Professional Documents
Culture Documents
Frederick A. Mumpton
Department of the Earth Sciences
State University College
Brockport, NY 14420
Contents
Page
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 10. Effect of Zeolite Supplement in
Natural Zeolites . . . . . . . . . . . . . . . . . . . . . . . . 127 Molasses-Based Diets of Young Pigs .,. 139
Chemistry and Crystal Structure of 11. Effect of Clinoptilolite Supplemental
Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128 in the Diet of Swine . . . . . . . . . . . . . . . . . 140
Properties of Zeolites. . . . . . . . . . . . . . . . . . 129 12. Occurrence of Diarrhea and Soft-Feces
Applications in Agronomy ......,,.,.. . . . 133 Among Calveson Diets Supplemented
Fertilizer and Soil Amendments . . . . . . . . 133 With 5% Clinoptilolite . . . . . . . . . . . . . . . 141
Pesticides, Fungicides, Herbicides. ,,.... 135 13. Effect of Zeolite Additions to Chicken
Heavy Metal Traps . . . . . . . . . . . . . . . . . . . 135 Droppings . . . . . . . . . . . . . . . . . . . . . . . . . . 142
Applications in Animal Husbandry . . . . . . . 136 14. Effect of Clinoptilolite Additions to the
Animal Nutrition . . . . . . . . . . . . . . . . . . . . . 136 Diet of Trout . . . . . . . . . . . . . . . . . . . . . . . 144
Poultry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 15. Reported Occurrences of Sedimentary
Swine . . . . . . . . . . . . . . . . . . . . . . .+....... 136 Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
Ruminants . . . . . . . . . . . . . . . . . . . . . . . . . . . 139 16. Countries Engaged in Zeolite Mining . . 150
Excrement Treatment . . . . . . . . . . . . . . . . . 141 17. Organizations Engaged in Zeolite/
Malodor and Moisture Control . . . . . . . . . 141 Agronomic Investigations . . . . . . . . . . . . 151
Methane Purification. . . . . . . . . . . . . . . . . . 142 18. Organizations Engaged in Animal
Aquacultural Applications . . . . . . . . . . . . . . . 143 Nutrition Studies Using Zeolites . . . . . . . 152
Nitrogen Removal From Closed or 19. Zeolite Property Holders and
Recirculation Systems . . . . . . . . . . . . . . . 143 Zeoagricultural Research Efforts. ..,,,. 153
Aeration Oxygen Production . . . . . . . . . . . 144
Fish Nutrition . . . . . . . . . . . . . . . . . . . . . . . . 144
Occurrence and Availability of Natural Figures
Zeolites .....,...,,.. . . . . . . . . . . . . . . . 144
FigureNo. ..
Page
Geological Occurrence. . . . . . . . . . . . . . . . . 144
Geographic Distribution . . . . . . . . . . . . . . . 146 l. Simple Polyhedron of Silicate and
Mining and Milling . . . . . . . . . . . . . . . . . . . 149 Aluminate Tetrahedra . . . . . . . . . . . . . . . . 130
Discussion, ..,,.... . . . . . . . . . . . . . . . . . . . . 150 2. Arrangements of Simple Polyhedra to
Agronomic Applications . . . . . . . . . . . . . . . 150 Enclose Large Central Cavities .., ...,, 130
Animal Nutrition Applications ., ..,.,.., 151 3. Solid Sphere Models of Synthetic
Excrement Treatment Applications . . . . . . 152 Zeolite and Chabazite . . . . . . . . . . . . . . . . 131
Conclusions and Recommendations . . . . . . . 152 4. Stylized Illustration of the Entry of
References .,.. . . . . . . . .,..,..+, . . . . . . . 155 Straight-Chain Hydrocarbons and
Blockage of Branch-Chain Hydrocarbons
Tables at Channel Apertures ,, ......,,,,,,., 131
5. Langmuir-Type Isotherm for Adsorption
Table No. Page on Crystalline Zeolites Illustrating
l. Representative Formulae and Selected Almost Complete Saturation at Low
Physical Properties of Important Partial Pressures of the Adsorbate ,,... 131
Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 6. Types of Ion-Exchange Isotherms for the
2. Growth Response of Radishes to Reaction As + BZ = AZ + Bs, . . . . . . . . . 132
Ammonium-Exchange Clinoptilolite . . . . 134 7. Change of Soil Nitrogen of Paddy Soil
3, Growth Response of Radishes to With Time . . . . . . . . . . . . . . . . . . . . . . . . . 133
Natural Clinoptilolite Plus Urea ,....., 134 8. Yield of Chrysanthemums as a Function
4. Caloric Efficiencies of Zeolite of Potassium Level Supplied by One-
Supplements in Poultry Feeding . . . . . . . 136 TimeAdditions of Clinoptilolite . . . . . . . 134
5. Apparent Caloric Efficiency of Zeolite 9. Cumulative Leachate NO3-N for Banded
in Chicken Rations . . . . . . . . . . . . . . . . . . 137 NH4-Exchanged Clinoptilolite and
6. Caloric Efficiency of Zeolite Banded Ammonium Sulfate ..,,,,,. . . . 135
Supplements in Swine Feeding . . . . . . . . 137 10. Methane-Purification System, Pales
7. Effect of Zeolite Diets on Health Verde Landfill . . . . . . . . . . . . . . . . . . . . . . 142
of Swine . . . . . . . . . . . . . . . . . . . . . . . . . . . 138 11. Field Exposure of Zeolite Beds ,,, ,,,.. 145
8. Effect of Prenatal Zeolite Diet on 12. Scanning Electron Micrograph of
Newborn Pigs, .,, . . ., ..,,.,.., ..,.,. 138 Clinoptilolite Laths With Minor Mordenite
9. Effect of Zeolite Supplementing the From a Saline-Lake Deposit Tuff Near
Diets of Early Weaned Pigs . . . . . . . . . . . 139 Hector, CA . . . . . . . . . . . . . . . . . . . . . . . . . 146
Chapter Vlll
AS agriculturalists the world over increase creases in the body weight and general “health”
their effort to expand crop and animal produc- of the animals (52). The use of zeolites in ra-
tion, more and more attention is being paid to tions also appeared to reduce odor and asso-
various mineral materials as soil amendments ciated pollution problems and to provide a
and as dietary supplements in animal hus- means of regulating the viscosity and nitrogen
bandry. The close relationship between the retentivity y of animal manure. These same zeo-
agricutura1 and geological sciences is not lites were also found to increase the ammoni-
new--crop production depends on the exist- um content of rice paddy soils when added
ence and maintenance of fertile soil and with normal fertilizers.
agronomists rely on knowledge of mineralogy
Although most of these were preliminary re-
and geochemist}’ of clays and other soil con-
sults and often published in rather obscure
stituents. In the animal sciences, the addition
journals or reports from local experiment sta-
of crushed limestone to chicken feed to
tions, they did suggest that zeolites could act
strengthen egg shells is well known, as is the
as traps or reservoirs for nitrogen both in the
use of bentonite as a binding agent in pelletized
body and in the soil. The growing awareness
anima1 feed stuffs.
