Vibrational analysis of dioptase Cu6Si6O18 · 6(H2O) and its puckered six-membered ring

The normal modes of vibration and their frequencies are calculated for dioptase, a mineral whose crystal structure (space group R or C _3i ² ) consists of puckered six-membered silicate rings (Si₆O₁₈) linked by Cu²⁺ ions and H₂O groups. The calculation employs a valence force potential consisting of central interactions between nearest neighbors and bond-bending interactions centered at the Si⁴⁺ and Cu²⁺ ions. The force constants are determined by fitting the calculated frequencies to values obtained by measuring the single-crystal Raman spectra. The calculated frequencies are in reasonable agreement with experiment, permitting assignment of normal modes to the observed spectral frequencies. Considerable mixing of Cu and H₂O motions with those of the ring is found for the Raman-active modes below 430 cm^-1. The normal modes and frequencies of the hypothetical isolated ring with C _3i symmetry are determined by neglecting all interactions between the rings and the surrounding Cu and H₂O. The identification of normal modes characteristic of the puckered six-membered silicate rings and the effect of the environment on these modes may prove useful in the interpretation of the Raman spectra of amorphous silicates.     

National-scale analysis of low flow frequency: historical trends and potential future changes

The potential impact of climate change on hydrological extremes is of increasing concern across the globe. Here, a national-scale grid-based hydrological model is used to investigate historical trends and potential future changes in low flow frequency across Great Britain. The historical analyses use both observational data (1891–2015) and ensemble data from a regional climate model (1900–2006). The results show relatively few significant trends in historical low flows (2- or 20-year return period), whether based on 7- or 30-day annual minima. Significant negative trends seen in some limited parts of the country when using observational data are generally not seen when using climate model data. The future analyses use climate model ensemble data for both near future and far future time periods (2020–2049 and 2070–2099 respectively), which are compared to a baseline sub-period from the historical ensemble (1975–2004). The results show future reductions in low flows, which are generally larger in the south of the country, at the higher (20-year) return period, and for the later time period. Reductions are more limited if the estimates of future potential evaporation include the effect of increased carbon dioxide concentrations on stomatal resistance. Such reductions in river flow could have significant impacts on the aquatic environment and on agriculture, and present a challenge for water managers, especially as reductions in water supply are likely to occur alongside increases in demand.     

Benthic megafauna on steep slopes at the Northern Mid‐Atlantic Ridge

The role of small‐scale (<10 km) habitat availability in structuring deep‐sea hard substratum assemblages is poorly understood. Epibenthic megafauna and substratum availability were studied on steep slopes at the Mid‐Atlantic Ridge from May to July 2010 northwest, northeast, southwest and southeast of the Charlie‐Gibbs Fracture Zone (CGFZ; 48–54°N) at between 2095 and 2601 m depth. Megafauna were six times denser north of the CGFZ compared with the south and differences in density were almost entirely driven by sessile fauna. There was no significant difference in habitat availability amongst sites. Rocky substratum made up 48% of the total area surveyed, with individual transects having between 0% and 82% rock. Assemblage structures were different amongst all superstations. The north was dominated by demospongids and hexactinellids, whereas the southern superstations were dominated by anthozoans and hexactinellids. Differences in megafaunal assemblages north and south of the CGFZ primarily reflected variations in demospongid and anthozoan species composition. With 213–1825 individuals·ha^?1, and 7–24 species per superstation, hexactinellids were the most species‐rich (36 species) and cosmopolitan taxa at the study site, supporting observations elsewhere along the ridge and in the CGFZ. The absence of significant differences in substrata availability suggested alternative drivers for density or percentage cover. The amount of hard substratum available only limited sessile megafauna density at one transect that was entirely covered with sediments. Species richness was highest for areas with intermediate values of substratum coverage (35–43% rock).     

Temporal dynamics and persistence of sponge assemblages in a Central Pacific atoll lagoon

Sponges are important components of coral reef fauna, although little is known of their temporal dynamics. Sponges dominate the lagoon system at Palmyra Atoll in the Central Pacific, which may not be its natural state. Here we examined the temporal variability and recruitment rates of these sponge assemblages to determine if they are stable and examined the evidence that a recent transition has occurred from a coral‐ to sponge‐dominated system. We found 24 sponge species in permanent quadrats in the lagoon between 2009 and 2011, and 11 species on our recruitment panels. The sponge assemblage composition and abundance did not vary significantly between years and appear stable. Many sponge recruits were found in both years that the panels were examined although higher rates were recorded in the second year of the study. While it seems very possible that a change to a sponge‐dominated lagoon is associated with declining environmental quality at Palmyra as a result of modifications over 70 years ago, without pre‐modification data on reef assemblage composition this remains speculative. Our observations of short‐term temporal stability in the sponge assemblages at Palmyra highlight the potential for sponge‐dominated reef states to be maintained in degraded reef environments that are seemingly unsuitable for coral survival.     

Paleoclimate histories improve access and sustainability in index insurance programs

Proxy-based climate reconstructions can extend instrumental records by hundreds of years, providing a wealth of climate information at high temporal resolution. To date, however, their usefulness for informing climate risk and variability in policy and social applications has been understudied. Here, we apply tree-ring based reconstructions of drought for the last 700 years in a climate index insurance framework to show that additional information from long climate reconstructions significantly improves our understanding of the underlying climate distributions and variability. We further show that this added information can be used to better characterize risk to insurance providers, in many cases providing meaningful reductions in long-term contract costs to farmers in stand-alone policies. The impact of uncertainty on insurance premiums can also be reduced when insurers diversify portfolios, and the availability of long-term climate information from tree rings across a broad geographic range provides an opportunity to characterize spatial correlation in climate risk across geographic regions. Our results are robust to the range of climate variability experienced over the last 400 years and in model simulations of the twenty-first century, even within the context of changing baselines due to low frequency variability and secular climate trends. These results demonstrate the utility of longer-term climate histories in index insurance applications. Furthermore, they make the case from a climate-variability perspective for the continued importance of such approaches to improving the instrumental climate record, even into a non-stationary climate future.