Theoretical studies on metal thioarsenites and thioantimonides: synergistic interactions between transition metals and heavy metalloids

Recently we established that the ternary complex, CuAsS(SH)(OH) has an unusually high stability and makes a large contribution to the total concentrations of both Cu and As in sulfidic solutions equilibrated with Cu and As sulfide minerals. This ternary complex has an unusual structure, containing a bond which is formally Cu(I)–As(III), along with a broken As–S bond. We have now found that complexes with similar structures exist for Au⁺ and Tl⁺ coordinated to AsS(SH)(OH)^-. However, such a direct metal–metalloid bond is not a requirement for stability. In fact, TlAsS(SH)(OH) is unstable while AuAsS(SH)(OH) is highly stable (compared to the aquo ion). Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ also form bonds to the As of AsS(SH)(OH), but without breaking any As–S bonds, and HgAsS(SH)(OH)⁺ and PbAsS(SH)(OH)⁺ are particularly stable complexes. Calculated structures are shown for these complexes, gas-phase energies are calculated, and formation constants in aqueous solution are estimated. The SbS(SH)(OH)^- ion forms analogous complexes, with similar stabilities. However, the Au⁺ complex of SbS(SH)(OH)^- is slightly less stable than the Cu⁺ complex, opposite to the order found for the AsS(SH)(OH)^- ligand. The Au⁺ and AuSH complexes of AsSSHOH^- or AsS(SH)₂ ^- may be implicated in "invisible gold" in arsenian pyrites. Vibrational frequencies are given for the AuAsS(SH)₃ ^- complex and the XANES energies of this complex and Au(SH)₂ ^- are compared. The existence of such strong complexes may explain the many correlations observed between the concentrations of coinage metals and metalloids.     

Magnetically enhanced coagulation of very small iron grains

Laboratory experiments, in which very small (approximately 20 nm) grains are produced in the presence of a magnetic field on the order of 100 Gauss in a low-pressure hydrogen atmosphere, have demonstrated that such smokes can become permanently magnetized. We show that magnetization results in an enormous enhancement in the coagulation efficiency of such materials even in the absence of external magnetic fields. Small iron grains should have been produced in the solar nebula by thermal processing of preexisting interstellar grains. If such processing occurred via high-energy electromagnetic events then the resultant magnetized grains could have triggered the formation of centimeter- to meter-sized protoplanetessimals by acting as "nets" capable of sweeping up nonconductive silicates suspended in the gas. It is possible that the presence of conductive fractal aggregates observed in modern-day protostellar disks could be explained by the enhanced coagulation efficiency of very small magnetized iron particles.     

A felsic dyke swarm formed under the sea: the Archean Hunter Mine Group,south-central Abitibi Belt,Quebec, Canada

An extensive rhyolitic dyke swarm has intruded subaqueous pyroclastic deposits, iron-formations, hyaloclastite breccias and lava flows of the 2730 Ma Hunter Mine Group (HMG) in the south-central part of the Archean Abitibi belt, Quebec. The dyke swarm has a minimum width of 500 m and can be traced perpendicular to the section for 2.4 km. Based on crosscutting relationships, chilled margins, quartz content and colour, five distinct dyke generations have been established. Each dyke generation has several magmatic pulses as indicated by parallel rows of columnar joints. Absence of brecciation between parallel rows suggests extremely brief intervals between magma pulses. The central parts of most dykes display inverted V-shaped patterns of columnar-joint convergence, inferred to indicate differential cooling during the late stages of dyke propagation. The dykes commonly display delicate spherulites suggesting rapid cooling, solidification temperatures between 400 and 600°C and penecontemporaneous devitrification. Quartz-feldspar aggregates in the groundmass have locally developed microgranophyric textures. Large spherulites near the chilled margins probably formed at temperatures below 400°C. Percolation of abundant water throughout the dyke complex is suggested by ubiquitous prominent chilled dyke margins. Development of a chilled margin 500 m along one dyke suggests that water percolated at least 500 m below the water/rock interface. Because the dykes intruded subaqueous pyroclastic deposits of similar composition, dyke emplacement below the sea floor is inferred. Interstratification of pillowed flows and brecciated pillowed flows containing rhyolite fragments at the top of the 4–5-km-thick sequence indicates that the central felsic complex probably never emerged during its evolutionary history, supporting the contention that the felsic dyke complex was emplaced beneath the Archean sea floor.     

