Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

Influence of the Load Wavelength on the Permeability of a Viscosity Interface in the Mantle

Assuming a radially stratified Newtonian mantle in a steady-state approximation, we demonstrate that the permeability of a viscosity interface at 660-km depth strongly depends on the wavelength of buoyancy forces driving the flow. The flow induced by long-wavelength loads penetrates through the boundary freely even if the viscosity increases by two orders. In contrast, the boundary is practically impermeable for short-wavelength loads located in the upper mantle. Thus, a stepwise increase of viscosity is a significant obstacle for small descending features in the upper mantle, but huge upper mantle downwellings, or upwellings formed in the-lower mantle can overcome it easily. This indicates that certain care is necessary in interpreting the seismic structure of the mantle by means of flow models. The global tomographic image includes only the first few degrees of the harmonic series and, consequently, its interpretation in terms of a present-day flow field results in a predominantly whole-mantle circulation even for extreme viscosity contrasts.     

Anaerobic methane oxidation and a deep H2S sink generate isotopically heavy sulfides in Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO₄²⁻-CH₄ transition where H₂S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H₂S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe²⁺ diffusing up from below. The H₂S-Fe²⁺ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO₄²⁻ and 10 yr for H₂S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO₄²⁻-CH₄ and H₂S-Fe²⁺ cause the trapping of isotopically heavy iron sulfide with δ³⁴S = +15 to +33‰ at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO₄²⁻ diffusing downward into the SO₄²⁻-CH₄ transition has an isotopic composition of +19‰, close to the +23‰ of H₂S diffusing upward. These isotopic compositions are, however, very different from the porewater SO₄²⁻ (+43‰) and H₂S (−15‰) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H₂S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth’s history.     

Seagrass as the main food source of Neaxius acanthus (Thalassinidea: Strahlaxiidae), its burrow associates, and of Corallianassa coutierei (Thalassinidea: Callianassidae)

Burrows of the thalassinidean shrimps Neaxius acanthus and Corallianassa coutierei are striking aspects in tropical seagrass beds of the Spermonde Archipelago, Indonesia. Burrow construction, behaviour, burrow type and associated commensal community were investigated to clarify the ecological role and food requirements of these shrimps and their commensals. Gut content analysis and stable-isotope data were used to unravel the food sources and the trophic interactions among the commensal community.Individuals of Neaxius acanthus were caught on Bone Batang Island. In narrow aquaria filled with sediment they constructed burrows resembling those found in the field. During burrow construction and maintenance only little sediment was brought to the surface, most was sorted and compacted to create a distinct lining. Maintenance work by single shrimps typically took about 5 min, after which the shrimp walked up to the entrance and rested for a similar period of time. There were no differences in behaviour between day and night. Intrasexual encounters inside the burrow were characterised by a high level of aggression and all resulted in one participant being driven out of the burrow. Intersexual encounters led to coexistence with both animals taking turns in burrow maintenance and guarding the entrance. Offered seagrass leaves were pulled underground, cut into pieces and eventually integrated into the lining. Burrows of Corallianassa coutierei resembled a deep U-shape. Chambers branching off halfway down and at the deepest point contained seagrass fragments. All steep parts of the burrow were lined similar to burrows of N. acanthus.No commensals were found associated with Corallianassa coutierei. However, burrows of Neaxius acanthus in the field typically contained a pair of shrimps, up to 8 individuals of the commensal bivalve Barrimysia cumingii and large numbers of gammarid amphipods. Other animals found associated with the burrow were the goby Austrolethops wardi, a palaemonid shrimp species and two species of tube-building polychaetes, one of which was also found as an epibiont on N. acanthus.Stable-isotope and gut content analyses indicate that the diet of Neaxius acanthus, its commensal Austrolethops wardi, and Corallianassa coutierei is mainly derived from detrital seagrass leaves, with a potential contribution of sediment organic matter and seagrass epiphytes. In contrast the isotopic signature of Barrimysia cumingii suggests the presence of symbiotic sulphide metabolism bacteria. This study underlines that, besides their interactions with the surrounding ecosystem, thalassinid shrimp burrows play an important role as a sub-habitat with a unique associated fauna.     

Salt accumulation in the loessial sequence in the Be'er Sheva Basin,Israel

Evidence of climatic changes is recorded in the salt content of the surface sediments in arid zones. In wetter periods airborne salts are removed downward by leaching to the groundwater, whereas in drier periods they accumulate. The period of salt accumulation in the loessial sediments of the northern Negev is about 10,000 yr. This period represents the recent aridification phase. The beginning of this stretch of time followed the last humid period in the region. Top paleo soil (calcic horizon) found in the region and dated 12,000 yr B.P. is an indicator of this humid period. This article is a contribution from the Agricultural Research Organization, The Volcani Center, Bet Datan, Israel, No. 1751E, 1986 series.     

On the nonlinear dynamics of the boundary layer of intense atmospheric vortex

The paper describes a stationary model of the boundary layer of a large-scale vortex. The model takes into account two types of nonlinearities: (1) advection of the momentum and centrifugal accelerations, that is related to large values of the Rossby number; (2) a nonlinear turbulent friction on the lower boundary (generally speaking, not only quadratic, but also more complicated). Nevertheless, the model may be studied analytically. This approach allows discovery and analysis of several universal regularities, which are not revealed by numerical modeling. The model provides the actual values for the speed of the surface wind and the angle of cross-isobar surface flow in the tropical cyclones.     

Latent heat effects of the major mantle phase transitions on low-angle subduction

Very low to zero shallow dip angles are observed at several moderately young subduction zones with an active trenchward moving overriding plate. We have investigated the effects of latent heat for this situation, where mantle material is pushed through the major mantle phase transitions during shallow low-angle subduction below the overriding plate. The significance of the buoyancy forces, arising from the latent heat effects, on the dynamics of the shallowly subducting slab is examined by numerical modeling. When a 32-Ma-old slab is overridden with 2.5 cm/yr by a continent, flat subduction occurs with a 4–5 cm/yr convergence rate. When latent heat is included in the model, forced downwellings cause a thermal anomaly and consequently thermal and phase buoyancy forces. Under these circumstances, the flat slab segment subducts horizontally about 350 km further and for about 11 Ma longer than in the case without latent heat, before it breaks through the 400-km phase transition. The style of subduction strongly depends on the mantle rheology: increasing the mantle viscosity by one order of magnitude can change the style of subduction from steep to shallow. Similarly, an overriding velocity of less than 1 cm/yr leads to steep subduction, which gradually changes to flat subduction when increasing the overriding velocity. However, these model parameters do not change the aforementioned effect of the latent heat, provided that low-angle subduction occurs. In all models latent heat resulted in a substantial increase of the flat slab length by 300–400 km. Varying the olivine–spinel transition Clapeyron slope γ from 1 to 6 MPa/K reveals a roughly linear relation between γ and the horizontal length of the slab. Based on these results, we conclude that buoyancy forces due to latent heat of phase transitions play an important role in low-angle subduction below an overriding plate.