The identification and quantification of the water associated with powdered clinoptilolite and clinoptilolite-bearing tuffs were made using thermogravimetric, vacuum gravimetric, and differential scanning calorimetric techniques. Inflection points on thermogravimetric curves at approximately 80° and 170°C correspond to changes in the proportions of externally adsorbed water to loosely bound zeolitic water and loosely bound zeolitic water to tightly bound zeolitic water, respectively. These three types of water can be differentiated by temperatures and heats of dehydration obtained from differential scanning calorimetry. These temperatures and heats of hydration are 75 ± 10°C and 59.2 ± 5.9 kJ/mole H2O, 171 ± 2°C and 58.7 ± 6.1 kJ/mole H2O, and 271 ± 4°C and 78.7 ± 7.0 kJ/mole H2O for external water, loosely bound water, and tightly bound water, respectively. The ratio of loosely bound zeolitic water to tightly bound zeolitic water determined in this study is similar to that reported in the literature from structural determinations, indicating that the desorption properties of clinoptilolite are determined by the specific positions of the water molecules in the structure.

Woolly erionite from the Reese River deposit, Nevada, is identical in appearance to that at the type locality, near Durkee, Oregon. Both of these erionites differ in appearance from all other erionite reported in the past 20 years from diverse rocks throughout the world which are described as prismatic or acicular in habit. The non-woolly erionites are especially common as microscopic crystals in diagenetically altered vitroclastic lacustrine deposits of Cenozoic age. The Reese River woolly erionite fills joints in gray to brownish-gray lacustrine mudstone of probably Pliocene age, in a zone about 1 m thick beneath a conspicuous gray vitric tuff. Compact masses of long, curly, woolly erionite fibers are in the plane of the joint and locally are associated with opal. Indices of refraction are ω = 1.468 and ε = 1.472; hexagonal unit-cell parameters are a = 13.186(2) Å, c = 15.055(1) Å, and V = 2267.1(0.9) Å3. A chemical analysis of woolly erionite yields a unit-cell composition of: Na1.01K2.84Mg0.3Ca1.69Al8.18Si27.84O72·28.51H2O.

The vitric matrix of pre-caldera acid tuff and tuff breccia of the Santorini volcano, Aegean Sea, Greece has been generally replaced by one or more of the following authigenic minerals: K-rich and (K,Ca)-rich clinoptilolite, mordenite, opal-CT, and clay minerals. Halite is also present in some samples. Initial compositional inhomogeneities between the dacitic blocks in tuff breccia and tuff seem to have controlled the type of K-rich heulandite-group zeolite that formed. Mordenite postdates the heulandite-group zeolites and opal-CT. Some mordenite has replaced the rims of glass shards. The alteration minerals are not related to vertical or lateral zonation, and the irregular distribution of their assemblages is attributed to variations in heat flow, ionic activity in interstitial waters, and permeability. The pyroclastic rocks were in a region of active heat flow during and after their emplacement. The formation of authigenic silicates may have led to the sealing of open spaces and fractures, imposing barriers to permeability and subdividing the original open system into smaller closed systems. As alteration progressed, some of the trapped water in each individual domain was consumed in hydration reactions. Salts could have been concentrated by such a process, and halite probably precipitated from solutions of appropriate composition in the individual closed systems.

