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G EOLOGY OF Z EOLITE Title Page

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I Wayan Warmada J I
warmada@yahoo.com
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∗ Laboratory of Mineral Resources, Geological Engineering, UGM
Terminology of zeolite
• The name ’zeolite’ was introduced by the
Swedish mineralogist Cronstedt in 1756 for
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certain silicate mineral in allusion to their be-
haviour on heating in a borax bread (Greek zeo Title Page

= boil; lithos = stone). Contents

• Definition: a zeolite mineral is a crystalline JJ II

substance with a structure chracterized by a J I

framework of linked tetrahedra, each consist- Page 2 of 39


ing of four O atoms surrounding a cation.
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– This framework contains open cavities in Full Screen

the form of channels and cages. These are Close

usually occupied by H2O molecules and


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extra-framework cations that are com-
monly exchangeable.
– The channels are large enough to allow
the passage of guest species. In the hy-
drated phases, dehydration occurs at tem- Home Page

peratures mostly below about 400◦ C and


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is largely reversible.
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– The framework may be interrupted by
(OH,F) groups; these occupy a tetrahe- JJ II

dron apex that is not shared with adjacent J I

tetrahedra. Page 3 of 39

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• Application of definition: relatively easy ex-
change of extra-framework cations at rela- Full Screen

tively low temperature is a characteristic fea- Close

ture of zeolites and zeolitic behaviour, but


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varies greatly from species to species.
Zeolite properties
• According to Breck (1974), the important
physical and chemical properties of zeolite
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are:
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– High degree of hydration Contents

– Low density and large void volume when JJ II


dehydrated
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– Stability of the crystal structure of many
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zeolites when dehydrated
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– Cation exchange properties
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– Uniform molecular-sized channels in the
dehydrated crystals Close

– Ability to adsorb gases and vapors Quit


– Catalytic properties

• Molecular sieves are materials that can selec-


tively adsorb molecules on the basis of their
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size, shape, or electrical charge (Clifton, 1987).
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• Commercial applications of zeolites are based


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on the following properties: molecular siev-
ing, ion exchange, adsorption, and catalysis. JJ II

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• Activated carbon, activated clays, aluminum
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oxide, and silica gels are also molecular
sieves. Go Back

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Zeolite classifications
Crystal Void Volume,
Zeolite Typical Unit-Cell Formula System %
Analcime Na16(Al16Si32O96)•16H2O Cubic 18 Home Page

Chabazite (Na2Ca)6(Al12Si24O72)•40H2O Hexagonal 47


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Clinoptilolite (Na4K4)(Al8Si40O96)•24H2O Monoclinic 39
Erionite (Na2Ca6K)9(Al9Si27O27)•27H2O Hexagonal 35 Contents

Ferrierite (Na2Mg2)(Al6Si30O70)•8H2O Orthorhombic 0


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Heulandite Ca4(Al8Si28O72)•24H2O Monoclinic 39
Laumontite Ca4(Al8Si16O48)•16H2O Monoclinic 34 J I

Mordenite Na8(Al8Si40O96)•24H2O Orthorhombic 28


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Phillipsite (Na2K)10(Al10Si22O62)•20H2O Orthorhombic 31
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Linde A† Na12(Al12Si12O48)•27H2O Cubic 47
Linde X† Na66(Al66Si106O364)•264H2O Cubic 50 Full Screen

Linde A and Linde X are synthetic phases
Source: Kogel et al. (2006) Close

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Specific Channel Thermal Ion-Exchange
Zeolite Gravity Dimensions, A Stability Capacity*
Analcime 2.24 – 2.29 2.6 High 4.54
Chabazite 2.05 – 2.10 3.7 × 4.2 High 3.81
Clinoptilolite 2.16 3.9 × 5.4 High 2.54 Home Page

Erionite 2.02 – 2.08 3.6 × 5.2 High 3.12


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Ferrierite 2.14 – 2.21 4.3 × 5.5 High 2.33
3.4 × 4.8 Contents

Heulandite 2.10 – 2.20 4.0 × 5.5 Low 2.91


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4.4 × 7.2
4.1 × 4.7 J I
Laumontite 2.20 – 2.30 4.6 × 6.3 Low 4.25
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Mordenite 2.12 – 2.15 2.9 × 5.7 High 2.29
Phillipsite 2.15 – 2.20 4.2 × 4.4 Low 3.87 Go Back

