Secondary Alteration Minerals Research Articles

The tensile strength of hydrothermally altered volcanic rocks

The tensile strength of volcanic rocks is an important parameter for understanding and modelling a wide range of volcanic processes, and in the development of strategies designed to optimise energy production in volcanic geothermal reservoirs. However, despite the near-ubiquity of hydrothermal alteration at volcanic and geothermal systems, values of tensile strength for hydrothermally altered volcanic rocks are sparse. Here, we present an experimental study in which we measured the tensile strength of variably altered volcanic rocks. The alteration of these rocks, quantified as the weight percentage of secondary (alteration) minerals, varied from 6 to 62.8 wt%. Our data show that tensile strength decreases as a function of porosity, in agreement with previous studies, and as a function of alteration. We fit existing theoretical constitutive models to our data so that tensile strength can be estimated for a given porosity, and we provide a transformation of these models such that they are a function of alteration. However, because porosity and alteration influence each other, it is challenging to untangle their individual contributions to the measured reduction in tensile strength. Our new data and previously published data suggest that porosity exerts a first-order role on the tensile strength of volcanic rocks. Based on our data and observations, we also suggest that (1) alteration likely decreases tensile strength if associated with mineral dissolution, weak secondary minerals (such as clays), and an increase in microstructural heterogeneity and (2) alteration likely increases tensile strength if associated with pore- and crack-filling mineral precipitation. Therefore, we conclude that both alteration intensity and alteration type likely influence tensile strength. To highlight the implications of our findings, we provide discrete element method modelling which shows that, following the pressurisation of a dyke, the damage within weak hydrothermally altered host-rock is greater and more widespread than for strong hydrothermally altered host-rock. Because the rocks in volcanic and geothermal settings are likely to be altered, our results suggest that future modelling should consider the tensile strength of hydrothermally altered volcanic rocks.

Clay mineral characteristics in volcanic tuffs of Dokdo, South Korea: implication on their genesis and evolution

Secondary alteration minerals like clays accompanied by volcanic activity can provide an important information on eruption cycle. Representative volcanic tuffs and seabed sediments were collected from the Dokdo volcanic island in East Sea, South Korea, to interpret eruption cycle based on clay mineral characteristics and other geochemical proxies (sulfur isotope composition, Si/Al, K/Al, among others). Tuffs are mainly composed of volcanic glass and hydrothermally altered phenocrysts. Secondary minerals such as clay mineral species in volcanic tuffs mostly were identified as smectite comprising dioctahedral sheets, based on expanding to 15.8 A after treatment with 1 M MgCl2 solution, and 060 reflections near at 1.48 A. Moreover, the results of infrared bands, based on (Al, Al)–OH (904–912 cm−1), (Al, Fe)–OH (865–877 cm−1), (Fe, Mg)–OH (778–798 cm−1) indicate the presence of dioctahedral sheets in clay mineral structure. Partially, occurrence of kaolinite and relatively low pH values and K/Al ratios at the Eolgulbawi tuff support chemical flexibility of clay mineral species. The δ34S value of Dongdo tuff (H2O–S: 15.3‰) is close to water leached sulfate, whereas Seodo tuff II including pyrite and native sulfur (− 5.5‰) shows a value of H2S-bearing volcanic gases. The similarity of chemical compositions between clay fractions and surrounding volcaniclastic rocks suggests that the smectite formed in low-temperature hydrothermal environments, where alkali elements were supplied under reducing conditions. Clay fractions separated from seabed sediments include diatom frustule with higher SiO2/Al2O3 ratios, and clay minerals contain mineral nitrogen originated from organic-rich seafloor sediments. Moreover, the δ34S values of seabed sediments (1.8‰, 8.4‰) indicate that the different origin of clay mineral species between tuffs and seabed sediments. It can be concluded that the alteration types and clay mineral characteristics are similar to the Surtseyan volcano, generally known as shallow-marine phreatomagmatic eruption and deposits. It further suggests that clay minerals sensitive to environmental change will be useful to interpret the volcanic environment characterized by explosive hydrovolcanic activities that occurred at the time of magma in contact with water before erupting into the atmosphere.

