Fluid inclusion modification by H2O and D2O diffusion: the influence of inclusion depth, size, and shape in re-equilibration experiments

The mobility of H₂O and D₂O by diffusion through quartz is illustrated with H₂O-rich fluid inclusions synthesized at 600 °C and 337 MPa, within the α-quartz stability field. Inclusions are re-equilibrated at the same experimental conditions within a pure D₂O fluid environment. Consequently, a gradient in volatile fugacities is the only driving force for diffusion, in the absence of pressure gradients and deformation processes. Up to 100 individual inclusions are analyzed in each experiment before and after re-equilibration by microscopic investigation, microthermometry, and Raman spectroscopy. Changes in fluid inclusion composition are obtained from the ice-melting temperatures, and density changes are obtained from total homogenization temperatures. After 1-day re-equilibration, inclusions already contain up to 11 mol % D₂O. A maximum concentration of 63 mol % D₂O is obtained after 40-day re-equilibration. D₂O concentration profiles in quartz are determined from the concentration in inclusions as a function of their distance to the quartz surface. These profiles illustrate that deep inclusions contain less D₂O than shallow inclusions. At equal depths, a variety of D₂O concentration is observed as a function of fluid inclusion size: Small inclusions are stronger effected compared with large inclusions. A series of 19-day re-equilibration experiments are performed at 300, 400, 500, and 600 °C (at 337 MPa), at the same conditions as the original synthesis. The threshold temperature of diffusion is estimated around 450 °C at 337 MPa, because D₂O is not detected in inclusions from re-equilibration experiments at 300 and 400 °C, whereas maximally 26 mol % D₂O is detected at 500 °C. Our study indicates that the isotopic composition of natural fluid inclusions may be easily modified by re-equilibration processes, according to the experimental conditions at 600 °C and 337 MPa.     

Circulation of the Venus upper mesosphere/lower thermosphere: Doppler wind measurements from 2001–2009 inferior conjunction,sub-millimeter CO absorption line observations

Sub-millimeter ¹²CO (346 GHz) and ¹³CO (330 GHz) line absorptions, formed within the mesospheric to lower thermospheric altitude (70–120 km) region of the Venus atmosphere, have been mapped across the nightside disk of Venus during 2001–2009 inferior conjunctions, employing the James Clerk Maxwell Telescope (JCMT). Radiative transfer analysis of these thermal line absorptions supports temperature and CO mixing profile retrievals, as described in a companion paper (Clancy et al., 2012). Here, we consider the analysis of the sharp line absorption cores of these CO spectra in terms of accurate Doppler wind profile measurements at 95–115 km altitudes versus local time (～8 pm–4 am) and latitude (～60N–60S). These Doppler wind measurements support determinations of the nightside zonal and subsolar-to-antisolar (SSAS) circulation components over a variety of timescales. The average behavior fitted from 21 retrieved maps of ¹²CO Doppler winds (obtained over hourly, daily, weekly, and interannual intervals) indicates stronger average zonal (85 m/s retrograde) versus SSAS (65 m/s) circulation at the 1 μbar pressure (108–110 km altitude) level. However, the absolute and relative magnitudes of these circulation components exhibit extreme variability over daily to weekly timescales. Furthermore, the individual Doppler wind measurements within each nightside mapping observation generally show significant deviations (20–50 m/s, averaged over 5000 km horizontal scales) from the simple zonal/SSAS solution, with distinct local time and latitudinal characters that are also time variable. These large scale residual circulations contribute 30–70% of the observed nightside Doppler winds at any given time, and may be most responsible for global variations in nightside lower thermospheric trace composition and temperatures, as coincidentally retrieved CO abundance and temperature distributions do not correlate with solution retrograde zonal and SSAS winds (see companion paper, Clancy et al., 2012). Limited comparisons of these nightside submillimeter results with dayside infrared Doppler wind measurements suggest distinct dayside versus nightside circulations, in terms of zonal winds in particular. Combined ¹²CO and ¹³CO Doppler wind mapping observations obtained since 2004 indicate that the average zonal and SSAS wind components increase by 50–100% between altitudes of 100 and 115 km. If gravity waves originating from the cloud levels are responsible for the extension of zonal winds into the thermosphere (Alexander, M.J. [1992]. Geophys. Res. Lett. 19, 2207–2210), such waves deposit substantial momentum (i.e., break) in the lower nightside thermosphere.     

The photometric periods of the nova-like cataclysmic variable LQ Pegasi (PG 2133+115)

We present a time-resolved differential photometric study and time series analysis of the nova-like cataclysmic variable star LQ Peg. We discover three periodicities in the photometry, one with a period of 3.42 ± 0.03 h, and another with a period of 56.8 ± 0.01 h. We interpret these to be the apsidal superhump and precessional periods of the accretion disk, respectively, and predict that the orbital period of LQ Peg is 3.22 ± 0.03 h. The third periodicity, with a period of 41.3 ± 0.01 h, we interpret to be the nodal precessional period of the accretion disk. We also report a flare that lasted four minutes and had an energy in visible light of (1.2 ± 0.3) × 10³⁶ ergs, or 10^4-5 times more energetic than the largest solar flares, comparable to the most energetic visible-light stellar flares known. We calculate the absolute magnitude of LQ Peg to be M_J = 4.78 ± 0.54, and its distance to be 800 ± 200 pc.     