of such phenomena and of the availability of
Recently, one group of minerals has emerged inexpensive natural zeolites in the Western
as having considerable potential in a wide va- United States and in geologically similar parts
riety of agricultural processes. This group of of the world has aroused considerable commer-
minerals is the zeolite group. The unique ion- cial interest. Zeolites are fast becoming the sub-
exchange, dehydration-rehydration, and ad- ject of serious investigation in dozens of agri-
sorption properties of zeolite materials prom- cultural laboratories both here and abroad.
ise to contribute significantly to many years of Some of the ways in which zeolites can con-
agricultural and aquacultural technology (60). tribute to more efficient crop and livestock pro-
duction are discussed below, along with their
Most of the initial research on the use of zeo-
role in the rapidly expanding areas of fish
lites in agriculture took place in the 1960s in
breeding and aquiculture. At this stage, the
Japan, Japanese farmers have used zeolite rock
number of published papers dealing with “zeo-
for years to control the moisture content and
agriculture “ is quite small, and hard data are
malodor of animal wastes and to increase the
few; however, the potential of these materials
pH of acidic volcanic soils. The addition of
in such areas is apparent, and zeolites show
small amounts of the zeolites clinoptilolite and
promise of contributing directly to increased
mordenite to the normal protein diet of pigs,
agricultural productivity in the years to come.
chickens, and ruminants gave noticeable in-
ZEOLITES
Zeolites are crystalline, hydrated aluminosil- some of their constituent elements without ma-
icates of alkali and earth metals that possess jor change of structure. Zeolites were discov-
infinite, three-dimensional crystal structures. ered in 1756 by Freiherr Axel Fredrick Cron-
They are further characterized by an ability to stedt, a Swedish mineralogist, who named
lose and gain water reversibly and to exchange them from the Greek words meaning “boiling
127
128
stones, “ in allusion to their peculiar frothing prompted intense commercial interest both
characteristics when heated before the miner- here and abroad. Many industrial applications
alogist’s blowpipe. Since that time, nearly 50 based on the exciting bag of chemical and phys-
natural species of zeolites have been recog- ical tricks of zeolites have been developed.
nized, and more than 100 species having no The commercial use of natural zeolites is still
natural counterparts have been synthesized in in its infancy, but more than 300,000 tons of
the laboratory. Synthetic zeolites are the main- zeolite-rich tuff is mined each year in the
stays of the multimillion-dollar molecular sieve
United States, Japan, Bulgaria, Hungary, Italy,
businesses that have been developed by Union
Yugoslavia, Korea, Mexico, Germany, and the
Carbide Corp., W. R. Grace& Co., Mobil Corp.,
Soviet Union. Natural zeolites have found ap-
Norton Co., Exxon Corp., and several other
plications as fillers in the paper industry, as
companies in the last 25 years in the United
lightweight aggregate in construction, in poz-
States and by chemical firms in Germany, zolanic cements and concrete, as ion-exchang-
France, Great Britain, Belgium, Italy, Japan,
ers in the purification of water and municipal
and the Soviet Union. sewage effluent, as traps for radioactive spe-
Natural zeolites have long been known to cies in low-level wastewaters from nuclear fa-
members of the geological community as ubiq- cilities, in the production of high purity oxy-
uitous, but minor constituents in the vugs and gen from air, as reforming petroleum catalysts,
cavities of basalt and other traprock forma- as acid-resistant absorbents in the drying and
tions. It was not until the late 1950s that the purification of natural gas, and in the removal
world became aware of zeolites as major con- of nitrogen compounds from the blood of kid-
stituents of numerous volcanic tuffs that had ney patients (58).
been deposited in ancient saline lakes of the
The applications and potential applications
Western United States or in thick marine tuff
of both synthetic and natural zeolites depend,
deposits of Italy and Japan. Since that time, of course, on their fundamental physical and
more than 2,000 separate occurrences of zeo-
chemical properties. These properties are in
lites have been reported from similar sedimen-
turn related directly to the chemical composi-
tary rocks of volcanic origin in more than 40
tion and crystal structure of individual species.
countries. The high purities and near-surface
location of the sedimentary deposits has
of parentheses are called structural cations, be- once the water is removed from a zeolite,
cause with oxygen they make up the tetrahe- considerable void space is available within
dral framework of the structure. Loosely bound both the simple polyhedra building blocks and
molecular water is also present in the struc- the larger frameworks formed by several poly-
tures of all natural zeolites, surrounding the ex- hedra. Although water and other inorganic and
changeable cations in large pore spaces. organic molecules would appear to be able to
move freely throughout a dehydrated zeolite
Whereas the framework structures of quartz
framework, the passageways leading into the
and feldspar are dense and tightly packed,
simple polyhedra are too small for all but the
those of zeolite minerals are remarkably open
smallest molecules to pass; however, ports or
and void volumes of dehydrated species as
channels up to 8 A in diameter lead into the
great as 50 percent are known (table 1). Each
large, three-dimensional cavities (figures 2a, 2b,
zeolite species has its own unique crystal struc-
3a, 3b).
ture and, hence, its own set of physical and
chemical properties. Most structures, however,
can be visualized as SiO4 and AlO4 tetrahedral Properties of Zeolites
linked together in a simple geometrical form.
Adsorption properties: Under normal condi-
This particular polyhedron is known as a trun-
tions, the large cavities and entry channels of
cated cube-octahedron. It is more easily seen
zeolites are filled with water molecules form-
by considering only lines joining the midpoints ing hydration spheres around the exchange-
of each tetrahedron, as shown in figure 1. able cations. Once the water is removed, usual-
Individual polyhedra may be connected in ly by heating to 3000 to 4000 C for a few hours,
several ways; for example, by double four-rings molecules having diameters small enough to
of oxygen atoms (figure 2a), or by double six- fit through the entry channels are readily ad-
rings of oxygen atoms (figure 2b), the frame- sorbed on the inner surfaces of the vacant cen-
work structures of synthetic zeolite A and the tral cavities. Molecules too large to pass
mineral faujasite, respectively. Solid-sphere through the entry channels are excluded, giv-
models of synthetic zeolite A and of the mineral ing rise to the well-known “molecular sieving”
chabazite are illustrated in figures 3a, 3b. property of most crystalline zeolites (figure 4).
Table 1.— Representative Formulae and Selected Physical Properties of Important Zeolites
a b
(a) Ball and peg model of truncated cube-octahedron. (b) Line drawing of truncated cube-octahedron,
lines connect centers of tetrahedral
Figure 2.—Arrangements of Simple Polyhedra to with a selectivity unlike that of almost all other
Enclose-Large Central Cavities sorbents. Thus, polar molecules such as water,
sulfur dioxide, hydrogen sulfide, and carbon
dioxide are preferential] y adsorbed by certain
zeolites over nonpolar molecules, such as meth-
ane, and adsorption p recesses have been de-
veloped using natural zeolites by which carbon
dioxide and other contaminants can be re-
moved from impure natural gas or methane
streams, allowing the gas to be upgraded to
high-Btu products. In addition, the small, but
finite, quadripole moment of nitrogen allows
it to be adsorbed selectively from air by a de-
a b
hydrated zeolite, producing oxygen-enriched
(a) Truncated cube-octahedra connected by double four-rings of oxy- streams at relatively low cost at room temper-
gen in structure of synthetic zeolite A. (b) Truncated cube-octahedra ature. Both of the above processes may find ap-
connected by double six-rings of oxygens in structure of faujasite.
plication in agricultural technology.
