Two diagenetic stages of zeolitic alteration were recognized in a study of a thin bed of rhyolitic ash that was deposited in Eocene Lake Gosiute (Laney Member of the Green River Formation). The ash bed can be traced for 30 km along strike and represents a single volcanic event. The bed was not buried deeply (<100°C), and originally it was compositionally homogeneous. Initially, the bed altered to clino-ptilolite, heulandite, an intermediate phase between these two zeolites, and mordenite. These early reactions involved the hydration and solution of glass by saline, alkaline solutions and the subsequent precipitation of zeolites. The variation in zeolite mineralogy is due to differences in interstitial fluid chemistry that resulted from either fluctuations in lake-water chemistry or the proximity of spring discharge. These reactions, exclusive of the addition of H2O, involved only minor amounts of mass transfer over very small distances. Later, after burial, the early-formed zeolites reacted with upward moving sodium carbonate brines that were produced by dewatering of underlying evaporite deposits. The sodium carbonate brines, in equilibrium with trona and nahcolite, elevated the activity of Na+ and produced analcime. These later dehydration reactions involved significant mass transfer.

The water adsorption capacity of zeolites is a function of pressure and temperature. Desorption of zeolites may be of three types, wherein the crystal lattice undergoes (1) no or little change, (2) a reversible change, or (3) an irreversible change. In the first two cases, the divariance of the zeolite-water vapor equilibrium results in networks of isobars, isotherms, and isosteres which can be transformed into a “characteristic” curve following the Polanyi-Dubinin theory. Because the volume of the micropores of a zeolite structure is constant, the isotherms and “characteristic” curve can be transformed linearly. During desorption, if the volume of the micropores varies due to a change of structure, the curves show linearity breaks.

On the basis of X-ray diffraction, differential thermal, and thermal gravimetric analyses, the equilibrium curves and structural changes of heulandite and stilbite were determined, using specially designed equipment. In the reversible adsorption range, heulandite shows no linearity breaks in the transforms and no structural variation. Stilbite, however, shows a linearity break in the transforms corresponding to a structural change.

An assemblage of clay minerals, Na-zeolites, Fe- and Sb-sulfides, and borates occurs in cavities in the basalt flow that underlies the main borax ore body exposed by the U.S. Borax open pit at Boron, Kern County, California. Analcime and saponite are widespread in cavities and fractures near the top of the basalt. Part of the basalt recently exposed, although restricted in distribution, contains a much more diverse assemblage of diagenetic minerals. Although only a few different minerals occur in each cavity, the composite order of deposition is: ferroan saponite, pyrrhotite, saponite, phillipsite, gmelinite, clinop-tilolite, herschelite, analcime, greigite, rhodochrosite, searlesite, borax, calcite, and colemanite. In some cavities early-formed zeolites appear to have dissolved as later ones crystallized.

Microprobe analyses of the zeolites yielded the following compositions: phillipsite, Na4.28K0.08(Al4.36-Si11.64O32)·xH2O (Si/Al = 2.67); gmelinite, Na6.64K0.10(Al6.80Si17.22O48· xH2O (Si/Al = 2.53); herschelite, Na2.96K0.24(Al3.21Si8.79O24)· xH2O (Si/Al = 2.75); clinoptilolite, Na6.48K0.56(Al7.15Si28.77O72) · xH2O (Si/Al = 4.02); analcime, Na14.02K0.09(Al13.33Si34.44O96)· xH2O (Si/Al = 2.58).

These zeolites formed by reactions between the basalt and evolving fluids, which were controlled by the development of an overlying, Na-borate lake. The wide distribution of saponite, analcime, and searlesite suggests that these minerals formed by the diagenetic reaction between basaltic glass and Na- borate water. The localized occurrence of the complex mineral assemblage, including some of the saponitic clay and the zeolites, phillipsite, gmelinite, and clinoptilolite, formed through a different process, perhaps deuteric or hydrothermal alteration of the basalt, before the lake developed. Because these zeolites are extraordinarily rich in Na, cation exchange may have taken place as the pore fluids became increasingly Na rich. In the latest stages of mineral growth, each of these zeolites was apparently partially dissolved and epitaxially overgrown by a second generation crystal, phillipsite on phillipsite, herschelite on gmelinite, and sodian heulandite on clinoptilolite.

