Mordenite and clinoptilolite have replaced glass shards and pumice in vitric tuffs that are the products of ash fall-out into lake basins of late Quaternary age in the Taupo Volcanic Zone. The vitric tuffs are intercalated with siltstone and diatomite and overlie pumice-rich, rhyolitic ignimbrite. A Zr/TiO2-Nb/Y immobile element ratio plot indicates that the vitric tuffs, like the ignimbrite, are of rhyolitic composition. X-ray diffraction and scanning electron microscopy studies indicate that the mordenite and clinoptilolite are accompanied by authigenic K-feldspar and Opal-CT. The zeolites and other authigenic minerals are very fine grained (<10 µm), with open meshes of acicular mordenite crystals that result in low densities (0.7–1.0 g cm−3) in mordenite-rich tuffs. From Pearce element ratio analysis of whole-rock chemical analyses, only Na and K appear to have been mobilized during alteration. The zeolite deposits are associated with sinter, hydrothermal eruption breccias and silicified fault breccias that represent surface or near-surface manifestations of geothermal activity. Plant material extracted from a sinter overlying one of the deposits has a 14C age of 8498±60 BP, which is interpreted to be the age of zeolite deposition for this deposit. Mordenite and clinoptilolite occur in the lower-T (60–110°C) parts of some active or recently active geothermal systems elsewhere in the Taupo Volcanic Zone. The main fluid in these systems is weakly saline (alkali-chloride) water heated by geothermal activity. The Ngakuru zeolite deposits are interpreted as the products of the reaction of vitric tuffs with this type of water in the near-surface part of recently active geothermal systems.

The Maramures Basin, in the Carpathian mountain belt of northern Romania on the border with the Ukraine, belongs to the eastern part of the Pannonian Basin. In the study area, extensional tectonic movements during the Miocene were coeval with silicic and intermediate volcanism in the inner part of the Eastern Carpathians. Throughout this region, explosive events have resulted in the deposition of pyroclastic flows and ash-fall deposits interbedded with marine sediments.

Several tuff units of Badenian (15–13.6 Ma) age occurring throughout the area are extensively zeolitized. These rocks occur as massive homogeneous beds, white to pale greenish-blue, and are commonly extensively jointed. In the Bârsana-Calinesti area and along the Morii Valley, two conspicuous tuff units that can be traced over many km are separated by a calcareous sandstone bed. Most tuffs have a vitroclastic texture in which former glass shards are pseudomorphed by clay minerals and clinoptilolite. Opal-CT commonly occurs as clumps of radiating rods that produce a spherical morphology. Also, rare celadonite is found in the lower greenish tuffs. Pyrogenic crystal fragments are quartz, plagioclase and biotite. Folded muscovite plates and fragments of basement rocks are dominant among the lithic clasts. Above the Bârsana Formation, a second series of white zeolitized tuff, the Ocna Sugatag Formation, is represented by at least two different units overlying an evaporite salt deposit. A large outcrop of a massive white tuff at this locality contains abundant fine-grained clinoptilolite and cation-exchange capacity values of >160 meq/100 g. Clinoptilolite-Ca is also present in the Sighetu tuff unit in the northern part of the Maramures Basin where a distinctive horizon contains plant remains preserved in spherical concretions. Plant material and algal limestones in the same succession strongly suggest that the marine depositional environment was close inshore, and shallow-rather than deep-water conditions are inferred. A mineralogically similar, unaltered, volcanic tuff found in the Coas area suggests that the precursor glass was rhyolitic (72–74% SiO2) with a high-K calc-alkaline affinity. We conclude that pervasive zeolitization is due to the interaction between seawater and vitroclasts at an early stage after deposition.

The present work is part of a study focused on the use of organo-zeolite conditioner to remediate soil polluted by toxic elements. The Neapolitan yellow tuff (NYT) was utilized as a component of an organo-mineral sorbent/exchanger soil conditioner with pellet manure (NYT/PM) to reduce the mobility of Cd and Pb and recover plant performance in heavily polluted soils from illegal dumps near Santa Maria La Fossa (Lower Volturno river basin, Campania Region, southern Italy). Pot experiments were performed by adding the NYT/PM mixture (1:1, w/w) to polluted soil at the rates of 0%, 25%, 50% or 75% (w/w). Wheat (Triticum aestivum) was used as the test plant. The addition of organo-zeolite NYT/PM mixture significantly reduced the DTPA (diethylene-triamine-pentaaceti c acid)-extractable Cd and Pb from 1.01 and 97.5 mg kg−1 in the polluted soil, to 0.14 and 11.6 mg kg−1, respectively, in the soil amended with 75% NYT/PM. The best plant response was observed in amended soil systems treated with 25% NYT/PM, whereas larger additions induced plant toxicities due to increased soil salinity.

