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 sequence of mineral reactions involving zeolites and other authigenic phases in tuffaceous sedimentary rocks can be explained by growth- and dissolution-reaction kinetics. Kinetic factors may determine the specific authigenic phases which form and the temporal and spatial constraints on the solution composition during irreversible dissolution and growth reactions in glass-bearing rocks. The glass phase generates a high level of supersaturation with respect to a variety of aluminosilicates in the pore fluid. The sequence of assemblages formed during a series of metastable reactions resembles an Ostwald step sequence. Metastable reactions occur because formation of less stable phases such as gels, clays, and disordered zeolites may lower the total free energy of the glass-bearing system faster than the growth of the stable assemblage including ordered feldspars, quartz, and micas. Eventually, after a series of steps, the most stable silicate assemblage for the bulk composition, temperature, and pressure may form. However, the formation of intermediate metastable phases can delay the attainment of equilibrium by as much as tens of millions of years.

The most prominent authigenic reaction in Holocene tuffaceous sediments at Teels Marsh, Nevada, is the hydration of rhyolitic glass by interstitial brines and the subsequent formation of phillipsite. This reaction has the form: rhyolitic glass + H2O → hydrous alkali alumninosilicate gel → phillipsite. Phillipsite is the most abundant authigenic phase in the tuffaceous sediments (>95%), analcime is the next most abundant phase, and clinoptilolite occurs as a trace mineral in the <2-mm fraction. Analcime forms by the reaction of phillipsite and Na+. Gaylussite and searlesite also are common authigenic phases at Teels Marsh. The concentration of silica in the interstitial brines is controlled by one or more of the authigenic reactions at less than 100 ppm. A stoichiometric equation for the reaction of phillipsite to analcime at Teels Marsh is:

$$0.43N{a + }\, + {K_{0.43}}N{a_{0.57}}AlS{i_{3.1}}{O_{8.2}}\, \cdot \,3.2{H_2}O\, \to \,NaAlS{i_2}{O_6}\, \cdot \,{H_2}O\, + \,1.1{H_4}Si{O_4}\, + \,0.43{K + }.$$

Sodium and potassium activities of brines associated with both phillipsite and analcime were used to estimate the equilibrium constant for this reaction as 3.04 × 10−5. The ΔG0 value for the reaction is +6.2 kcal/mole at 25°C and 1 atm pressure. The estimated ΔG0 value of phillipsite, using this reaction, is −1072.8 kcal/mole at 25°C and 1 atm.

Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence that makes up part of the Eocene Siletz River Volcanics in the central Coast Range, Oregon. Regional zoning of zeolite assemblages is not apparent; the zeolites formed in joints, fractures, and interstices, although most occur in central cavities of basalt pillows. The zeolites and associated minerals identified, in general order of paragenetic sequence, are smectite, pyrite, calcite (small spheres), thomsonite, natrolite, analcime, scolecite, mesolite, stilbite, heulandite, apophyllite, chabazite, mordenite, calcite (scalenohedra and twinned rhombohedra), laumontite, and amethystine quartz. Common three-mineral assemblages are: natrolite-analcime-stilbite, stilbite-heulandite-chabazite, stilbite-apophyllite-chabazite, and natrolite-mesolite-laumontite.

Alteration of basaltic glass, which was initially abundant, appears to have been an important factor in formation of the zeolites. Isotopic data suggest that zeolitization occurred during a low-temperature (60°–70°C) submarine hydrothermal event, or by reactions of cold (∼10°C) meteoric water with basalt over a long time. The occurrence of different mineral assemblages in cavities of adjacent basalt pillows indicates that these minerals crystallized in closed systems that were isolated as fractures and joints were sealed by deposition of smectite and early zeolites. Although the total chemical composition of the mineral assemblages in cavities is similar, different mineral species formed because of the sensitivity of zeolite minerals to slight variations in physical and chemical conditions within individual cavities.

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 lacustrine Sucker Creek Formation (Miocene) of eastern Oregon includes unaltered vitric tuffs as well as tuffs altered to the following diagenetic fades: (1) bentonite, (2) interbedded bentonite and opal-CT, (3) K-clinoptilolite, and (4) Ca-clinoptilolite. Bentonite beds contain Fe-rich smectite (8–10 wt. % Fe2O3), quartz, plagioclase, and Ca-clinoptilolite. Opal-CT-rich layers contain inorganic silica (opal-CT), Fe-rich smectite, and minor diatoms. K-clinoptilolite beds typically contain clinoptilolite that can be extremely K-rich (≤7.6 wt. % K2O), opal-CT, smectite, plagioclase, and K-feldspar. This diagenetic facies also includes smectitic tuff and unaltered tuff. Ca-clinoptilolite beds contain Ca-clinoptilolite, quartz, K-feldspar, smectite, and illite.