Dehydration-rehydration properties: Because
The internal surface area available for adsorp-
of the uniform nature of the pores of structural
tion ranges up to several hundred square me-
cages, crystalline zeolites have fairly narrow
ters per gram, and some zeolites are capable
pore-size distributions, in contrast to other
of adsorbing up to about 30 weight percent of
commercial absorbents, such as activated alu-
a gas, based on the dry weight of the zeolite.
mina, carbon, and silica gel. Adsorption on zeo-
In addition to their ability to separate gas lites is therefore characterized by Langmuir-type
molecules on the basis of size and shape, the isotherms, as shown in figure 5. Here, percent
unusual charge distribution within a dehy- of adsorption capacity is plotted against par-
drated void volume allows many species with tial pressure of the adsorbate gas. Note that al-
permanent dipole moments to be adsorbed most all of the zeolite’s adsorption capacity for
Figure 3.—Solid Sphere Models of Synthetic Zeolite and Chabazite
a b
(a) Solid-sphere model of the crystal structure of synthetic zeolite A (b) Solid-sphere model of the crystal structure of chabazite
Figure 4.—Stylized Illustration of the Entry of Straight. Figure 5.—Langmuir-Type Isotherm for Adsorption on
Chain Hydrocarbons and Blockage of Branch-Chain Crystalline Zeolites Illustrating Almost Complete
Hydrocarbons at Channel Apertures Saturation at Low Partial Pressures of the Adsorbate
pres with the 0.8 to 1.0 meq per gram cation- Cation exchange between a zeolite (Z) and
exchange capacity of bentonite, the only other a solution (S) is usually shown by means of an
significant ion-exchanger found in nature, exchange isotherm that plots the fraction of the
exchanging ion (X) in the zeolite phase against
Cation-exchange capacity is basically a func- that in the solution (figure 6). If a given cation
t ion of the degree of substitution of aluminum shows no preference of either the solution or
for silicon in the zeolite framework: the greater the zeolite, the exchange isotherm would be the
the substitution, the greater the charge defi- straight line “a” at 45 0. If the zeolite is moder-
ciency of the structure, and the greater the
ately or very selective for the cation in solution,
number of alkali or alkaline earth atoms re-
curve b and c would result, respectively. If the
quired for electrical neutrality. In practice, zeolite is rejective of a particular cation, curve
however, the cation-exchange capacity is de- d would result. Such is the selectivity of clin-
pendent on a number of other factors as well,
optilolite for cesium or ammonium, for exam-
In certain species, cations can be trapped in ple. Clinoptilolite will take up these ions readily
structural positions that are relatively inacces-
from solutions even in the presence of high
sible, thereby reducing the effective exchange concentrations of competing ions, a facility
capacity of that species for that ion, Also, ca- that was exploited by Ames (4) and Mercer, et
tion sieving may take place if the size of the
al. (50), in their development of an ion-ex-
exchanging cat ion is too large to pass through
change process to remove ammoniacal nitro-
the entry channels into the central cavities of gen from sewage effluent.
the structure.
Unlike most noncrystalline ion exchangers,
such as organic resins or inorganic alumino-
silicate gels (mislabeled in the trade as “zeo-
lites”), the framework of a crystalline zeolite
dictates its selectivity toward competing ions.
The hydration spheres of high-charge, small- Figure 6.—Types of Ion-Exchange Isotherms for the
size ions (e. g., sodium, calcium, magnesium)
prevent their close approach in the cages to the
seat of charge of the framework; therefore ions
of low charge and large size (e. g., lead, barium,
potassium), that normally do not have hydra-
tion spheres are more tightly held and selec-
tively taken up from solution than are other
ions, The small amount of aluminum in the
composition of clinoptilolite, for example, re-
sults in a relatively low cation-exchange capac-
ity (about 2.3 meq/g); however, its cation selec-
tivity is:
Cesium > Rubidium > Potassium > Ammonium >
Barium > Strontium > Sodium
APPLICATIONS IN AGRONOMY
Fertilizer and Soil Amendments optilolite was mixed with a Texas clay soil, al-
though the overall ion-exchange capacity of the
Based on their high ion-exchange capacity soil was increased. He attributed these conflict-
and water retentivity, natural zeolites have ing results to the fact that the Japanese soils
been used extensively in Japan as amendments contained much less clay, thereby accounting
for sandy soils, and small tonnages have been for their inherent low ion-exchange capacity
exported to Taiwan for this purpose (52,31), and fast-draining properties. The addition of
The pronounced selectivity of clinoptilolite for zeolite, therefore, resulted in a marked im-
large cations, such as ammonium and potas- provement in the soil’s ammonium retentivity.
sium, has also been exploited in the prepara- These conclusions support those of Hsu, et al.
tion of chemical fertilizers that improve the (31), who found an increase in the effect of zeo-
nutrient-retention ability of the soils by promot- lite additions to soil when the clay content of
ing a slower release of these elements for up- the soil decreased. Although additions of both
take by plants, In rice fields, where nitrogen montmorillonite and mordenite increase the
efficiencies of less than 50 percent are not un- cation-exchange capacity of upland soils, the
common, Minato (52) reported a 63 percent im- greater stability of the zeolite to weathering al-
provement in the amount of available nitrogen lowed this increase to be retained for a much
in a highly permeable paddy soil 4 weeks af- longer period of time than in the clay-enriched
ter about 40 tons/acre zeolite had been added soils (22),
along with standard fertilizer (figure 7), Turner
(84), on the other hand, noted little change in Using clinoptilolite tuff as a soil conditioner,
the vitrification of added ammonia when clin- the Agricultural Improvement Section of the
Yamagata Prefectural Government, Japan, re-
Figure 7.—Change of Soil Nitrogen of Paddy Soil ported significant increases in the yields of
With Time wheat (13 to 15 percent), eggplant (19 to 55 per-
cent), apples (13 to 38 percent), and carrots (63
percent) when from 4 to 8 tons of zeolite was
added per acre (83). Small, but significant im-
provements in the dry-weight yields of sor-
ghum in greenhouse experiments using a sandy
loam were noted when 0.5 to 3.0 tons of clinop-
tilolite per acre was added along with normal
fertilizer (47). However, little improvement was
found when raising corn under similar condi-
tions. Hershey, et al. (29), showed that clinop-
tilolite added to a potting medium for chrysan-
themums did not behave like a soluble K
source, but was very similar to a slow-release
fertilizer, The same fresh-weight yield was
achieved with a one-time addition of clinop-
tilolite as with a daily irrigation of Hoagland’s
solution, containing 238 ppm K, for three
months (total of 7 g potassium added), with no
apparent detrimental effect on the plants (fig-
ure 8).
Experiments by Great Western Sugar Co. in
Vertical water seepage in soil = 1.35 cm/day (Yamagata Prefecture
Longmont, CO, using clinoptilolite as a soil
Board of Agriculture and Forestry, 1966; reported in Minato, 1968.) amendment, resulted in a significant increase
134
Figure 8.— Yield of Chrysanthemums as a Function tops also increased with the zeolite treatment
of Potassium Level Supplied by One-Time Additions compared with an ammonium sulfate control
of Clinoptilolite
(table 2). These authors also found that natu-
ral clinoptilolite added to soil in conjunction
with urea reduced the growth suppression that
normally occurs when urea is added alone (ta-
ble 3). The presence of zeolites also resulted
in less NO3-N being leached from the soil (fig-
ure 9).
