Experiments on zeolitization were conducted on four synthetic monocationic glasses (Na, K, Ca, or Mg-rich glass) with Si/Al molar ratios of 2.67, similar in acidity to many volcanic glasses of partially zeolitized Italian tuffs. The products of the hydrothermal treatment at 100, 150, and 200°C of single glasses or glass mixtures with deionized H2O or monosaline solutions (NaCl, KCl, CaCl2) were characterized by X-ray diffraction, thermal, microscopic and chemical analyses. Chemical analyses of mother liquors were also performed. Mineral assemblages, containing chabazite, phillipsite, analcime, and K-feldspar, very similar to those found in altered, volcaniclastic alkali-trachytic or trachytic glass deposits were produced. Potassium was essential to chabazite and phillipsite crystallization, although phillipsite was obtained also in Ca-Na mixed systems. Sodium was necessary for analcime formation. Calcium plays only a secondary role in zeolitization, and magnesium does not favor zeolite crystallization but promotes the formation of smectite. Glass composition determines the mineral assemblages obtained and hence in those commonly found in nature.

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.

Geologic mapping and crystal-chemical analysis of Middle-Upper Miocene volcanics in the Sandıklı-Afyonkarahisar region of Turkey, coupled with published zeolite analyses has revealed that western Turkey hosts unique zeolitic mineral assemblages with distinct paragenetic sequences. The present investigation focused on pyroclastic deposits, including low to intermediate potassic trachytic/trachyandesitic tuffs (LPT) and high potassic tephriphonolitic, tephritic, and trachybasaltic tuffs (HPT), each of which contains various styles of zeolites. Optical petrography, X-ray powder diffraction, and chemical analyses have revealed varying degrees of lithification, probably related to differences in initial emplacement temperature, depositional mechanism and thickness, chilling rate, and extent of mafic composition. Zeolitization was further influenced by meteoric flushing in a hydrologically open system. Chabazite in the LPT from the Selçik area occurs extensively as coatings and infillings of pores. Phillipsite in the HPT found in the Ballık, Küfeke, and Ömerkuyu areas dominates the assemblage and is accompanied by chabazite and minor amounts of analcime. Analcime was probably generated by alteration of leucite which is found as a pyrogene mineral. Alkali zeolites or Ca-bearing zeolites formed as a consequence of the addition of Ca and/or the removal of Na (i.e. dissolution of analcime). The paragenetic sequence may be described as: analcime/phillipsite → chabazite → calcite. The characterization of these assemblages may lead to better exploitation strategies for natural zeolitic resources in the region.

The Plio-Pleistocene deposits of the Olduvai Basin in northern Tanzania consist of a sequence of lacustrine and fluvial sediments. They contain various amounts of zeolite minerals, the formation of which is related to an interaction of volcanic material or detrital clays with saline alkaline lake water and groundwater. Petrographic characteristics of zeolite occurrences provide information about their conditions of formation. They were studied for all four main stratigraphical units that are recognized at Olduvai (Beds I to IV), sampled in the southeastern part of the basin. In the lake-margin deposits of Bed I and the lower part of Bed II, chabazite is the dominant zeolite mineral accompanied by phillipsite and minor amounts of erionite and clinoptilolite. Chabazite commonly occurs as part of altered volcanic rock fragments, characterized by partial or complete dissolution of volcanic glass and the formation of chabazite inside vesicles, following the development of thin smectite coatings. It also formed within the sediment matrix, requiring extended periods of impregnation of the deposits by saline alkaline solutions. Chabazite also occurs extensively as coatings and infillings of pores, developed during periods of subaerial exposure which were characterized by high groundwater levels. Phillipsite formed at a later stage, from more evolved solutions, with higher K/Na ratios than during chabazite formation. The fluvial deposits of Bed IV, Bed III and the upper part of Bed II have a high analcime content. They also contain various amounts of chabazite, phillipsite and natrolite. All zeolite minerals mainly occur in pores. The predominance of analcime indicates a higher salinity and alkalinity than during the preceding period with sedimentation and diagenesis in a lake margin environment. Early development of zeolite occurrences, shortly after the deposits became exposed during breaks in sedimentation, is recorded for some intervals, where zeolites are covered by illuvial clay coatings or by sparitic carbonate cement. In most intervals, however, zeolites mainly formed at a later stage.

