Cation substitution in synthetic meridianiite (MgSO<Subscript>4</Subscript>·11H<Subscript>2</Subscript>O) I: X-ray powder diffraction analysis of quenched polycrystalline aggregates

Meridianiite, MgSO₄·11H₂O, is the most highly hydrated phase in the binary MgSO₄–H₂O system. Lower hydrates in the MgSO₄–H₂O system have end-member analogues containing alternative divalent metal cations (Ni²⁺, Zn²⁺, Mn²⁺, Cu²⁺, Fe²⁺, and Co²⁺) and exhibit extensive solid solution with MgSO₄ and with one another, but no other undecahydrate is known. We have prepared aqueous MgSO₄ solutions doped with these other cations in proportions up to and including the pure end-members. These liquids have been solidified into fine-grained polycrystalline blocks of metal sulfate hydrate + ice by rapid quenching in liquid nitrogen. The solid products have been characterised by X-ray powder diffraction, and the onset of partial melting has been quantified using a thermal probe. We have established that of the seven end-member metal sulfates studied, only MgSO₄ forms an undecahydrate; ZnSO₄ forms an orthorhombic heptahydrate (synthetic goslarite), MnSO₄, FeSO₄, and CoSO₄ form monoclinic heptahydrates (syn. mallardite, melanterite, bieberite, respectively), and CuSO₄ crystallises as the well-known triclinic pentahydrate (syn. chalcanthite). NiSO₄ forms a new hydrate which has been indexed with a triclinic unit cell of dimensions a = 6.1275(1) Å, b = 6.8628(1) Å, c = 12.6318(2) Å, α = 92.904(2)°, β = 97.678(2)°, and γ = 96.618(2)°. The unit-cell volume of this crystal, V = 521.74(1) ų, is consistent with it being an octahydrate, NiSO₄·8H₂O. Further analysis of doped specimens has shown that synthetic meridianiite is able to accommodate significant quantities of foreign cations in its structure; of the order 50 mol. % Co²⁺ or Mn²⁺, 20–30 mol. % Ni²⁺ or Zn²⁺, but less than 10 mol. % of Cu²⁺ or Fe²⁺. In three of the systems we examined, an ‘intermediate’ phase occurred that differed in hydration state both from the Mg-bearing meridianiite end-member and the pure dopant end-member hydrate. In the case of CuSO₄, we observed a melanterite-structured heptahydrate at Cu/(Cu + Mg) = 0.5, which we identify as synthetic alpersite [(Mg_0.5Cu_0.5)SO₄·7H₂O)]. In the NiSO₄- and ZnSO₄-doped systems we characterised an entirely new hydrate which could also be identified to a lesser degree in the CuSO₄- and the FeSO₄-doped systems. The Ni-doped substance has been indexed with a monoclinic unit-cell of dimensions a = 6.7488(2) Å, b = 11.9613(4) Å, c = 14.6321(5) Å, and β = 95.047(3)°, systematic absences being indicative of space-group P2₁/c with Z = 4. The unit-cell volume, V = 1,176.59(5) ų, is consistent with it being an enneahydrate [i.e. (Mg_0.5Ni_0.5)SO₄·9H₂O)]. Similarly, the new Zn-bearing enneahydrate has refined unit cell dimensions of a = 6.7555(3) Å, b = 11.9834(5) Å, c = 14.6666(8) Å, β = 95.020(4)°, V = 1,182.77(7) ų, and the new Fe-bearing enneahydrate has refined unit cell dimensions of a = 6.7726(3) Å, b = 12.0077(3) Å, c = 14.6920(5) Å, β = 95.037(3)°, and V = 1,190.20(6) ų. The observation that synthetic meridianiite can form in the presence of, and accommodate significant quantities of other ions increases the likelihood that this mineral will occur naturally on Mars—and elsewhere in the outer solar system—in metalliferous brines.     

Relative sea-level history from the Lambert Glacier region, East Antarctica, and its relation to deglaciation and Holocene glacier readvance

We present a relative sea-level (RSL) history, constrained by AMS radiocarbon-dated marine-freshwater transitions in isolation basins from a site adjacent to the Lambert Glacier, East Antarctica. The RSL data suggest an initial ice retreat between c. 15,370 and 12,660 cal yr B.P.. Within this period, meltwater pulse IA (mwp IA, between c. 14,600-14,200 and 14,100-13,700 cal yr B.P.) occurred; an exceptionally large ice melting event, inferred from far-field sea-level records. The RSL curve shows a pronounced highstand of approximately 8 m between c. 7570-7270 and 7250-6950 cal yr B.P. that is consistent with the timing of the RSL highstand in the nearby Vestfold Hills. This is followed by a fall in RSL to the present. In contrast to previous findings, the isolation of the lakes in the Larsemann Hills postdates the isolation of lakes with similar sill heights in the Vestfold Hills. An increase in RSL fall during the late Holocene may record a decline in the rate of isostatic uplift in the Larsemann Hills between c. 7250-6950 and 2847-2509 cal yr B.P., that occurred in response to a documented mid-Holocene glacier readvance followed by a late-Holocene retreat.     