A micro-Raman and X-ray study of erupted submarine pyroclasts from El Hierro (Spain) and its' astrobiological implications

The pumice volcanic samples could have possible connections to the evolution of life and give us insight about their bio-geochemical processes related. In this regard, the samples from the volcanic eruption from La Restinga (El Hierro, Spain) in 2011 have been mainly studied by means of Raman spectroscopy. The research also includes analysis of XRD, Scanning Electron Microscopy and Optical Microscopy to support the Raman analysis. The results show that the Raman methods and mineral analyses are in strong agreement with the results obtained from other authors and techniques. The internal white foamy core (WFC) of the studied pumice samples shows amorphous silica, Fe-oxides, Ti-oxides, quartz, certain sulfates, carbonates, zeolites and organics. On the other hand, the external part (dark crust – DC) of these samples mainly presents primary-sequence mineralogy combined with some secondary alteration minerals such as olivine, feldspar, pyroxene, amorphous silica, and Fe-oxide. Raman spectroscopy detected other minerals not yet reported on these samples like barite, celestine and lepidocrocite. Also, the different chemometric and calibration methods for Raman spectroscopy in elemental composition, mineral classification and structural characterization has been successfully applied.From the astrobiological perspective, the research was also complemented with comparisons to other similar samples from terrestrial analogs. The main consideration was taking into account the proposed hypothesis regarding the potential behavior of the pumice as a substrate for the evolution of life. Furthermore, the detailed analysis from La Restinga eruption is coherent with the mineral phases and processes discussed from previous literature. The white internal part fulfills the conditions to work as an organic reservoir, confirmed by the detection of organic matter and selected minerals that could be used as energy sources for bacterial communities. The external layers of the samples work as a shielding layer to protect the organics from decay in extreme conditions. Finally, here we have demonstrated that the characteristics and advantages of Raman spectroscopy could help to assess and understand the possible biogenicity and alteration processes of any geological sample to be found on Mars.

Evidence for oxygen-isotope exchange in refractory inclusions from Kaba (CV3.1) carbonaceous chondrite during fluid-rock interaction on the CV parent asteroid

We report on the mineralogy, petrology, and in situ measured oxygen-isotope compositions of three Fluffy Type A Ca,Al-rich inclusions (FTA CAIs) and two amoeboid olivine aggregates (AOAs) from the CV3.1 carbonaceous chondrite Kaba. The FTA CAIs are aggregates of several inclusions composed of spinel, Al,Ti-diopside, and gehlenitic melilite replaced to various degrees by anorthite; they are surrounded by the Wark-Lovering rim layers made of spinel, anorthite, Al-diopside, and forsterite. One of FTA CAIs contains a relict ultrarefractory inclusion composed of Sc-rich Al,Ti-pyroxene, spinel, and Zr-rich oxides. The AOAs are aggregates of Ca- and/or Al-rich minerals (spinel, anorthite, and Al,Ti-diopside) surrounded by forsterite ± Fe,Ni-metal condensates; Fe,Ni-metal is almost entirely replaced by magnetite and Fe,Ni-sulfides. Neither the FTA CAIs nor the AOAs show evidence for being melted after aggregation, and contain very minor secondary alteration minerals resulted from fluid-rock interaction on the CV parent asteroid. These include magnetite, fayalite, hedenbergite, phyllosilicates, and Fe-bearing Ti-free Al-diopside; secondary anorthite of asteroidal origin is absent in Kaba CAIs and AOAs. There are large variations in Δ17O (deviation from the terrestrial fractionation line = δ17O − 0.52 × δ18O) within the individual FTA CAIs and AOAs: anorthite and melilite are systematically 16O-depleted (Δ17O range from ∼−14 to ∼−2‰) relative to the uniformly 16O-rich forsterite and Al,Ti-diopside (Δ17O ∼ −25 to −20 ± 2‰, 2σ). Scandium-rich Al,Ti-pyroxene has 16O-poor composition (Δ17O ∼ −4‰). Many anorthite and melilite analyses plot close to or along mass-dependent fractionation line with Δ17O of −1.5 ± 1‰ (average ± 2SD) defined by the aqueously-formed magnetite and fayalite from Kaba, and, therefore, corresponding to Δ17O of an aqueous fluid that operated on the CV parent asteroid. We conclude that anorthite and probably melilite in the Kaba FTA CAIs and AOAs experienced postcrystallization oxygen-isotope exchange with this fluid. The similar process must have affected plagioclase/plagioclase mesostasis and probably melilite in refractory inclusions and chondrules from CV3 chondrites of higher petrologic types [e.g., Allende (CVoxA3.6) and Efremovka (CVred3.1–3.4)], which appear to have experienced higher temperature metasomatic alteration than Kaba and were subsequently metamorphosed.We conclude that the carbonaceous chondrite anhydrous mineral (CCAM) line defined by oxygen-isotope compositions of whole-rock and mineral separates of Allende CAIs and having a slope of 0.94 is not the primary nebular line. Instead this line results from superposition of the nebular slope-1 line recorded by the primitive chondrule mineral (PCM) line, the mass-dependent fractionation line with slope of ∼0.5 defined by the secondary minerals, and the minerals which experienced oxygen-isotope exchange with an aqueous fluid.

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments.

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 107, zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in “simpler” secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars.