Based on its chemistry and mineralogy, the bentonite appears to have been derived from dacitic volcanic ash. Chemical considerations and the close spatial relationship between beds of bentonite and opal-CT suggest that the diagenetic alteration of glass to smectite provided silica to the adjacent opal-CT beds. Based on the presence of late-stage Ca-clinoptilolite, alteration appears to have proceeded in a relatively closed chemical system.

Based on the composition of preserved vitric tuff, the zeolitic tuffs appear to be derived from rhyolitic ash, which diagenetically altered in an open hydrologic system and produced vertical zonations in mineralogy. In this model, bentonite horizons at the top of the K-clinoptilolite diagenetic fades formed by reaction of volcanic glass with dilute fluids that had a relatively low (Na+ + K+ + Ca2+)/H+ activity ratio and ${\mathrm{a}}_{{\mathrm{H}}_4{\mathrm{S}\mathrm{i}\mathrm{O}}_4}$, whereas the underlying K-clinoptilolite beds formed from reactions between glass and dilute fluids having a higher (Na+ + K+ + Ca2+)/H+ activity ratio and ${\mathrm{a}}_{{\mathrm{H}}_4{\mathrm{S}\mathrm{i}\mathrm{O}}_4}$. Unaltered vitric ash between these beds may represent zones of higher permeability that inhibited secondary mineral alteration. Ca-clinoptilo-lite-rich beds appear to have undergone alteration similar to K-clinoptilolite-rich beds as well as to have been subjected to later, low-temperature (perhaps 75°–150°C) hydrothermal alteration which enhanced cation exchange in the zeolite and formed quartz from opal-CT.

A method using a finite, first-order Markov chain is presented to estimate rate constants for zeolite formation from experimental nuclear magnetic resonance (NMR) data on the abundance of different silica oligomers. An experimental design is suggested by which this method can be implemented. The method uses weighted least squares to estimate transition probabilities from aggregate NMR data. Rate constants, equilibrium constants, and free energies of elementary zeolite-forming reactions can be estimated. Hypothetical zeolite-forming reactions can also be modeled. An example of modeling, using hypothetical data, shows how zeolite formation can result from reactions involving mainly silica cyclic tetramers.

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.

The structure, chemistry and distribution of hydrothermal alteration and weathering products of feldspars and glass in 3 samples of Yucca Mountain tuffs (GSW G4 borehole at a depth of 1531 ft (464 m) and USW GU3 borehole at 1406 ft (426 m) from the Calico Hills Formation and USW G4 at a depth of 272 ft (82.4 m) from the Topobah Springs Member) were examined by high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM). Alteration products are of interest because they may influence the form and distribution of contaminants released from the proposed high-level nuclear waste repository. Samples from the Calico Hills Formation contain alkali-bearing aluminosilicate glass and its alteration products. Zeolites appear to have formed from compositionally similar glass by recrystallization, probably under hydrothermal conditions. Crystals are fibrous and frequently no more than a few tens of nanometers in diameter. Porous aggregates of few-nanometer-diameter, poorly crystalline silica spheres (probably opal C-T) develop adjacent to corroded glass surfaces and zeolite crystals. Finely crystalline Fe-rich smectites coat etched glass surfaces, zeolites and feldspar crystals and occur within opal-like silica aggregates. Microstructures in the clay-dominated coatings and details of smectite-glass interfaces suggest that clays grow in orientations controlled by heterogeneously retreating surfaces and from constituents released at associated glass dissolution sites. The alteration assemblage also includes finely crystalline hematite, goethite, Mn-oxide films and illite formed by alteration of muscovite. The zeolitized sample contains abundant opal-like silica whereas glass in the unzeolitized sample is weathered to smectite-like clays. These differences may be attributed to hydrological and consequent geochemical factors resulting from the higher porosity of zeolitized samples. Exsolved alkali feldspar, which occurs as micron-sized crystals in the Calico Hills Formation and as phenocrysts and in the groundmass of the devitrified Topobah Springs Member, are almost unaltered. Feldspar alteration is confined to cracks and grain boundaries, where minor, poorly crystalline, Fe-bearing aluminosilicate alteration products are developed. In these tuffs, most of the porosity, permeability, high surface area and capacity to affect solution chemistry are associated with products of glass alteration.

