Easily Accessible Rare-Earth-Containing Phosphonium Room-Temperature Ionic Liquids: EXAFS, Luminescence and Magnetic Properties

A range of liquid rare-earth chlorometallate complexes with alkyl-phosphonium cations, [P666 14]+, has been synthesised and characterised. EXAFS confirmed the predominant liquid-state speciation of the [LnCl6]3- of the series with Ln = Nd, Eu, Dy. The crystal structure of the shorter-alkyl-chain cation analogue [P4444]+ has been determined and exhibits a very large unit cell. The luminescence properties, with visible light emissions of the liquid Tb, Eu, Pr and Sm and the NIR emissions for the Nd and Er compounds were determined. The effective magnetic moments were measured and fitted for the Nd, Tb, Ho, Dy, Gd and Er samples.

Chironomid-based reconstructions of summer air temperature from lake deposits in Lyndon Stream, New Zealand spanning the MIS 3/2 transition

We present chironomid-based temperature reconstructions from lake sediments deposited between ca 26,600 cal yr BP and 24,500 cal yr BP from Lyndon Stream, South Island, New Zealand. Summer (February mean) temperatures averaged 1 1C cooler, with a maximum inferred cooling of 3.7 1C. These estimates corroborate macrofossil and beetle-based temperature inferences from the same site and suggest climate amelioration (an interstadial) at this time. Other records from the New Zealand region also show a large degree of variability during the late Otiran glacial sequence (34,000–18,000 cal yr BP) including a phase of warming at the MIS 2/3 transition and a maximum cooling that did not occur until the global LGM (ca 20,000 cal yr BP). The very moderate cooling identified here at the MIS 2/3 transition confirms and enhances the long-standing discrepancy in New Zealand records between pollen and other proxies. Low abundances (o20%) of canopy tree pollen in records from late MIS 3 to the end of MIS 2 cannot be explained by the minor (o5 1C) cooling inferred from this and other studies unless other environmental parameters are considered. Further work is required to address this critical issue.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

Solutes determine the temperature windows for microbial survival and growth

Microbial cells, and ultimately the Earth's biosphere, function within a narrow range of physicochemical conditions. For the majority of ecosystems, productivity is cold-limited, and it is microbes that represent the failure point. This study was carried out to determine if naturally occurring solutes can extend the temperature windows for activity of microorganisms. We found that substances known to disorder cellular macromolecules (chaotropes) did expand microbial growth windows, fungi preferentially accumulated chaotropic metabolites at low temperature, and chemical activities of solutes determined microbial survival at extremes of temperature as well as pressure. This information can enhance the precision of models used to predict if extraterrestrial and other hostile environments are able to support life; furthermore, chaotropes may be used to extend the growth windows for key microbes, such as saprotrophs, in cold ecosystems and manmade biomes.

Dinoflagellate cyst-based reconstructions of mid to late Holocene winter sea-surface temperature and productivity from an anoxic fjord in the NE Pacific Ocean

Published contemporary dinoflagellate distributional data from the NE Pacific margin and estuarine environments (n = 136) were re-analyzed using Canonical Correspondence Analysis (CCA) and partial Canonical Correspondence Analysis (pCCA). These analyses illustrated the dominant controls of winter temperature and productivity on the distribution of dinoflagellate cysts in this region. Dinoflagellate cyst-based predictive models for winter temperature and productivity were developed from the contemporary distributional data using the modern analogue technique and applied to subfossil data from two mid to late Holocene (~5500 calendar years before present–present) cores; TUL99B03 and TUL99B11, collected from Effingham Inlet, a 15 km long anoxic fjord located on the southwest coast of Vancouver Island that directly opens to the Pacific Ocean through Barkley Sound. Sedimentation within these basins largely comprises annually deposited laminated couplets, each made up of a winter deposited terrigenous layer and spring to fall deposited diatomaceous layer. The Effingham Inlet dinoflagellate cyst record provides evidence of a mid-Holocene gradual decline in winter SST, ending with the initiation of neoglacial advances in the region by ~3500 cal BP. A reconstructed Late Holocene increase in winter SST was initiated by a weakening of the California Current, which would have resulted in a warmer central gyre and more El Niño-like conditions.