NEAR-INFRARED EFFECTIVENESS ON DEGRADED CORE IN TROPICAL CLIMATES

In tropical climates, postdrilling oxidation of sulfide-rich core can severely degrade drill core, producing low-temperature iron oxyhydroxides, sulfates, and clays. Variable growth of these secondary minerals in exposed drill core, combined with the hydration and degradation of primary hydrothermal minerals, may lead to the production of spurious results in near-infrared (NIR) spectroscopic studies. However, the NIR technique can remain an effective tool in assessing hydrothermal alteration, even in extremely degraded core. We have assessed the usefulness of the NIR technique on degraded core at the Ladolam gold deposit, Papua New Guinea. Here, we seek to determine whether the primary alteration mineralogy had been significantly transformed by postdrilling oxidation over several years of weathering. In doing so, the study tested whether NIR analysis can be an effective tool in the discrimination of primary hydrothermal minerals in degraded core. Our study was made possible using semiquantitative X-ray diffraction (QXRD) analyses of a drill hole in 2004, where samples were collected at 50-m intervals. We subsequently repeated NIR and QXRD analyses on the same drill core in 2012. After nine years of storage, the drill core had degraded considerably, with the growth of jarosite and other sulfates. Despite this, XRD results from 2004 and 2012 show no major differences in the primary alteration mineralogy. Closely spaced NIR analyses were conducted at 1-m intervals to increase the chance of obtaining a spectrum of the primary mineralogy and to exclude secondary oxidation minerals. The drill core, where possible, was broken immediately prior to analysis to obtain a fresh surface. On average, over a 10-m interval, approximately 25% of the NIR spectra did not contain secondary minerals and relict primary alteration minerals could be detected. The remaining spectra were affected by the occurrence of secondary jarosite, gypsum, and/or residual water, but in most cases, the primary alteration mineralogy could be determined. We conclude that NIR analyses remain an effective tool in the construction of geological deposit models when logging degraded historic core, even for sulfide-rich core that has degraded in tropical environments.

Chemical composition of waters in a former Cu-As mine: water–rock interaction, REE systematics and stability of secondary copper minerals

Waters in the vicinity of natural geochemical anomalies such as hydrothermal ore deposits potentially mobilize heavy metals by interaction with primary hydrothermally formed minerals. On the other hand, secondary alteration minerals can retain some of these heavy metals and effectively immobilize them. In order to understand the chemical evolution of waters in such a system, the best way is to compare different waters from various sample locations in a well-defined locality. Thereby one can compare the importance of parameters such as variable flow paths, flow velocities, fluid-host rock interaction and the various sources and sinks of major and trace elements. This was done for the Cu and As deposit of Neubulach in the northern Schwarzwald, Germany. Flowing and dripping waters from three sites in the abandoned mine were sampled monthly over 14 months. The waters were analyzed with respect to their major and trace element concentrations including rare earth elements (REE) to evaluate their seasonal and spatial variation. The three sample types collected from different depths in the mine have different flow paths and are influenced to different extents by the sandstone host rocks, by overlying carbonates and by the hydrothermal barite quartz vein with Cu-Bi-As ores, mainly tennantite, exploited from the former mine. The sample site in the upper part of the mine (“HGS water”) is about 30 m below surface and the amount of water dripping from the roof of the adit is strongly dependent on the precipitation. By contrast, the water collected in the lower part of the mine (about 100 m below surface) is dripping constantly throughout the year and forms abundant calcite sinters (“sinter water”). A third sample was collected monthly from the mine drainage adit (again about 100 m below surface), that collects water from the entire mine (“flowing water”). Elevated Cl and Na concentrations and increased Cl/Br ratios in the HGS waters taken in the winter months during snow melt indicate input of road salt and therefore show the direct influence of surface runoff. By contrast, the sinter water compositions do not show any variation during the year, which suggests that these waters are unaffected by short-time input from the surface; their chemical composition is determined by water-rock interaction only. Rare earth element patterns and Rb/Cs values indicate interaction with clay minerals whereas Cu and As systematics show that tennantite dissolution is incongruent. Although inverse modelling shows that reaction of surface water with the observed phases in the host rocks and in the hydrothermal vein nicely explains the water compositional variations, speciation modeling and calculations of thermodynamic stabilities of various Cu arsenates suggest that secondary alteration minerals may form metastably.