Montmorillonite and K-feldspar deposits of potential economic interest occur in the Late Oligocene-Miocene tuffs of the Vizcarra Formation in the state of Durango, Mexico. The two minerals were formed separately from rhyodacitic to rhyolitic pyroclastic deposits in a closed hydrologie system and diagenetically altered following two different patterns. In material deposited on dry land the glass was completely replaced by K-feldspar, and the interstices between the replaced glass bubbles and shards were filled with chalcedony, quartz, and albite. Pyroclastic material deposited in an alkaline lacustrine environment were diagenetically altered to montmorillonite, which formed the bentonitic tuffs widely exposed beneath the K-feldspar-rich tuff. These bentonitic tuffs contain as much as 85% montmorillonite plus authigenic chalcedony and quartz. Pyrogenic sanidine, quartz, and oxybiotite, coarse glass shards, and clastic grains make up about 8% of the clay-rich tuffs. The composition of the montmorillonite corresponds to the formula (Si3.88Al0.12)(Al1.41Mg0.59)O10(OH)2(Ca0.07Mg0.11,Na0.28K0.06). The montmorillonite is dioctahedral, the surface acidity is of the Lewis type, and the clay swells to one- and two-layer complexes. The cation-exchange capacity is 64 meq/100g; base exchange is Ca2+, 15; Mg2+, 20; Na+, 4.1; and K+, 1.0 meq/100 g. Its interlamellar charge is 18.6 microcoulombs/cm2. Dacitic pyroclastics were deposited later at higher elevations along the margins of the basin. Percolating solutions apparently removed a siliceous leachate from the dacitic glass and partially altered it to clinoptilolite.

Phillipsite is a common constituent in diagenetically altered rhyolitic vitric tuffs of Cenozoic saline, alkaline-lake deposits where it occurs as spherulites or aggregates of prismatic crystals. This phillipsite has chemical and physical properties that differ from phillipsites that occur in rocks of other compositions and depositional environments, but previously it had not been completely characterized. Published analyses of five samples from four deposits in the southwestern United States show that the phillipsite is very siliceous and alkalic; the Si/(Al + Fe3+) ratio is 3.08–3.37, alkalis greatly exceed the divalent exchangeable cations, and the Na/K ratio is 1.05–3.05. The mean index of refraction (1.451–1.470) is much lower than that generally reported for the phillipsite group and can be correlated with the relatively high Si and alkali contents. Monoclinic unit-cell parameters show the following ranges: a = 9.931–9.991 Å, b = 14.142–14.155 Å, c = 8.650–8.706 Å, ß = 124.57–125.07°, and V = 1000.3–1007.4 Å3. The especially small b dimension is consistent with the high Si content.

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.

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.

Three samples of volcanic tuff were hydrothermally altered at ∼82°C in a soxhlet apparatus for periods from 745 to 2706 h. The samples correspond to partially altered specimens of volcanic tuff with 6 wt. % (T3a) and 9 wt. % (T3b) smectite and to the calcination product of the latter (T3c). The calcination treatment melted the smectite in the sample. Untreated samples and alteration products were studied by X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetry (TG), scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, and oxygen isotope analysis. DTA-TG of the <2-µm size fractions showed that there was a small increase of smectite relative to glass after alteration for samples T3a and T3b, with the amount of smectite increasing exponentially with time. No smectite formed in sample T3c. These results suggest that smectite acts as a nucleation site for the precipitation of new smectite. The amount of glass in the <2-µm size fraction increased, although slightly decreased relative to smectite. SEM-EDX analysis showed smectite with the approximate structural formula of Na0.22K0.08Mg0.12Ca0.03VI(Al1.47Fe0.05Mg0.48)IV(Si3.97Al0.03)O10(OH)2.

Oxygen isotope composition of the <2-µm size fraction became enriched in 18O by alteration, the >2-µm size fraction of T3b did not vary, and that of T3c was depleted in 18O. Our results are consistent with three processes during alteration: 1) oxygen isotope exchange between volcanic glass and water, 2) neoformation of smectite, and 3) hydration and consequent hydroxylation of the calcined glass.

Silicic vitric tuffs of the Alaçatı (Çeşme) area, west of Izmir (Turkey), are partly altered to authigenic zeolites and clay minerals. Mordenite and clinoptilolite-heulandite accompanied by smectite are the main alteration products of the tuffs. Scanning electron microscope examination indicates that mordenite forms mainly from a gel-like precursor and to a lesser degree from volcanic glass. Mordenite and clinoptilolite-heulandite have formed by the hydrolysis and dissolution of silicic vitric tuffs by thermal waters which circulated through the fracture zone into porous vitric tuffs. These thermal waters, which resulted from mixing of thermal (Na-Cl type) and groundwaters, provided the extra Na and Ca that are necessary for the formation of mordenite. Various percentages of calcite are present in the altered tuffs. The enrichment of calcite in the altered tuffs indicates that thermal waters supply Ca, sourced from dissolution of Triassic carbonate rocks.

