Direct measurements of latent heat during crystallization and melting of a ugandite and an olivine basalt

Step-scanning calorimetric measurements using a Setaram HT1500 calorimeter were performed between 800 and 1400°C on two natural samples: a ugandite from the East African rift and an olivine basalt from the western Mexican arc. Our measurements provide the first in-situ quantitative assessment of enthalpy during melting of initially crystalline natural samples. The distribution of latent heat across the liquidus-solidus intervals of the two samples is distinctly different, reflecting significant variation in the sequence and abundance of mineral phases during melting (clinopyroxene and leucite in the ugandite; olivine, clinopyroxene, and plagioclase in the basalt). Our data further indicate that the common assumption of a uniform distribution of latent heat across the liquidus-solidus interval of a magma is a reasonable approximation for the olivine basalt, but is grossly in error for the ugandite. This is due to cotectic precipitation of leucite and clinopyroxene, leading to a large, disproportionate release of latent heat early in the crystallization sequence. The implication for the thermal history of a crystallizing ugandite magma is that therate of heat loss during conductive cooling will unitially be more rapid than the average rate. The net result will be to produce lower magmatic temperatures after a given cooling interval relative to models assuming a uniform release of latent heat. An additional series of scanning calorimetric experiments were performed at variable rates (1,2 and 3°/min) to evaluate the role of kinetics on the distribution of enthalpy during both melting and crystallization of the ugandite and olivine basalt. The results indicate that clinopyroxene is the most important mineral phase in controlling the shapes of the enthalpy profiles during cooling; this is due to its large enthalpy of fusion and its tendency for sluggish nucleation, followed by rapid crystallization at temperatures that vary with cooling rate. The resolution of the calorimeter (in terms of heat detected per unit time) is also important in determining the shapes of theobserved enthalpy profiles during these rapid scans. Estimates based on the observed calorimetric signal associated with melting of olivine, and the lack of a calorimetric signal during melting of leucite, combined with known enthalpies of fusion for the two phases, indicate detection limits of approximately 0.6–1.2 kJ per 5 min increments.     

Speleogenesis in aeolian calcarenite: A case study in western Victoria

Most studies of karst landscapes and their processes have been concerned with consolidated, often well-jointed limestones. There are particular problems involved in the study of karst procesess in softer, less-compact limestones such as chalk, coral reefs, and aeolian calcarenite. Previous studies in aeolian calcarenite indicated these problems and a scheme was developed of speleogenesis in aeolian calcarenite. A study of karst processes in aeolian calcarenite at Bats Ridge in western Victoria has developed this scheme further. The karst features and processes at Bats Ridge are an integral part of the landscape of a mid-Pleistocene calcarenite dune system. The resolution of problems of the rapid subaerial speleogenesis in the area is achieved by the synthesis of the known karst features of the ridge and the geology and geomorphology of the area. Karst development on this aeolianite ridge depends on lithological conditions as well as the availability of aggressive water capable of solution. The diagenesis of the calcarenite is occurring now and must have been occurring by the mid-Pleistocene. This simultaneous lithification of the carbonate dunes into aeolian calcarenite rock and the development of solutional karst features in the dunes is the characteristic feature of the speleogenesis in this area. It is the formation of a hardened kankar layer (cap rock) in the dunes of sufficient compressive and tensile strength to support cavities, which is the result of these interrelated factors, that has strongly determined the formation of the karst features.     

Isotope and trace element geochemistry of sediments from the Barbados Ridge-Demerara Plain region,Atlantic Ocean

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb${}^{206}\text{Pb}{}^{204}\text{Pb}$ up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and${}^{143}\text{Nd}{}^{144}\text{Nd}$ increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas.Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of “normal” depleted MORB.     

Hafnium/rare earth element fractionation in the sedimentary system and crustal recycling into the Earth's mantle