Removal of Fluoride from Aqueous Solutions by Adsorption Using a Siliceous Mineral of a Kenyan Origin

The problem of high fluoride in water sources in Africa and the rest of the developing world has exacerbated in the latest past due to increasing shortage of water. More people are being exposed to high water fluoride resulting in elevated levels of fluorosis in the societies. Fluoride (F) adsorption from solutions using a siliceous mineral from Kenya (M1) was studied on batch basis and results verified on high fluoride water using fixed‐bed column experiments. About 100% batch F adsorption was achieved at 200 mg/L F concentration, 0.5 g/mL adsorbent dosage, 303–333 K, and pH 3.4 ± 0.2. Based on Giles classifications, F adsorption isotherm was found to be an H3 type isotherm. The equilibrium data was correlated to Freundlich and Langmuir models and the maximum Langmuir adsorption capacity was found to be 12.4 mg/g. Column experiments were conducted for different fluoride concentrations, bed depths, and flow rates. The F breakthrough curves were analyzed using the Thomas model and efficient F adsorption was found to occur at low flow rates and low influent concentrations. The Thomas F adsorption capacity (11.7 mg/g) was consistent with the Langmuir isotherm capacity showing that M1 could be applied as an inexpensive medium for water defluoridation.     

The crystal structure of cualstibite-1M (formerly cyanophyllite), its revised chemical formula and its relation to cualstibite-1T

The crystal structure of the rare secondary mineral cualstibite-1M (formerly cyanophyllite), originally reported to have the chemical formula 10CuO·2Al₂O₃·3Sb₂O₃·25H₂O and orthorhombic symmetry, was solved from single-crystal intensity data (Mo-Kα X-radiation, CCD area detector, 293 K, 2θ_max?=?80) collected on a twinned crystal containing very minor Mg. The mineral is monoclinic, P2₁/c (no. 14), with a?=?9.938(1), b?=?8.890(1), c?=?5.493(1) Å, β?=?102.90(1)°, V?=?473.05(11) ų; R1(F)?=?0.0326. All crystals investigated turned out to be non-merohedric twins. The atomic arrangement has a distinctly layered character. Brucite-like sheets composed of two [4?+?2]-coordinated (Cu,Al,Mg) sites are linked by weak hydrogen-bonding (O···O?~?2.80 Å) to isolated regular Sb(OH)₆ octahedra (<Sb-O>?=?1.975 Å). The layered, pseudotrigonal character explains the perfect cleavage and the proneness to twinning. The Sb site is fully occupied and the two (Cu,Al,Mg) sites have occupancies of Cu_0.79Al_0.17Mg_0.04 and Cu_0.72Al_0.23Mg_0.05. The Cu-richer site shows a slightly stronger Jahn-Teller-distortion. The resulting empirical formula, which necessitates a H₂O-for-OH substitution to obtain charge balance, is (Cu_2.23Al_0.63Mg_0.14)(OH)_5.63(H₂O)_0.37[Sb⁵⁺(OH)₆]. The ideal chemical formula is (Cu,Al)₃(OH)₆[Sb⁵⁺(OH)₆], with Cu:Al = 2:1. The structure is closely related to those of trigonal cualstibite-1T [Cu₂AlSb(OH)₁₂, P-3, with ordered Cu-Al distribution in the brucite sheets], and its Zn analogue zincalstibite-1T [Zn₂AlSb(OH)₁₂]. Cualstibite-1M and cualstibite-1T are polytypes and, together with zincalstibite-1T, zincalstibite-9R and omsite, belong to the cualstibite group within the hydrotalcite supergroup, which comprises all natural members of the large family of layered double hydroxides (LDH).     

Climate drying and associated forest decline in the lowlands of northern Guatemala during the late Holocene

Palynological studies document forest disappearance during the late Holocene in the tropical Maya lowlands of northern Guatemala. The question remains as to whether this vegetation change was driven exclusively by anthropogenic deforestation, as previously suggested, or whether it was partly attributable to climate changes. We report multiple palaeoclimate and palaeoenvironment proxies (pollen, geochemical, sedimentological) from sediment cores collected in Lake Petén Itzá, northern Guatemala. Our data indicate that the earliest phase of late Holocene tropical forest reduction in this area started at ∼ 4500 cal yr BP, simultaneous with the onset of a circum-Caribbean drying trend that lasted for ∼ 1500 yr. This forest decline preceded the appearance of anthropogenically associated Zea mays pollen. We conclude that vegetation changes in Petén during the period from ∼ 4500 to ∼ 3000 cal yr BP were largely a consequence of dry climate conditions. Furthermore, palaeoclimate data from low latitudes in North Africa point to teleconnective linkages of this drying trend on both sides of the Atlantic Ocean.     