A one dimensional wind profile model with stability and eddy viscosity estimations from sodar data

In a one-dimensional wind profile model, methods for eddy viscosity and stability estimations from sodar data have been evaluated with soundings. For eddy viscosity parameterization the ageostrophic method and mixing-length theory have been investigated. Three methods for estimating the static stability have been evaluated; a wind profile adjustment method, gravity wave analysis of sodar backscatter and flux profile functions for windspeed and standard deviation of vertical wind-speed. The wind profile model with variable momentum flux (VF) with height shows better results than an earlier constant flux model (Bergström, 1986). The VF model can be used for extending the sodar profile up to 1500 m.     

The ‘suitcase hypothesis’: Can entrainment of meroplankton by eddies provide a pathway for gene flow between Madagascar and KwaZulu-Natal,South Africa?

Similarities in the marine fauna found off the coasts of southern Madagascar and KwaZulu-Natal Province (KZN), South Africa, led to the development of the ‘suitcase project,’ with the aim of establishing whether eddies that form off southern Madagascar may package and transport biological material across the Mozambique Channel, facilitating connectivity and gene flow. Meroplankton (larval stages of fishes and benthic invertebrates) were collected on the Madagascan shelf and along a transect through a cyclonic eddy in the Mozambique Channel. The samples were analysed using microscopy and DNA barcoding, seeking to identify species known to be common to both the southeast coast of Madagascar and the east coast of South Africa and thereby to reveal potential indicators of connectivity between these regions. The greatest zooplankton biovolume in the upper 200 m occurred on the shelf, followed by in the western part of the eddy and in the region outside the eddy to the west, and was lowest in the region outside the eddy to the east. The meroplankton were dominated by taxa of coastal origin and these were also most abundant on the shelf and in the western part of the eddy, with the lowest abundances in the region outside the eddy to the east. The findings show greater zooplankton biovolumes and larval abundances and the presence of reef-associated larval assemblages on the Madagascan shelf and along the transect through the cyclonic eddy, providing support for the suitcase hypothesis that planktonic organisms are entrained within eddies as they propagate south-westwards of the Madagascan shelf.     

Neoproterozoic A‐type magmatism in the Western Sierras Pampeanas (Argentina): evidence for Rodinia break‐up along a proto‐Iapetus rift?

A‐type orthogneisses of mid Neoproterozoic age (774 ± 6 Ma, U‐Pb SHRIMP zircon age), are reported for the first time from the Grenvillian basement of the Western Sierras Pampeanas in Argentina. These anorogenic meta‐igneous rocks represent the latest event of Rodinia break‐up so far recognized in Grenvillian basement exposures across Andean South America. Moreover, they compare well with A‐type granitoids and volcanic rocks along the Appalachian margin of Laurentia (Blue Ridge), thus adding to former evidence that the Western Sierras Pampeanas Grenvillian basement was left on the conjugate rifted margin of eastern Laurentia during Rodinia break‐up and the consequent opening of the Iapetus ocean.     

