The crystal structure of bøgvadite (Na2SrBa2Al4F20)

The crystal structure of bøgvadite, Na₂SrBa₂Al₄F₂₀, has been solved and refined to a R₁ factor of 4.4 % from single-crystal data (MoKα X-ray diffraction, CCD area detector) on a sample from the cryolite deposit at Ivittuut, SW Greenland. Bøgvadite is monoclinic, P2₁/n space group, with unit cell parameters a?=?7.134(1), b?=?19.996(3) and c?=?5.3440(8) Å, β?=?90.02(1)^o. A close proximity of the crystal structure to an orthorhombic symmetry and the presence of the two twin components in a nearly 1:1 ratio suggest that the investigated bøgvadite crystal has originally formed as a high-temperature orthorhombic polymorph which on cooling transformed to the stable low temperature monoclinic structure. The bøgvadite crystal structure has groupings of cation-fluoride coordination polyhedra similar to those found in the crystal structures of the genetically closely associated minerals jarlite and jørgensenite. However, its structure type is different from the latter two. The fluoridoaluminate framework of bøgvadite consists of infinite zig-zag chains of cis-connected AlF₆ coordination octahedra. The ¹ _∞[AlF₅] chains are interconnected by infinite chains of Na-F coordination polyhedra which extend in the same direction. Na is coordinated by nine F atoms if its full surrounding is taken in consideration, but makes significant chemical bonds only to closest five. The chains of AlF₆ and NaF₉ coordination polyhedra form double layers. In the centre of layers, relatively large voids in the form of pentagonal antiprisms are occupied by Sr atoms which make chemical bonds with the closest six F atoms. Between the SrF₁₀ coordinations in the centre of layers run empty channels. The double layers are interconnected by Ba atoms which are coordinated by eight F atoms and fill the spaces between the layers. Bøgvadite belongs to the group of fluoridoaluminates with infinite chains of cis-connected AlF₆ coordination octahedra, alike those found in the crystal structures of Ba-fluoridoaluminates.     

Thermal stability of extended clusters in dravite: a combined EMP,SREF and FTIR study

A dravite from Yemen of near end-member composition was treated in air and hydrogen atmospheres at 600–900 °C to reveal changes in Mg and Al order over the octahedrally coordinated Y and Z sites, and to explore related changes in the characteristic vibrational bands in the principal (OH)-stretching frequency. Relevant information was obtained using electron microprobe analysis (EMPA), structural refinement (SREF) and polarized infrared (IR) single-crystal spectroscopy. Overall, the EMPA, SREF and IR data show that only minor changes occur during thermal treatment up to at least 800 °C, including variations in structural parameters, Mg–Al order–disorder and (OH)-stretching bands, indicating limited hydrogen loss. Untreated and treated dravite samples have very similar long-range and short-range atomic structures, which may be related to the occurrence of stable Al–Mg extended clusters around the O1 (=W) and O3 (=V) sites: ^W(F)–^Y(MgMgMg)–^V(OH)₃–^Z[AlAlAlAlAl(Al,Mg)]; ^W(OH)–^Y(MgMgAl)–^V(OH)₃–^Z[AlAlAlAlAl(Al,Mg)]; ^W(O^2–)–^Y(AlAlAl)–^V(OH)₃–^Z[AlAlAlAlAl(Al,Mg)]. These extended clusters remain stable to temperatures close to the observed start of decomposition (~900 °C).     

A controlling factor approach to estuary classification

A new approach to the classification of estuaries is described. The estuary environment classification (EEC) is based on a hierarchical view of the abiotic components that comprise the environments of estuaries. The EEC postulates that climate, oceanic, riverine and catchment factors ‘control’ a hierarchy of processes and broadly determine the physical and biological characteristics of estuaries. The classification differentiates estuaries at four levels of detail. Level 1 differentiates global scale variation based on differences in climatic and oceanic processes, which are discriminated by the factors: latitude, oceanic basins and large landmasses. Level 2 differentiates variation in estuary hydrodynamic processes, which are discriminated by estuary basin morphometry, river and oceanic forcing. Level 3 differentiates variation among estuaries that are due to catchment processes, which are discriminated by catchment geology and catchment land cover. The approach has been applied to all the estuaries in New Zealand using existing data sources. Estuaries were assigned class membership at each level of the classification by applying criteria in the form of decision rules to the database of assignment characteristics. GIS was then used to map the estuaries with classes being defined by colour at any level of the classification. The resulting map provides a multi-scale spatial framework that is suitable for many environmental or conservation management applications.     