Near-surface temperature cycling of stone and its implications for scales of surface deterioration

Many previous studies into internal temperature gradients within stone have assumed smooth, exponential increases and decreases in sub-surface temperatures in response, for example, to diurnal patterns of heating and cooling and these have been used to explain phenomena such as large-scale contour scaling. This high-resolution experimental study, in which a porous limestone block was subjected to alternate surface heating and cooling using an infrared lamp, demonstrates that internal temperature gradients in response to short-term environmental cycles (measured in minutes) can in fact be complex and inconsistent. Results confirm the significance of very steep temperature/stress gradients within the outer 10 mm or less of exposed stone. Below this the data indicate complex patterns of temperature reversals, the amplitudes of which are attenuated with depth and which are influenced in their intensity and location by variations in the relative duration of heating and cooling phases. It is suggested that the reversals might represent ‘interference patterns’ between incoming and outgoing thermal waves, but whatever their origin they are potentially important because they occur within the zone in which many stone decay processes, especially salt weathering, operate. These processes invariably respond to temperature and moisture fluctuations, and short-term interruptions to insolation could, for example, trigger these fluctuations on numerous occasions over a day. In particular, the reversals occur at a scale that is commensurate with decay by multiple flaking and could indicate an underlying control on this previously little-researched pattern of weathering. In the context of this publication, however, the main lesson to be learned from this study is that differing scales of behaviour require different scales of enquiry.

Influence of strain and polycrystalline ordering on magnetic properties of high moment rare earth metals and alloys

Despite being the most suitable candidates for solenoid pole pieces in state-of-the-art superconductor- based electromagnets, the intrinsic magnetic properties of heavy rare earth metals and their alloys have gained comparatively little attention. With the potential of integration in micro- and nanoscale devices, thin films of Gd, Dy, Tb, DyGd and DyTb were plasma-sputtered and investigated for their in-plane magnetic properties, with an emphasis on magnetisation vs. temperature profiles. Based on crystal structure analysis of the polycrystalline rare earth films, which consist of a low magnetic moment FCC layer at the seed interface topped with a higher moment HCP layer, an experimental protocol is introduced which allows the direct magnetic analysis of the individual layers. In line with the general trend of heavy lanthanides, the saturation magnetisation was found to drop with increasing unit cell size. In-situ annealed rare earth films exceeded the saturation magnetisation of a high-moment Fe65Co35 reference film in the cryogenic temperature regime, proving their potential for pole piece applications; however as-deposited rare earth films were found completely unsuitable. In agreement with theoretical predictions, sufficiently strained crystal phases of Tb and Dy did not exhibit an incommensurate magnetic order, unlike their single-crystal counterparts which have a helical phase. DyGd and DyTb alloys followed the trends of the elemental rare earth metals in terms of crystal structure and magnetic properties. Inter-rare-earth alloys hence present a desirable blend of saturation magnetisation and operating temperature.

Reduction of the temperature sensitivity of Halomonas hydrothermalis by iron starvation combined with microaerobic conditions

The limits to biological processes on Earth are determined by physicochemical parameters, such as extremes of temperature and low water availability. Research into microbial extremophiles has enhanced our understanding of the biophysical boundaries which define the biosphere. However, there remains a paucity of information on the degree to which rates of microbial multiplication within extreme environments are determined by the availability of specific chemical elements. Here, we show that iron availability and composition of the gaseous phase (aerobic vs. microaerobic) determine susceptibility of a marine bacterium, Halomonas hydrothermalis, to sub-optimal and elevated temperature and salinity by impacting rates of cell division (but not viability). In particular, iron starvation combined with microaerobic conditions (5 % v/v of O2, 10 % v/v of CO2, reduced pH) reduced sensitivity to temperature across the 13 °C range tested. These data demonstrate that nutrient limitation interacts with physicochemical parameters to determine biological permissiveness for extreme environments. The interplay between resource availability and stress tolerance, therefore, may shape the distribution and ecology of microorganisms within Earth's biosphere.