Yucca Mountain is being studied as a potential site in southern Nevada for an underground, high-level nuclear waste repository. A major consideration for selecting this site is the presence of abundant zeolites in Miocene ash-flow tuffs underlying the region. Beneath Yucca Mountain four diagenetic mineral zones have been recognized that become progressively less hydrous with depth.

Zone I, the shallowest zone, is 375–584 m thick in the central part of Yucca Mountain, but 170 m thick to the north. Zone I contains vitric tuffs that consist of unaltered volcanic glass and minor smectite, opal, heulandite, and Ca-rich clinoptilolite. Zone II thins south to north from 700 to 480 m and is characterized by complete replacement of volcanic glass by clinoptilolite with and without mordenite, and by lesser amounts of opal, K-feldspar, quartz, and smectite. Zone III thins south to north from 400 to 98 m thick and consists of analcime, K-feldspar, quartz, and minor calcite and smectite. Heulandite occurs locally at the top of zone III in the eastern part of Yucca Mountain. Zone IV occurs in the deepest structural levels of the volcanic pile and is characterized by albite, K-feldspar, quartz, and minor calcite and smectite.

Clinoptilolite and heulandites in zone I have uniform Ca-rich compositions (60–90 mole % Ca) and Si:Al ratios that are mainly between 4.0 and 4.6. In contrast, clinoptilolites deeper in the volcanic sequence have highly variable compositions that vary vertically and laterally. Deeper clinoptilolites in the eastern part of Yucca Mountain are calcic-potassic and tend to become more calcium-rich with depth. Clinoptilolites at equivalent stratigraphic levels on the western side of Yucca Mountain have sodic-potassic compositions and tend to become more sodium-rich with depth. Despite their differences in exchangeable cation compositions these two deeper compositional suites have similar Si:Al ratios, generally between 4.4 and 5.0. Analcimes have nearly pure end-member compositions, typical of these minerals formed by diagenetic alteration of siliceous volcanic glass; however, K-feldspars are Si-rich compared to the ideal feldspar formula.

Bulk-rock contents of Si, Na, K, Ca, and Mg of zeolitic tuffs generally differ significantly from stratigraphically equivalent vitric tuffs, suggesting that zeolite diagenesis took place in an open chemical system. Both the whole rock and the clinoptilolite are relatively rich in Ca and Mg in the eastern part of Yucca Mountain and rich in Na in the western part. The Ca- and Mg-rich compositions of the zeolitized tuffs in the eastern part of Yucca Mountain may be due to cation exchange by the sorptive minerals with ground water partially derived from underlying Paleozoic carbonate aquifers.

Diagenetic zones become thinner and occur at stratigraphically higher levels from south to north across Yucca Mountain, probably due to a higher geothermal gradient in the northern part of the area. The diagenetic zones were established when the geothermal gradient was greater than it is today, probably during the thermal event associated with the development of the Timber Mountain-Oasis Valley caldera complex north of Yucca Mountain.

The oxygen isotopes of albite, quartz, and zeolites from the Hokonui Hills, New Zealand, constrain crystallization temperatures and the type of pore fluids present during diagenesis. A section of altered vitric tuffs in this region contains an extremely sharp reaction boundary between a heulandite-chlorite assemblage containing fresh detrital plagioclase and a laumontite-albite-quartz assemblage. A laumontite vein follows the local joint pattern and forms the reaction boundary, suggesting that laumontitization occurred as a result of fracturing and increased fluid flow during uplift. The albite (δ18O = +15.0)-quartz (δ18O = +19.9 to +20.5) geothermometer constrains the temperature of alteration between 145° and 170°C with a pore water δ18O of +1.8 to +3.5. The tuff was buried to an estimated maximum temperature of about 225°C, indicating that alteration occurred after maximum burial.