A calorimetric method for determining isothermal partial and integral heats of hydration reactions ($\text{Δ}{\overline{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\bar H_{{\rm{R,}}T,\,P}}$ and $\text{Δ}{\stackrel{\sim }{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\tilde H_{{\rm{R,}}T,\,P}}$, respectively) in zeolites and other mineral hydrates is presented. The method involves immersing a dehydrated sample in a humid gas stream under isothermal conditions within a thermal analysis device that records simultaneous differential scanning calorimetric (DSC) and thermogravimetric analysis (TGA) signals. Monitoring changes in sample mass (corresponding to extent of reaction progress) coincident with a quantitative measurement of heat flow allows for direct detection of $\text{Δ}{\overline{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\bar H_{{\rm{R,}}T,\,P}}$ as a function of the extent of hydration, which can be integrated to determine $\text{Δ}{\stackrel{\sim }{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\tilde H_{{\rm{R,}}T,\,P}}$. In addition, it eliminates uncertainties associated with imprecise knowledge of the starting and final states of a sample during hydration. Measurement under isothermal conditions removes uncertainties associated with heat capacity effects that complicate interpretations of DSC measurements of dehydration heats conducted under traditional scanning temperature conditions. Example experiments on the zeolites natrolite, analcime and chabazite are used to illustrate strategies for quantifying $\text{Δ}{\overline{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\bar H_{{\rm{R,}}T,\,P}}$ and $\text{Δ}{\stackrel{\sim }{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\tilde H_{{\rm{R,}}T,\,P}}$ and minimizing errors associated with baseline uncertainties. Results from this method agree well with previously published values determined by other calorimetric techniques and regression of phase equilibrium data. In the case of chabazite, the results allowed detailed measurements of the variation in $\text{Δ}{\overline{H}}_{\text{R,}T,P}$${\rm{\Delta }}{\bar H_{{\rm{R,}}T,\,P}}$ for energetically different water types encountered progressively as the sample absorbed water. This technique complements and in many cases improves the quality of thermodynamic data obtained through phase equilibrium observations and other calorimetric techniques.

Natural zeolites may represent one of the greatest under-utilized resources of the mineral world. Even with their unique character and properties, issues of consistency, homogeneity and purity preclude them from many premium applications. We report a simple method to upgrade mineral sedimentary Na-chabazite from the well known Bowie, Arizona, deposit to near synthetic purity and consistency. During this alkaline-silicate digestion process, initially soft chabazite ore granules gain substantial mechanical strength. This may allow direct employment in adsorption and purification processes without the need for binding and forming. These granules manifest significantly improved adsorption properties, including enhanced water and CO2 adsorptivity.

Mineral chabazite has shown the unusual ability to surface template nanometal particles, especially Ag. A chabazite analog was synthesized from delaminated metakaolin. The chabazite formed retained the platy morphology of the base clay. This morphology is ideal for displaying surface-supported nanometal particles. The synthetic chabazite analog demonstrated the ability to form and support large concentrations of Ag nanoparticles, as observed in the related natural mineral. Due to greater Al content, the synthetic chabazite manifests significantly improved capacity for the formation of such Ag nanoparticles. As in the case of the mineral chabazite, surface Ag nanoparticles of high uniformity were observed in the range of 5–6 nm.

This paper presents results from comparative thermogravimetric, calorimetric and pozzolanic activity analyses of five natural zeolite samples from Bulgaria, Slovakia, Philippines, USA and North Korea. The zeolites actively participate in the hydration processes of cement. Their activity in the early stage of hydration is based mainly on the large surface area of the particles while, in the later stages of activation, chemical reactions occur between the products of the hydration of cement and the soluble SiO2 that is present in the bulk of the zeolites. It has been shown that in all cement pastes which contain zeolite additives, the quantity of portlandite is lower than that in pure cement paste or is even totally absent. The amounts of hydration products are greater when 30% zeolite is used than when 10% zeolite is added (excluding the sample with chabazite). The lowest pozzolanic activity is shown by chabazite, which possessed the lowest SiO2/Al2O2 ratio.