Nitrogen loads to New Zealand aquatic receiving environments: comparison with regulatory criteria

ABSTRACT

There is concern about the deteriorating nutrient status of aquatic receiving environments in New Zealand. We estimated the amount by which current nitrogen (N) concentrations and loads exceed criteria in rivers, lakes and estuaries nationally. Criteria corresponded to national ‘bottom-line’ (i.e. minimal) environmental objectives set by government policy. Three metrics were evaluated: (1) degree of compliance describes the current TN loads in receiving environments relative to criteria; (2) catchment N status describes the acceptability of catchment N loads compared to criteria; and (3) excess load indicates the amount by which the N load exceeds the maximum allowable load (kg yr^?1). Non-compliance with N criteria was broadly distributed nationally particularly in low-elevation catchments. Catchments with unacceptable N status constituted at least 31% of New Zealand’s land area, which corresponds to at least 43% of the country’s agricultural land. The national excess load was estimated to be at least 19.1 Gg yr^?1. We are 97.5% confident that estimated excess loads exceed zero for nine of 15 regions and for the nation as a whole. The analyses provide a strategic assessment of where reductions in N emissions are required to achieve the minimal national objectives.     

Understanding U.S. public support for domestic climate change policies

In the U.S., public support for federal, state and local efforts to reduce greenhouse gases (GHGs) continues to be a crucial element of the political viability of these proposals. We present a detailed analysis of the reasons given by the general public of Michigan and Virginia for supporting or rejecting a number of policies that could be implemented to meet GHG reductions. The data allow us to analyze the relationships between reasons provided by respondents, social psychological and demographic characteristics, and policy support. This analysis can provide policymakers pragmatic guidance in (1) developing tactics to engage the public that build on current concerns about climate change policies and (2) crafting and communicating policies that garner support from various segments of the public. This analysis also raises theoretical questions regarding the relationship between public discourse on environmental issues and the formation of public policy support. We suggest that future efforts to understand the U.S. dynamics of public support for climate change policies could benefit from understanding the public discursive and the reasoning processes that underlie public opinion formation.     

Temporal trends of mercury in marine biota of west and northwest Greenland

Temporal trends in mercury concentrations ([Hg]) during the last two to three decades were determined in liver of shorthorn sculpin, ringed seal and Atlantic walrus from northwest Greenland (NWG, 77 degrees N) and in liver of shorthorn sculpin and ringed seal from central west Greenland (CWG, 69 degrees N) during the last decade. Stable-nitrogen (delta(15)N) and carbon (delta(13)C) isotope values were determined in muscle of ringed seals to provide insight into potential trophic level changes through time. Log-linear regressions on annual median [Hg] did not reveal any temporal trend in shorthorn sculpin from CWG and NWG and walrus from NWG. In ringed seals from NWG, an increase in [Hg] of 7.8% per year was observed. When based on delta(15)N-adjusted [Hg] this rate increased to 8.5% but was still non-significant. In ringed seal from CWG no trend was found in [Hg] during the period 1994-2004. However, during the last part of the period (1999-2004) the [Hg] increased significantly. Including tissue delta(15)N values as a covariate had a marked effect on these results. The annual changes in delta(15)N-adjusted [Hg] was estimated to -5.0% for the whole period and 2.2% during the last 5 years compared to -1.3% and 12.4%, respectively, for the non-adjusted [Hg].     

Earthquake response of a multiblock nuclear reactor graphite core: Experimental model vs simulations

The complex dynamics of a quarter‐scale model of a graphite nuclear reactor core, representative of the second generation of British advanced gas‐cooled nuclear reactors, is investigated numerically and experimentally. Advanced gas‐cooled nuclear reactor cores are polygonal, multilayer, arrays of graphite bricks, with each brick allowed to rock by design relative to each other in accordance with the boundary conditions. A 35 000 DOF, nonlinear finite element model of the core created by Atkins Nuclear, was analysed on a high performance computing facility at the University of Bristol, and a corresponding 8 t physical model, equipped with 3200 data acquisition channels, was built and tested on the University of Bristol 6‐DOF shaking table. In this paper, the two models are subjected to a series of (1) synthetic earthquake and (2) idealised harmonic input motions. The experimental data are used to compare and verify the two models and explore the dynamics of the core. A kinematic model of the response is also developed based solely on geometric constraints. The results are presented in the form of response maps and graphs. Important conclusions are drawn as to the dynamics and earthquake response of such systems, which inform numerical model validation. It is found that contrary to the case of a small number of rocking blocks that exhibit highly complex response patterns, the behaviour of the model at hand is both smooth and repeatable. An analogy between the response of the core and that of dense granular matter exhibiting particle interlocking and dilatancy is highlighted.