Framework oxygen was extracted from zeolites by reaction with ClF3 after the zeolites were thermally dehydrated in a vacuum. Laumontite was dehydrated at 300°C, and stilbite at 150°C. The precision of the method is typically about ±0.45‰. Fractionation curves for dehydrated zeolites are based on a general expression from the literature for feldspars, which depends only on the Si/Al ratio of the mineral. Measured δ18O values for laumontite in the groundmass of the altered tuff were +14.4‰. The laumontite-quartz pair constrains the temperature to between 139° and 162°C, in excellent agreement with the albite-quartz pair, and supporting the petrographic observation of co-crystallizing albite-laumontite.

Oxygen isotope values for fracture-filling laumontite in the vitric tuff, as well as those for groundmass and vein laumontite from other parts of the stratigraphic section, cluster around +14.5, suggesting that laumontite probably crystallized under similar conditions throughout much of the section. Oxygen isotope values for stilbite veins from various parts of the section indicate that this mineral crystallized at lower temperatures than the laumontite, for a given fluid isotopic composition, in agreement with the observed cross-cutting of laumontite by stilbite.

Heulandite-group zeolites are abundant in the Miocene pyroclastics from Western Anatolia, Turkey. We investigated the relation between the I(111)/I(3¯11) intensity ratios measured by X-ray diffraction (XRD) and the content of exchangeable cations for 15 samples of natural heulandite-group minerals gathered from the Gördes and Bigadiç regions of Western Anatolia. The intensity ratios range from 0.77 to 0.94 in natural heulandites and from 1.38 to 1.80 in natural clinoptilolites. The data obtained from Na-, K- and Ca-exchanged forms of a heulandite and clinoptilolite show that the intensity ratio increases with Na-, K- and Ca-exchange in heulandite and also with Na- and K-exchange in clinoptilolite, whereas it decreases with Ca-exchange in clinoptilolite. The intensity ratios were calculated using the known structural data of clinoptilolites to understand the effect of positions, amounts and kinds of exchangeable cations and water molecules. An increase in Na and Ca may increase or decrease the intensity ratio, depending on their sites and occupancies. Potassium causes a significant increase in the intensity ratio and an increase in Mg decreases the intensity ratio. There is a strong correlation between the intensity ratio I(111)/I(3¯11) and (Na + K)/(Ca + Mg) ratio and thermal stability, both of which have been used to characterize heulandite-group minerals.

The vitric component of the silicic pyroclastic flows and surge deposits (Prassa ignimbrite unit), from the northwestern exposures of the pyroclastics formation of Polyegos Island, South Aegean Sea Volcanic Arc in Greece, is replaced by authigenic zeolite and clay minerals. Mordenite dominates, and clinoptilolite (heulandite type 3), illite and illite-smectite (I-S) are subordinate. Opal-CT, quartz, feldspar, biotite and halite complete the mineralogical suite. In the southwestern part of the pyroclastics formation (Myrsini pyroclastics unit), kaolinite, halloysite, alunite and amorphous silica are the major mineralogical constituents as a result of a strong hydrothermal alteration by solutions enriched in SO42-. Scanning electron microscope (SEM) examination proved that the 1st type of zeolites formed within the area were heulandite minerals, following the formation of smectite, as a result of the activity of pore fluids within the volcaniclastic pile. There was no substantial evidence to support a hypothesis that mordenite was formed with the heulandite minerals after the initial stages of glass dissolution, other than some very minor mordenite that was formed from a gel-like type of material. The majority of mordenite present is most often draped over and formed from the crystals of heulandite minerals. Heulandite minerals often show advanced dissolution effects. The mineral dissolution was due to the emplacement of rhyolite lava domes and flows and the associated temperature rise and circulation of hydrothermal fluids, which had also mixed with seawater. The volcanic activity raised the temperature and changed the pore fluid chemistry, and the more unstable members of the heulandite minerals group were transformed to mordenite. Clinoptilolite (heulandite type 3), which was found within a few samples, was thermally more stable than any heulandite type 1 or 2 phases initially present. Therefore, clinoptilolite was either transformed more slowly or within a very few cases, it has not been affected at all. A heulandite-minerals-derived material acted as the major precursor for the formation of mordenite. The temperature increase within the area and the later hydrothermal alteration effect are also indicated by the illitization of the smectite. Mordenite is also found to have formed from I-S clays. Overall, mordenite formed as a result of elevated temperature and high Na+ concentration.