Rheological, porosimetric, and SEM studies of cements with additions of natural zeolites (chabazite, mordenite and clinoptilolite) were investigated. The addition of 5% zeolite to cement pastes had a plastifying effect. The increase in the rheological parameters of aqueous cement–zeolite suspensions began after additions of more than 10% zeolite. At a water/solid ratio (w/s) = 0.5 all compositions exhibited similar rheological behaviour for yield stress and maximum shear stress values. At lower w/s values the rheology depended on the zeolite used, decreasing in the order Sl (clinoptilolite, Nižny Hrabovec deposit, Slovakia), M (mordenite, Philipines), Bp (clinoptilolite, Beli Plast deposit, Bulgaria), NM (clinoptilolite, Saint Cloud deposit, New Mexico) and Ch (chabazite, Nasm Yan deposit, Korea).

After 28 days of hydration the mixtures containing 10% Bp clinoptilolite, mordenite, and Sl clinoptilolite (up to 30%) had unchanged specific pore volumes but additions of 10% and 30% of chabazite and NM clinoptilolite and of 30% mordenite and Bp clinoptilolite lead to increases in the total specific pore volume compared to the neat cement paste. Between the 28th and 180th days of hydration the specific volume of the pores in all the cement-zeolite pastes decreased due to the filling of the pores with products from the pozzolanic reaction between the zeolites and the hydration products of the cement.

The pozzolanic reaction between zeolite and the hydration products of cement is enhanced by the zeolite content in the samples and depends on the Si/Al ratio (clinoptilolite (Si/Al >4.5), mordenite (Si/Al >5), chabazite (Si/Al <2.5)) and the surface area (clinoptilolite from Slovakia has the smallest crystallites and, hence, the greatest reactive surface area).

A natrolite-cemented palagonite ash tuff unit is reported in a palaeo-basin in northeast Jordan. Phillipsite and chabazite are also identified. The zeolites were formed due to transformation of volcanic glass granules into palagonite by the reaction with percolating water in a closed hydrological system. Consequently, Si, Al, Ca, Na and K are leached out and precipitated in a series of authigenic layers developed at the extreme edge of the granules. The recorded paragenetic sequence is smectite → phillipsite → chabazite → natrolite → analcime → calcite. The natrolite studied is chemically similar to those reported in the literature with minor variations. The phillipsite and chabazite studied are chemically different from the other Jordanian phillipsite and chabazite reported. The latter are chemically equivalent to those formed under open hydrological systems, whereas the phillipsite and chabazite in this study are chemically equivalent to those formed in saline lakes and arid soil environments. This conclusion is based on the (Na+K)/(Na+K+Ca+Mg) ratio and the Si/Al ratio.

The effect of mechanical activation on the ion-exchange selectivity of natural zeolites from Russia, namely clinoptilolite-bearing tuffs and chabazites, was studied. The structural modifications and thermal properties were investigated, and the specific surface area and porosity of mechanically activated zeolites were determined. At activation doses of up to 1.0 kJ g–1 the main processes are the breakdown of the zeolite particles and pore structure changes. At greater activation doses amorphization takes place. It was shown that during the initial stage of activation in most cases the clinoptilolite selectivity for Sr2+ increased slightly and then decreased; the selectivity for Cu2+ increased 100 times; and the selectivity of chabazite-1 for Sr2+ increased 300 times.