2.8 × 4.8
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3.3
Linde A† 1.99 4.2 High 5.48 Close

Linde X† 1.93 7.4 High 4.73


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Linde A and Linde X are synthetic phases; * in meq/100g (calculated from unit-cell formula).
Geology of zeolite
Mineralogy
• Zeolites occur in a variety of geologic set- Home Page

tings, mostly as alteration or authigenic min- Title Page

erals, low temperature-low pressure minerals


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in metamorphic systems, secondary minerals
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in weathered zones, or in veins.
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• Nine zeolites commonly occur in sedimentary
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rocks: analcime, chabazite, clinoptilolite, eri-
onite, ferrierite, heulandite, laumontite, mor- Go Back

denite, and phillipsite. Full Screen

• Analcime and clinoptilolite are by far the most Close

abundant. Quit
• Chabazite, clinoptilolite, erionite, mordenite,
and phillipsite are the only zeolite minerals
with commercial applications today.

• Erionite, which has been classified as a human Home Page

carcinogen, has only limited industrial appli- Title Page

cations.
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• These five are the only zeolites that are JJ II

abundant in nature and have adequate ion- J I


exchange, absorbency
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• The basic structure of zeolites consists of Go Back

(AlSi)O4 tetrahedra, wherein each oxygen is


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shared by two tetrahedra: thus, the atomic ra-
tio O:(Si+Al) is 2. Close

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• The net negative charge of the structure is
balanced by exchangeable cations, which are
loosely held within the central cavities and
surrounded by water molecules.
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Origin Title Page

• Zeolite minerals occur in several geologic set- Contents

tings and can be formed from a variety of start-


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ing vitric or lithic material within an extended
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range of physiochemical conditions.
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• Volcanic glass of acid to intermediate compo-
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sition is the most common precursor for zeo-
lite minerals. Less common precursors include Full Screen

microcrystalline quartz, opal, and feldspars. Close

• Nearly all the minable zeolite deposits in the Quit


world occur as zeolitized ash fall tuffs in-
terbedded with lacustrine sediments, zeoli-
tized vitroclastic tuffs in volcanic rocks, and
zeolitized vitrophyres and vitroclastic tuffs as
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a result of hydrothermal alteration.
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• Pressure, temperature, and time are three im-


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portant factors that produce zeolite alteration
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of the vitric precursor.
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• The composition of the vitric component and
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the composition of the reactive pore water that
contains cations such as H+ , Na+ , Ca2+ , K+ , Go Back

and H4SiO4 are important factors needed to Full Screen

produce zeolitic alteration.


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• Based on zeolite geologic setting, mineralogy, Quit


and genesis, Sheppard (1973) classified zeolite
deposits into the following types:

– Closed system: deposits formed from


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volcanic materials in hydrologically
closed, saline/alkaline lake systems. Title Page

Erionite, chabazite, and phillipsite chrac- Contents

terize the saline, alkaline-lake deposits.


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– Open system: deposits formed in hydro-
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logically open, freshwater lake or ground-
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water systems. Clinoptilolite and mor-
denite are the principal zeolites of open- Go Back

system deposits. Full Screen

– Burial metamorphic: deposits formed Close

by low-grade, burial metamorphism (or


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burial diagenetic deposits). With increase
of depth, the deposits usually contain
zone of (1) fresh ash, (2) alkali clinoptilo-
lite, (3) clinoptilolite–mordenite, (4) anal-
cime, and (5) albite.
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– Hydrothermal or hot spring: deposits


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formed by hydrothermal or hot spring ac-
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tivity.
– Deep marine: deposits formed in deep JJ II

marine environments, i.e., clinoptilolite J I

and phillipsite. Marine zeolites form Page 13 of 39


at low temperatures and may replace as
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much as 80% of the marine sediments.
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– Weathered zone: deposits formed in soils,
most commonly from volcanic materials. Close

Analcime has been reported in alkaline, Quit


saline soils in the eastern San Joaquin Val-
ley, California.

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a-d) glass shards (de’Gennaro et al., 2000)


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a) amorphous gel-like phase; b) initial glass alteration product with Full Screen
fibrous aspect; c) acicular cluster (phillipsite?); d) phillipsite crystals
(de’Gennaro et al., 2000) Close

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e) phillipsite crystals lining cavities in glass shard; f) glass shard; g) euhe- Full Screen
dral chabazite crystals; h) acicular cluster covering glass shards structure
(de’Gennaro et al., 2000) Close

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a) zeolitized spherulites; b) clinoptilolite crystal on glass shard; c) heulan-


dite crystal coating bubble walls; d) opal-CT lephispheres on clinoptilolite Close

(Cerri et al., 2001).