The pyroclastic sediments studied here contained varied amounts of zeolite and were formed in the saline alkaline Tuzgölü Basin following the alteration of dacitic volcanic materials during the Early to Late Miocene. The present study focused on the geological-geochemical properties of the zeolites and describes their formation. Mineralogical and chemical compositions were determined by X-ray diffraction, scanning electron microscopy, optical microscopy, and inductively coupled plasma mass spectrometry. Results indicated that the zeolitic tuffs consisted mainly of heulandite/clinoptilolite (Hul/Cpt), chabazite, erionite, and analcime associated with smectite. Smectite, calcite, and dolomite are abundant in the clay and carbonate layers which alternate with the zeolitic tuffs. K-feldspar, gypsum, and hexahydrite (MgSO4·6H2O) were also found in some altered tuffs and clay-marl layers as accessory minerals. The zeolite and other authigenic minerals showed weak stratigraphic zonation. Some vitric tuff layers contained no zeolite minerals and others were found to consist of almost pure Hul/Cpt and chabazite layers with economic potential. The rare earth elements (REE), large ion lithophile elements (LILE), and high-field strength elements (HFSE) in the Hul/Cpt-rich tuffs and vitric tuffs were enriched or depleted relative to the precursor rock, while many major elements were slightly or significantly depleted in all zeolitic tuffs. The amounts of REE in the chabazite- and erionite-rich tuffs were generally smaller than those in the precursor rock. The middle and heavy REE (MREE and HREE, respectively) were abundant in the Hul/Cpt-rich tuffs, tuffs, and smectitic bentonites. Chondrite-normalized REE values of the sample groups are characterized by sub-parallel patterns with enrichment in LREE relative to HREE. The mineral assemblages and geological setting indicated that zeolite diagenesis occurred in a saline-alkaline basin. The δ18O and δD compositions of the Hul/Cpt, chabazite, and smectite indicated that the minerals formed at low to moderate temperatures and that some of the zeolitization occurred due to diagenetic alteration under closed-system conditions that varied according to the nature of the basin and with the composition and physical properties of the volcanic materials.

Tuffs of the Tertiary Colbún Formation near Quinamávidain central southern Chile have been mapped and their mineralogy analyzed. The pyroclastic rocks present a maximum outcropping thickness of 120 m and are dominated by vitreous lapilli and minor lithic tuffs, the products of active volcanism nearby. About 10% of the tuffs consist of lenses of fine banded tuffs with a high leaf content that were deposited in shallow lakes during quiescent periods between periods of volcanic activity. This tuff sequence is pervasively transformed to clinoptilolite/heulandite and mordenite with variable amounts of plagioclase, minor quartz and smectite. Factors thought to have influenced this conversion to zeolites are a humid climate following deposition combined with a slightly elevated heat flow. Local hydrogeological conditions have modified the cation-hydrogen ion ratios across the study area favoring the formation of clinoptilolite/heulandite and mordenite with medium-minor smectite in the center and south, and a more abundant presence of smectite in the north of the study area.

Natural tuff samples in western Anatolia (Türkiye) originating from Miocene rhyolitic–pyroclastic rocks with >80 wt.% heulandite/clinoptilolite zeolites were investigated for their surface characteristics determined according to nitrogen adsorption after degassing at 150°C (specific surface area, pore volume and pore diameter). Additionally, these surface characteristics were correlated with the cationic compositions of the heulandite/clinoptilolite group minerals. The examined samples were characterized by two main pore diameters that were not related to specific surface area and pore volume but were partially related to the types and occupancy of extra-framework cations. One set of samples has a pore diameter of ~24 Å, total cation content (Na + K + Ca + Mg) ranging from 3.46 to 4.40 and a (Na + K)/(Ca + Mg) ratio ranging from 0.34 to 0.92. The total cation contents and (Na + K)/(Ca + Mg) ratios of the remaining samples with a pore diameter of ~37 Å are 4.30–5.08 and 1.48–2.85, respectively. After degassing at 300°C, there is a slight difference in the pore diameters of these two sets of samples (~37 and 38 Å). The pore sizes of the samples with a (Na + K)/(Ca + Mg) ratio < 1 (heulandite composition) increased from 24 to 36–38 Å with increasing degassing temperature, whereas the pore sizes of the samples with a (Na + K)/(Ca + Mg) ratio > 1 (clinoptilolite composition) increased from 37 to only 38–39 Å. However, there is no correlation between the Si/Al ratios and the cation-exchange capacities of the samples and their surface characteristics obtained by degassing at the two temperatures.