A gonnardite-thomsonite-chabazite-calcite assemblage forms a cement in the Foveaux Formation, a fossiliferous gabbroic boulder bed that accumulated at the base of a sea cliff cut in a Permian igneous complex during late Oligocene±early Miocene time. Gonnardite was the earliest zeolite to form, locally following minor calcite. It was followed epitaxially by thomsonite, co-precipitating with chabazite. Crystal habits indicate a low-temperature origin. The maximum temperature to which the deposit may have been subjected is estimated as not more than ∽30°C. The chabazites are Ca-poor chabazite-K and chabazite-Na. Representative electron microprobe analyses are as follows, all + nH2O:

• thomsonite: Na3.77Ca7.73(Al19.39Si20.65)O80 and Na3.78K0.04Ca7.25Mg0.05(Al19.13Si21.05)O80;

• gonnardite: Na6.95K0.03Ca4.73(Al16.99Si23.15)O80 and Na8.56K0.03Ca4.05(Al17.32Si22.84)O80;

• chabazite-K: Na1.18K1.72Ca0.08Mg0.23(Al3.51Si8.49)O24 and Na1.67K1.92Ca0.18Mg0.17(Al4.11Si7.85)O24;

• chabazite-Na: Na2.51K1.13Ca0.17Mg0.02(Al4.08Si7.93)O24.

Such a Si-poor zeolite assemblage is unusual for marine sediments and is attributed to precipitation from marine water impoverished in silica in the gabbroic boulder bed and interacting with shell material and calcic plagioclase. In contrast, a dioritic clast in the boulder bed provides an example of less silica-poor zeolites originally formed in the parent igneous complex. Veinlets in the clast contain scolecite averaging Na1.19Ca7.36(Al15.84Si24.14)O80.nH2O, and mesolite averaging Na5.13K0.03Ca5.24 (Al15.93Si24.13)O80.nH2O, in part as sub-microscopic intergrowths. The composition of scolecite closely corresponds to the most Na-rich scolecite reported hitherto.

Apophyllite, analcite, chabazite, prehnite and stilbite are described from pectolite-, chlorite-, calcite- and quartz-bearing veins and joint coatings in the late Carboniferous quartz dolerite of the Whin Sill of the northern Pennines. These veins represent the final hydrothermal stages in the sill's emplacement and are not related to the widespread lead-zinc-barium-fluorite mineralization of the northern Pennine orefield. Thermogravimetric studies of apophyllites from the two Whin Sill occurrences reveal that at one locality the minreal is fluorapophyllite, at the other hydroxyapophyllite.

Phacolite from Mitaki, Sendai City, Japan, has a core of penetration-twinned chabazite. The crystal has a convex (0001) face on which many twin individuals are produced by a two-dimensional nucleation mechanism, resulting in complicated twinning during growth. Both the r and the faces repeat finely during growth because of twinning, resulting in {112̄3} sectors with polysynthetic twinning. Finally, single structures nucleate on the crystal edges [211̄] and develop along the (112̄3) face, penetrating each other near the centre of the face.

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.

Supposed 'merlinoite' crystals from Monte Somma, Vesuvius (Italy) and Fosso Attici, north of Rome (Italy) represent highly twinned coherent intergrowths between merlinoite and phillipsite on a submicroscopic level. The MER (Immm, a ≈ 14.1, b ≈ 14.2, c ≈ 9.9 Å) and PHI (P 21/m, a ≈ 9.9, b ≈ 14.3, c ≈ 8.7 Å, β = 124.8°) frameworks of similar composition are assembled from identical tetrahedral units, though with a different connectivity. Coherent intergrowth and twinning of the two frameworks lead to P42/mnm pseudosymmetry, which is diagnostic of the intergrowth. Under ambient conditions merlinoite has Immm symmetry or I4/mmm if twinned. a low-symmetry model of space group P121/m1 (a ≈ 14.2, b ≈ 14.2, c ≈ 10 Å, β = 90°) allows structure refinement and quantification of the two frameworks.

Upon in situ dehydration to 250°C the evolution of the unit-cell volume of the Monte Somma merlinoite/phillipsite intergrowth displays an intermediate trend between previously studied pure merlinoite from the Khibiny massif (Russia) and Ba-rich phillipsite.

The Monte Somma crystal studied by temperature-dependent single-crystal X-ray diffraction methods also contained a subordinate chabazite inclusion with no coherent structural relationship to the merlinoite/phillipsite framework. Thus, the modification of the chabazite framework on dehydration could also be studied.