The resistance to acidic and sulfate attack of Portland-pozzolan cement containing 35 wt.% of zeolite was compared with that of unamended Portland cement. Mortar specimens kept in 0.5% and 1.0% HCl solution, 5% Na2SO4 solution, and in reference water for 365 and 720 days were tested using a set of physical-mechanical and chemical techniques. The ability of mortars containing zeolitic cements with 15 to 50 wt.% of zeolite to protect steel against corrosion was verified by a potentiodynamic method. Mortar with zeolitic cement performs better when exposed to 1% HCl solution due to the presence of a finer pore matrix, a hydrate phase poorer in CaO-containing hydration products with lower leachability, and the high resistance of zeolite material itself to acidic attack, compared with Portland cement and siliceous sand. The improved sulfate resistance of the mortar with zeolitic cement is caused by the decreased C3A in the cement blend in comparison with that in Portland cement, a reduction in SO3 binding into the cement paste and decreased amount of CaO-containing hydration products capable of reacting with a sulfate solution forming voluminous reaction products, and consequent crack propagation, large expansion and structural disintegration. Passivation of steel in mortars with blends of Portland cement to zeolite percentage ratios of 85/15, 75/25 and 65/35 by weight is comparable to that of Portland cement mortar. This is particularly important because the mortar with zeolitic cement exhibits late strengths similar to that of Portland cement mortar. This confirms that zeolitic cement can replace Portland cement in many applications with the advantage of higher resistance to acidic and sulfate attack.

The thermal behavior of two clinoptilolites from an epiclastic and a pyroclastic deposit of central-northern Sardinia and of their exchanged forms (Li, Na, K, Cs, Mg, Ca, Sr and ammonium) were investigated by differential thermal analysis and thermogravimetry up to 1000°C. Their thermal stability was studied by evaluating the residual crystallinity (expressed as rehydration capacity) after 2 h thermal treatments at 450, 600 and 900°C. The water loss at 1000°C was linearly related to the radius (r) and the charge (z) of the exchangeable cations by the equations r2/z or r3/z, which are proportional to the inverse of the charge density over the surface or to the charge density over the volume of the cations.

The cation composition plays a crucial role in determining the thermal behavior of clinoptilolite. The presence of cations such as Cs or K, which have low surface or volume charge densities, was found to increase the thermal resistance. In particular, the crystallinity of Cs- and K-exchanged forms of both clinoptilolites was not affected by thermal treatment at 450°C and was only slightly reduced by thermal treatment at 600°C.

Predicting the thermal behavior of natural and cation-exchanged forms of these clinoptilolites can provide useful information for possible applications in catalysis, in the case of high thermal stability, or for thermal transformation into ceramics or lightweight aggregates.

The Li+ ion is used frequently as an environmentally acceptable surrogate for sorbing radionuclides in field tracer tests, and experiments using Li are an important part of assessing the potential transport of radionuclides in saturated alluvium south of Yucca Mountain, Nevada, the site of a proposed nuclear waste repository. Equilibrium partition constants (Li+ Kds) were measured using batch studies incorporating a wide range of Li+ concentrations and two different grain-size fractions of alluvium samples from multiple depth intervals in two wells. Cation exchange capacity, surface area, bulk mineralogy from quantitative X-ray powder diffraction, and trace Mn- and Fe-oxyhydroxide mineralogy from extractive studies were evaluated as predictors for linearized Li+ Kd values (K1in) in the alluvium. Many of the predictor variables are correlated with each other and this was considered in the analysis. Linearized Kd values were consistently higher for fine particle-size fractions than for coarse fractions. Single and multivariate linear regression analyses indicated that the clinoptilolite + smectite content, taken together as a combined variable, was the best predictor for Li+ sorption in the alluvium, although clinoptilolite content was clearly a better predictor when the two variables were considered separately in simple linear regressions. Even so, Li+ Klin predictions based on clinoptilolite and smectite abundance were accurate only to within about ±100%. This uncertainty suggests that there is either a high inherent variability in Li+ Klin values or that additional alluvium characteristics not measured or evaluated here may play an important role in simple Li+ cation exchange in the alluvium.