Both zeolite treatments apparently made con-
siderably more ammonium available to the
plants, especially when clay-poor soils were
employed. The authors suggested that ammo-
nium-exchanged clinoptilolite acted as a slow-
release fertilizer, whereas, natural clinoptilo-
lite acted as a trap for ammonium that was pro-
duced by the decomposing urea, and thereby
prevented both ammonium and nitrate toxic-
ity by disrupting the bacterial vitrification
process. The ammonium selectivity of zeolites
was exploited by Varro (85) in the formulation
of a fertilizer consisting of a 1:1 mixture of sew-
age sludge and zeolite, wherein the zeolite ap-
parently controls the release of nitrogen from
the organic components of the sludge.
Coupled with its valuable ion-exchange prop-
erties which allow a controlled release of mi-
cronutrients, such as iron, zinc, copper, man-
Figure 9. —Cumulative Leachate N03-N for Banded issued to Aleshin, et a], (2), for grouting com-
NH4-Exchanged Clinoptilolite and Banded
Ammonium Sulfate (Lewis, et al., 1980)
pound containing 3 to 5 percent clinoptilolite
to control herbicide percolation from irrigation
canals to ground waters.
Using clinoptilolite from the Itaya r-nine, Hayhurst and Willard (27) confirmed many
Yamagata Prefecture, and mondenite from of Onagi’s observations and reported small in-
Karawago, Miyagi Prefecture, Onagi (67) found creases in FEV for Leghorn roosters over a 40-
that Leghorn chickens required less food and day period, especially during the first 10 days.
water and still gained as much weight in a 2- The birds were fed a diet containing 7.5 per-
week trial as birds receiving a control diet. cent clinoptilolite crushed and mixed directly
Feed efficiency values (FEV) l were markedly with the normal rations. Feces were noticea-
higher at all levels of zeolite substitution; feed- bly dryer and less odoriferous. Unfortunate\,
stuffs containing 10 percent zeolite gave rise only 17 birds were used in the study and ex-
to efficiencies more than 20 percent greater tensive statistical evaluation of the results
than those of normal rations (table 4). Adverse could not be made.
effects on the health or vitality of the birds were
not noted, and the droppings of groups receiv- Swine
ing zeolite diets contained up to 25 percent less Kondo and Wagai (39) evaluated the use of
moisture than those of control groups, after a zeolites in the diets of young and mature York-
1 Weight gain/feed intake, excluding zeolite, shire pigs in 60- and 79-day experiments, re-
spectively, and found that the weight gain of over a 12-week period and realized a 4-percent
animals of both ages receiving diets contain- decrease in the cost of producing body weight.
ing 5 percent clinoptilolite was from 25 to 2 9 They also noted a decrease in malodor and
percent greater than that of animals receiving moisture content of the excrement, Toxic or
normal diets (table 6). Feed supplemented with other adverse effects were not noted for any
zeolites gave rise to feed efficiencies about 35 of the test animals described. On the contrary,
percent greater than those of normal rations the presence of zeolites in swine rations ap-
when fed to young pigs, but only about 6 per- pears to contribute measurably to the well-
cent greater when given to older animals. In being of the animals. Tests carried out on 4,000
addition, the particle size of the feces of the head of swine in Japan showed that the death
control group was noticeably coarser than that rate and incidence of disease among animals
of the experiment group, suggesting that the fed a diet containing 6 percent clinoptilolite
digestive process was more thorough when was markedly lower than for control animals
zeolites were added to the diet. The feces of over a 12-month period (83). As shown in ta-
animals in the control group were also richer ble 7, the decrease in the number of cases of
in all forms of nitrogen than zeolite-fed ani- gastric ulcers, pneumonia, heart dilation, and
mals, indicating that the zeolites contributed in the overall mortality is remarkable, The sav-
toward a more efficient conversion of feedstuff ings in medicine alone amounted to about 75
nitrogen to animal protein. cents per animal, to say nothing of the in-
creased value of a larger number of healthy
The digestibility of crude protein and nitro-
pigs.
gen-free extracts tended to be improved as zeo-
lite was substituted for wheat bran in swine In one test, the addition of zeolite to the diet
diets at levels from 1 to 6 percent over a 12- of piglets severely afflicted with scours markedly
week period (24,26). Anai, et al. (5), reported reversed the progress of this disease within a
similar results using 5 percent zeolite for 8 pigs few days (53). Four underdeveloped Laundry
pigs were fed a diet containing 30 percent zeo- gave rise to improved FEVs and increased lit-
lite for the first 15 days and 10 percent zeolite ter weight at parturition (46), The earlier the
for the remaining part of a month-long exper- zeolite was added, the greater was the appar-
iment. The severity of the disease decreased ent effect.
almost at once, and feces of all pigs were hard
and normal after only 7 days. Although the pigs Similar studies were conducted at Oregon
consumed an average of 1.75 kg of zeolite per State University with young swine using ra-
head per day, no ill effects were noted, and tions containing 5 percent clinoptilolite (16).
once they had recovered from diarrhetic ail- Although lesser increases in growth rates were
ments, the pigs regained healthy appetites and found than in the Japanese studies, the inci-
became vital. A recent Japanese patent disclo- dence of scours was significantly reduced for
sure claimed a method of preventing and treat- animals receiving the zeolite diet. Currently,
ing gastric ulcer in swine by the addition of heavy doses of prophylactic antibiotics are
zeolite to their diets (49); supportive data, how- used to control such intestinal diseases, which,
ever, were not reported. left unchecked, result in high mortality among
young swine after they are weaned. Federal
Apparently the vitalizing effect of a zeolite regulations are becoming increasingly strin-
diet can be transferred from mother to off- gent in this area, and if antibiotics are prohib-
spring. Experiments at the Ichikawa Livestock ited, other means must be found to control such
Experiment Station, where 400 g of clinoptilo- diseases. Natural zeolites may be the answer.
lite was fed each day to pregnant sows and con-
tinued through the 35-day weaning period of In a preliminary study involving 16 early
their offspring, showed substantial increase in weaned pigs over a 19-day period, animals on
the growth rate of the young pigs, As shown an antibiotic-free diet containing 10 percent
in table 8, test animals weighed from 65 to 85 clinoptilolite gained about 5 percent more
percent more than control-group animals at the weight per pound of feed than those on a con-
end of the weaning period (9). Young pigs trol diet without antibiotics and about 4 per-
whose dams received the zeolite diet also suf- cent more than those on an antibiotic-enriched
fered almost no attacks of diarrhea, while those diet (table 9) (70). The small number of pigs
in control groups were severely afflicted with used, however, limits the significance of these
scours, greatly inhibiting their normal growth. findings. In another study, a 30 percent im-
The addition of 5 percent zeolite to the rations provement in FEVs occurred for 35 young pigs
of pregnant sows 20 to 90 days after mating on a molasses-based diet when 7.5 percent
clinoptilolite was substituted in the diet dur- as urea and diuret, are added to the diets of cat-
ing the 35 to 65 kg growth period (table 10) (10). tle, sheep, and goats, researchers introduced
Feces of the zeolite-fed animals were also less both natural and synthetic zeolites into the ru-
liquid than those on a control diet. men of test animals (87). Ammonium ions
formed by the enzyme decomposition of NPN
The addition of zeolites had little effect on
were immediately ion exchanged into the zeo-
the FEVs in the 65 to 100 kg growth range.