Among long-lived radioactive parent-daughter element pairs, the ratio Lu/Hf is strongly fractionated relative to constant Sm/Nd in the Earth's sedimentary system. This is caused by high resistance to chemical weathering of the mineral zircon (Zr,Hf)SiO₄. Zircon-bearing sandy sediments on and near continents have very low Lu/Hf, while deep-sea clays have up to three times the chondritic Lu/Hf ratio. Turbidity currents mechanically carry the low-Lu/Hf sandy material onto the ocean floor. The results are important for the crust-to-mantle recycling discussion, where most recycled materials would be subducted oceanic sediments. Such sediment should be capable of explaining the HfNd mantle isotopic variation by mixing with peridotite, but in fact any average pelagic sediment has Nd/Hf and Lu/Hf too high to allow mixing curves to pass through the Hf/Nd isotopic array. The array could only be reproduced by subduction of turbidite sandstone with pelagic sediment in the approximate ratio 1.2 to 1, and by maintaining a good mixture between the two components. At least today, turbidites are available for subduction only at locations quite different and distant from those where pelagic sediments may be recycled; furthermore, mantle isotopic variation shows that the mantle often cannot mix itself well enough to homogenize these widely-separated sedimentary components to the degree required. The Lu/Hf fractionations place a severe restriction on the ability of recycled sediments to explain mantle isotopic patterns.     

Automatic sampling of stream water during storm events in small remote catchments

In order to study the relationship between water composition and stream flow rate, it is desirable to sample at a frequency related to flow rate, especially during storm events. In a rural catchment of 18 ha near Oxford, the rate of rainfall was found to be linearly related to discharge on the rising limb of the stream hydrograph. A sampling system was therefore designed in which electrical pulses from a tipping-bucket raingauge were used to initiate and control the action of an automatic water sampler. A threshold rainfall intensity is set above which sampling commences. Sampling then continues at regular increments of rainfall until the intensity drops below the threshold, after which sampling occurs at regular intervals during the period that the stream flow reverts to normal. The CMOS electrical circuits which control the sampling also operate a cassette tape recorder which records the time of each tip of the raingauge and operation of the sampler. Since the sytem is designed to impose very little additional load on the battery which powers the water sampler, and can operate unattended for at least a fortnight, it is ideal for use in small, remote catchments. The system has been extended to include measurements of water temperature and could provide other measurements as well.     

Origin and stratigraphy of phreatomagmatic deposits at the Pleistocene Sinker Butte Volcano, Western Snake River Plain, Idaho

Sinker Butte is the erosional remnant of a very large basaltic tuff cone of middle Pleistocene age located at the southern edge of the western Snake River Plain. Phreatomagmatic tephras are exposed in complete sections up to 100 m thick in the walls of the Snake River Canyon, creating an unusual opportunity to study the deposits produced by this volcano through its entire sequence of explosive eruptions. The main objectives of the study were to determine the overall evolution of the Sinker Butte volcano while focusing particularly on the tephras produced by its phreatomagmatic eruptions. Toward this end, twenty-three detailed stratigraphic sections ranging from 20 to 100 m thick were examined and measured in canyon walls exposing tephras deposited around 180° of the circumference of the volcano.Three main rock units are recognized in canyon walls at Sinker Butte: a lower sequence composed of numerous thin basaltic lava flows, an intermediate sequence of phreatomagmatic tephras, and a capping sequence of welded basaltic spatter and more lava flows. We subdivide the phreatomagmatic deposits into two main parts, a series of reworked, mostly subaqueously deposited tephras and a more voluminous sequence of overlying subaerial surge and fall deposits. Most of the reworked deposits are gray in color and exhibit features such as channel scour and fill, planar-stratification, high and low angle cross-stratification, trough cross-stratification, and Bouma-turbidite sequences consistent with their being deposited in shallow standing water or in braided streams. The overlying subaerial deposits are commonly brown or orange in color due to palagonitization. They display a wide variety of bedding types and sedimentary structures consistent with deposition by base surges, wet to dry pyroclastic fall events, and water saturated debris flows.Proximal sections through the subaerial tephras exhibit large regressive cross-strata, planar bedding, and bomb sags suggesting deposition by wet base surges and tephra fallout. Medial and distal deposits consist of a thick sequence of well-bedded tephras; however, the cross-stratified base-surge deposits are thinner and interbedded within the fallout deposits. The average wavelength and amplitude of the cross strata continue to decrease with distance from the vent. These bedded surge and fall deposits grade upward into dominantly fall deposits containing 75–95% juvenile vesiculated clasts and localized layers of welded spatter, indicating a greatly reduced water-melt ratio. Overlying these “dryer” deposits are massive tuff breccias that were probably deposited as water saturated debris flows (lahars). The first appearance of rounded river gravels in these massive tuff breccias indicates downward coring of the diatreme and entrainment of country rock from lower in the stratigraphic section. The “wetter” nature of these deposits suggests a renewed source of external water. The massive deposits grade upward into wet fallout tephras and the phreatomagmatic sequence ends with a dry scoria fall deposit overlain by welded spatter and lava flows.Field observations and two new ⁴⁰Ar–³⁹Ar incremental heating dates suggest the succession of lavas and tephra deposits exposed in this part of the Snake River canyon may all have been erupted from a closely related complex of vents at Sinker Butte. We propose that initial eruptions of lava flows built a small shield edifice that dammed or disrupted the flow of the ancestral Snake River. The shift from effusive to explosive eruptions occurred when the surface water or rising ground water gained access to the vent. As the river cut a new channel around the lava dam, water levels dropped and the volcano returned to an effusive style of eruption.     