An assessment of hydrothermal alteration in the Santiaguito lava dome complex, Guatemala: implications for dome collapse hazards

A combination of field mapping, geochemistry, and remote sensing methods has been employed to deter- mine the extent of hydrothermal alteration and assess the potential for failure at the Santiaguito lava dome complex, Guatemala. The 90-year-old complex of four lava domes has only experienced relatively small and infrequent dome collapses in the past, which were associated with lava ex- trusion. However, existing evidence of an active hydrother- mal system coupled with intense seasonal precipitation also presents ideal conditions for instability related to weakened clay-rich edifice rocks. Mapping of the Santiaguito dome complex identified structural features related to dome growth dynamics, potential areas of weakness related to erosion, and locations of fumarole fields. X-ray diffraction and backscat- tered electron images taken with scanning electron microsco- py of dacite and ash samples collected from around fumaroles revealed only minor clay films, and little evidence of alter- ation. Mineral mapping using ASTER and Hyperion satellite images, however, suggest low-temperature (<150 °C) silicic alteration on erosional surfaces of the domes, but not the type of pervasive acid-sulfate alteration implicated in collapses of other altered edifices. To evaluate the possibility of internal alteration, we re-examined existing aqueous geochemical data from dome-fed hot springs. The data indicate significant wa- ter-rock interaction, but the Na-Mg- Kg eoindicator suggests only a short water residence time, and δ 18 O/δ Dr atios show only minor shifts from the meteoric water line with little precipitation of secondary (alteration) minerals. Based on available data, hydrothermal alteration on the dome complex appears to be restricted to surficial deposits of hydrous silica, but the study has highlighted, importantly, that the 1902 eruption crater headwall of Santa Maria does show more advanced argillic alteration. We also cannot rule out the pos- sibility of advanced alteration within the dome complex inte- rior that is not accessible to the methods used here. It may therefore be prudent to employ geophysical methods to make further assessments in the future.

The unequilibrated enstatite chondrites

The enstatite chondrites formed under highly reducing (and/or sulfidizing) conditions as indicated by their mineral assemblages and compositions, which are sharply different from those of other chondrite groups. Enstatite is the major silicate mineral. Kamacite is Si-bearing and the enstatite chondrites contain a wide variety of monosulfide minerals that are not present in other chondrite groups. The unequilibrated enstatite chondrites are comprised of two groups (EH3 and EL3) and one anomalous member (LEW 87223), which can be distinguished by differences in their mineral assemblages and compositions. EH3 chondrites have >1.8wt.% Si in their kamacite and contain the monosulfide niningerite (MgS), whereas EL3 chondrites have less than 1.4wt.% Si in their kamacite and contain the monosulfide alabandite (MnS). The distinct mineralogies, compositions and textures of E3 chondrites make comparisons with ordinary chondrites (OCs) and carbonaceous chondrites (CCs) difficult, however, a range of recrystallization features in the E3s are observed, and some may be as primitive as type 3.1 OCs and CCs. Others, especially the EL3 chondrites, may have been considerably modified by impact processes and their primary textures disturbed. The chondrules in E3 chondrites, although texturally similar to type I pyroxene-rich chondrules, are sharply different from chondrules in other chondrite groups in containing Si-bearing metal, Ca- and Mg–Mn-rich sulfides and silica. This indicates formation in a reduced nebular environment separate from chondrules in other chondrites and possibly different precursor materials. Additionally the oxygen isotope compositions of E3 chondrules indicate formation from a unique oxygen reservoir. Although the abundance, size distribution, and secondary alteration minerals are not always identical, CAIs in E3 chondrites generally have textures, mineral assemblages and compositions similar to those in other groups. These observations indicates that CAIs in O, C and E chondrites all formed in the reservoir under similar conditions, and were redistributed to the different chondrite accretion zones, where the secondary alteration took place. Thus, chondrule formation was a local process for each particular chondrite group, but all CAIs may have formed in the similar nebular environment. Lack of evidence of water (hydrous minerals), and oxygen isotope compositions similar to Earth and Moon suggest formation of the E chondrites in the inner solar system and make them prime candidates as building blocks for the inner planets.

Early solar system processes recorded in the matrices of two highly pristine CR3 carbonaceous chondrites, MET 00426 and QUE 99177

The mineralogy and bulk compositions of the matrices of the CR chondrites MET 00426 and QUE 99177 have been studied using a combination of SEM, EPMA, and TEM techniques. The matrices of these two chondrites are texturally, chemically, and mineralogically similar and are characterized by significant FeO-enrichments with respect to other CR chondrite matrices, nearly flat refractory lithophile patterns, variable volatile element patterns, and a simple mineral assemblage dominated by amorphous silicate material and Fe,Ni sulfides. Fine-grained, crystalline silicate phases such as olivine and pyroxene appear to be extremely rare in the matrices of both meteorites. Instead, the mineralogy of matrices and fine-grained rims of both meteorites consists of abundant amorphous FeO-rich silicate material, containing nanoparticles of Fe,Ni sulfides (troilite, pyrrhotite, and pentlandite). Secondary alteration minerals that are characteristic of other CR chondrites (e.g., Renazzo and Al Rais), such as phyllosilicates, magnetite, and calcite are also rare. The texture and mineralogy of the matrices of MET 00426 and QUE 99177 share many features with matrices in the primitive carbonaceous chondrites ALH A77307 (CO3.0) and Acfer 094 (unique). These observations show that MET 00426 and QUE 99177 are very low petrologic type 3 chondrites that have escaped the effects of aqueous alteration, unlike other CR chondrites, which are typically classified as petrologic type 2. We suggest that these meteorites represent additional samples of highly primitive, but extremely rare carbonaceous chondrites of petrologic type 3.00, according to the classification scheme of Grossman and Brearley (2005). The highly pristine nature of MET 00426 and QUE 99177 provides important additional insights into the origins of fine-grained materials in carbonaceous chondrites. Based on our new observations, we infer that the amorphous silicate material and nanosulfide particles that dominate the matrices of these meteorites formed in the solar nebula by rapid condensation of material following high-temperature events, such as those that formed chondrules.