lite structure and held there for several hours
Heeney (28) supplemented normal corn-soy ra-
until released by the regenerative action of
tions of 36 pigs with 2,5 and 5 percent clinop-
Na + entering the rumen in saliva during the
tilolite in a 120-day experiment (table 11). He
found little overall difference in the FEVs; how- after-feeding fermentation period. Both in vivo
ever, for the first 30 days after weaning, FEVs and in vitro data showed that up to 15 percent
of the NH 4 + in the rumen could be taken up
of 0.455 and 0.424 were obtained for 2.5 and
by the zeolite. Thus, the gradual release of
5.0 percent zeolite, respectively, compared
NH 4 + allowed rumen micro-organisms to syn-
with a value of 0.382 for the control animals,
thesize cellular protein continuously for easy
an increase of about 15 percent due to the pres-
ence of zeolites in the diet. Little improvement assimilation into the animals’ digestive sys-
tems. The zeolite’s ability to act as a reservoir
was noted between 30 and 120 days of the
for NH4 + “. . . permits the addition of supple-
treatment.
mental nitrogen to the animal feed while pro-
tecting the animal against the production of
Ruminants toxic levels of ammonia” in the rumen (87).
In an attempt to reduce the toxic effects of Clinoptilolite added to the feed of young
high NH, + content of ruminal fluids when calves improved their growth rate by stimulat-
nonprotein nitrogen (NPN) compounds, such ing appetite and decreased the incidence of di-
C
lncluding zeolite
lntake less zeolite
‘Excluding zeolite.
140
a
Table 11 .—Effect of Clinoptilolite Supplemental in the Diet of Swine
2.50/o 50/0
Control Clinoptilolite Clinoptilolite
-.
Average initial weight (lb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31.6---- 31.7 31.7
30-days:
Average weight (lb)..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61.0 62.2 62.5
Average daily weight gain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.09 1.12 1.17
Feed/pound of gain (lb)b . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.62 2.20 2.36
Feed efficiency valuec . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.382 0,455 0.424
60-days:
Average weight (lb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105.7 107.3 106.2
Average daily weight gain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.59 1.61 1,52
Feed/pound of gain (lb)b . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.80 3.05 3.09
c
Feed efficiency value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.357 0.328 0.324
90-days:
Average weight (lb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153.7 149.6 150.0
Average daily weight gain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.72 1.51 1,57
Feed/pound of gain (lb)b . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.33 3.43 3.67
c
Feed efficiency value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.300 0.292 0.272
120-days:
Average weight (lb) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188.2 177.8 176.4
Average daily weight gain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.56 1.28 1.27
Feed/pound of gain (lb)b. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.94 5,63 4.30
Feed efficiency valuec . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.254 0.178 0.233
Overall
Average daily weight gain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.49 1.40 1.37
Feed/pound of gain (lb)b . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.42 3.45 3.34
c
Feed efficiency-value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.292 0.290 0.299
aFrom Heeney (1977), 6 pigs in each treatment. Control diet - 76.9% ground corn, 20% soybean 011 meal, 1.5% dicalcium phosphate, 0.5% CaCo3, 0.5% salt, 0.1%
trace mineral 0.25% vitamin premix, 025°/0 ASP250 antibiotic Zeolite diets contained 25 and 5°A replacement of corn.
b
Excluding zeolite
CWeight gain/feed Intake, excluding zeolite
arrhea and soft feces (38). Five percent zeolite er quality meat. These differences were re-
was added to the normal grass and hay diets flected in the overall higher prices obtained for
of lo-and 184-day-old heifer calves over a 180- the test animals and a 20 percent greater profit.
day period. The animals on the zeolite-supple- In addition, diarrhea and other intestinal ail-
mented diets gained approximately 20 percent ments were noticeably less prevalent in the ani-
more weight than those in control groups, and mals on the zeolitc diet, and the excrement
although the test calves consumed more feed, from these animals was significantly less odor-
the feeding costs per kilogram of weight gained iferous, again testifying to the retentivity of
were significantly less than for control animals. clinoptilolite for ammonia. It is unfortunate
No deleterious effects were noted, and the fe- that a higher level of zeolite was not used in
ces of the test animals contained slightly less these experiments; earlier studies in the United
water and fewer particles of undigested solids. States showed that as much as 40 percent clay
The incidence of diarrhea and soft-feces was could be added to animal rations without ad-
markedly less in zeolite-fed calves than in con- verse effects (68),
trol animals (table 1 2 )
One study found increased protein digestion
Watanabe, et al. (86) raised six young bul- when 5 percent powdered clinoptilolite was
locks for 329 days on a diet containing 2 per- added to a high-volubility protein diet of 18 Hol-
cent clinoptilolite, along with 72 percent digest- stein steers and cows over a 118-day period;
ible nutrients and 11 percent crude protein. however, statistically significant weight in-
Although little difference in the final weights creases were not noted, The addition of 2 per-
of test and control animals was noted, test cent zeolite to the rations of cows was effec-
steers showed slightly larger body dimensions tive in preventing diarrhea and in increasing
and reportedly dressed out to give slightly high- milk product ion (20). These effects were appar-
141
— —— ——.—
Table 12.–Occurrence of Diarrhea and Soft-Feces Among Calves on Diets Supplemented With
5 % C l i n o p t i l o l i t ea
—
Incidence of diarrhea Incidence of soft-feces
-
Grass-fed Hay-fed Control Grass-fed Hay-fed Control
30 . . . . . . . . . . . . . . . . . . . . . . . . . . 0 0 4 0 0 4
36-60 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0 1 2 9 4 13
61-90 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . O 0 2 1 1 13
91-120 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 0 1 2 0 13
121-150 . . . . . . . . . . . . . . . . . . . . . . . . . . . O 0 4 4 0 8
151-184. . . . . . . . . . . . . . . . . . . . . . . . . . . 0 0 0 0 0 0
Total 1 1 — 13 16 5 51
aData summarized from Kondo etal (1969)
Table 13.—Effect of Zeolite Additions to produced during the digestion process, giving
Chicken Droppings rise to low-Btu products that are extremely cor-
Property 2.1 3:1 5:1 10,1 Control rosive. Nevertheless, the process is still an at-
Moisture content (%) 123 131 134 157 185 tractive one, and Goeppner and Hasselmann
Maggot content (counts per (21) estimated that a billion cubic feet of 700
unit area) 38 101 172 387 573 Btu/ft 3 methane gas could be produced by treat-
Ammonia generation (relative
quantities) 315 370 245 500 450 ing the 250,000 tons of manure produced each
aOnagi (1965) Clinoptilolite was spread on droppings of Leghorn chickens day in the United States. The methane pro-
every third day for a 15-day period The total amount of droppings iS the same
in all tests, I ncluding the control duced by the anaerobic digestion of the organic
wastes of a typical New York State dairy farm
ment, whilc at the same time retain the valu- of 60 head may be equivalent to the farm’s en-
able fertilizer components and meet ecologi- tire fossil-fuel requirements (32).
