Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

The sulfide (H₂S/HS^?) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [ $ {\text{S}}_{\text{x}}^{2 - } $ ] and thiosulfate [ $ {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } $ ], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H₂S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10^?3 ??M/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.     

Characteristics and regional classification of the copepod community in Ariake Bay with note on comparison with 3 decades ago

Ariake Bay, Kyushu Island, has recently exhibited environmental degradation in the form of red tides and anoxic bottom water. To determine the characteristics and regional classification of the copepod community, zooplankton surveys were made throughout the bay in three cruises each in October 2004, January 2005 and March 2009 by vertical tows of a 0.1-mm-mesh plankton net. Oithona davisae was the most abundant in January and March, and Microsetella norvegica in October. Cluster analysis revealed that the copepod community from each cruise was generally separated into the inner to eastern-middle region and the western-middle to mouth region. A SIMPER analysis revealed that dissimilarity between the groups and similarity within each group were mainly due to the dominant species, but the similarities within the outer-region group in January and March were mostly contributed by Paracalanus parvus s.l. A non-metric multidimensional scaling with bubble plots of environmental variables and a BIOENV analysis showed that transparency was more different between the two groups than temperature and salinity. As compared with two similarly sized, eutrophic bays (Tokyo and Osaka Bays), Ariake Bay differs from Tokyo Bay in the dominance of M. norvegica and from Osaka Bay in the high abundance of O. davisae even in the colder season. The dominant species and the regional classification of the copepod community in the bay were similar to those in the studies in the 1970s, suggesting that the copepod community has not notably changed during the last 3 decades.     

A brief review of Agenian rhinocerotids in Western Europe

The Agenian is the earliest Neogene European Land Mammal Age. It encompasses the mammalian zones MN1 (23.03–22.7 Ma) and MN2 (22.7–20.0 Ma) and roughly coincides with the Aquitanian standard age. Agenian mammalian assemblages from Western Europe encompass a mixture of rhinocerotid taxa of Oligocene affinities and of Miocene newcomers, mostly recorded in France, Germany, Switzerland, and to a lesser extent, Spain. Rhinocerotidae are documented by seven species referred to five genera (Pleuroceros pleuroceros, Protaceratherium minutum, Plesiaceratherium aquitanicum, Mesaceratherium paulhiacense, Diaceratherium lemanense, D. asphaltense, and D. aginense), further attesting to a low suprageneric diversity. Their systematics, morphology, ecology, stratigraphical and geographical ranges are detailed in the present article. Occurrences and geographical ranges of all seven rhinocerotid species are illustrated on palaeogeographical maps of the circum-Mediterranean region at 23 Ma (MN1) and 21 Ma (MN2). The richest Agenian localities (Paulhiac, MN1; Laugnac, MN2) record a specific diversity similar to that of Orleanian rhinocerotid assemblages, with up to five/six associated species. All Agenian rhinocerotid species from Western Europe are endemic to the concerned region, which is consistent with the complete geographic isolation of Western Europe by earliest Miocene times. However, all five genera are documented by twin species in coeval localities of South and Central Asia, which implies (1) vicariant speciation events by latest Oligocene times and (2) the existence of intermittent pathways for terrestrial megamammals such as rhinocerotids during the concerned interval.     

Morphology and modern sedimentary deposits of the macrotidal Marapanim Estuary (Amazon,Brazil)

The northern Brazilian coast, east of the Amazon River is characterized by several macrotidal estuarine systems that harbor large mangrove areas with approximately 7600 km². The Marapanim Estuary is influenced by macrotidal regime with moderate waves influence. Morphologic units were investigated by using remote sensing images (i.e., Landsat-7 ETM+, RADARSAT- 1 Wide and SRTM) integrated with bathymetric data. The modern sedimentary deposits were analyzed from 67 cores collected by Vibracore and Rammkersonde systems. Analysis of morphology and surface sedimentary deposits of the Marapanim River reveal they are strongly influenced by the interaction of tidal, wave and fluvial currents. Based on these processes it was possible to recognize three distinct longitudinal facies zonation that revels the geological filling of a macrotidal estuary. The estuary mouth contain fine to medium marine sands strongly influenced by waves and tides, responsible for macrotidal sandy beaches and estuarine channel development, which are characterized by wave-ripple bedding and longitudinal cross-bedding sands. The estuary funnel is mainly influenced by tides that form wide tidal mudflats, colonized by mangroves, along the estuarine margin, with parallel laminations, lenticular bedding, root fragments and organic matter lenses. The upstream estuary contains coarse sand to gravel of fluvial origin. Massive mud with organic matter lenses, marks and roots fragments occur in the floodplain accumulates during seasonal flooding providing a slowly aggrading in the alluvial plain. This morphologic and depositional pattern show easily a tripartite zonation of a macrotidal estuary, that are in the final stage of filling.     