A physical model for shear-wave velocity prediction1

The clay-sand mixture model of Xu and White is shown to simulate observed relationships between S-wave velocity (or transit time), porosity and clay content. In general, neither S-wave velocity nor S-wave transit time is a linear function of porosity and clay content. For practical purposes, clay content is approximated by shale volume in well-log applications. In principle, the model can predict S-wave velocity from lithology and any pair of P-wave velocity, porosity and shale volume. Although the predictions should be the same if all measurements are error free, comparison of predictions with laboratory and logging measurements show that predictions using P-wave velocity are the most reliable. The robust relationship between S- and P-wave velocities is due to the fact that both are similarly affected by porosity, clay content and lithology. Moreover, errors in the measured P-wave velocity are normally smaller than those in porosity and shale volume, both of which are subject to errors introduced by imperfect models and imperfect parameters when estimated from logs. Because the model evaluates the bulk and shear moduli of the dry rock frame by a combination of Kuster and Toksöz’ theory and differential effective medium theory, using pore aspect ratios to characterize the compliances of the sand and clay components, the relationship between P- and S-wave velocities is explicit and consistent. Consequently the model sidesteps problems and assumptions that arise from the lack of knowledge of these moduli when applying Gassmann's theory to this relationship, making it a very flexible tool for investigating how the v_P-v_s relationship is affected by lithology, porosity, clay content and water saturation. Numerical results from the model are confirmed by laboratory and logging data and demonstrate, for example, how the presence of gas has a more pronounced effect on P-wave velocity in shaly sands than in less compliant cleaner sandstones.     

Geochemistry of waters in the Valley of Ten Thousand Smokes region, Alaska

Meteoric waters from cold springs and streams outside of the 1912 eruptive deposits filling the Valley of Ten Thousand Smokes (VTTS) and in the upper parts of the two major rivers draining the 1912 deposits have similar chemical trends. Thermal springs issue in the mid-valley area along a 300-m lateral section of ash-flow tuff, and range in temperature from 21 to 29.8°C in early summer and from 15 to 17°C in mid-summer. Concentrations of major and minor chemical constituents in the thermal waters are nearly identical regardless of temperature. Waters in the downvalley parts of the rivers draining the 1912 deposits are mainly mixtures of cold meteoric waters and thermal waters of which the mid-valley thermal spring waters are representative. The weathering reactions of cold waters with the 1912 deposits appear to have stabilized and add only subordinate amounts of chemical constituents to the rivers relative to those contributed by the thermal waters. Isotopic data indicate that the mid-valley thermal spring waters are meteoric, but data is inconclusive regarding the heat source. The thermal waters could be either from a shallow part of a hydrothermal system beneath the 1912 vent region or from an incompletely cooled, welded tuff lens deep in the 1912 ash-flow sheet of the upper River Lethe area.Bicarbonate-sulfate waters resulting from interaction of near-surface waters and the cooling 1953–1968 southwest Trident plug issue from thermal springs south of Katmai Pass and near Mageik Creek, although the Mageik Creek spring waters are from a well-established, more deeply circulating hydrothermal system. Katmai caldera lake waters are a result of acid gases from vigorous drowned fumaroles dissolving in lake waters composed of snowmelt and precipitation.     

Minor and trace elements in HF-soluble zircons

Electron probe analysis of a group of HF-soluble zircons from porphyroids of the Thuringian Forest, Germany, established yttrium, phosphorus, and iron to be the significant minor constituents. It is believed that these elements render the zircon structure HF-soluble. The Y content varies from about 6500–48000 ppm=0.83–6.10% Y₂O₃; the P concentrations range from a low of about 790 to a maximum of 4000 ppm=0.18–0.92% P₂O₅; the Fe content varies from about 400–15000 ppm=0.06–2.10% Fe₂O₃. Although both Y and P are distributed throughout each given grain, they are sometimes mutually enriched in growth zones. These zones are also resolved in reflected light micrographs and the electron images.