Effects of the secondary minerals of the natural pozzolans on their pozzolanic activity

Natural pozzolans have been widely used as substitutes for Portland cement, because of their binding properties. Some of them are natural volcanic rocks which contain secondary minerals such as clays and zeolites corresponding to products of the alteration of the rock. The objective of this study was to document the potential effect of the secondary minerals on the strength development of pozzolanic mortars. We chose to investigate this effect by thermally destabilising these minerals in three different pozzolanic deposits (poz-1, poz-2 and poz-3). We first did a detailed mineralogical study, to identify the occurrence and the nature of the different secondary minerals. Kaolinite is abundant in poz-1 and different types of zeolite were identified in poz-2 and poz-3. Thermal treatments were monitored by X-ray Diffraction (XRD) analysis, in order to document mineralogical transformations. The effect on the pozzolanic activity has been tested by strength measurements on normalised mortars at 1, 7 and 28 days. Strength of all blended cements is enhanced while destabilising secondary alteration minerals. For kaolinite, we showed that a strength improvement occurs as soon as it is destructured, even if it is not transformed in metakaolin. For zeolites, destabilisation takes place at low temperature (350 °C), but as recrystallisation products are easily formed, activation temperature window is narrow. Endly, we have evidence that the presence of calcite in pozzolans has an effect on early strength. Therefore this study is giving new perspectives for a better use of natural pozzolanic materials in the cement industry.

A review of meteorite evidence for the timing of magmatism and of surface or near‐surface liquid water on Mars

There is widespread photogeological evidence for ubiquitous water flowing on the surface of Mars. However, the age of surface and near‐surface water cannot be deduced with high precision from photogeology. While there is clear evidence for old and young fluvial features in the photogeologic record, the uncertainty in the absolute calibration of the Martian crater flux results in uncertainties of ±1.5 Gyr in the middle period of Martian geologic history. Aqueous alteration of primary igneous minerals produces secondary minerals in Martian meteorites. Here we use the ages of secondary alteration minerals in Martian meteorites to obtain absolute ages when liquid water was at or near the surface of Mars. Aqueous alteration events in Martian meteorites occurred at 3929 ± 37 Ma (carbonates in ALH84001), 633 ± 23 Ma (iddingsite in nakhlites), and 0–170 Ma (salts in shergottites). Furthermore, these events appear to be of short duration, suggesting episodic rather than continuous aqueous alteration of the meteorites. The Martian meteorites appear to be contaminated by Martian surface Pb characterized by a 207Pb/206Pb ratio near 1. Lead of this composition could be produced by water‐based alteration on the Martian surface. The high 129Xe/132Xe ratio in the Martian atmosphere compared to Martian meteorites indicates fractionation of I from Xe within ∼100 Myr after nucleosynthesis of 129I. Such fractionation is difficult to achieve through magmatic processes. However, water very efficiently fractionates I from Xe, raising the intriguing possibility that Mars had a liquid water ocean within its first 100 Myr.1.

Secondary alteration of the impactite and mineralization in the basal Tertiary sequence, Yaxcopoil‐1, Chicxulub impact crater, Mexico

