Mantle-derived gaseous components in ore-forming fluids of the Xiangshan uranium

The Xiangshan U deposit, the largest hydrothermal U deposit in China, is hosted in late Jurassic felsic volcanic rocks although the U mineralization post dates the volcanics by at least 20 Ma. The mineralization coincides with intrusion of local mantle-derived mafic dykes formed during Cretaceous crustal extension in South China. Ore-forming fluids are rich in CO2, and U in the fluid is thought to have been dissolved in the form of UO2 (CO3)22− and UO2 (CO3) 34− complexes. This paper provides He and Ar isotope data of fluid inclusions in pyrites and C isotope data of calcites associated with U mineralization (pitchblende) in the Xiangshan U deposit. He isotopic compositions range between 0.1 and 2.0Ra (where Ra is the 3He/4He ratio of air=1.39×10−6) and correlates with 40Ar/36Ar; although there is potential for significant 3He production via 6Li(n,α)3H(β)3He reactions in a U deposit (due to abundant neutrons), nucleogenic production cannot account for either the 3He concentration in these fluids, nor the correlations between He and Ar isotopic compositions. It is more likely that the high 3He/4He ratios represent trapped mantle-derived gases. A mantle origin for the volatiles of Xiangshan is consistent with the δ13C values of calcites, which vary from −3.5‰ to −7.7‰, overlapping the range of mantle CO2. The He, Ar and CO2 characteristics of the ore-forming fluids responsible for the deposit are consistent with mixing between 3He- and CO2-rich mantle-derived fluids and CO2-poor meteoric fluids. These fluids were likely produced during Cretaceous extension and dyke intrusion which permitted mantle-derived CO2 to migrate upward and remobilize U from the acid volcanic source rocks, resulting in the formation of the U deposit. Subsequent decay of U within the fluid inclusions has reduced the 3He/4He ratio, and variations in U/3He result in the range in 3He/4He observed with U/3He ratios in the range 5–17×103 likely corresponding to U concentrations in the fluids b0.2 ppm.

Characteristics and alteration origins of matrix minerals in volcaniclastic kimberlite of the Muskox pipe (Nunavut, Canada)

The matrix of volcaniclastic kimberlite (VK) from the Muskox pipe (Northern Slave Province, Nunavut, Canada) is interpreted to represent an overprint of an original clastic matrix. Muskox VK is subdivided into three different matrix mineral assemblages that reflect differences in the proportions of original primary matrix constituents, temperature of formation and nature of the altering fluids. Using whole rock X-ray fluorescence (XRF), whole rock X-ray diffraction (XRD), microprobe analyses, back-scatter electron (BSE) imaging, petrography and core logging, we find that most matrix minerals (serpentine, phlogopite, chlorite, saponite, monticellite, Fe-Ti oxides and calcite) lack either primary igneous or primary clastic textures. The mineralogy and textures are most consistent with formation through alteration overprinting of an original clastic matrix that form by retrograde reactions as the deposit cools, or, in the case of calcite, by precipitation from Ca-bearing fluids into a secondary porosity. The first mineral assemblage consists largely of serpentine, phlogopite, calcite, Fe-Ti oxides and monticellite and occurs in VK with relatively fresh framework clasts. Alteration reactions, driven by deuteric fluids derived from the juvenile constituents, promote the crystallisation of minerals that indicate relatively high temperatures of formation (> 400 °C). Lower-temperature minerals are not present because permeability was occluded before the deposit cooled to low temperatures, thus shielding the facies from further interaction with fluids. The other two matrix mineral assemblages consist largely of serpentine, phlogopite, calcite, +/- diopside, and +/- chlorite. They form in VK that contains more country rock, which may have caused the deposit to be cooler upon emplacement. Most framework components are completely altered, suggesting that larger volumes of fluids drove the alteration reactions. These fluids were likely of meteoric provenance and became heated by the volcaniclastic debris when they percolated into the VK infill. Most alteration reactions ceased at temperatures > 200 °C, as indicated by the absence or paucity of lower-temperature phases in most samples, such as saponite. Recognition that Muskox VK contains an original clastic matrix is a necessary first step for evaluating the textural configuration, which is important for reconstructing the physical processes responsible for the formation of the deposit.