Sedimentary zeolites clinoptilolite, mordenite and erionite occur as diagenetic products of ash falls of rhyolitic composition from the Oligocene Chichindaro Formation at the limits of the Mexican Volcanic Belt with the Mexican Highland. These zeolitic tuffs were formed from open hydrologic environments where rhyolitic glass altered to clinoptilolite + opal-C and to clinoptilolite + mordenite + erionite + opal-C. The process of diagenesis was hydrolysis associated with the removal of SiO2, K2O, and Na2O from the rhyolitic precursor and enrichment of Al2O3, MgO, and CaO. The crystallization of clinoptilolite occurs at ratios of SiO2/Al2O3 between 4.91 and 7.14 and (K2O + Na2O)/(MgO + CaO) from 2.19 to 0.79. Formation of clinoptilolite appears to be directly from glass and through a vitreous proto-zeolite intermediate. The zeolitic tuff is in contact with a vitric tuff where ash falls were devitrified to K-feldspar and diagenetically altered to smectite + opal-C.

In Northwestern Mexico, the Miocene basins that disrupted the Sierra Madre Occidental Province are filled with sandstones and conglomerates (the Báucarit Formation) cemented mainly by zeolites of the heulandite-clinoptilolite group. Few volcanic tuffs are intercalated in the sediments for which four different groups of samples have been defined. These groups correspond to a gradation in the alteration of the glassy matrix. Group 1 is characterized by the preservation of the glassy matrix and the presence of disseminated patches of clay minerals with a continuous variation between aluminous Al-montmoril-lonite and ferric smectite end-members. Heulandite-group zeolites and opal C-T are also present. Group 2 is characterized by a nearly complete replacement of volcanic glass by a more homogeneous Al-montmorillonite. In some samples, heulandite-group zeolites are present as clusters on clay minerals. The primary vitroclastic texture is generally preserved and relict glass is present in small amounts. In group 3, the secondary assemblage is dominated by heulandite-group zeolite crystals as pseudomorphs of shards and pumiceous fragments. Discrete illite is present in all samples. Textures are exceptionally well-preserved. Group 4 is characterized by the presence of heulandite and clay minerals in which the Mg-Fe smectite end-member is more magnesian than in other groups. The original texture is not preserved.

The following are deduced from the mass-balance calculations: the alteration of the tuffs leads to a strong Mg- and Ca- and, to a lesser degree, Fe-enrichment, and to Na and K depletion. Zeolites account for Ca-enrichment and clay minerals are host for Fe and Mg. As a consequence, alteration may have occurred under open system conditions and the most likely source for the high Ca and Mg gains is a fluid circulating through the underlying volcaniclastic sediments and underlying mid-Tertiary volcanics of the bimodal (basaltic-rhyolitic) sequence. However, those fluids may have been rather dilute and weakly alkaline.

As estimated temperatures are between 85 and 125°C and as there is only a low burial, it is proposed that hot fluids are responsible for the alteration of volcanic glass. A decrease with time in the initial permeability of the tuffs is consistent with the observed evolution of the changing Al-smectite toward a more magnesian composition.

The matrix of the Pliocene volcaniclastics from the Akrotiri area of the Santorini island (Greece) is dominated by clinoptilolite. Smectite, occasionally illite-smectite, opal-CT, cristobalite and mordenite are also present. The clinoptilolite-rich samples were heated at 460 and 560°C for 12 h and the reductions in the intensity of the 020 diffraction peak were measured. Electron microprobe analysis (EMPA) was then used to study the chemical composition of the clinoptilolite. Statistical analysis proved a strong and quantifiable relationship between the reduction of the 020 diffraction peak of the clinoptilolite and the Na/K ratio. A representative set of microprobe analyses of clinoptilolite was performed before any correlation with thermal behavior was attempted. The presence of K in the structure of clinoptilolite as well as its relationship with Na are most important in the thermal behavior of clinoptilolite.

The Lower Pleistocene bentonite deposits of Eastern Milos, Greece have been formed at the expense of volcaniclastic rocks under submarine conditions. Systematic variation of the major chemical elements reveals that the deposits were formed from different precursors which were erupted from different volcanic centers belonging to at least two separate volcanic provinces. The volcanic eruptions were probably subaqueous. The major authigenic phases are smectite, K-feldspar, opal-CT and the zeolites mordenite and clinoptilolite. The deposits have a complex history and have been affected by hydrothermal alteration.