cal standards. A recent development of Reserve Synthetic
In swine raising, pigs fed a diet containing Fuels, Inc., using the adsorption properties of
10 percent cinoptilolite had feces richer in all natural zeolites, suggests that this methane can
forms of nitrogen after drying than those from be economically upgraded to high-Btu prod-
control groups (vide supra) (39). As a result of ucts. In 1975, this company opened a methane-
this study and of other investigations, about 25 recovery and purification plant to treat meth-
tons of clinoptilolite per month is spread on ane gas produced by decaying organic matter
the floors of a Sapporo swine-raising facility in the Pales Verde landfill near Los Angeles,
to adsorb urine and other liquid wastes (82). As shown schematically in figure 10, raw gas
The buildings were said to be dry, clean, and containing about 50 percent methane and 40
considerably less odoriferous. In Akita Prefec-
ture, Japan, a zeolitic mudstone is used to treat
offensive odors and to reduce moisture content
Figure 10. —Methane-Purification System,
of swine excrement (30). The dried manure is Pales Verde Landfill
then sold as an inexpensive rice fertilizer.
An innovative application of zeolites in ex-
crement treatment was patented and involves
the addition of a natural zeolite and ferrous sul-
fate to chicken droppings (37), The ferrous sul-
fate inhibits zymosis and decomposition of the
droppings, and the zeolite stabilizes the hygro-
scopic nature of this compound and captures
N H4 + produced in the manure. The mixture
is dried at 120 0 to 150 0 C and used as an odor-
less, organic fertilizer, It is also used as a pro-
tein-rich feedstuff for fish, fowl, and domes-
tic animals.
Methane Purification
Although it is well known that anaerobic di-
gestion of animal excrement and other organic
wastes produces an impure methane-gas prod-
uct, this source of energy has generally been
ignored for anything except local or in-house
use (32). One major drawback is the fact that
in addition to methane, copious quantities of
carbon dioxide and sulfur compounds are also
143
percent carbon dioxide is fed to two pretreat- feet of methane meeting pipeline specifications
ment vessels to remove moisture, hydrogen sul- is produced each day and delivered to local
fide, and mercaptans. The dry gas is then utility companies (65). Such a zeolite-adsorp-
routed through three parallel columns packed tion process to upgrade impure methane pro-
with pellets of dehydrated chabazite/erionite duced by the digestion of animal manure ap-
and carbon dioxide is removed by adsorption pears to be technically feasible and awaits
on the zeolite. Approximately 1 million cubic detailed economic and engineering evaluation.
AQUACULTURAL APPLICATIONS
In recent years, more and more fish products exchange might be a useful alternative to bio-
have found their way to the dinner tables and filtration for NH 4+-removal and have the ad-
feeding troughs of every country, and the com- vantages of low cost and high tolerance to
mercial breeding and raising of fish as a source changing temperatures and chemical condi-
of protein is becoming a major business in the tions (33).
United States and other countries, Many vari-
Unpublished tests conducted in 1973 at a
eties of fish, however, are extremely sensitive
working hatchery near Newport, OR, indicated
to minor fluctuations in such factors as water
that 97 to 99 percent of the NH, + produced
temperature, pH, O2 , H2 S, and NH 4 +. The
in a recirculating system was removed by clinop-
chemical and biological environment of aqua-
tilolite ion-exchange columns (34). Trout also
cultural systems must be maintained within
remained healthy during a 4-week trial when
close limits at all times. Processes based on the
zeolite ion exchange was used to regulate the
selective adsorption and ion-exchange proper-
nitrogen content of tank waters (69), Becker In-
ties of several natural zeolites for oxygen aer-
dustries of Newport, OR, in conjunction with
ation of hatchery and transport water and for
the U.S. Army Corps of Engineers, has devel-
the removal of toxic nitrogen from tanks and
oped a single-unit purification facility for
breeding ponds may contribute significantly to
hatchery-water reuse. The system incorporates
increased product ion for human and animal
a zeolite ion-exchange circuit for nitrogen re-
consumption.
moval and is designed to handle typical con-
centrations and conditions encountered at
most of the 200 fish hatcheries operating in the
Nitrogen Removal From Closed Pacific Northwest (34).
or Recirculation Systems
A similar ammonium-ion removal system
In closed or recirculating aquacultural sys- using zeolite ion exchange for fish haulage ap-
tems, NH 4 + produced by the decomposition plications, where brain damage due to excess
of excrement and unused food is one of the NH, + commonly results in sterility, stunted
leading causes of disease and mortality in fish. growth, and high mortality has also been de-
I n oxygen-poor environments, even a few veloped (63). Three-way cartridges and filters
parts-per-million NH 4 + can lead to gill dam- containing granular clinoptilolite will also be
age, hyperplasia, and substantial reduction in available for home aquaria. The U.S. Fish and
growth rates (42). Biological vitrification is a Wildlife Service investigated zeolite ion-ex-
common means of removing NH 4 + from cul- change processes for the treatment of recircu-
ture waters; however, processes similar to lating waters in tank trucks used to transport
those used in municipal sewage-treatment channel catfish from Texas hatcheries to the
plants based on zeolite ion exchange have been Colorado River in Arizona (48). If NH 4+ can
found to be effective in controlling the nitro- be removed, the number of fish hauled in such
gen content of hatchery waters (40). Zeolite ion trucks can be nearly tripled.
144
beds of nearly pure ash. Successive eruptions 1. deposits formed from volcanic materials
resulted in sequences of ash layers interstrati- in hydrologically ‘ c l o s e d " s a l i n e
fied with normal lake or marine S ediments, lake systems;
such as mudstoncs, silt stone, sandstones, and 2. deposits formed in hyrdrologially ‘open”
limestones, as well as beds of diatomite, ben- fresh-water lake or ground watcr systems;
tonite, and chert (figure 1 I). 3. deposits formed in marine environments;
4. deposits formed by low-grade, burial meta-
The layers of volcanic ash (called volcanic
morphism;
tuff) vary in thickness from less than a centi- 5. deposits formed by hydrothermal or hot-
metcr to several hundred meters and may
spring activity in bedded S ediments:
stretch for 10 kilometers. Many of these bed-
6. deposits formed from volcanic materials
ded tuffs have been transformed almost com- in alkaline soils;
pletely into well-formed, micrometer-size zeo- 7. deposits formed without direct evidence
litc minerals. Zeolitically altered tuffs occur in
of volcanic precursors.
relatively young sedimentary rocks in diverse
geological environments. Sedimentary zeolite The most common zeolites in sedimentary
deposits of this kind have been classified into deposits are analclime, chabazite, c1inoptilolite,
the following types, with many gradations be- erionite, heulandite, laumontite, mordenite,
tween the types, Sheppard (77), Mumpton (54), phillipsite, and wairakite, with clinoptilolite
and Munson and Sheppard (62): ranking first in abundance. Except for heulan-
thigenic silicate minerals in sedimentary rocks, tions, they have only limited in-house geologi-
their existence as major constituents of altered cal expertise to service their blossoming min-
volcanic tuffs is still not common knowledge eral industry.