Late Holocene changes in ultraviolet radiation penetration recorded in an East Antarctic lake

Late Holocene changes in the ultraviolet radiation (UVR) penetration in a lake in the Larsemann Hills (East Antarctica) were reconstructed using sediment core proxies based on fossil pigments (scytonemins and its derivatives) and siliceous microfossils. The influence of changes in lake depth on the UVR proxy was excluded by applying a correction, based on the non-linear relation between modern scytonemin concentrations and lake depth in a regional reference data set, and the record of past lake depths inferred using a diatom based transfer function in the sediment core. Results showed four well-defined maxima in the UVR proxy during the last 1600–1800 years, centred around 1820–1780, 1580–1490, 790–580 and 680–440 AD. Several mechanisms may account for these observed changes in UVR penetration, including past variability in cloud cover, atmospheric turbidity, ozone column depth, snow cover on the lake ice, DOM concentrations and lake-ice thickness and transparency resulting from temperature fluctuations. Although some gaps remain in our knowledge of scytonemin production in relation to the limnology of Antarctic lakes, the results highlight the importance and potential of the sediments in these highly transparent water bodies as archives of changes in past UVR receipt at the Earth’s surface.     

The Influence of Streambed Heterogeneity on Hyporheic Flow in Gravelly Rivers

Deposits of open‐framework gravel occurring in gravelly streambeds can exert a significant influence on hyporheic flow. The influence was quantified using a numerical model of the hyporheic zone. The model included open‐framework gravel stratasets represented with commonly observed characteristics including a volume fraction of about one‐third of the streambed sediment, a hydraulic conductivity two orders of magnitude greater than other strata present, and a spatial connectivity forming preferential‐flow pathways. The influence of open‐framework gravel stratasets on hyporheic flow was much greater than the influence of the channel morphology including meanders, point bars, dunes, and ripples. Seventy percent of the total hyporheic exchange occurred across 30% of the channel boundary at locations of open‐framework gravel stratasets. The maximum local interfacial flux rates occurred at these locations, and were orders of magnitude greater than those at other locations. The local flux rates varied by six orders of magnitude over the channel boundary. The composite flow rate through the model with open‐framework gravel stratsets was an order of magnitude greater than that through an equivalent but homogeneous model.     

Malta's external security

For a small country whose main relevance to the outside world has always been its strategic location and whose known history has been moulded by that fact, security has been remarkably low on the list of priorities on Maltas national agenda since independence. In recent years, security has become an issue of keen political debate, although security per se may not be the real reason why the subject has been brought out into the limelight by both government and opposition. More than just an issue in its own right, security began featuring rather more as a function of the main direction of Maltas foreign policy, which during the past decade has been focused on relations with the European Union.     

An investigation of the multi-scale temporal variability of beach profiles at Duck using wavelet packet transforms

In an earlier paper a particular discrete wavelet transform (DWT) was used to study the complex variation of beach profile changes. However, use of the DWT requires that the sequence of spatial and temporal resolution is fixed as a dyadic sequence, which means that the variability over longer intervals is not characterised well. Here we introduce the discrete wavelet packet transform (DWPT) that uses an adaptive scaling to partition the data variance, according to an entropy cost function. The advantages of this approach are demonstrated by its application to the study of temporal variability of a 22 year record of beach profile data from the Field Research Facility (FRF) at Duck, North Carolina, USA. Time series of beach elevations at three locations across a particular profile are investigated in detail. We conclude that the DWPT provides a superior analysis of non-stationary time series to that of the DWT, with improved resolution of the scale intervals of the variability. The beach elevation around the shoreline is shown to respond at both sub-annual and interannual scales, but variability at an annual scale is weak. Moving seaward into deeper water, the variance is partitioned into fewer and longer scales. It is confirmed that elevation changes around the inner bar at Duck exhibit a strong interannual variation consistent with Plant et al. (Plant, N.G., Holman, R.A. and Freilich, M.H., 1999. A simple model for interannual sandbar behaviour. Journal of Geophysical Research 104(C7), 15755–15776). Around 23% of the variance around the inner bar is explained at the temporal scale of 64–128 months, which is consistent with the bar behaviour of 6 years found by Ruessink et al. (Ruessink, B. G., Wijnberg, K. M., Holman, R. A., Kuriyama, Y. and Van Enckevort, I. M. J., 2003. Intersite comparison of interannual nearshore bar behaviour. Journal of Geophysical Research, 108 (C8): 1–12). A significant new finding is, however, that about 26% of the variance is attributable to temporal scales of 16–21.3 months. Reconstruction of the wavelet packet components for individual temporal scales is shown to provide a means for identifying the impact and scale of non-stationary events, such as storms, on the beach response. This provides further information that can be used to interpret the morphological changes in terms of the forcing processes and also serves to inform morphodynamic modelling.     