Structural and clumped-isotope constraints on the mechanisms of displacement along low-angle detachments

Despite years of research on low-angle detachments, much about them remains enigmatic. This thesis addresses some of the uncertainty regarding two particular detachments, the Mormon Peak detachment in Nevada and the Heart Mountain detachment in Wyoming and Montana.

Constraints on the geometry and kinematics of emplacement of the Mormon Peak detachment are provided by detailed geologic mapping of the Meadow Valley Mountains, along with an analysis of structural data within the allochthon in the Mormon Mountains. Identifiable structures well suited to constrain the kinematics of the detachment include a newly mapped, Sevier-age monoclinal flexure in the hanging wall of the detachment. This flexure, including the syncline at its base and the anticline at its top, can be readily matched to the base and top of the frontal Sevier thrust ramp, which is exposed in the footwall of the detachment to the east in the Mormon Mountains and Tule Springs Hills. The ~12 km of offset of these structural markers precludes the radial sliding hypothesis for emplacement of the allochthon.

The role of fluids in the slip along faults is a widely investigated topic, but the use of carbonate clumped-isotope thermometry to investigate these fluids is new. Faults rocks from within ~1 m of the Mormon Peak detachment, including veins, breccias, gouges, and host rocks, were analyzed for carbon, oxygen, and clumped-isotope measurements. The data indicate that much of the carbonate breccia and gouge material along the detachment is comminuted host rock, as expected. Measurements in vein material indicate that the fluid system is dominated by meteoric water, whose temperature indicates circulation to substantial depths (c. 4 km) in the upper crust near the fault zone.

Slip along the subhorizontal Heart Mountain detachment is particularly enigmatic, and many different mechanisms for failure have been proposed, predominantly involving catastrophic failure. Textural evidence of multiple slip events is abundant, and include multiple brecciation events and cross-cutting clastic dikes. Footwall deformation is observed in numerous exposures of the detachment. Stylolitic surfaces and alteration textures within and around “banded grains” previously interpreted to be an indicator of high-temperature fluidization along the fault suggest their formation instead via low-temperature dissolution and alteration processes. There is abundant textural evidence of the significant role of fluids along the detachment via pressure solution. The process of pressure solution creep may be responsible for enabling multiple slip events on the low-angle detachment, via a local rotation of the stress field.

Clumped-isotope thermometry of fault rocks associated with the Heart Mountain detachment indicates that despite its location on the flanks of a volcano that was active during slip, the majority of carbonate along the Heart Mountain detachment does not record significant heating above ambient temperatures (c. 40-70°C). Instead, cold meteoric fluids infiltrated the detachment breccia, and carbonate precipitated under ambient temperatures controlled by structural depth. Locally, fault gouge does preserve hot temperatures (>200°C), as is observed in both the Mormon Peak detachment and Heart Mountain detachment areas. Samples with very hot temperatures attributable to frictional shear heating are present but rare. They appear to be best preserved in hanging wall structures related to the detachment, rather than along the main detachment.

Evidence is presented for the prevalence of relatively cold, meteoric fluids along both shallow crustal detachments studied, and for protracted histories of slip along both detachments. Frictional heating is evident from both areas, but is a minor component of the preserved fault rock record. Pressure solution is evident, and might play a role in initiating slip on the Heart Mountain fault, and possibly other low-angle detachments.