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e) opal-CD lephisphere encrusting clinoptilolite; f) encrusting opal-CT; g)
fibrous mordenite; h) adularia-like K-feldspar crystals (Cerri et al., 2001).
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a) cavity filled by quartz; b) subtle quartz vein; c) tardive quartz vein in


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plagioclase; d) analcime crystals (Cerri et al., 2001).
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e) subtle sedimentary structures; f) clinoptilolite cementing detrital clasts;
g) opal-CT lephispheres along with clinoptilolite crystals; h) smectite ag- Close
gregates and clinoptilolite crystals (Cerri et al., 2001).
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Characterizations
• Natural zeolite minerals are identified primar-
ily by their crystal habit.
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• The principal methods of zeolite identification Title Page

are XRD and scanning electron microscopy


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(SEM). Neither optical microscopy nor differ-
ential thermal analysis (DTA) is particularly JJ II

useful for identifying zeolite minerals. J I

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– X-ray Diffraction
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– Scanning Electron Microscopy
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– Optical Microscopy
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– Different Thermal Analysis
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• In characterizing zeolitic materials for com-
mercial uses, it is important to quantify other
physical and chemical properties required by
the specific application.
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• The following are physical and chemical prop- Title Page

erties and tests that may typically be required:


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wet chemical analysis; CEC; specific gravity
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and bulk density; brightness, whiteness, and
color; hydration/dehydration; gas adsorption; J I

attrition in water; internal and external surface Page 22 of 39

are; pore size; and volume.


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Zeolite characteristics
A B

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C D
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A) analcime; B) chabazite; C) heulandite; D) laumontite Quit


A B

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C D Contents

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A) zeolite outcrop (Serut); B) Sidomulyo; C-D) zeolite hand specimen from


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Sidomulyo
A B

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C D
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A-B) chabazite in thin section, PPL and XPL; C) heulandite, XPL; D) lau-
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montite, XPL.
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A B

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C D JJ II

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A) mordenite crystals, in SEM; B) clinoptilolite; C-D) mordenite and
clinoptilolite. All sample from Sidomulyo.
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1–2) chabazite; 3) phillipsite; 4) heulandite (Passaglia & Vezzalini, 1985)
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a) acicular crystals of phillipsite; b) rhombohedral chabasite; c) phillipsite-
chabazite; d) analcime (de’Gennaro et al., 2000) Close

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Zeolite applications
• The principal uses of zeolites at this time are:

– Amonium-ion removal from sewage and Home Page

industrial effluents, aquarium, and com- Title Page

mercial fish farms


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– Odor control in animal absorbents, floor


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and carpet cleaning products, and indus-
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trial floor absorbents
– Removal of heavy metal ions from nu- Page 29 of 39

clear, mine, and industrial effluents Go Back

– Agricultural applications as soil condi- Full Screen

tioners and animal feed supplements


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– Desiccants used to adsorb water vapor in


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sealed containers and packaging
– Carriers for bacteria and enzymes
– Gas separation
– Catalysis
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• Agricultural products: zeolites are used as soil Title Page


conditioners and fertilizer extenders, particu-
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larly in Japan, Cuba and Eastern Europe.
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• Animal nutrition: adding clinoptilolite to an-
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imal feed in controlled amounts increase uti-
lization of feed and decrease ammonia stress Page 30 of 39

in animal digestive system. Go Back

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• Aquaculture: zeolite are used in aquarium,
fish farms, and fish hatcheries to avoid the Close

buildup of ammonia to toxic levels. Quit


• Catalysis and petroleum refining: zeolite with
large channel sizes have large internal surface
areas and can catalyze many type of reactions.

• Desiccants: activated chabazite is used as a Home Page

carrier and desiccant in packaged enzymes Title Page

and bacteria used to inoculate silage. Partially


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activated clinoptilolite and chabazite are used
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as anticacking agents in cattle feeds containing
mineral and organic supplements. J I

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• Dimension stone: zeolitic tuffs have been used
for thousand of years as lightweight, durable Go Back

dimension stone. Zeolitic tuffs have low bulk Full Screen

densities, are weather resistant, have superior


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insulating properties, and can be easily cut
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into attractive stone.
• Gas separation: zeolites are used to separate
nitrogen and oxygen to produce a gas stream
containing up to 95 % oxygen. Mordenite ap-
pears to be the best natural zeolite for oxy-
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gen generation, although clinoptilolite and
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chabazite have also been used.
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• Ion-exchange applications: the ability of ex-
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change cations is one of the most important
properties of zeolites. Cation-exchange capac- J I

ity is a measure of the number of cations per Page 32 of 39

unit weight available for exchange.