The alteration minerals in the Alaçatı (Çeşme) area do not seem to be laterally zoned. The occurrence of the zeolites seems to be related to inferred fracture zones trending NE—SW. These fracture zones are important because they provide porosity and permeability in the tuffs for zeolite formation. The large glass content and permeability of tuffs accompanied by the favorable hydrochemical condition resulted in zeolitization of the Alaçatı (Çeşme) area.

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.

Miocene rifting and associated rhyolitic (K-rich) volcanism resulted in the deposition of pyroclastic material in the central Simav graben, near Karacaderbent, Turkey. The pyroclastics were deposited in a lacustrine environment, altered to clinoptilolite-rich tuffs and cross-cut by several transform faults along which hydrothermal fluids circulated. Petrography and quantitative phase analysis by X-ray diffraction show that the Karacaderbent tuff consists mainly of the diagenetic products clinoptilolite, opal CT, smectite, and celadonite. Electron microprobe analyses and cation exchange capacity (CEC) measurements confirm the predominance of K-rich clinoptilolite. Near fault zones, clinoptilolite was replaced by authigenic opal CT and alkali feldspar, and the remaining clinoptilolite was enriched in Na. Silicification around fault zones was confirmed by X-ray fluorescence. Zeolitization of K-rich rhyolitic starting materials took place under mildly alkaline, low-salinity conditions, probably in a closed hydrologic system. The subsequent hydrothermal alteration along faults had only a minor impact. The homogeneous nature, large (74–87 wt.%) clinoptilolite content, large CEC, and K-rich composition of the deposit favor exploitation of this material for applications in agriculture, horticulture, and waste-water purification; as feed additives; and as pozzolans for cement production.

This paper analyzes the reuse of ancient tuff blocks in early medieval architecture in Rome, in both papal and private structures. The blocks are a well-known phenomenon, but they have not yet received any focused study. Short discussions in earlier scholarship have typically described them in utilitarian terms. I first identify a pattern of targeted reuse in papal building projects. I then argue that they would also have had symbolic value for an independent papacy wanting to display power. For later private builders, I propose that the blocks became prestige materials displayed on the houses of an ever-tightening aristocracy eager to be seen within some of the city's most important monumental spaces. I consider how the city's ancient monuments and their pieces were viewed in the early medieval period and how the blocks’ ancient contexts contributed to the symbolic value that I identify in them.

Felsic tuff as a direct fallout deposit is known from one small area in the Kyrenia Range, north Cyprus, within deep-sea terrigenous turbidites. Nearby tuffaceous siltstones contain compositionally similar felsic volcanic rocks (c. 5–10%), mixed with terrigenous material. Sedimentary evidence indicates that the fallout tuff was variable reworked locally, whereas the tuffaceous siltstones are interpreted as turbidites mixed with terrigenous material derived from Anatolia. U–Pb dating of zircons that were extracted from a sample of relatively homogeneous tuff yielded a dominant age of 16.64 ± 0.12 Ma (Burdigalian). Zircon trace-element analysis indicates predominant derivation from within-plate-type felsic magma. Whole-rock chemical analysis of the tuffaceous sediments as a whole is compatible with a felsic arc source, similar to the post-collisional magmatism within Anatolia. Regional comparisons suggest that the nearest volcanism of similar age and composition is located c. 500 km away, within the Kırka area (Eskişehir region) of the Western Anatolia Volcanic Province. Evidence of tephra dispersal in the western Mediterranean region and climatic modelling suggests E-wards prevailing winds and therefore tephra transport over southern Anatolia and adjacent areas during early Miocene time. The north Cyprus tuffs could represent powerful Minoan (Plinian)-type eruptions in western Anatolia, coupled with SE-wards tephra transport during and soon after the onset of post-collisional magmatism.