Stable isotope composition of smectite in suevites at the Ries crater, Germany: Implications for hydrous alteration of impactites

The 24-km diameter Ries crater, Germany, exhibits well-preserved crater filling and surficial melt-rich breccia deposits that are believed to have been altered by post-impact hydrothermal fluids. The alteration mineralogy of the crater filling breccias is characterized by clay (smectite, chlorite) and a zeolite assemblage, and secondary clay phases (smectite, minor halloysite) in surficial melt-bearing breccia deposits. Using stable isotope analysis of secondary smectitic clay fractions, evidence of significant hydrous alteration of impactites at large water/rock ratios was found. The estimated fluid temperatures, using data derived by delta(18)O and delta D fractionation, suggest smectite precipitation in surficial breccias in equilibrium with meteoric fluids at temperatures 16 +/- 5 degrees C in agreement with the long-term variation of modern precipitation in the area. The stable isotope composition of smectite in crater-fill breccia, however, suggests a trend of monotonously increasing temperatures from 43 to 112 degrees C. with increasing depth through the breccia sequence. This demonstrates a different origin of alteration and temperature distribution for the surficial and crater filling melt-bearing impact breccias in the Ries crater. Our results suggest that the inverted structure of hydrothermal systems observed in some terrestrial impact craters, including the Ries crater, could indicate the initial configuration of a thermal anomaly in the crater filling sequence, but which is replaced with a normal hydrothermal convection in crater proper, during the course of post-impact cooling. (C) 2010 Elsevier B.V. All rights reserved.

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondonia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondonia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Barbara deposit (Rondonia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sri (+/-W, +/-Ta, +/-Nb), and base-metal suite (Zn-Cu-Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0-19 wt.% NaCl eq.) CO2-bearing aqueous fluids homogenizing at 245-450 degreesC, and (2) aqueous solutions with low CO2, low to moderate salinity (0-14 wt.% NaCl eq.), which homogenize between 100 and 340 T. In the Santa Barbara deposit, the early inclusions are represented by (1) low-salinity (5-12 wt.% NaCl eq.) aqueous fluids with variable CO2 contents, homogenizing at 340 to 390 T, and (2) low-salinity (0-3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320380 degreesC. Cassiterite, wolframite, columbite-tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0-6 wt.% NaCl eq.) CO2-free aqueous solution, which homogenizes at (100-260 degreesC) and characterizes the sulfide fluorite-sericite association in the Correas deposit. The late fluid in the Santa Barbara deposit has lower salinity (0-3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240-450 degreesC, and 1,0-2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (delta(18)O quartz from 9.9parts per thousand to 10.9parts per thousand, deltaDH(2)O from 4.13parts per thousand to 6.95parts per thousand) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 degreesC. In the Santa Barbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 degreesC, respectively), and that for the cassiterite-quartz-veins is 415 degreesC. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (delta(18)O(qtz-H2O)=5.5-6.1parts per thousand) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (delta(18)O(mica-H2O)=33-9.8parts per thousand) suggest mixing with meteoric water. Late muscovite veins (delta(18)O(qtz-H2O)=-6.4parts per thousand) and late quartz (delta(18)O(mica-H2O)=-3.8parts per thousand) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor coluChange in the redox conditions related to mixing-of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit. (C) 2004 Elsevier B.V. All rights reserved.

Preliminary mineralogy and ore petrology of the intermediate-sulfidation pallancata deposit, Ayacucho, Peru

