The photoelectron spectra of some Tl-Sb sulphosalts

The results of X-ray induced photoelectron spectroscopy (XPS) experiments on several phases of the ternary system Tl-Sb-S are reported. The binding energies of the inner S, Sb and Tl electrons increase with increasing quantities of Sb and decreasing amounts of Tl in these compounds. This is explained by the influences of the proportions of the bonded metals on the effective electron affinity of S. The higher proportions of the more electronegative element bonded to S cause the increase of its effective electron affinity. The results for Tl₂S (carlinite), Tl₃SbS₃, TlSbS₂ (weissbergite), TlAsS₂ (lorandite) and Sb₂S₃ (antimonite) can be interpreted in this way. The results for Tl₄S₃ suggest a predominantly covalent character of bonding for both Tl(III) and Tl(I), which are present in this sulfide. From comparison with Tl₃SbS₄ it could be supposed that Tl(III)-S bond has a more covalent character than Sb(V)-S bond. The results for Tl₃SbS₄ are in agreement with crystal structure data and the results of Moessbauer spectroscopy. For AsS (realgar) the binding energies of the inner electrons of As and S significantly increase, showing that the electrons in molecular orbitals are less strongly bonded to individual atoms, as compared to pure elements. The results for the amorphous TlSb₅S₈ (corresponding in composition to parapierrotite) suggest that in amorphous compound the Tl-S bonding is stronger and the coordination of Tl more regular than in a crystalline one.     

Possible Evidence of Long-Term Oscillations in the Solar Atmosphere

We have obtained the temporal correlation function, Q(t), from time sequences of Caii K filtergrams and Dopplergrams from Antarctica, Taiwan Oscillation Network (TON) and Solar and Heliospheric Observatory (SOHO). Q(t) gives the time evolution of the pattern under examination, supergranulation in this case. It has been found that Q(t) shows oscillatory signals of both 5-min and long-term periods. The 5-min oscillations are suppressed by averaging the images over 10 min. An exponential decay curve which represents the lifetime trend of supergranules, is fitted to Q(t) and subtracted out. The Q(t) residuals thus obtained contain the oscillatory component and are then subjected to a periodogram analysis. Significant periodicities in the range of 1.4–10 hours have been noted. The causes of these oscillations are not fully known at present, but the instrumental and atmospheric factors can be ruled out, pointing to solar origin. Various possibilities are discussed. Some of the observed periodicities may be considered as probable candidates for long-term oscillations in the Sun, such as the elusive gravity modes.     

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.     

Prospects for the GLAS Rayleigh laser beacon on the 4.2-m WHT

The scientific exploitation of adaptive optics (AO) with natural guide stars is severely constrained by the limited presence of bright guide stars for wavefront sensing. Use of a laser beam as an alternative means to provide a source for wavefront sensing has the potential of drastically improving the sky coverage for AO. For this reason at the 4.2-m William Herschel Telescope a project was started to develop a Rayleigh laser beacon to work together with the existing NAOMI adaptive optics instrumentation and the OASIS integral field spectrograph. This paper presents the rationale for this development, highlights some of the technical aspects, and gives some expected performance measures.     

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.