Computing Lippmann Diagrams from Direct Calculation of Mixing Properties of Solid Solutions: Application to the Barite-Celestite System

The Lippmann diagram for the system(Ba, Sr)SO₄-H₂O was computed at 25 °Cby determining the solid-phase activity coefficientsfrom first principles calculations. Directcalculations of the mixing properties of thebarite-celestite series indicate this solid solutionbehaves as non-ideal and non-regular. At 25 °C,the enthalpy of mixing shows a minimum around 50 mole% SrSO₄ due to an ordering tendency. Thefree energy of mixing shows two minima that delimit awide and symmetric miscibility gap (from 2.1 to 97.9 mole% SrSO₄) at this temperature. The excessfree energy of mixing requires a Guggenheim expansionseries of 5 terms to be described, where the termswith odd exponents are null as a consequence of thesymmetric distribution of the mixing properties withcomposition. The Lippmann diagram shows a peritecticpoint that corresponds to the composition of an aqueoussolution which is simultaneously at equilibrium withthe two extremes of the miscibility gap. The largedifference between the solubility products of theendmembers involves a strong preferential partitioningof the less soluble endmember towards the solid phase,which explains the extremely Ba-poor composition ofthe aqueous solution (aqueous activity fraction forBa²⁺ = 0.000446 ) at the peritectic point.     

Emplacement of the Ardara pluton (Ireland): new constraints from magnetic fabrics, rock fabrics and age dating

The Ardara pluton as part of the Donegal batholith was intruded into Neoproterozoic metasediments and metadolerites at mid-crustal levels. The emplacement mechanism of the Ardara granite is very controversial, and mechanisms ranging from diapirism, ballooning and stoping followed by nested diapirism have been proposed. Magnetic fabrics, rock fabrics and K/Ar dating of micas are used here to constrain the emplacement history. The compositional zoning of the Ardara pluton is clearly reflected in the different bulk magnetic susceptibilities between the outer quartz monzodiorite and the central granodiorite, whereas the intervening tonalite is of intermediate nature. The magnetic carriers are characterized by the anisotropy of the magnetic susceptibility (AMS), thermomagnetic measurements and through high field analyses (HFA). The separation of the ferrimagnetic and paramagnetic contributions revealed that biotite and magnetite control the AMS in the quartz monzodiorite. Both minerals are oriented in such a way that their summed contribution is constructive and originates from the shape fabric of magnetite and the texture of biotite. Biotite is responsible mainly for the AMS in the tonalite and granodiorite. The magnetic foliation can be directly related to the macroscopic foliation and also to the D4 structures in the country rocks. The foliation is consistent with the geometry of the roughly circular shape and has a mostly steep to vertical dip. Towards the central granodiorite the magnetic foliation dies out, although plagioclase texture measurements indicate a weak magmatic shape fabric. With the exception of the tail, the K_max axes (magnetic lineation) vary from steeply to gently plunging. The so-called lineation factor is approximately 1.01 and therefore points to a less significant axial symmetry. These observations coincide with strain estimates on mafic enclaves that show a very consistent pattern of K ∼0 flattening strain. Texture analyses of biotite and quartz additionally support the observations made by the strain analyses and the magnetic fabric data. Microstructural investigations give evidence that the fabrics are associated with the emplacement over a range of temperatures from truly magmatic to high-temperature solid-state conditions. The age of the intrusion is still under discussion, but a new cooling age was determined by K/Ar dating of biotite at 403.7±8 Ma corresponding to a temperature range between 450 and 300°C. For a mylonite along the southern contact between the Ardara pluton and the country rock a K/Ar muscovite age of 378.8±7 Ma indicates a minimum age for the shear zone when the Ardara pluton must have already been cooled down below 350±50°C. Received: 28 January 1999 / Accepted: 28 December 1999