Abstract The 65 Ma Chicxulub impact crater formed in the shallow coastal marine shelf of the Yucatán Platform in Mexico. Impacts into water‐rich environments provide heat and geological structures that generate and focus sub‐seafloor convective hydrothermal systems. Core from the Yaxcopoil‐1 (Yax‐1) hole, drilled by the Chicxulub Scientific Drilling Project (CSDP), allowed testing for the presence of an impact‐induced hydrothermal system by: a) characterizing the secondary alteration of the 100 m‐thick impactite sequence; and b) testing for a chemical input into the lower Tertiary sediments that would reflect aquagene hydrothermal plume deposition. Interaction of the Yax‐1 impactites with seawater is evident through redeposition of the suevites (unit 1), secondary alteration mineral assemblages, and the subaqueous depositional environment for the lower Tertiary carbonates immediately overlying the impactites.The least‐altered silicate melt composition intersected in Yax‐1 is that of a calc‐alkaline basaltic andesite with 53.4–56 wt% SiO2(volatile‐free). The primary mineralogy consists of fine microlites of diopside, plagioclase (mainly Ab 47), ternary feldspar (Ab 37 to 77), and trace apatite, titanite, and zircon. The overprinting alteration mineral assemblage is characterized by Mg‐saponite, K‐montmorillonite, celadonite, K‐feldspar, albite, Fe‐oxides, and late Ca and Mg carbonates. Mg and K metasomatism resulted from seawater interaction with the suevitic rocks producing smectite‐K‐feldspar assemblages in the absence of any mixed layer clay minerals, illite, or chlorite. Rare pyrite, sphalerite, galena, and chalcopyrite occur near the base of the impactites. These secondary alteration minerals formed by low temperature (0–150°C) oxidation and fixation of alkalis due to the interaction of glass‐rich suevite with down‐welling seawater in the outer annular trough intersected at Yax‐1. The alteration represents a cold, Mg‐K‐rich seawater recharge zone, possibly recharging higher temperature hydrothermal activity proposed in the central impact basin. Hydrothermal metal input into the Tertiary ocean is shown by elevated Ni, Ag, Au, Bi, and Te concentrations in marcasite and Cd and Ga in sphalerite in the basal 25 m of the Tertiary carbonates in Yax‐1. The lower Tertiary trace element signature reflects hydrothermal metal remobilization from a mafic source rock and is indicative of hydrothermal venting of evolved seawater into the Tertiary ocean from an impact‐generated hydrothermal convective system.

Recharge flux to ocean-ridge black smoker systems: a geochemical estimate from ODP Hole 504B

We use the Sr-isotopic composition of rock and anhydrite, as a monitor of fluid composition, in DSDP/ODP Hole 504B to calculate the recharge flux to the axial high-temperature hydrothermal circulation. The fluid and rock Sr-isotope profiles are well fit by a tracer transport mass-balance model that approximates fluid–solid exchange by linear kinetics. The calculated time-integrated flux of 1.7±0.2×106 kg m−2 is significantly less than the 5×106 kg m−2 calculated from thermal models that assume all magma is intruded into a high-level magma chamber at the base of the sheeted dykes. Our low flux is consistent with the observed thermal structure as recorded by secondary alteration minerals in Hole 504B and the intrusion of magma as lenses distributed through the lower oceanic crust. It leaves open the questions as to how the lower oceanic crust cools and how seawater geochemical budgets balance.

Hydrothermal alteration at the Lonar Lake impact structure, India: Implications for impact cratering on Mars

Abstract— The 50,000 year old, 1.8 km diameter Lonar crater is one of only two known terrestrial craters to be emplaced in basaltic target rock (the 65 million year old Deccan Traps). The composition of the Lonar basalts is similar to martian basaltic meteorites, which establishes Lonar as an excellent analogue for similarly sized craters on the surface of Mars. Samples from cores drilled into the Lonar crater floor show that there are basaltic impact breccias that have been altered by post‐impact hydrothermal processes to produce an assemblage of secondary alteration minerals. Microprobe data and X‐ray diffraction analyses show that the alteration mineral assemblage consists primarily of saponite, with minor celadonite, and carbonate. Thermodynamic modeling and terrestrial volcanic analogues were used to demonstrate that these clay minerals formed at temperatures between 130°C and 200°C. By comparing the Lonar alteration assemblage with alteration at other terrestrial craters, we conclude that the Lonar crater represents a lower size limit for impact‐induced hydrothermal activity. Based on these results, we suggest that similarly sized craters on Mars have the potential to form hydrothermal systems, as long as liquid water was present on or near the martian surface. Furthermore, the Fe‐rich alteration minerals produced by post‐impact hydrothermal processes could contribute to the minor iron enrichment associated with the formation of the martian soil.

Calcium‐aluminum‐rich inclusions and amoeboid olivine aggregates from the CR carbonaceous chondrites