among the geologists of many countries. Be-
During the late 1950s and 1960s the geologi-
cause of their inherently fine crystal size, zeo-
cal similarity}’ of the Western United States and
lites are not easily identified by ordinary micro-
northern Mexico led geologists to speculate
sscopic techniques and have often been missed
about the existence of zeolite deposits south of
by geologists and mineralogists studying these
the border. It was not until 1972, however, that
formations. In general, zeolite identification re-
this author (56) discovered the first such de-
quircs sophisticated X-ray diffraction and elec-
posit in southern Oaxaca after visiting a large
tron microscopic equipment not available in
stone quarry during an unrelated project. The
many geological laboratories; however, once
rock was being used as a local dimension stone
a particular soft, lightweight, clay-like rock
and closely resembled zeolitic tuffs that were
from a particular area is identified in the lab-
being quarried in Japan. Subsequently, the Oax-
oratory as a zeolite rock, similar materials are
acan rock was shown to consist of about 90
easy to locate in the field.
percent clinoptilolite and mordenite. Shortly
Table 15 lists the countries where zeolites thereafter, several similar deposits were discov-
have been reported from sedimentary rocks of ered in this part of Mexico and Mexican scien-
volcanic origin and estimates the chances of tists quickly learned to recognize zeolitic tuffs
discovering additional deposits in these coun- in the field. One deposit was spotted in a road
tries. Sedimentary zeolites have been found on cut while driving past it at 50 miles per hour,
every continent, although few have been re- suggesting that many more await discovery
ported from the Middle East, Latin America, with only minimal exploration efforts. As a re-
or the East Indies, mainly because geologists sult of these discoveries, at least three other de-
in these regions generally have been unaware posits of sedimentary zeolites have been found
of the widespread occurrence of zeolites in in the northern part of the country by Mexi-
altered volcanic tuffs. Wherever zeolites have can geologists who are now atune to the exis-
been found, however, man has used the soft, tence of zeolites in volcanogenic environments
lightweight tuffs for hundreds of years as eas- and to their potential applications in industrial
ily carved stone in a variety of structures rang- and agricultural technology.
ing from walls and foundations of buildings to
Similar to Mexico, major parts of the central
barns and corrals to house livestock. Zeolitic
Anatolian region of Turkey are covered by
blocks have been found in buildings associated
thick sequences of Tertiary volcanic rocks, but,
with the Mayan pyramids at Monte Alban and
with the exception of a few minor occurrences
Mitla in southern Mexico (56) and are used
of analcime in saline-lake environments, re-
today in the construction of modern dwellings
ports of zeolites in the volcanogenic sedimen-
in the Tokaj region of eastern Hungary. Zeo-
tary rocks of this country have been rare. The
lites are mined in only a dozen countries (ta-
principal reason for this is simply lack of ex-
ble 16), but the potential is much greater. ploration combined with a lack of knowledge
The high probability of finding minable de- about the potential applications of such mate-
posits of zeolites in countries where they have rials in industry. Turkey’s few geologists have
not yet been reported, but where there has been been more occupied with their chrome and
considerable volcanic activity in the past, is il- borate resources, which are exported in large
lustrated by the discovery of major bodies of quantities to acquire badly needed currency.
sedimentary zeolites in Mexico and in central In 1977, however, several low-grade occur-
Turkey in the early and late 1970s, respectively. rences of erionite and chabazite were uncov-
Both countries show promise of becoming ma- ered in Turkey’s Cappadocia region, along with
jor suppliers of mineral raw materials in the a major deposit of clinoptilolite (7). In 1979, a
years to come, but, as with most developing na- second major deposit was discovered by the au-
148
Zeolite .
Minable Minor
—
Chances for
Country species deposit occurrence finding deposit
Europe:
Belgium Laumontite x Poor
Bulgaria Clinoptilolite xxx Excellent
Mordenite x Excellent
Analcime x Poor
Czechoslovakia Clinoptilolite x Good
Denmark Clinoptilolite x Poor
Finland Laumontite x Poor
France Clinoptilolite xxx Good
Germany Chabazite xx Good
Phillipsite xx Good
Analcime xx Poor
Great Britain Analcime x Poor
Clinoptilolite x Poor
Laumontite x Poor
Hungary Clinoptilolite xx Excellent
Mordenite x Excellent
Italy Chabazite xxx Excellent
Phillipsite xxx Excellent
Analcime x Good
Poland Clinoptilolite xx Excellent
Romania Clinoptilolite xx Excellent
Soviet Union Clinoptilolite xxx Excellent
Mordenite xx Excellent
Chabazite x Good
Analcime x Good
Laumontite x Good
Spain Clinoptilolite x Good
Mordenite x Good
Switzerland Clinoptilolite x Poor
Laumontite xx Poor
Turkey Clinoptilolite xx Excellent
Erionite xx Excellent
Chabazite xx Excellent
Analcime x Excellent
Yugoslavia Clinoptilolite xxx Excellent
Analcime x Good
Mordenite x Excellent
Erionite x Good
North America:
Canada Laumontite x Poor
Clinoptilolite x Good
Cuba Clinoptilolite xx Excellent
Mordenite x Excellent
Guatemala Clinoptilolite x Excellent
Mexico Clinoptilolite xx Excellent
Mordenite xx Excellent
Analcime x Good
Erionite x Excellent
Phillipsite x Excellent
Panama Clinoptilolite x Excellent
West Indies Wairakite x Poor
Clinoptilolite x Excellent
Africa:
Angola Clinoptilolite x Good
Botswana Clinoptilolite x Good
Congo Analcime x Good
Egypt Heulandite x Good
Kenya Phillipsite x Excellent
Erionite x Excellent
149
thor (59) and R. A. Sheppard of the U.S. Geo- face deposits overlain by a few to no more than
logical Survey, accompanied by a Turkish ge- 25 meters of overburden. The zeolite beds are
ologist, with a minimum of field effort. This usually flat-lying and vary only slightly in thick-
indicates a widespread distribution of such ma- ness along the length of the deposit. Shallow
terials in volcanogenic sedimentary rocks in drilling is usually required to outline the areas
this country. of highest grade, but many deposits are mined
by simple projection of the bed behind the out-
crop, Commonly, the exposed bed can be bro-
Mining and Milling ken in the mine by bulldozers or rippers; in
places small amounts of blasting are required.