Se investiga la compleja mineralogía del Yacimiento de Pallancata (6º productor de plata del mundo) y se establecen las condiciones de formación (P.T) basadas en la petrología de las menas comparada con los datos de mineralogía experimental y en la petrografía y microtermometría de inclusiones fluídas en la ganga silicatada, resultando un depósito típicamente caracterizado como epitermal de sulfuración intermedia.ABSTRACT:Pallancata is a world-class intermediate-sulfidation epithermal deposit, hosted by upper Miocene volcanics of the south-central Peruvian Andes in a sinuous N70ºW, ∼75º SW strike-slip structure, with wide (up to 35 m) pull-apart dilation zones related to bends of the vein strike. The structural evolution of the vein from earlier brecciation to later open space infill resembles the Shila Paula district (Chauvet et al. 2006). Fluid inclusion petrography and microthermometry show that ore deposition is related to protracted boiling of very diluted, mainly meteoric fluids, starting at 250–260 ºC, under ∼300 m hydrostatic head. The mineralogical-petrological study reveals a complex sequence of mineralization (eight stages) and mineral reactions consistent with Ag2S enrichment or Sb2S3 depletion, or both, during cooling over the temperature range 250–200 ºC: pyrite, sphalerite, galena, miargyrite, pyrargyrite-proustite, chalcopyrite, polybasite-pearceite, argentite (now acanthite), and Au–Ag alloy (“electrum”). This Ag2S enrichment and Sb2S3depletion during cooling may be explained by decay of a Ag-rich galena precursor at deeper levels (Pb2S2–AgSbS2 solid solution), which rapidly becomes unstable with decreasing temperature, producing residual (stoichiometric) PbS and more mobile Ag and Sb sulfide phases, which migrated upward and laterally away from the thermal core of the system. The core is still undisclosed by mining works, but the available geochemical evidence (logAg/log Pb ratios decreasing at depth) is consistent with this interpretation, implying a deeper potential resource. Data from sulfide geothermometry, based on mineral equilibria, document the thermal evolution of the system below 200 ºC (stephanite, uytenbogaardtite, jalpaite, stromeyerite, mckinstryite, among others). The end of the most productive stages (3, 4, and 5) is marked by the precipitation of stephanite at temperatures below 197 ± 5 ºC, but precipitation of residual silver continues through the waning stages of the hydrothermal system down to <93.3 ºC (stromeyerite) or in a supergene redistribution (stage 8, acanthite II).

The Provenance and Geochemical Alteration of Bermudan Eolianites

Large calcareous eolianites cover the remote island of Bermuda, accounting for more than 90% of the limestone bedrock. This study examines the sedimentology and geochemistry of these eolianites to better understand Pleistocene oceanography and the meteoric alteration of subtropical carbonate sediments. Cluster analyses reveal that the eolian carbonate sediments fall into two natural groups that represent lagoonal and reefal end members of marine sediment production. Coral fragments are uncharacteristically absent, possibly destroyed prior to their incorporation into eolian deposits by endolithic microboring organisms or broken up during transport. Sediment assemblages lead to the following interpretations of the Bermudan offshore environment: (1) the Ledge Flats reef system along the southwestern coast has been active since MIS 11, contributing coralline algal-rich sediment to the northern beaches of Sandy’s Parish and acting as an energy barrier in the south, allowing for low energy sedimentation in the quiet back- reef region; (2) on the northeastern coast, the low energy back-reef region landward of the Ledge Flats has thrived since MIS 11; (3) during MIS 5e, slightly warmer water temperatures led to the hindrance of coralline algal growth along the southern coast and in the North Lagoon. These are the first interpretations of Pleistocene marine assemblages on Bermuda. Meteoric fluids progressively transformed the pristine carbonate sediments into hardened limestones in a predictable solubility-dependent manner. The progressive alteration is coincident with: (1) divergence of δ18O and δ13C values from those similar to unaltered sediment towards those of calcrete, due to interaction with CO2-charged meteoric fluids; (2) depletion of elements with low partitioning coefficients and low meteoric concentrations, such as barium, boron, magnesium, potassium, sodium, strontium, and uranium; (3) enrichment of iron from Terra Rossa-hosted iron oxides; (4) enrichment of aluminum via detrital minerals sourced from protosol horizons; and (5) manganese concentrations that remain uncharacteristically low, owing to the lack of a consistent manganese source. Elemental correlations are useful for characterizing meteoric diagenesis, assuming the primary mineralogy is recognized, all components have been fully altered, and inter-particle cements are ubiquitous.