This work examines a tuff from the Tinebdar deposit located in Sidi Aich (east Algeria) for possible use as an alternative material for the adsorption of Asucryl red (a textile dye). Natural tuff represents an economic and environmentally friendly alternative compared to synthetic zeolites. The starting materials were characterized by means of powder X-ray diffraction, Brunauer–Emmett–Teller-specific surface area and pore diameter analysis. Batch experiments were performed and various parameters that have an effect on the adsorption process (i.e. pH, clay amount, contact time and initial concentration) were investigated. The <125 μm grain-size fraction of the tuff contains 45 wt.% mordenite. The adsorption equilibrium was established in 10 min and the adsorption kinetics were better described by the second-order kinetic model. The adsorption isotherm of the results obtained fits better to the Langmuir and Timkin models. The adsorption capacity qt varies from 60 to 70 mg g–1 with temperature increasing from 293 to 333 K. The thermodynamic nature of the adsorption process was determined by calculating ΔH°, ΔS° and ΔG° values. The positive value for ΔH° confirms that the adsorption is endothermic.

A previously undocumented type of wetland is described from the Atacama Desert in northern Chile (3000 m above sea level), sustained exclusively by direct precipitation and perched above the regional water table. Geomorphological mapping, pedostratigraphy, geochemistry, and analysis of contemporary vegetation is used to understand wetland formation and dynamics during historical and present time periods. The paleowetland deposits overlie a Miocene tuff that acts as an impermeable barrier to water transfer and creates conditions for local shallow ground water. These deposits include several paleosols that were formed during periods when precipitation increased regionally at 7755–7300, 1270, 545, and 400–300 cal yr BP. The similarity in timing with other palaeohydrological records for the Atacama implies that paleosols from this wetland are proxies for reconstructing past changes in local and regional hydrological cycle. Archaeological investigations have revealed the presence of two small farms from the Late Intermediate period, i.e., during the earliest wetter phase represented by the paleosols. Both farms are located near the paleowetland deposits, which suggests that local inhabitants exploited these water sources during late pre-Hispanic times. Results of this study improve knowledge of settlement patterns during this and earlier cultural periods.

A thin (100 m) cover of flat-lying, Recent, calcite-rich tuff at Ndale near Fort Portal, Uganda, unconformably overlies steeply dipping Precambrian metamorphic rocks. It is locally radioactive owing to uranium-rich pyrochlore minerals and lesser amounts of zircon, monazite, titanite, and an unidentified thorium phosphate. In one concentrate, four grains of uranpyrochlore and one grain of uranoan pyrochlore showed a positive linear correlation of Ti with U, and negative linear correlations of Ti with Na, F and Sr. Ta remained high and relatively constant [11 anal., ave. 14.5 (0.6)% Ta2O5]. In the same concentrate the composition of a separate grain of uranoan pyrochlore did not plot on these lines and Ta was comparatively low [2 anal., ave. 4.5 (0.3)% Ta2O5]. The data suggest two separate paths of differentiation. However, zoned grains were not observed. Unit cells were cubic with a = 10.351 ± 0.002 Å for a grain with 12.9% UO2tot and 10.333 ± 0.002 Å for a grain with 26.6% UO2tot. On heating in air the cell size decreased, possibly due to oxidation of U4+. The crystalline nature of these minerals can be attributed to a very young (4000–5000 yr) geological age.