Abstract— Calcium‐aluminum‐rich refractory inclusions (CAIs) in CR chondrites are rare (&lt;1 vol%), fairly small (&lt;500 μm) and irregularly‐shaped, and most of them are fragmented. Based on the mineralogy and petrography, they can be divided into grossite ± hibonite‐rich, melilite‐rich, and pyroxene‐anorthite‐rich CAIs. Other types of refractory objects include fine‐grained spinel‐melilite‐pyroxene aggregates and amoeboid olivine aggregates (AOAs). Some of the pyroxene‐anorthite‐rich CAIs have igneous textures, and most melilite‐rich CAIs share similarities to both the fluffy and compact type A CAIs found in CV chondrites. One major difference between these CAIs and those in CV, CM, and CO chondrites is that secondary mineral phases are rare.In situ ion microprobe analyses of oxygen‐isotopic compositions of 27 CAIs and AOAs from seven CR chondrites demonstrate that most of the CAIs are 16O‐rich (δ17O of hibonite, melilite, spinel, pyroxene, and anorthite &lt; −22‰) and isotopically homogeneous within 3–4‰. Likewise, forsterite, spinel, anorthite, and pyroxene in AOAs have nearly identical, 16O‐rich compositions (−24‰ &lt; δ17O &lt; −20‰). In contrast, objects which show petrographic evidence for extensive melting are not as 16O‐rich (δ17O less than −18‰). Secondary alteration minerals replacing 16O‐rich melilite in melilite‐rich CAIs plot along the terrestrial fractionation line.Most CR CAIs and AOAs are mineralogically pristine objects that largely escaped thermal metamorphism and secondary alteration processes, which is reflected in their relatively homogeneous 16O‐rich compositions. It is likely that these objects (or their precursors) condensed in an 16O‐rich gaseous reservoir in the solar nebula. In contrast, several igneous CAIs are not very enriched in 16O, probably as a result of their having melted in the presence of a relatively 16O‐poor nebular gas. If the precursors of these CAIs were as 16O‐rich as other CR CAIs, this implies either temporal excursions in the isotopic composition of the gas in the CAI‐forming regions and/or radial transport of some CAI precursors into an 16O‐poor gas. The absence of oxygen isotope heterogeneity in the primary minerals of melilite‐rich CAIs containing alteration products suggests that mineralogical alteration in CR chondrites did not affect oxygen‐isotopic compositions of their CAIs.

Experimental hydrothermal alteration of a martian analog basalt: Implications for martian meteorites

Abstract—A number of martian meteorite samples contain secondary alteration minerals such as Ca‐Mg‐Fe carbonates, Fe oxides, and clay minerals. These mineral assemblages hint at hydrothermal processes occurring in the martian crust, but the alteration conditions are poorly constrained. This study presents the results of experiments that examined the alteration of a high‐Fe basalt by CO2‐saturated aqueous fluids at 23 and 75 °C and by mixed H2O‐CO2vapors at 200 and 400 °C and water‐rock ratios of 1:1 and 1:10. Results indicate that observable alteration of the basalt takes place after runs of only seven days. This alteration includes mobilization of silica into phases such as opal‐CT and quartz, as well as the formation of carbonates, oxides, and at some conditions, zeolites and hydrous silicates. The degree of alteration increases with run temperature and, in high‐temperature vapor experiments, with increasing water content of the vapor. The degree of alteration and the mineralogy observed in the martian meteorites suggests that none of these samples were exposed to aqueous fluids for long periods of time. Nakhla and Lafayette probably interacted with water for relatively brief periods of time; if so, silica may have been leached from the parent rocks by the altering fluids. Allan Hills 84001 shows possible evidence for very limited interaction with an aqueous fluid, but the overall slight degree of alteration described for this meteorite strongly suggests that it never interacted extensively or at high temperature with any water‐bearing fluid. Elephant Moraine A79001 may not have been altered by aqueous fluids at all. The results of this study best support models wherein the meteorite parent rocks were wetted intermittently or for brief periods of time rather than models that invoke long‐term reaction with large volumes of water.Our experiments studied alteration of a high‐Fe basalt by dilute, CO2‐saturated, aqueous solutions at 23 and 75 °C and by mixed H2O‐CO2vapors at 200 and 400 °C. The results suggest that alteration of the parent rock takes place even after very short reaction times of seven days. All experiments produced carbonate minerals, including calcite, and in some cases, magnesite, siderite, and ankerite. A free silica phase, either opal, quartz, or hydrated silica, formed in most experiments. More altered experiments also contained minerals such as zeolites and hydrous phyllosilicates. Clay minerals were not observed to form in any experiments.In aqueous fluids, higher temperature corresponded with a higher degree of alteration, whereas changing fluid composition had no observable effect. In high‐temperature vapors, the degree of alteration was controlled by temperature and the proportion of H2O to CO2, with water‐rock ratio also playing a role in transport of silica.Application of these results to martian meteorites that contain secondary alteration minerals suggests that none of the martian rocks underwent extensive interaction with aqueous fluids. Nakhla and Lafayette contain clay minerals, which suggests that they interacted with water to some extent, possibly at elevated temperatures. Although ALH84001 shows possible evidence of very limited interaction with aqueous fluids, EETA79001 does not. These results support models for the alteration of these meteorites that do not invoke long‐term interaction with water or reaction with large volumes of water. Except for some models for alteration of ALH84001, this conclusion agrees with most of the literature on alteration of martian meteorites.