The San Blas Pluton: An example of Carboniferous plutonism in the Sierras Pampeanas, Argentina

New geochronological and geochemical data are reported for the San Blas Pluton (SBP), in the northwestern Sierra de Velasco, Sierras Pampeanas, which intrudes Ordovician granitoids developed during the Famatinian orogeny. A precise Carboniferous age of 340±3 Ma is established by U–Pb dating of zircon using a sensitive high-resolution ion microprobe (SHRIMP). The SBP illustrates several petrological and geochemical characteristics of previously reported Carboniferous granitoids in the Sierras Pampeanas. Their generation is consistent with a regional reheating of the crust at approximately 342 Ma, which resulted in the formation of relatively large amounts of granitic melts that were emplaced in higher crustal levels along master fractures (older master shear zones of Lower Paleozoic age). The SBP can be chemically defined as a typical A-type granitoid related to postcollisonal or postorogenic magmatism. Its high REE content and extraordinarily high U and Th concentrations may have economic significance. Many previously published Devonian and Carboniferous K–Ar dates are reset Ordovician ages, but the existence of other Carboniferous bodies in the Sierra de Velasco cannot be discounted until detailed mapping of the whole Sierra is completed.     

Petrological,geochemical, isotopic,and geochronological constraints for the Late Devonian–Early Carboniferous magmatism in SW Gondwana (27–32°LS): an example of geodynamic switching

International Journal of Earth Sciences - We report a study integrating 13 new U–Pb LA-MC-ICP-MS zircon ages and Hf-isotope data from dated magmatic zircons together with complete...     

Riverine influence determines nearshore heterogeneity of nutrient (C,N, P) content and stoichiometry in the KwaZulu-Natal Bight,South Africa

Riverine influences on nearshore oceanic habitats often have detrimental consequences leading to algal blooms and hypoxia. In oligo- to mesotrophic systems, however, nutrient delivery via rivers may stimulate production and even be a vital source of nutrients, as may nutrient supplements from upwelling. We investigated the nutrient content (C, N, P) and stoichiometry of sediment, and several pelagic, benthopelagic and benthic species in the KwaZulu-Natal (KZN) Bight, a narrow shelf area on the south-east coast of South Africa, bordering the Agulhas Current. Three suggested nutrient sources to the bight are the Thukela River in the central region of the bight, upwelling in the northern part and a semi-permanent eddy (Durban Eddy) in the southern part. Elemental content of the various groups studied showed significantly higher values for most groups at the site near the Thukela River. C:P and N:P were highest in the southern part of the bight, and lowest near the Thukela Mouth or at Richards Bay in the north, indicating the latter were the P-richer sites. Sediment organic matter showed lowest elemental content, as expected, and zooplankton stoichiometry was highest compared to all other biotic groups. Environmental heterogeneity played a greater role in organismal C, N and P content and stoichiometry compared to phylogeny, with the exception of the differences in C:P and N:P of zooplankton. From this bight-wide study, the higher elemental content and lower ratios at the Thukela Mouth site supported previous findings of the importance of coastal nutrient sources to the bight ecosystem. Reductions in river flow for water use in the catchment areas may therefore have negative consequences for the productivity of the entire ecosystem.     

Characterisation of the dietary relationships of two sympatric hake species,Merluccius capensis and M. paradoxus,in the northern Benguela region using fatty acid profiles

The two sympatric species of Cape hake, Merluccius capensis and M. paradoxus, have been the main targets of bottom-trawl fisheries off Namibia for several decades. The feeding ecology of these hakes has been studied mainly using stomach content analyses and thus there remain some gaps in our knowledge about food assimilated over the longer term. In this study, we used fatty acid (FA) profiles to characterise the dietary relationships of M. capensis and M. paradoxus. Muscle samples from hake (n=110) and their known prey (n=68) were collected during trawl surveys off Namibia during 2011. Significant differences between the neutral FA profiles of the hake populations were detected in December 2011 but not in January 2011, an indication of temporal variations in diet and resource partitioning. Comparisons of the neutral FAs in hake and the total FAs of potential prey showed no clear trophic connections, with the exception of flying squid Todarodes sagittatus, which had FA profiles very similar to those of M. paradoxus in December 2011. Our results highlight the complex and temporally shifting relationships that exist between hake and the large pool of prey available to them, and between the two hake species that overlap in their feeding habits and distribution within the highly productive Benguela Current region.