Bromine and iodine concentrations in sediments and pore fluids of ODP Leg 112

At the Peruvian convergent margin, two distinct pore fluid regimes are recognized from differences in their Cl- concentrations. The slope pore fluids are characterized by low Cl- concentrations, but elevated Br- and I- concentrations due to biogenic production. The shelf pore fluids exhibit elevated Cl- and Br- concentrations due to diffusive mixing with an evaporitic brine. In the slope pore fluids, the Br-, I-, and NH4+ concentrations are elevated following bacterial decomposition of organic matter, but the I- concentrations are in excess of those expected based on mass balance calculations using NH4+ and Br- concentrations. The slope sediment organic matter, which is enriched in iodine from oxidationreduction processes at the oxygenated sediment-water interface, is responsible for this enrichment. The increases in dissolved I- and the I- enrichments relative to NH4+ and Br- correlate well with sedimentation rates because of differential trapping following regeneration. The pore-fluid I-/Br- ratios suggest that membrane ion fiitration is not a major cause of the decreases in Cl- concentrations. Other possible sources for low Cl- water, including meteoric water, clathrate dissociation, and/or mineral dehydration reactions, imply that the diluting component of the slope low-Cl- fluids has flowed at least 1 km through the sediment. The low bottom-water oxygenation in the shelf is responsible for the low (if any) enrichment of iodine in the shelf sediments. Fluctuations in bottom-water oxygen concentrations in the past, however, may be responsible for the observed variations in the sediment I/Br ratios. Comparison of Na+/Cl- and Br-/Cl- molar ratios in the pore fluids shows that the shelf high-Cl- fluid formed from mixing with a brine that formed from seawater concentrated by twelve to nineteen times and probably was modified by halite dissolution. This dense brine, located below the sediment sections drilled, appears to have flowed a distance >500 km through the sediment.

Geochemistry of pore fluids from ODP Leg 134 sites

Depending on the temperature and the extent of diagenetic alteration of fluid chemistry, fluid flow at convergent margins may transfer important quantities of heat and mass between the crust and seawater, thereby influencing global mass, isotopic and heat budgets. In the North Aoba Basin, an intra-arc basin located at the New Hebrides Island Arc, alteration of volcanic ash to clay minerals and zeolites forms a CaCl2 brine, perhaps in less than 1 to 3 m.y. The brine results from an exchange of Ca for Na, K, and Mg, and an increase in Cl concentrations to a maximum of 1241 mM. The Cl increase is partly due to the transfer of H2O from the pore fluid into authigenic minerals, but water mass balances, d18O-Cl correlations, and Br/Cl ratios suggest that there is a source of Cl in the sediments. Concentration profiles indicate that Li is transferred from the fluid to solid phase at depths <300 meters below seafloor (mbsf), but at greater depths it is transferred from the solid to fluid phase, at temperatures possibly as low as 25°C. In the accretionary wedge extensive fluid flow appears to be confined to highly faulted regions. Although Cl concentrations less than seawater value are common at convergent margins, the New Hebrides margin contains little low-Cl fluid. Br/Cl ratios suggest the low-Cl fluid is from dilution, and d18O values indicate the water may be derived from mineral dehydration and mixing with meteoric water. The New Hebrides margin exhibits few surface manifestations of venting (e.g., sulfide-oxidizing benthic biological communities, carbonate crusts, mud volcanoes) and thus fluid fluxes may be smaller than at many other margins.

Bajo de la Alumbrera copper-gold deposit: Stable isotope evidence for a porphyry-related hydrothermal system dominated by magmatic aqueous fluids