Grazing under experimental hypercapnia and elevated temperature does not affect the radula of a chiton (Mollusca, Polyplacophora, Lepidopleurida)

Chitons (class Polyplacophora) are benthic grazing molluscs with an eight-part aragonitic shell armature. The radula, a serial tooth ribbon that extends internally more than half the length of the body, is mineralised on the active feeding teeth with iron magnetite apparently as an adaptation to constant grazing on rocky substrates. As the anterior feeding teeth are eroded they are shed and replaced with a new row. The efficient mineralisation and function of the radula could hypothetically be affected by changing oceans in two ways: changes in seawater chemistry (pH and pCO(2)) may impact the biomineralisation pathway, potentially leading to a weaker or altered density of the feeding teeth; rising temperatures could increase activity levels in these ectothermic animals, and higher feeding rates could increase wear on the feeding teeth beyond the animals' ability to synthesise, mineralise, and replace radular rows. We therefore examined the effects of pH and temperature on growth and integrity in the radula of the chiton Leptochiton asellus. Our experiment implemented three temperature (similar to 10, 15, 20 degrees C) and two pCO(2) treatments (similar to 400 mu atm, pH 8.0; similar to 2000 mu atm, pH 7.5) for six treatment groups. Animals (n = 50) were acclimated to the treatment conditions for a period of 4 weeks. This is sufficient time for growth of ca. 7-9 new tooth rows or 20% turnover of the mineralised portion. There was no significant difference in the number of new (non-mineralised) teeth or total tooth row count in any treatment. Examination of the radulae via SEM revealed no differences in microwear or breakage on the feeding cusps correlating to treatment groups. The shell valves also showed no signs of dissolution. As a lineage, chitons have survived repeated shifts in Earth's climate through geological time, and at least their radulae may be robust to future perturbations.

Understanding the Flash Sintering of Rare-Earth-Doped Ceria for Solid Oxide Fuel Cell

A novel electrical current applied technique known as flash sintering has been applied to rapidly (within 10 min) densify electrolytes including Ce_0.8Gd_0.2O_1.9 (GDC20), Ce_0.9Gd_0.1O_1.95 (GDC10), and Ce_0.8Sm_0.2O_1.9 (SDC20) for application in Solid Oxide Fuel Cells (SOFCs). The densification temperature for the three electrolytes was 554°C, 635°C, and 667°C, respectively, which is far below conventional sintering temperatures. All specimens after flash sintering maintained the pure fluorite structure and exhibited a well-densified microstructure. To investigate the flash-sintering mechanism, we have applied Joule heating effect with blackbody radiation theory, and found that this theory could reasonably interpret the flash-sintering phenomenon by matching theoretically calculated temperature with the real temperature. More importantly, one of the materials inherent properties, the electronic conductivity, has been found correlated with the onset of flash sintering, which indicates that the electrons and holes are the primary current carriers during the start of flash-sintering process. As a result, potential densification mechanisms have been discussed in terms of spark plasma discharge.

The high-energy environment in the super-Earth system CoRoT-7

High-energy irradiation of exoplanets has been identified to be a key influence on the stability of these planets' atmospheres. So far, irradiation-driven mass-loss has been observed only in two Hot Jupiters, and the observational data remain even more sparse in the super-Earth regime. We present an investigation of the high-energy emission in the CoRoT-7 system, which hosts the first known transiting super-Earth. To characterize the high-energy XUV radiation field into which the rocky planets CoRoT-7b and CoRoT-7c are immersed, we analyzed a 25 ks XMM-Newton observation of the host star. Our analysis yields the first clear (3.5σ) X-ray detection of CoRoT-7. We determine a coronal temperature of ≈ 3 MK and an X-ray luminosity of 3 × 1028 erg s-1. The level of XUV irradiation on CoRoT-7b amounts to ≈37 000 erg cm-2 s-1. Current theories for planetary evaporation can only provide an order-of-magnitude estimate for the planetary mass loss; assuming that CoRoT-7b has formed as a rocky planet, we estimate that CoRoT-7b evaporates at a rate of about 1.3 × 1011 g s-1 and has lost ≈4-10 earth masses in total.

X-Ray Emission from the Super-Earth Host GJ 1214

Stellar activity can produce large amounts of high-energy radiation, which is absorbed by the planetary atmosphere leading to irradiation-driven mass loss. We present the detection and an investigation of high-energy emission in a transiting super-Earth host system, GJ 1214, based on XMM-Newton observations. We derive an X-ray luminosity of LX = 7.4 × 1025 erg s-1 and a corresponding activity level of log (LX /L bol) ~ -5.3. Further, we determine a coronal temperature of about ~3.5 MK, which is typical for coronal emission of moderately active low-mass stars. We estimate that GJ 1214 b evaporates at a rate of 1.3× 1010 g s-1 and has lost a total of ≈2-5.6 M ⊕.