The mining of zeolites in bedded sedimen- In thinner deposits, care must be taken to elim-
tary deposits is a relatively straightforward inate overlying and underlying clays and vol-
process requiring only a minimum of equip- canic ash from the ore to preserve purity, but
ment and trained personnel. Almost all of the in some of the thicker deposits this poses no
known zeolite deposits being mined are sur- problem,
150
Processing the raw ore is dependent on the plications may require that the zeolite he ion-
envisioned end use. Water-purification appli- exchanged to an ammonium or potassium form
cations require a fine-sand fraction that must before being shipped to the consumer. In such
be prepared from the ore by crushing and cases, the pulverized and screened product
screening whereas fertilizer and animal nutri- must be subjected to a series of washes with
tion uses will likely make use of finely pow- chloride or sulfate salts of these elements,
dered material. In general, preparation in- washed with water to e1iminate excess salts,
volves only crushing, screening, and bagging. filtered, dried, and bagged. In 1980, crushed
Where particle size is critical, the screened ore could be produced i n the United States for
product must be washed to remove undersize about $30 to $40/ton.
material and then dried. More sophisticated ap-
DISCUSSION
Agronomic Applications either case, the zeolite appears to act as a slow-
release fertilizer, selectively holding such ele-
Although zeolites have been used for many ments in its structure for long periods of time,
years in Japan as soil amendments, they are thereby increasing the efficiency of such ad-
only now becoming the subject of serious in- ditives and reducing the total cost of fertiliza-
vestigation in the United States as slow-release tion. Although the data available are not une-
fertilizers, moisture-control additives to low- quivocal, the greatest success appears to have
clay soils, traps for heavy metals, carriers of been with root crops such as sugar beets, car-
pest icicles, fungicides, and herbicides, and de- rots, and radishes, where nitrogen is a vital nu-
caking agents in fertilizer storage. As soil trient. The optimum level of application, how-
amendments they appear to retain moisture ever, must still be determined for various types
and i reprove the overall ion-exchange capac- of soils and for the particular crop in question,
it y of sandy and volcanic soils. Studies are be- as must the frequency and exact mode of ap-
ing carried out on both pure zeolite and on zeo- plication, the optimum particle size of the zeo-
lite that has been pretreated with nutritive lite, and the nature of chemical pretreatment
elements, such as potassium or ammonium. In of the zeolite.
151
ing such uses for natural zeolites in this Similar projects are in progress in Cuba and
country. The projects have generally been Hungary, where deposits of clinoptilolite and
sponsored by grants or contracts from compa- mordenite are abundant. The intense interest
nies that themselves are developing applica- in the several socialistic countries mentioned
tions for zeolites in one or more areas of tech- above undoubtedly stems from their efforts to
nology, or they have been funded by the use their own natural resources and thereby
institutions themselves and make use of zeo- reduce their dependency on foreign sources of
lite products provided free or at low cost by expensive fertilizers and animal rations. These
the companies. Table 19 summarizes the agri- same objectives, of course, are desired by each
cultural research efforts of companies that hold developing nation—maximum use of local raw
properties of natural zeolites. In addition, materials and minimal use of imported prod-
other, nonproperty holding organizations, such ucts that must be purchased with hard curren-
as International Minerals & Chemical Corp., cy. Where they can be found within a particu-
Cargill, Inc., and Lowe’s, Inc., have also been lar nation or where they can be obtained from
involved in the development of uses of natu- neighboring countries at minimum cost, nat-
ral zeolites in agriculture. ural zeolites have the potential to increase the
agricultural productivity of that nation by re-
Overseas, six to eight agricultural stations in
ducing the need for or increasing the efficiency
Japan continue to investigate natural zeolites
of chemical fertilizers and animal feedstuffs.
as soil amendments and dietary supplements;
Pratley Perlite Mining Co., which owns a large To convert the agricultural promise of natu-
c1inoptilolite deposit in South Africa, has made ral zeolites into commercial reality, a concerted
several studies of the use of zeolites in the ra- effort must be made in the United States and
tions of swine and poultry; and a recent Bul- elsewhere by both the private sector and by
garian-Soviet symposium on natural zeolites State and Federal funding organizations. The
contained seven papers on animal-nutrition ap- studies to date have been mainly of a prelimi-
plications and two on soil-amendment uses, nary nature—radishes have been grown instead
‘Second Bulgaria n-%t’iet Symposium on Natu ra] Zeolites, of potatoes, and rats have been raised instead
Kardzhali, Bulgaria, Oct. 11-14, 1$)79, of beef cattle—or of limited duration or extent.
Little information has been developed to illum- from both the United States and the develop-
inate the long-term benefits or adverse impacts ing nations. The contribution of the United
on food production. Many of the companies States would be both geological and agricul-
sponsoring this research have considered the tural expertise in zeolite technology, whereas
results proprietary, and rightfully so, but work- the contribution of the developing nations
ers in the field are therefore unable to obtain would be a willingness to search for deposits
the latest information, a situation that often re- of zeolites and a willingness to carry out some
sults in massive duplication of effort. Large- necessary long-term or large-scale testing un-
scale testing of zeolites under sustained field der field conditions. Any implementation plan
conditions and projects involving statistically should begin with a series of visits by a team
significant numbers of animals are greatly of zeolite experts from the United States to
needed at this juncture. Such projects will re- selected developing nations in the world where
quire continuous funding by State and Federal zeolites are known or have a high probability
agencies, or perhaps, international agencies if of occurring. In addition to a leader who would
the results are to be applied to developing na- have a broad background in zeolite technology,
tions. It would be extremely instructive to carry the team would consist of four to eight geolo-
out such testing in several developing nations gists, agronomists, animal nutritionists, and
themselves, where agricultural practices are agricultural engineers who are not only experi-
not as finely tuned as in the United States. enced in the use of zeolites in agriculture or
in the occurrence of zeolites in volcanogenic
The actual introduction of natural zeolites sedimentary formations, but who can incite an
into specific agricultural processes should pose enthusiasm in others for the wonderful things
no major problems. Crushed and sized mate- that zeolites can do. The team would include:
rial could be added to the fields directly or
banded into the soil either alone or with nor- ● a geologist who is not only knowledgea-
mal fertilizers using standard equipment. Like- ble about the occurrence of zeolites in such
wise, the zeolite could be mixed as a powder environments, but who is capable of work-
or fine granules with normal feedstuffs pro- ing with local resource people to find and
vided for livestock, or be inserted as a bolus evaluate potential deposits of zeolites in
into the stomachs of ruminants. It could also these countries;
● an agronomist or plant scientist with con-
be sprinkled on or mixed with manure accumu-
lations on a daily basis for nutrient retentivity. siderable experience in the use of zeolites
to improve crop productivity;
None of these processes would require spe- c an animal nutritionist with the necessary
cial machinery; in fact, all could be carried out expertise in the use of zeolites as dietary
by hand, if such were the common practice in supplements in animal nutrition; and
that country. Users would, of course, need to ● an agricultural engineer who has worked
be instructed as to the correct amount to ap- with zeolites in excrement treatment to im-
ply to fields or to mix with normal rations, and prove the health of confined livestock or
the optimum time to apply it for specific crops, the ammonium retentivity of animal wastes.
and considerable educational efforts may be The agricultural engineer would also pro-
necessary to convince the small farmer of the vide practical experience to the team.
benefits of zeolite additives. In this regard, zeo-
lites are no different than any innovative pro- Prior to the first visit to a developing nation,
cedure that many farmers are slow to accept. the team would arm itself with the latest infor-
mation in the field by visiting the leading ex-
Because the use of zeolites in agricultural periment stations and research laboratories in
processes has not yet reached the proven or this country and abroad where zeoagricultural
commercial stage, any scenario developed to investigations are being carried out, Special
introduce this promising technology into de- emphasis would be placed on the recent work
veloping nations would involve contributions in Japan and in countries of Eastern Europe.
155
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