A new method for calculation of layer charge and charge distribution of smectites is proposed. The method is based on comparisons between X-ray diffraction (XRD) patterns of K-saturated, ethylene glycol-solvated, oriented samples and calculated XRD patterns for three-component, mixed-layer systems. For the calculated patterns it is assumed that the measured patterns can be modeled as random interstratifications of fully expanding 17.1 Å layers, partially expanding 13.5 Å layers and non-expanding 9.98 Å layers. The technique was tested using 29 well characterized smectites. According to their XRD patterns, smectites were classified as group 1 (low-charge smectites) and group 2 (high-charge smectites). The boundary between the two groups is at a layer charge of −0.46 equivalents per half unit-cell. Low-charge smectites are dominated by 17.1 Å layers, whereas high-charge smectites contain only 20% fully expandable layers on average. Smectite properties and industrial applications may be dictated by the proportion of 17.1 Å layers present. Non-expanding layers may control the behavior of smectites during weathering, facilitating the formation of illite layers after subsequent cycles of wetting and drying. The precision of the method is better than 3.5% at a layer charge of −0.50; therefore the method should be useful for basic research and for industrial purposes.

The rheological characteristics of purified bentonite suspensions as a function of exchangeable cation $({\text{Ca}}^{2+},{\text{NH}}_4^{+},{\text{Li}}^{+})$$({\rm{C}}{{\rm{a}}^{2 + }},{\rm{NH}}_4^ + ,\;{\rm{L}}{{\rm{i}}^ + })$ are studied at three different clay concentrations (40 gL−1, 60 gL−1, 80 gL−1). A Herschel-Bulkley model is used to determine rheological parameters such as yield value, consistency and fluidification index. The flow curves are typical for shear thinning fluids but differ on two points; presence of yield stress and/or thixotropy. The Li suspensions are not yield stress fluid, and the thixotropy is weakly expressed only for the 80 gL−1 suspension. On the contrary, Ca-clay suspension flow curves always present yield stress and a large thixotropic area. The NH4-clay suspensions exhibit an intermediate behavior as there is no thixotropy, but a yield stress appears for the most concentrated suspension. These differences in macroscopic mechanical properties are discussed with reference to the suggested microscopic clay organization in suspension.

Rb-Sr and oxygen isotope studies, in addition to K-Ar isotopic determinations published previously, are reported on diagenetic and hydrothermal fundamental particles (particle thickness of 0.03 to 0.05 nm and particle ab size of 0.02–0.05 µm) of the East-Slovak Basin. The combined data set allows us to ascertain the crystallization conditions of the illite material from two bentonite units collected at two basinal sites located ~20 km apart, and characterized by prolonged diagenetic conditions induced by progressive burial. A bentonite rock characterized by a short hydrothermal event from the Zempleni mountains to the SW of the East-Slovak basin is also studied.

For the two first sites, the δ18O values increase in one case and decrease in the other, when the size of the diagenetic fundamental particles from bentonite samples increases. These variations suggest that temperature increased in one and decreased in the second of the two samples collected in the basin, while the particles were growing. In the case of the hydrothermal bentonite, the δ18O values of the different size-fractions consisting of fundamental particles remain about constant, suggesting constant temperature and fluid chemistry.

The Rb-Sr dates of the fundamental particles of the three bentonite rocks were systematically higher than the corresponding K-Ar ages. The 87Sr/86Sr ratios, which are initially involved in the particle nucleation, appeared higher than that of contemporaneous sea-water. In all cases, the initial 87Sr/ 86Sr ratio decreases when particle size increases, which implies supply of external Sr into the bentonite units. This external Sr seems to have had an 87Sr/86Sr ratio close or identical to that of the contemporaneous sea water. This means that Sr, probably of sea-water origin, progressively diffused from host shales into the bentonite units, during burial diagenesis. In turn it favors the suggestion made previously about diffusion of K from shales into the bentonite layers during illitization of the smectite from these units.