A voluminous avalanche-induced lahar from Citlaltépetl volcano, Mexico: Implications for hazard assessment

During the late Pleistocene the ancestral edifice of Citlaltépetl volcano (also known as Pico de Orizaba) collapsed to form a clay-rich deposit that extends 85 km from its source, has a volume of 1.8 km 3, and covers an area of 143 km 2 east of the volcano. The deposit has clay content ranging from 10 to 16% and contains secondary alteration minerals such as smectite and kaolinite. The deposit's features suggest that it had an origin as a sector collapse of hydrothermally altered rock that transformed from a debris avalanche to a cohesive lahar very close to its source. The presence of glacier ice and a hydrothermal system during late Pleistocene times apparently provided a source of pore water which enhanced the hydrothermal alteration of the summit of Citlaltépetl and was the origin of most of the water for the lahar. This deposit and several others suggest that glaciated volcanoes are sites where hydrothermal alteration and resulting cohesive lahars are most likely. Although cohesive lahars and debris avalanches both have origins as sector collapses, cohesive lahars are more mobile than similar-sized debris avalanches. Thus potential hazard of edifice collapse at glaciated volcanoes, especially those with large volumes of hydrothermally altered rock, includes the possibility of large-volume cohesive lahars.

Geochemistry, mineralogy, and geology of the Jason Pb-Zn deposits, Macmillan Pass, Yukon, Canada

Three separate stratiform Pb-Zn deposits occur on the Jason property in the Macmillan Pass area of the Yukon, Canada. The deposits are contained within chert conglomerates and finer grained clastic rocks of Middle to Late Devonian age. The deposits are on the eastern margin of the Cambro-Ordovician Selwyn basin and are associated with a fault-bounded, second or third-order subbasin, referred to as the MacPass graben.Three different facies of mineralization and associated sedimentation have been defined on the basis of field relationships, drill core descriptions and correlations, and detailed petrography, Facies A comprises massive to thick-bedded galena and sphalerite with abundant pyrrhotite and pyrite. This facies is extensively crosscut by galena-bearing quartz siderite and quartz ankerite veins and has the highest combined Pb-Zn-Ag concentrations. Facies A is proximal to the hydrothermal source represented by the veins. Facies B has a mineralogic assemblage and textures common to facies A but is considerably thinner. Abundant soft sediment deformation features indicate facies B formed from slumping of unstable accumulations of material from facies A. Facies C contains well-bedded sphalerite, chert, and barite laminae and is distal to the hydrothermal source. Secondary alteration and pore-filling minerals found in facies C include celsian, kaolinite, ankerite, and a complex suite of rare Ba carbonates.Fluid inclusions in quartz, siderite, and ankerite within veins crosscutting facies A indicate that the ore-forming fluids were NaCl brines (9 equiv. wt %) with temperatures of approximately 250 degrees C. Sulfur isotope data indicate that the sulfides within the three separate deposits had a common sulfur source, probably reduced seawater sulfate. Barite in the laminated facies C has delta 34 S values consistent with coeval Devonian seawater. The sulfide minerals are approximately 10 per mil lighter than coeval seawater.A maximum water depth of 420 m for venting of hydrothermal fluids was determined by combining fluid inclusion data with boiling curves for H 2 O-NaCl. Brine densities indicate the hydrothermal plume may have reached the seawater surface and dispersed laterally to form the barite in facies C. Accumulations, on unstable slopes, of thick deposits of sulfide slumped to cause thinning and soft sediment deformation of facies B. Since facies B is a sedimentary feature, not necessarily proximal or distal to the vent, it may or may not contain barite.

Disseminated and epigenetic Pb–Zn mineralisation in Ordovician mudstone, Galloway

Synopsis Significant base metal anomalies in drainage and overburden in the Penkiln Burn area, near Newton Stewart, are spatially associated with the outcrop of a sequence of siliceous mudstone, siltstone and chert. Pb is particularly enriched in drainage samples, reaching approximately 1% close to a mineralised gossan zone, mainly in the secondary lead phosphate plumbogummite. Three varieties of mineralisation have been recognised: Early fine disseminations, chiefly sphalerite and pyrite, in the mudstone and siltstone characterised by Zn levels between 500 and 1000 ppm. Fine stratiform pyrite laminae adjacent to the mineralised horizons and interbedded cherts containing disseminated sphalerite support a probable syngenetic, exhalative origin. A swarm of dioritic minor intrusions carry disseminated sulphides and have elevated metal contents, most notably Zn (up to 2000 ppm). This mineralisation is considered to have a primary igneous source. Mineralisation related to veining and alteration involving both the remobilisation of the disseminated sulphides and hydrothermal effects. Thin quartz veinlets containing sphalerite and galena locally elevate base metal levels so that Pb reaches 7000 ppm in places. The veins usually contain some secondary alteration minerals which become dominant at the altered margins of dykes and in fault-bounded gossans where a low temperature mineral assemblage includes plumbogummite and beudantite. In the gossans Pb ranges up to 4.5% but Zn has been preferentially leached.