Fingerprint of tropical climate variability and sea level in sediments of the Cariaco Basin during the last glacial period

High‐resolution palaeorecords of climate are critical to improving current understanding of climate variability, its sensitivity and impact on the environment in the past and in the future. Sediments from the Cariaco Basin off the coast of Venezuela have proven to be sensitive recorders of tropical palaeoclimate variability down to an annual scale. However, the fingerprint of climate and sea level in the sediments of the last glacial period is still not completely understood. In this study, lamination analysis of sediments from the Cariaco Basin is extended to the last glacial period. Detailed sedimentological and geochemical analysis (laser ablation–inductively coupled plasma–mass spectrometry) reveals couplets of light‐coloured, terrigenous‐rich and dark‐coloured, biogenic opal‐rich laminae, which are interpreted to reflect the seasonal migration of the Intertropical Convergence Zone. In addition, a previously undescribed, nearly pure terrigenous lamina type is observed, which is referred to hereafter as a ‘C‐layer’. The C‐layers in the sedimentary sequence are interpreted as flood layers that originate from local rivers. The occurrence of these C‐layers is investigated for two core locations in the Cariaco Basin over the last 110 kyr by continuous X‐ray fluorescence scanning. Dansgaard–Oeschger oscillations are most clearly traced by proxies reflecting productivity and marine organic matter content of the sediment. In contrast, the abundance of terrigenous material differs at times between the two sites. On an interglacial to glacial timescale, the ability to record events causing C‐layers is likely to be influenced by changes in sea level and source proximity. On a millennial scale, both sediment cores contain more C‐layers during warmer interstadials compared with colder stadials during Marine Isotope Stage 3. This finding implies that interstadials were not only wetter than stadials, but probably also characterized by increased rainfall variability, leading to an enhanced frequency of flooding events in the hinterland of the Cariaco Basin.     

Stress–strain behavior of cement-improved clays: testing and modeling

The results of a series of laboratory tests on unimproved and cement-improved specimens of two clays are presented, and the ability of a bounding surface elastoplastic constitutive model to predict the observed behavior is investigated. The results of the oedometer, triaxial compression, extension, and cyclic shear tests demonstrated that the unimproved soil behavior is similar to that of soft clays. Cement-improved specimens exhibited peak/residual behavior and dilation, as well as higher strength and stiffness over unimproved samples in triaxial compression. Two methods of accounting for the artificial overconsolidation effect created by cement improvement are detailed. The apparent preconsolidation pressure method is considerably easier to use, but the fitted OCR method gave better results over varied levels of confining stresses. While the bounding surface model predicted the monotonic behavior of unimproved soil very well, the predictions made for cyclic behavior and for improved soils were only of limited success.     

Fundamental changes in the activity of the natrocarbonatite volcano Oldoinyo Lengai, Tanzania

With a paroxysmal ash eruption on 4 September 2007 and the highly explosive activity continuing in 2008, Oldoinyo Lengai (OL) has dramatically changed its behavior, crater morphology, and magma composition after 25 years of quiet extrusion of fluid natrocarbonatite lava. This explosive activity resembles the explosive phases of 1917, 1940–1941, and 1966–1967, which were characterized by mixed ashes with dominantly nephelinitic and natrocarbonatitic components. Ash and lapilli from the 2007–2008 explosive phase were collected on the slopes of OL as well as on the active cinder cone, which now occupies the entire north crater having buried completely all earlier natrocarbonatite features. The lapilli and ash samples comprise nepheline, wollastonite, combeite, Na-åkermanite, Ti-andradite, resorbed pyroxene and Fe–Ti oxides, and a Na–Ca carbonate phase with high but varying phosphorus contents which is similar, but not identical, to the common gregoryite phenocrysts in natrocarbonatite. Lapilli from the active cone best characterize the erupted material as carbonated combeite–wollastonite–melilite nephelinite. The juvenile components represent a fundamentally new magma composition for OL, containing 25–30 wt.% SiO₂, with 7–11 wt.% CO₂, high alkalies (Na₂O 15–19%, K₂O 4–5%), and trace-element signatures reminiscent of natrocarbonatite enrichments. These data define an intermediate composition between natrocarbonatite and nephelinite, with about one third natrocarbonatite and two thirds nephelinite component. The data are consistent with a model in which the carbonated silicate magma has evolved from the common combeite–wollastonite nephelinite (CWN) of OL by enrichment of CO₂ and alkalies and is close to the liquid immiscible separation of natrocarbonatite from carbonated nephelinite. Material ejected in April/May 2008 indicates reversion to a more common CWN composition.