Cypermethrin induces glutathione S-transferase activity in the shore crab,Carcinus maenas

Cypermethrin is a synthetic pyrethroid that is particularly toxic to crustacea. It is therefore applied as a chemotherapeutant in the salmonid aquaculture industry for the treatment of sea lice infestations. After use, cypermethrin is released directly into the marine environment, to be diluted by fresh seawater. The shore crab, Carcinus maenas is found in the vicinity of fish farms, and may come into contact with released cypermethrin. The detoxification enzyme, glutathione S-transferase (GST) has been implicated in cypermethrin metabolism in terrestrial arthropods, but this has not yet been demonstrated in crustacea. In this paper we investigate the response of GST activity in Carcinus to cypermethrin exposure, and also the time course of the induction process. GST activity is significantly increased in Carcinus exposed to nominal concentrations of 50 and 500 ng/l of water-borne cypermethrin. Carcinus demonstrate a significant elevation in GST activity following intra-cephalothoracic injection with 10 ng of cypermethrin. GST activity returns to basal levels after 36 h. The potential application of GST activity in Carcinus as a biomarker of cypermethrin exposure is discussed.     

Ancient graphite in the Eoarchean quartz-pyroxene rocks from Akilia in southern West Greenland I: Petrographic and spectroscopic characterization

Because all known Eoarchean (>3.65 Ga) volcano-sedimentary terranes are locked in granitoid gneiss complexes that have experienced high degrees of metamorphism and deformation, the origin and mode of preservation of carbonaceous material in the oldest metasedimentary rocks remain a subject of vigorous debate. To determine the biogenicity of carbon in graphite in such rocks, carbonaceous material must be demonstrably indigenous and its composition should be consistent with thermally altered biogenic carbon as well as inconsistent with abiogenic carbon. Here we report the petrological and spectroscopic characteristics of carbonaceous material, typically associated with individual apatite grains, but also with various other minerals including calcite, in a >3.83 Ga granulite-facies ferruginous quartz-pyroxene unit (Qp rock) from the island of Akilia in southern West Greenland. In thin sections of the fine-grained parts of Akilia Qp rock sample G91-26, mapped apatites were found to be associated with graphite in about 20% of the occurrences. Raman spectra of this carbonaceous material had strong G-band and small D-band absorptions indicative of crystalline graphite. Three apatite-associated graphites were found to contain curled graphite structures, identified by an anomalously intense second-order D-band (or 2D-band) Raman mode. These structures are similar to graphite whiskers or cones documented to form at high temperatures. Raman spectra of apatite-associated graphite were consistent with formation at temperatures calculated to be between 635 and 830 °C, which are consistent with granulite-facies metamorphic conditions. Three graphite targets extracted by focused ion beam (FIB) methods contained thin graphite coatings on apatite grains rather than inclusions sensu stricto as inferred from transmitted light microscopy and Raman spectroscopy. TEM analyses of graphite in these FIB sections showed a (0 0 0 2) interplanar spacing between 3.41 and 3.64 Å for apatite-associated graphite, which is larger than the spacing of pure graphite (3.35 Å) and may be caused by the presence of non-carbon heteroatoms in interlayer sites. Samples analyzed by synchrotron-based scanning transmission X-ray microscopy (STXM) also confirmed the presence of crystalline graphite, but abundances of N and O heteroatoms were below detection limit for this method. Graphite in the Akilia Qp rock was also found to occur in complex polyphase mineral assemblages of hornblende ± calcite ± sulfides ± magnetite that point to high-temperature precipitation from carbon-bearing fluids. These complex mineral assemblages may represent another generation of graphitization that could have occurred during the amphibolite-facies metamorphic event at 2.7 Ga. Several observations point to graphitization from high-temperature fluid-deposition for some of the Akilia graphite and our results do not exclude a biogenic source of carbon in graphite associated with apatite, but ambiguities remain for the origin of this carbon.