Diagenetic alteration in two tuff horizons (the lower and upper tuff units) in the GoÈrdes region of Turkey led to the formation of mainly heulandite-clinoptilolite-type zeolites and also clay and silica minerals and K-feldspar. Possible variations in the climate and geological environment followed by variations in the hydrological system and the composition of the Miocene lake water and groundwater at that time resulted in the mineralogical facies. The lower tuffs are unaltered or slightly altered in the northern part and are more altered, particularly to zeolite (clinoptilolite) in the southern part of the study area. Heulandite and K-feldspar are mainly authigenic minerals in the upper tuff unit. The ammonium-exchange capacities of the 16 samples were investigated to understand the effects of the mineralogical composition on their ion-exchange capacities, which vary in the range 0.19-2.00 mEq/g. It is observed that the ion-exchange capacities are strongly dependent on the zeolite contents of the rocks. The correlation coefficient of this linear relation is 0.86. The most significant increase in ammonium-exchange capacity (from 0.2 to ~1.0 mEq/g) was observed when the zeolite contents increased from 0 to 30 wt.%. The second increase in exchange capacity was observed for samples containing >80 wt.% zeolite. Although there is no significant effect from the other authigenic minerals, smectite has a positive effect, and K-feldspar and opal-CT have almost no effect on the ion exchange capacities.

A zeolite found in a soil profile developed in Danian chalk was studied. The results showed that it is a heulandite, temperature-stable to above 600°C with a Si/Al ratio of 2.88 and almost completely K-exchanged. The mineral probably formed under burial diagenetic conditions in the chalk formation.

The unstable glassy component of the Oligocene tuffaceous sediments of the Metaxades area, Thrace, Greece, has undergone extensive zeolitic diagenetic alteration. The authigenic minerals occur as crypto- to micro-crystalline aggregates making up most of the matrix in the altered tuffs and as precipitates in cavities produced by dissolved glass fragments. Glass-shard pseudomorphs are ubiquitous and most of them are partly filled by one or more of the minerals smectite, heulandite, mordenite and silica.

The heulandite group zeolites are mostly high-silica calcium-rich heulandites showing intermediate thermal behaviour between most heulandites and clinoptilolites. Their Si/Al ratios are similar to clinoptilolite (4.74–5.19) but their divalent/monovalent cation ratios (1.5–3.24) are partly superposed onto the ratios of heulandite group 1 and 2 and differ considerably from the values of the relevant ratio in clinoptilolite. Rare K-rich clinoptilolite crystals have been identified in one sample only.

Based on field observations, compositions and paragenetic relationships of coexisting authigenic minerals and the absence of critical phases such as laumontite, analcime or authigenic albite, it is suggested that the Metaxades pyroclastic rocks underwent burial diagenesis intermediate between Iijima's (1978) zones II and III commonly developed in silica saturated environments.

This report embodies recommendations on zeolite nomenclature approved by the International Mineralogical Association Commission on New Minerals and Mineral Names. In a working definition of a zeolite mineral used for this review, interrupted tetrahedral framework structures are accepted where other zeolitic properties prevail, and complete substitution by elements other than Si and Al is allowed. Separate species are recognized in topologically distinctive compositional series in which different extra-framework cations are the most abundant in atomic proportions. To name these, the appropriate chemical symbol is attached by a hyphen to the series name as a suffix except for the names harmotome, pollucite and wairakite in the phillipsite and analcime series. Differences in spacegroup symmetry and in order—disorder relationships in zeolites having the same topologically distinctive framework do not in general provide adequate grounds for recognition of separate species. Zeolite species are not to be distinguished solely on Si : Al ratio except for heulandite (Si : Al < 4.0) and clinoptilolite (Si : Al ⩾ 4.0). Dehydration, partial hydration, and over-hydration are not sufficient grounds for the recognition of separate species of zeolites. Use of the term ‘ideal formula’ should be avoided in referring to a simplified or averaged formula of a zeolite.

