Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O±Al2O3

The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H₂O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al₂O₃ in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.     

Effects of the North Atlantic Oscillation and wind waves on salt marsh dynamics in the Danish Wadden Sea: a quantitative model as proof of concept

Long-term eustatic sea-level variation has been recognized as a primary factor affecting the hydrological and geomorphic dynamics of salt marshes. However, recent studies suggest that wind waves influenced by atmospheric oscillations also may play an important role in many coastal areas. Although this notion has been conceptually introduced for the Wadden Sea, no modeling attempts have been made yet. As a proof of concept, this study developed a simulation model using the commercially available STELLA® software, based on long-term data on water level and sedimentation collected at a back-barrier marsh on the Skallingen peninsula in Denmark. In the model, the frequency (number year^–1) of wind-driven extreme high water level (HWL) events (>130 cm Danish Ordnance Zero) was simulated in terms of the North Atlantic Oscillation (NAO) index. Then, surface accretion (cm year^–1) and submergence duration (h year^–1) were simulated for the period 1933–2007. The model showed good performances: simulated rates of surface accretion and simulated durations of submergence decreased from 1950 to 1980, the point at which the NAO shifted from its negative to its positive phase, and increased thereafter. Despite continuous increases in surface elevation, increases in simulated submergence duration were apparently due to wind-driven HWL events, which generally increased in frequency after 1980. These findings for the Danish Wadden Sea add to the growing body of evidence that the role of atmospheric oscillations—e.g., the NAO—as drivers of wind-generated water level variations merits more attention in assessing the impact of climate change on coastal marshes.     

Evidence for estrogenic endocrine disruption in an offshore flatfish, the dab (Limanda limanda L.)

Dab (Limanda limanda) caught in UK offshore waters show evidence of being exposed to estrogenic endocrine disrupters at a relatively low level. Two of 449 males caught between June and July 2005 had markedly elevated levels of vitellogenin (VTG; 21 and 750 microg/ml) and the remainder ranged from <0.01 to 8.6 microg/ml. Omitting the two outliers, there was a very significant positive relationship with the mass of individual males (a feature noted in previous studies on cod). Mean VTG concentrations in males differed significantly between sites. The site with the highest mean (1.6 microg/ml) was North East of the Dogger Bank and the site with the lowest (0.04 microg/ml) was in Cardigan Bay. Mean VTG concentrations in all North Sea fish were significantly higher than English Channel and Irish Sea fish, but this difference disappeared when fish mass was taken into account. VTG concentrations showed no relationship to water depth, stage of sexual maturity or age of the males. Sixty selected male plasmas were assayed for 17beta-estradiol but only two had measurable amounts (assay limit 0.04 ng/ml). Despite being the start of summer, the gonads of many of the males and females (especially those caught in the North Sea) showed signs of sexual maturity (presence of sperm in males and vitellogenic eggs in females). Many females had high VTG concentrations (up to 14 mg/ml) and 78 out of 80 had measurable concentrations of 17beta-estradiol. The cause of elevated VTG levels in male dab is unknown. As seen in cod, the presence of affected males does not appear to be linked to proximity to land or to known point sources of endocrine disrupters. However, our data, showing that larger fish are more likely to have elevated VTG concentrations, suggests a gradual accumulation by marine fish, probably through feeding, of persistent (probably relatively weak) estrogenic compounds.     

Heterogeneity and thermal modeling of ground water

Heat transport in aquifers is becoming an increasingly important topic due to recent growth in the use of ground water in thermal applications. However, the effect of heterogeneity on heat transport in aquifers has yet to be examined in the same detail as it has been for solute transport, and it is unclear what effect this may have on our ability to create accurate models. This study examines this issue through stochastic modeling using the geostatistics for two aquifers with low and high degrees of heterogeneity. The results indicate that there is considerable uncertainty in the distribution of heat associated with injection of warm water into an aquifer. Heterogeneity in the permeability field was also found to slightly reduce the ability to recover this introduced heat at a later time. These simulations also reveal that hydrodynamic macrodispersion is an important consideration in some heat flow problems.     