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• Medical and personal care applications: the Full Screen

U.S. armed forces uses zeolite products that


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stop bleeding from wounds by promoting clot-
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ting. Clinoptilolite has been used successfully
as a polishing agent in fluoride-containing
toothpaste by allowing a higher level of fluo-
ride to remain in anionic form.

• Natural gas purification: chabazite has been Home Page

used to seperate carbon dioxide, hydrogen sul- Title Page

fide, and other gases from methane produced


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from natural gas and oil wells.
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• Nuclear waste treatment and handling: J I


chabazite and clinoptilolite are used in
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treatment, handling, and containment in en-
gineering structures for the storage of nuclear Go Back

wastes. Full Screen

• Odor control: natural zeolites, particularly Close

clinoptilolite, adsorb ammonia ions. Natu- Quit


ral zeolites, notably clinoptilolite, chabazite,
and phillipsite, have also been used for odor
control in personal products (e.g., in athletic
shoes).
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• Paper fillers: natural zeolites, especially Title Page

clinoptilolite, have been used as fillers in some


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special paper products.
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• Pozzolan and cement: pozzolan is a naturally J I


occuring cementaceous material that can re-
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place up to 25 % of the portland cement in con-
crete. Zeolitic tuff have been used as pozzolan Go Back

in many places in the world. Full Screen

• Sewage treatment: clinoptilolite and chabazite Close

remove ammonia and some heavy metals Quit


from sewage and other effluent streams.

• Solar energy and heat exchange: chabazite


and clinoptilolite absorb and release heat
from solar radiation for air conditioning, Home Page

refrigeration, and water heating applications. Title Page

• Stack gas cleanup: natural zeolites can be used Contents

to remove sulfur dioxide from stack gases of JJ II

coal-burning power plants. Clinoptilolite and J I


mordenite can adsorb as much as 200 mg of
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SO2 per gram of zeolite under static conditions
and as much as 40 mg under dynamic condi- Go Back

tions. Full Screen

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Occurrences (Java Island)
West Java
• Nanggung (Bogor) Home Page

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• Bayah and Leuwidamar (Lebak)
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• Geger Bitung, Cisolok, and Cikembar (Suk-


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abumi)
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• Cikalong (Tasikmalaya) Page 36 of 39

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Central Java and Yogyakarta
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• Wadaslintang (Wonosobo) Close

• Nanggulan (Kulonprogo) Quit


• Serut, Sampang, Hargomulyo, Gedangsari,
and Sidomulyo (Gunung Kidul)

• Trembono (Klaten)
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East Java Title Page

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• G. Cagak, Wonosidi (Pacitan)
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• Slahung (Ponorogo)
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• Kali Tengah (Blitar) Page 37 of 39

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• Tembarejo and Sumbermajing (Malang)
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References
• Cerri, G., Cappelletti, P., Langella, A.,
de’Gennaro, M. (2001) Zeolitization of Oligo-
Home Page
Miocene volcaniclastic rocks from Logudoro
(northern Sardinia, Italy). Contrib Mineral Title Page

Petrol, v. 140, pp. 404–421. Contents

• Coombs, D.S. (Chairman) (1998) Recom- JJ II

mended nomenclature for zeolite minerals: re- J I

port of the subcommittee on zeolites of the Page 38 of 39


International Mineralogical Association Com-
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mission on New Minerals and Mineral Names.
Mineralogical Magazine, v. 62, pp. 533–571. Full Screen

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• Graham, I.T., Pogson, R.E., Colchester, D.M.,
Baines, A. (2003) Zeolite crystal habits, com- Quit
positions, and paragenesis; Blackhead Quarry,
Dunedin, New Zealand. Mineralogical Maga-
zine, v. 67, pp. 625–637.

• Kogel, J.E., Trivedi, N.C., Barker, J.M., Home Page

Krukowski, S.T. (eds) (2006) Industrial Miner- Title Page

als & Rocks, 7th Edition, SME, Inc., Colorado.


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