Newly recognized species in compositional series are as follows: brewsterite-Sr, -Ba; chabazite-Ca, - Na, -K; clinoptilolite-K, -Na, -Ca; dachiardite-Ca, -Na; erionite-Na, -K, -Ca; faujasite-Na, -Ca, -Mg; ferrierite-Mg, -K, -Na; gmelinite-Na, -Ca, -K; heulandite-Ca, -Na, -K, -Sr; levyne-Ca, -Na; paulingite-K, -Ca; phillipsite-Na, -Ca, -K; stilbite-Ca, -Na.

Key references, type locality, origin of name, chemical data, IZA structure-type symbols, space-group symmetry, unit-cell dimensions, and comments on structure are listed for 13 compositional series, 82 accepted zeolite mineral species, and three of doubtful status. Herschelite, leonhardite, svetlozarite, and wellsite are discredited as mineral species names. Obsolete and discredited names are listed.

The Tertiary volcano-sedimentary sequence of the Feres basin (Thrace, NE Greece), includes lavas of andesitic–rhyolitic composition as well as volcaniclastic rocks, pyroclastic flows and pyroclastic fall deposits principally of dacitic–rhyodacitic composition. The pyroclastic flow deposits frequently show intense devitrification, vapour-phase crystallization and evidence of fumarolic activity, which involves deposition of scapolite in pore spaces. The Feres basin can be subdivided on the basis of mineral alteration assemblages: (1) the Pefka region; characterized by intense hydrothermal alteration of the volcanic rocks and mineral zoning(silicic, argillic, sericitic and propylitic zones) with polymetallic mineralization, and (2) the remainder of the basin; where the volcaniclastic rocks are characterized by the alteration of volcanic glass to zeolites (clinoptilolite, heulandite, mordenite, analcime), clay minerals (smectite, illite, celadonite, chlorite), SiO2 polymorphs (cristobalite, opal-CT, quartz), K-feldspar and calcite. Laumontite is also present as an alteration product of plagioclase, with stilbite sporadically occurringin veinlets. Locally, rhyolites are also altered to zeolites (clinoptilolite and/or mordenite). The zeolitization process has occurred rapidly with the depositional environment, temperature, rate of cooling(of the volcanic rocks), nature and temperature of the mineral-forming fluids and composition of the parent material controllingthe formation of zeolites.

This study focused on the mineralogical and physico-chemical properties of heulandite/clinoptilolite (Heu/Cpt)-rich zeolitic tuffs SE of Ankara (Turkey) and evaluated their potential for use as adsorbents. The main Heu/Cpt minerals correspond to the intermediate type and the Cpt-type of the heulandite series. Minor chabazite, erionite and rarely analcime and accessory feldspars, mica, smectite, and quartz were also detected. Three types of Heu were recognized according to their thermal behaviour. Cpt (type-III Heu) was thermally stable at 600°C, whereas type-I Heu collapsed and type-II Heu partially collapsed. The Si/Al ratios of the Hul/Cpt ranged from 3.54 to 5.03, the Γ parameter (Γ = Ca/Al + 0.115*Al) varied between 0.78 and 1.85 and Al + Fe3+ varied between 6.27 and 8.00. The Na, K and Ca contents of Heu/Cpt varied widely and the Heu had an intermediate composition between types II and III. The Mg + Ca content is greater than the Na + K content in Heu-type II and smaller in Heu-type III zeolites. The BET surface area and the pore-size of the samples varied between 10.15 and 194.27 m2/g, and between 1.41 and 12.42 nm, respectively. The N2 adsorption and desorption isotherms were comparable, but the adsorption/desorption capacity is greater in type III than in type II Heu zeolites. The cation exchange capacities of the Heu/Cpt-rich samples ranged from 185 to 280 meq/100 g.