Improving SST reconstructions from coral Sr/Ca records: multiple corals from Tahiti (French Polynesia)

We reconstruct SST from coral Sr/Ca ratios measured at three coral cores taken from the lagoon of Tahiti (French Polynesia). Two coral cores were drilled from the same coral colony (one horizontally and one vertically), and a third core was drilled vertically from another coral growing at a different site. We evaluate several Sr/Ca records as proxies for regional SST variations: (1) the three single-core records from Tahiti, (2) an average Sr/Ca record computed from the two cores drilled from the same coral colony, (3) an average Sr/Ca record computed from all three Tahiti cores, and (4) an average Sr/Ca record computed from the three Tahiti cores and a fourth core taken from a different island (Rarotonga). On a monthly scale, the average Sr/Ca record including the four coral cores from Tahiti and Rarotonga shows the best correlation with regional SST. The variance of the SST reconstruction is very realistic and the residual SST is low. This suggests that reconstructing SST from average proxy records gives a better representation of regional SST variations. Of the three Tahiti cores, the one that was drilled horizontally shows the best correlation with grid-SST on an annual mean scale. All three Tahiti corals show much larger interannual SST variations than that indicated by grid-SST.     

Patterns of Pacific decadal variability recorded by Indian Ocean corals

We investigate Pacific Decadal Oscillation (PDO) signals recorded by two bimonthly resolved coral δ¹⁸O series from La Réunion and Ifaty (West Madagascar), Indian Ocean from 1882 to 1993. To isolate the main PDO frequencies, we apply a band pass filter to the time series passing only periodicities from 16 to 28 years. We investigate the covariance patterns of the coral time series with sea surface temperature (SST) and sea level pressure (SLP) of the Indian and Pacific Oceans. In addition, the empirical orthogonal functions of the filtered SST and SLP fields (single and coupled) are related to the filtered coral times series. The covariance maps show the typical PDO pattern for SST and SLP, confirming the coupling between the Indian and Pacific Oceans. Both corals show the strongest signal in boreal summer. The La Réunion (Ifaty) coral better records SST (SLP) than SLP (SST) pattern variability. We suggest that the filtered La Réunion coral δ¹⁸O represents δ¹⁸O of seawater that varies with the South Equatorial Current, which, in turn, is linked with the SST PDO. The filtered Ifaty coral δ¹⁸O represents SST and is remotely linked with the SLP PDO variability. A combined coral record of the Ifaty and La Réunion boreal summer δ¹⁸O series explains about 64% of the variance of the coupled SST/SLP PDO time series. AGU OS06 special issue “Ocean’s role in climate change—a paleo perspective”.     

Deep groundwater mediates streamflow response to climate warming in the Oregon Cascades

Recent studies predict that projected climate change will lead to significant reductions in summer streamflow in the mountainous regions of the Western US. Hydrologic modeling directed at quantifying these potential changes has focused on the magnitude and timing of spring snowmelt as the key control on the spatial–temporal pattern of summer streamflow. We illustrate how spatial differences in groundwater dynamics can also play a significant role in determining streamflow responses to warming. We examine two contrasting watersheds, one located in the Western Cascades and the other in the High Cascades mountains of Oregon. We use both empirical analysis of streamflow data and physically based, spatially distributed modeling to disentangle the relative importance of multiple and interacting controls. In particular, we explore the extent to which differences in snow accumulation and melt and drainage characteristics (deep ground water vs. shallow subsurface) mediate the effect of climate change. Results show that within the Cascade Range, local variations in bedrock geology and concomitant differences in volume and seasonal fluxes of subsurface water will likely result in significant spatial variability in responses to climate forcing. Specifically, watersheds dominated by High Cascade geology will show greater absolute reductions in summer streamflow with predicted temperature increases.     