The geological features of bentonites coupled by the presence of abundant authigenic K-feldspar indicate that alteration of the parent volcanoclastic rocks took place under low temperatures and is probably not related to hydrothermal alteration, which is a separate event. Hydrothermal alteration has modified both the mineralogical characteristics and the properties of bentonites. Alteration of the parent rocks to bentonites was favoured by high water: wall rock ratios and fluid flow and is associated with leaching and subsequent removal of Na, K and Ca. The source of Mg was the parent rocks and only small scale Mg-uptake from the sea water has probably taken place. The formation of authigenic K-feldspar has probably been favoured by a high K+/H+ activity ratio and high Si activity of the pore fluid. Such conditions might have been favoured by the pH conditions and the cooling history of the parent rocks.

The ammonium acetate saturation (AMAS) method was used to study the cation-exchange capacity (CEC) of zeolitic volcaniclastic materials from Santorini and Polyegos Islands, Greece. The AMAS method was tested with respect to the time required to saturate the samples of zeolites with ammonium (NH4+) ions, the efficient liberation of NH4+ ions, and the suitability of two widely used techniques to measure ammonia (NH3) (Kjeldahl ammonia distillation technique and the ammonia electrode technique). By using the inductively coupled plasma-mass spectrometry (ICP-MS) technique and measuring the number of cations exchanged during ammonium acetate (NH4OAc) saturation, it was found that the saturation period for zeolitic materials must be increased to 12-day cycles to ensure effective saturation. Following NH4OAc saturation, the AMAS method produces NH4+ solutions, after the NH4+-saturated samples of zeolites are washed with 10% NaCl. The amount of the NH4+ ions in solution (i.e., exchangeable cations) is a measure of the CEC. The NH4+ ions can not be directly measured and must be converted to NH3. The Kjeldahl ammonia distillation technique and the ammonia electrode technique for measuring NH3 give identical CEC results. However, the ammonia electrode technique, when used directly with the NH4+ samples of zeolite without 10% NaCl treatment, generally gives higher CEC values. The amount of NH4+ treated (converted to NH3), when the NH4+-saturated zeolitized samples were used directly, was higher than the amount of the NH4+ treated when the NH4+ solutions were obtained after washing the NH4+-saturated zeolitized samples with 10% NaCl. Therefore, washing with 10% NaCl does not facilitate the release of all NH4+ initially within the zeolite structure. A modified AMAS technique is proposed for measuring the CEC of zeolitic material.

The chemical and the mineralogical composition of a group of pumiceous tuffs associated with recent salic volcanic episodes from Tenerife (Canary Islands) have been studied. The investigation focused on the two main types of pyroclastic deposits of the zone: ash-flows and ash-falls. The samples can be classified chemically as trachytic and phonolitic rocks with an intermediate silica content and a high percentage of alkali cations (Na+ and K+). The mineralogical composition, determined by X-ray diffraction, scanning electron microscopy, and optical microscopy, shows the occurrence of zeolites (mainly phillipsite, with lesser chabazite and analcime), associated with the parent glass. K-feldspar (sanidine) and calcite are accessory minerals. Zeolites are significantly more abundant in the ash-flow deposits. Zeolite formation by hydrothermal weathering in closed-system conditions varies according to the nature and the origin of the pyroclastic deposits. Tenerife phillipsites differ from typical diagenetic, lacustrine, and deep-sea phillipsites, both in chemical and mineralogical features. Alkali cations exceed divalent cations in the unit-cell that, assuming a monoclinic symmetry, has the following parameters: a = 8.46–10.55 Å, b = 14.21–14.40 Å, c = 7.80–8.70 Å, and β = 105°–110°.

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.

Smectite and zeolites were formed from a volcanic glass as the products of reaction with NaOH solution at 90°C and 100°C under atmospheric pressure. Formation conditions of smectite and various zeolites were determined by the ratio of the amounts of volcanic glass (g) to NaOH (g) in the solution. Smectite was formed under the condition that the values of weight of volcanic glass (g)/(NaOH(g)/40) are between 0.5 and 6. Fe was an important constituent of the octahedral layer of smectite.