The Şile Region contains discontinuous, cyclic, thin coal beds and industrial clay deposits that were accumulated in lacustrine basins which received extensive volcanoclastic sediments due to transport of highly weathered calc-alkaline volcanic rocks. The Sülüklü area has the largest kaolin deposit in this region. Cyclic kaolinization depended on the degree of leaching of Si and alkalis in cyclic swamp environments and, therefore, kaolinite contents vary in each discontinuous lens-shaped clay bed and underclay within the basin. The kaolins comprise disordered kaolinite, illite, smectite, gibbsite, quartz, pyrite, anatase, K-feldspar and goethite. Depth-related changes in the distribution of clay minerals, associated with coal beds, are indicative of organic acid-mineral reactions. Kaolinite crystallization initiated at the edges of sericitic mica sheets in the form of composite kaolinite stacks. The small size (<1 µm), morphology and poor crystallinity of kaolinite crystals suggest that kaolinization post dated transportation. Primary or secondary origins of particles can be determined from the stacking sequences of kaolinite particles using high-resolution transmission electron microscopy images. Kaolinite stacks always contain a small amount of illite, but smectite is only present in the middle and upper levels. Gibbsite is a main constituent of refractory bauxitic clays locally found as discontinuous lenses and exploited from the lower level of the basin.

Genesis of kaolin deposits took place in two stages: first, there was in situ weathering of the oldest andesitic agglomerates, tuffs and ashes at the base of the lacustrine basin coupled with discharge of shallow thermal waters which were initiated by local hydrothermal alteration; second, surface weathering enhanced transportation of altered rocks from the surrounding hills into the lacustrine basin. Kaolinization took place in cyclic swamp environments, as indicated by the presence of cyclic thin- to thick-bedded coals that provided necessary humic and fulvic acids for the post-depositional alteration of altered volcanic rocks to kaolin in dysaerobic, relatively low-pH conditions in saturated groundwater zones.

The Raman spectra of many kaolins are dominated by bands from ancillary anatase. Fired samples of a commercial anatase-bearing kaolin from the Jari River deposit in Brazil showed significant variations of Raman spectra as a function of the firing temperature. The spectra showed the full range of anatase bands up to a firing temperature of 900°C. From 950°C the background increased significantly, leading to an unfavorable signal/noise ratio that allowed observation of only the most intense (Eg) band at ~144 cm−1. X-ray diffraction (XRD), however, confirmed that this band, which persists up to 1200°C, results from anatase. Two factors may be responsible for the high thermal stability of anatase in this sample: its relatively large particle size of ~120 nm and possible reactions with Si and Al that become liberated during kaolinite breakdown. When evaluated with circumspection, Raman and XRD data on anatase can serve as ‘thermometers’ to elucidate the thermal history of fired anatase-bearing kaolins and other anatase-bearing clays.

Several micas containing different octahedral and interlayer cations were synthesized at different temperatures under conventional- and microwave-hydrothermal conditions and these phases were characterized by powder X-ray diffraction, solid-state magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy, scanning electron microscopy and Fourier transform infrared spectroscopy. A Zn K-mica with Zn in the octahedral sheets and K in the interlayers was synthesized in the temperature range 150–200°C and a novel Zn Rb-mica with Zn in the octahedral sheets and Rb in the interlayers was synthesized at 200°C. The synthesis of either Mg, Co or Ni K-micas, however, was found to be difficult or impossible at these low temperatures. Solid-state 29Si MAS-NMR revealed that the Al in the tetrahedral sites is disordered with several nearest-neighbor Si environments. In general, microwave-assisted hydrothermal conditions led to better crystallization of the Zn K-micas compared with the conventional method.

The effects of ultrasound treatment on the mean particle size, crystal structure, crystallite dimensions and specific surface area of natural muscovite and biotite samples have been investigated. Sonication of macroscopic flakes of muscovite and biotite produced a drastic particle-size reduction. The conditions for the preparation of micron and submicron-sized muscovite and biotite particles of narrow particle-size distribution by sonochemistry are described. The effect of sonication on particle-size reduction is more significant for muscovite than for biotite. Thus, for long sonication times (100 h), submicron and micron particles are predominant in muscovite and biotite, respectively. The resulting materials are crystalline, as assayed by X-ray diffraction, only broadening of the diffraction lines due to size-reduction was observed. Nuclear magnetic resonance studies revealed that the coordination of Al and Si was not modified by the treatment. Chemical analysis showed that the composition of the sample was not affected by the sonication except for a small contamination by Ti from the tip cup of the sonication instrument.