The crystal and melt structure of spinel and alumina at high temperature: An in-situ XANES study at the Al and Mg K-edge

We present structural information obtained on spinel and alumina at high temperature (298-2400 K) using in-situ XANES at the Mg and Al K-edges. For spinel, ^[4](Al_x,Mg_1−x)^[6](Al_2−x,Mg_x)O_4, with increasing temperature, a substitution of Mg by Al and Al by Mg in their respective sites is observed. This substitution corresponds to an inversion of the Mg and Al sites. There is a significant change in the Al K-edge spectra between crystal and liquid, which can be attributed to a change of the ^[6]Al normally observed in corundum at room temperature, to a mixture of ^[6]Al-^[4]Al in the liquid state. This conclusion is in good agreement with previous ²⁷Al NMR experiments. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.     

Ultraviolet spectral reflectance properties of common planetary minerals

Ultraviolet spectral reflectance properties (200-400 nm) of a large number of minerals known or presumed to exist on the surfaces of Mars, the Moon, and asteroids, and in many meteorites, were investigated. Ultraviolet reflectance spectra (200-400 nm) of these minerals range from slightly blue-sloped (reflectance decreasing toward longer wavelengths) to strongly red-sloped (reflectance increasing toward longer wavelengths). Most exhibit one or two absorption features that are attributable to FeO charge transfers involving Fe³⁺ or Fe²⁺. The UV region is a very sensitive indicator of the presence of even trace amounts (<0.01 wt%) of Fe³⁺ and Fe²⁺. The major Fe³⁺O absorption band occurs at shorter wavelengths (∼210-230 nm), and is more intense than the major Fe²⁺O absorption band (∼250-270 nm). Ti-bearing minerals, such as ilmenite, rutile and anatase exhibit UV absorption bands attributable to Ti⁴⁺O charge transfers. While the positions of metal-O charge transfer bands sometimes differ for different minerals, the variation is often not diagnostic enough to permit unique mineral identification. However, iron oxides and oxyhydroxides can generally be distinguished from Fe-bearing silicates in the 200-400 nm region on the basis of absorption band positions. Within a given mineral group (e.g., low-calcium pyroxene, olivine, plagioclase feldspar), changes in Fe²⁺ or Fe³⁺ abundance do not appear to result in a measurable change in absorption band minima positions. Absorption band positions can vary as a function of grain size, however, and this variation is likely due to band saturation effects. The intensity of metal-O charge transfers means that some minerals will exhibit saturated UV absorption bands even for fine-grained (<45 μm) powders. In cases where absorption bands are not saturated (e.g., Fe²⁺O bands in some plagioclase feldspars and pyroxenes), changes in Fe²⁺ content do not appear to cause variations in band position. In other minerals (e.g., olivine), changes in band positions are correlated with compositional and/or grain size variations, but this is likely due to increasing band saturation rather than compositional variations. Overall, we find that the UV spectral region is sensitive to different mineral properties than longer wavelength regions, and thus offers the potential to provide complementary capabilities and unique opportunities for planetary remote sensing.     

Mesospheric vertical thermal structure and winds on Venus from HHSMT CO spectral-line observations

We report vertical thermal structure and wind velocities in the Venusian mesosphere retrieved from carbon monoxide (¹²CO J=2-1 and ¹³CO J=2-1) spectral line observations obtained with the Heinrich Hertz Submillimeter Telescope (HHSMT). We observed the mesosphere of Venus from two days after the second Messenger flyby of Venus (on 5 June 2007 at 23:10 UTC) during five days. Day-to-day and day-to-night temperature variations and short-term fluctuations of the mesospheric zonal flow were evident in our data. The extensive layer of warm air detected recently by SPICAV at 90-100 km altitude is also detected in the temperature profiles reported here.These data were part of a coordinated ground-based Venus observational campaign in support of the ESA Venus Express mission. Furthermore, this study attempts to cross-calibrate space- and ground-based observations, to constrain radiative transfer and retrieval algorithms for planetary atmospheres, and to contribute to a more thorough understanding of the global patterns of circulation of the Venusian atmosphere.