Alteration zones at the gold-rich Bajo de la Alumbrera porphyry copper deposit in northwestern Argentina are centered on several porphyritic intrusions. They are zoned from a central copper-iron sulfide and gold-mineralized potassic (biotite-K-feldspar +/- quartz) core outward to propylitic (chlorite-illite-epidote-calcite) assemblages. A mineralized intermediate argillic alteration assemblage (chlorite-illite +/- pyrite) has overprinted the potassic alteration zone across the top and sides of the deposit and is itself zoned outward into phyllic (quartzinuscovite-illite +/- pyrite) alteration. This study contributes new data to previously reported delta(18)O and delta D compositions of fluids responsible for the alteration at Bajo de la Alumbrera, and the data are used to infer likely ore-forming processes. Measured and calculated delta(18)O and delta D values of fluids (+8.3 to +10.2 and -33 to -81 parts per thousand, respectively) confirm a primary magmatic origin for the earliest potassic alteration phase. Lower temperature potassic alteration formed from magmatic fluids with lower delta D values (down to -123 parts per thousand). These depleted compositions are distinct from meteoric water and consistent with degassing and volatile exsolution of magmatic fluids derived from an underlying magma. Variability in the calculated composition of fluid associated with potassic alteration is explained in terms of phase separation (or boiling). if copper-iron sulfide deposition occurred during cooling (as proposed elsewhere), this cooling was largely a result of phase separation. Magmatic water was directly involved in the formation of overprinting intermediate argillic alteration assemblages at Bajo de la Alumbrera. Calculated delta(18)O and delta D values of fluids associated with this alteration range from +4.8 to +8.1 and -31 to -71 per mil, respectively Compositions determined for fluids associated with phyllic alteration (-0.8 to +10.2 and -31 to -119 parts per thousand) overlap with the values determined for the intermediate argillic alteration. We infer that phyllic alteration assemblages developed during two stages; the first was a high-temperature (400 degrees-300 degrees C) stage with D-depleted water (delta D = -66 to -119 parts per thousand). This compositional range may have resulted from magma degassing and/or the injection of new magmatic water into a compositionally evolved hydrothermal system. The isotopic variations also can be explained by increased fluid-rock interaction. The second stage of phyllic alteration occurred at a lower temperature (similar to 200 degrees C), and variations in the modeled isotopic compositions imply mixing of magmatic and meteoric waters. Ore deposition that occurred late in the evolution of the hydrothermal system was probably associated with further cooling of the magmatic fluid, in part caused by fluid-rock interaction and phase separation. Changing pH and/or oxygen fuoracity may have caused additional ore deposition. The ingress of meteoric water appears to postdate the bulk of mineralization and occurred as the system at Bajo de la Alumbrera waned.

Contribution of thickened drinks, food and enteral and parenteral fluids to fluid intake in hospitalised patients with dysphagia

Background Studies amongst older people with acute dysphagic stroke requiring thickened fluids have assessed fluid intakes from combinations of beverage, food, enteral and parenteral sources, but not all sources simultaneously. The study aimed to comprehensively assess total water intake from food, beverages, enteral and parenteral sources amongst dysphagic adult in-patients receiving thickened fluids. Methods Patients requiring thickened fluid following dysphagia diagnosis were recruited consecutively from a tertiary teaching hospital’s medical and neurosurgical wards. Fluid intake from food and beverages was assessed by wastage, direct observation and quantified from enteral and parenteral sources through clinical medical records. Results No patients achieved their calculated fluid requirements unless enteral or parenteral fluids were received. The mean daily fluid intake from food was greater than from beverages whether receiving diet alone (food 807±363mL, food and beverages 370±179mL, p<0.001) or diet with enteral or parenteral fluid support (food 455±408mL, food and beverages 263±232mL, p<0.001). Greater daily fluid intakes occurred when receiving enteral and parenteral fluid in addition to oral dietary intake, irrespective of age group, whether assistance was required, diagnosis and whether stage 3 or stage 2 thickened fluids were required (p<0.05). After enteral and parenteral sources, food provided the most important contribution to daily fluid intakes. Conclusions The greatest contribution to oral fluid intake was from food, not beverages. Designing menus and food services which promote and encourage the enjoyment of fluid dense foods, in contrast to thickened beverages, may present an important way to improve fluid intakes of those with dysphagia. Supplemental enteral or parenteral fluid may be necessary to achieve minimum calculated fluid requirements.

Petrology and geochemistry of the Quaternary Caldera-forming, Phonolitic Granadilla Eruption, Tenerife (Canary Islands)