In the Putorana region of the Siberian continental flood basalt province, tuffs form thin layers or small bodies between single basaltic lava flows. Based on our fieldwork, these ash fall deposits have relatively small volumes (≤100 000 m3) compared with the associated basaltic flows and the tuffs of the adjacent Noril'sk region in the north. Six tuff units with different degrees and modes of alteration were analysed by XRD, SEM and XRF in order to determine mineralogical and chemical changes which occurred during progressive alteration. Pyroxene compositions and immobile element ratios suggest that the tuffs were derived from a basaltic lava like the flood basalts. Post-eruptive, low-temperature alteration processes have significantly changed the primary composition of the tuffs. Therefore the different tuffs have variable petrography, mineralogy and geochemistry (MgO 5.2–9.2 wt %, SiO2 33.6–69.1 wt % and TiO2 0.6–1.6 wt %) compared to the tholeiitic basalts in which they are interbedded. Crystallization of secondary minerals, such as carbonate, clay minerals, zeolites and analcime, occurred from circulating fluids. The results show that the fluid compositions varied significantly between the different tuffs. This implies that the elements behaved differently depending on the circulating agent, which led to the formation of different minerals. In addition, two samples show an input of quartz, derived either by wind from terrigenous sediments or generated by magma–sediment interaction, and one sample was deposited in a subaqueous, possibly lacustrine environment. These results indicate that the conditions during alteration varied despite the close spatial relationship of the tuffs and that a generalization about the alteration processes cannot be made in the Putorana region. The analyses of the clay minerals show alteration of chlorite to vermiculite. Interestingly, corrensite (a regularly stacked, 50/50 mixed layered clay mineral composed of chlorite and vermiculite) is still preserved in two samples. This indicates different alteration stages in the different tuff outcrops. The state of alteration deduced from immobile element ratios, plagioclase compositions and mineral assemblages shows contradictory results. This suggests that the state of alteration is best deduced from clay minerals, as one can follow this process step by step.

Thin, but laterally widespread, fallout ash tuff layers interbedded with complex fluviolacustrine successions of the Carboniferous–Permian late Variscan intermontane Saar–Nahe Basin in southwestern Germany provide important tephrostratigraphic markers in the purely continental depositional setting. The tuffs are rhyolitic to rhyodacitic and indicate geochemical affinities to Moldanubian Variscan S-type granitoids. The volcanic ashes are suggested to have been derived from the general region of the central and northern Black Forest (southwestern Germany) and the northern Vosges (eastern France) at 100–150 km distance south of the Saar–Nahe Basin. Six tuff beds from the Jeckenbach and Odernheim subformations (Meisenheim Formation, Glan Group) have been correlated within the basin over a distance of 50 km by mapping and whole-rock geochemical fingerprinting. In each subformation, three tuffs can be well distinguished using geochemical discriminant function analysis. Additional comparisons of trace and rare-earth element contents provide further criteria for the differentiation of individual tuff beds. These discriminations show that the tuffs have unique chemical fingerprints, probably reflecting differences in the original composition of the parent volcanic tephra. Thus, chemical differences between the tephrostratigraphic markers are geologically significant and provide a powerful tool for establishing tuff layer identification and correlation within the complex sedimentary sequence of the Saar–Nahe Basin. They also provide clues to the tectonomagmatic settings of the source volcanoes.

In an attempt to establish a chronology for volcanic neck emplacement and so elucidate petrogenesis, isotopic studies have been carried out on various cumulate inclusions, blocks and megacrysts which occur chiefly in association with tuffs infilling several Scottish vents. K-Ar ages of 13 samples of low-pressure cumulate minerals (biotite, hornblende and pyroxene) from necks in East Fife indicate crystallisation at shallow depth at 314 Ma. U-Pb analyses of zircons are concordant at 318 Ma suggesting they are also members of this suite and their formation is penecontemporaneous with the Namurian volcanic activity which is welldocumented stratigraphically. By 295 Ma crystallisation of anorthoclase megacrysts had been completed, perhaps from the fractionated residuum. An eruption from considerable depth (within the stability field of garnet precipitation) then broke through to the surface bearing high-pressure megacrysts. This penetrated and disrupted the early cumulates carrying them to the surface and producing the diverse vent assemblages. K-Ar dating of basanites suggest that the Duncansby Ness neck in Caithness was emplaced around 270 Ma in the early Permian. For two Fife necks the balance of evidence favours an age of 290 Ma (Stephanian) for this final explosive activity associated with vent formation.