

e~

10

12

14

Equilibrium

10

12

Equilibrium

c.ozlc. ( r a g N l -L)

c o n e . ( r a g N l -L)

(e)

4
3

0
0

Equilibrium

Fig. 3.

cone.

(rag

N l-t)

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).

M. P. Bernal, J. M. Lopez-Real

32

due to the readily available exchange sites for this ion

on the surface,
Ammonia-adsorption

isotherm

Experimental results of the ammonia-adsorption isotherm 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 exposure to the ammonia atmosphere, in order to avoid any
possible blocking of the internal channels by water
adsorption. According to Hayhurst (1978), in the zeolite 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 phillipsite (Hayhurst, 1978).
The experimental results obtained fitted to both
Langmuir and first-order models. As with the ammonium-adsorption isotherm, coefficients of determination 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.

ammonia diffusion into the atmosphere;

intraparticular diffusion of ammonia in the gaseous phase;
-- adsorption of ammonia gas on the zeolite surface
(internal channels);
- - equilibrium between the ammonia gas and ammonia 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 individual characteristic of the materials has a direct influence 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 pretreatment 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 ammonium-adsorption capacity of zeolite clinoptilolite to be
more than 10 times greater than the ammonia adsorp-

Parameter values, eoefficients of determination and standard error ofestimate

Material ~

Z1
Z2
Z3
Z4
S

adsorption of ammonia gas in these materials. The

adsorption processes include the following individual
reactions:

Langmuir model

First-order model

Nm~

R2

SE

Nm~

R2

SE

10.103
14"155
6"255
8"365
4"552

0-5529
0.266 1
1"3718
1"519 7
1-7068

0"993***
0-994***
0.993***
0.993***
0"996***

0.6323
0.7878
0.4663
0.653 3
0.2729

8"950
11-368
5"646
7.413
3"913

0.4197
0.2586
0-9643
1"1891
1.3925

0"984***
0"990***
0-983***
0.984***
0-989***

0"9532
0"9966
0.7497
0"965 5
0"4327

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.
~

for ammonia-adsorptionisotherm

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 adsorption 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 adsorption 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, University 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 clinoptilolite. 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, Wisconsin, 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. Occurrence, Properties and Use, eds L. B. Sand & E A. Mumpton. Pergamon Press, Oxford, pp. 463-70.
Harter, R. D. (1984). Curve-fit errors in Langmuir adsorption 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 representation 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 treatment. 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 (attapulgite), sepiolite, talc, pyrophyllite, and zeolites. In
Minerals in Soil Environments, eds J. B. Dixon & S. B.
Weed. Soil Science Society of America, Madison, Wisconsin, pp. 435-71.