The Granadilla eruption at 600 ka was one of the largest phonolitic explosive eruptions from the Las Cañadas volcano on Tenerife, producing a classical plinian eruptive sequence of a widespread pumice fall deposit overlain by an ignimbrite. The eruption resulted in a major phase of caldera collapse that probably destroyed the shallow-level magma chamber system. Granadilla pumices contain a diverse phenocryst assemblage of alkali feldspar + biotite + sodian diopside to aegirine–augite + titanomagnetite + ilmenite + nosean/haüyne + titanite + apatite; alkali feldspar is the dominant phenocryst and biotite is the main ferromagnesian phase. Kaersutite and partially resorbed plagioclase (oligoclase to sodic andesine) are present in some eruptive units, particularly in pumice erupted during the early plinian phase, and in the Granadilla ignimbrite at the top of the sequence. Associated with the kaersutite and plagioclase are small clots of microlitic plagioclase and kaersutite interpreted as quenched blebs of tephriphonolitic magma within the phonolite pumice. The Granadilla Member has previously been recognized as an example of reverse-then-normal compositional zonation, where the zonation is primarily expressed in terms of substantial variations in trace element abundances with limited major element variation (cryptic zonation). Evidence for cryptic zonation is also provided by the chemistry of the phenocryst phases, and corresponding changes in intensive parameters (e.g. T, f O2, f  H2O). Geothermometry estimates indicate that the main body of phonolite magma had a temperature gradient from 860 °C to ∼790 °C, with hotter magma (≥900 °C) tapped at the onset and terminal phases of the eruption. The reverse-then-normal chemical and thermal zonation reflects the initial tapping of a partially hybridized magma (mixing of phonolite and tephriphonolite), followed by the more sequential tapping of a zoned and relatively large body of highly evolved phonolite at a new vent and during the main plinian phase. This suggests that the different magma types within the main holding chamber could have been laterally juxtaposed, as well as in a density-stratified arrangement. Correlations between the presence of mixed phenocryst populations (i.e. presence of plagioclase and kaersutite) and coarser pumice fall layers suggest that increased eruption vigour led to the tapping of hybridized and/or less evolved magma probably from greater depths in the chamber. New oxygen isotope data for glass and mineral separates preclude syn-eruptive interaction between the vesiculating magma and hydrothermal fluids as the cause of the Sr isotope disequilibrium identified previously for the deposit. Enrichment in radiogenic Sr in the pumice glass has more likely been due to low-temperature exchange with meteoric water that was enriched in 87Sr by sea spray, which may be a common process affecting porous and glassy pyroclastic deposits on oceanic islands.

Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: A sequence through neomorphism of aragonite to calcite

Rare earth element geochemistry in carbonate rocks is utilized increasingly for studying both modern oceans and palaeoceanography, with additional applications for investigating water–rock interactions in groundwater and carbonate diagenesis. However, the study of rare earth element geochemistry in ancient rocks requires the preservation of their distribution patterns through subsequent diagenesis. The subjects of this study, Pleistocene scleractinian coral skeletons from Windley Key, Florida, have undergone partial to complete neomorphism from aragonite to calcite in a meteoric setting; they allow direct comparison of rare earth element distributions in original coral skeleton and in neomorphic calcite. Neomorphism occurred in a vadose setting along a thin film, with degradation of organic matter playing an initial role in controlling the morphology of the diagenetic front. As expected, minor element concentrations vary significantly between skeletal aragonite and neomorphic calcite, with Sr, Ba and U decreasing in concentration and Mn increasing in concentration in the calcite, suggesting that neomorphism took place in an open system. However, rare earth elements were largely retained during neomorphism, with precipitating cements taking up excess rare earth elements released from dissolved carbonates from higher in the karst system. Preserved rare earth element patterns in the stabilized calcite closely reflect the original rare earth element patterns of the corals and associated reef carbonates. However, minor increases in light rare earth element depletion and negative Ce anomalies may reflect shallow oxidized groundwater processes, whereas decreasing light rare earth element depletion may reflect mixing of rare earth elements from associated microbialites or contamination from insoluble residues. Regardless of these minor disturbances, the results indicate that rare earth elements, unlike many minor elements, behave very conservatively during meteoric diagenesis. As the meteoric transformation of aragonite to calcite is a near worst case scenario for survival of original marine trace element distributions, this study suggests that original rare earth element patterns may commonly be preserved in ancient limestones, thus providing support for the use of ancient marine limestones as proxies for marine rare earth element geochemistry.