Very unusual rocks consisting of natrolite (>95 vol.%) ± pargasite (<5 vol.%) and rarealbite (<1 vol. %) have been discovered in the Kop mountain range, eastern Turkey. We propose to call these rocks ‘natrolitite’ and ‘pargasite natrolitite’. They were produced by Na Si metasomatism of dikes and stocks of diorite through replacement of the intermediate primary igneous plagioclase to produce natrolite. The metasomatic alteration produced concentric elliptical zones characterized by distinct mineral assemblages centered on intrusions of diorite. The Central Zone 1 consists of variably albitized diorite with preserved magmatic textures (albite ± andesine ± pargasite ± quartz). Transition Zone 2 comprises natrolite-bearing diorite (natrolite ± albite ± andesine ± pargasite ± calcite ± quartz). Marginal Zone 3 is a rock made up almost entirely of natrolite (natrolite ± pargasite ± albite ± calcite ± chlorite). Outer Zone 4 occurs along the boundary between the natrolitite and the surrounding serpentinite and consists of listvenite, a rock which comprises magnesite, quartz, calcite, mica, talc, and hematite, indicating a role for CO2 in the metasomatic reactions, consistent with the presence of calcite in the alteration zones. Zone 5 consists essentially of brecciated serpentinite with numerous hydrothermal quartz veins and calcite veins. Whole-rock compositions document an increase in Na2O, Al2O3, and H2O from the core (central zone) to themargin while CaO, MgO, and SiO2 decrease. Plagioclase abundance and composition also varies outwards from the central core rocks where it occurs as a primary magmatic phase (∼95 vol.% An41−38) to the alteration zones (<5 vol.% An32−37) due to partial to complete replacement of plagioclase by natrolite with or without rare albite. The natrolites exhibit little variation in Si/Al ratios, ranging between 1.45 and 1.61, and are similar in composition to those reported in the literature. Accompanying pargasitic amphibole also becomes progressively more sodic in composition from the core rocks to the marginal zone rocks. Our analysis indicates that albitization preceded the formation of natrolite and that the formation of natrolite, instead of other more typical alteration minerals (e.g. analcime and paragonite), reflects Na metasomatism at lower chemical potentials for Al2O3 and SiO2. Potential sources of Na could be hypersaline brines or leaching of country rocks, such as trondhjemites. The fluids were driven in hydrothermal convection cells set up by theintrusion of thediorites.

Sedimentary zeolite occurrences are widespread in Central and Western Anatolia, Turkey. Erionite occurrences in Central Anatolia have significant health implications for inhabitants of the region. The widespread occurrences of zeolites are generally associated with volcano-sedimentary rocks and consist of low-temperature forms. The aim of the work was to define specifically the formation mechanism and chemical characteristics of these volcano-sedimentary deposits, and particularly, the stability conditions for erionite. The first step was to construct chemical potential diagrams and calculate thermodynamic data for erionite and Ca-saponite. Then, equilibrium activity diagrams were calculated for the zeolites and related minerals in the system of Ca-Na-K-Mg-Fe-Al-Si and H2O. Stability diagrams for log [aCa2+/(aH+)2] — log [aNa+/aH+] and log [aCa2+/(aH+)2] — log [aK+/aH+] for various saturation phase activities of Al3+ and SiO2 (aq) were plotted for sedimentary conditions. The coexisting phases and chemical characteristics of the each deposit were evaluated by examination of the activity diagrams. Deposits which do not include some of the common sedimentary zeolites, possibly have high Al3+ activity (equal to or greater than gibbsite saturation) or low SiO(aq) activity (less than quartz saturation) during formation. In addition, erionite was found to be very sensitive to the alkalinity of the system and is stable in only a limited range of thermochemical conditions.

The polymer model provides a relatively simple and robust basis for estimating the standard Gibbs free energies of formation (ΔGfo) and standard enthalpies of formation (ΔHfo) of clay minerals and other aluminosilicates with an accuracy that is comparable to or better than can be obtained using alternative techniques. The model developed in the present study for zeolites entailed the selection of internally consistent standard thermodynamic properties for model components, calibration of adjustable model parameters using a linear regression technique constrained by ΔGfo and ΔHfo values retrieved from calorimetric, solubility, and phase-equilibrium experiments, and assessments of model accuracy based on comparisons of predicted values with experimental counterparts not included in the calibration dataset. The ΔGfo and ΔHfo predictions were found to average within ±0.2% and ±0.3%, respectively, of experimental values at 298.15 K and 1 bar. The latter result is comparable to the good accuracy that has been obtained by others using a more rigorous electronegativity-based model for ΔHfo that accounts explicitly for differences in zeolite structure based on differences in framework density and unit-cell volume. This observation is consistent with recent calorimetric studies indicating that enthalpies of transition from quartz to various pure-silica zeolite frameworks (zeosils) are small and only weakly dependent on framework type, and suggests that the effects on ΔHfo of differences in framework topology can be ignored for estimation purposes without incurring a significant loss of accuracy. The relative simplicity of the polymer model, together with its applicability to both zeolites and clay minerals, is based on a common set of experimentally determined and internally consistent thermodynamic properties for model components. These attributes are particularly well suited for studies of the effects of water-rock-barrier interactions on the long-term safety of geologic repositories for high-level nuclear waste (HLW).