Retention of arsenic and phosphorus in iron-rich concretions of Tagus salt marshes

Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O₂ takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O₂ and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g⁻¹ and 3.1 μmol g⁻¹, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g⁻¹), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g⁻¹ and 1.6 mmol g⁻¹, respectively) and of cracks (5.1 μmol g⁻¹ and 0.47 mmol g⁻¹). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.     

Simple determination of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) using solid-phase microextraction and gas chromatography-mass spectrometry

Solid-phase microextraction (SPME) is a simple, sensitive and less destructive method for the determination of dimethylsulfide (DMS) in seawater. Combined with detection by gas chromatography-mass spectrometry (GC-MS), the method had sufficient sensitivity (minimum detectable concentration of DMS was 0.05 nM), and practical levels of reproducibility (relative standard deviation ≤7%) and linearity (r ² > 0.995) over a wide concentration range (0.5 to 910 nM). The protocol developed was applied to a Sagami Bay water sample to determine concentrations of DMS and DMSP, and in situ DMSP-lyase activity.     

Eddy Shedding from the Kuroshio Bend at Luzon Strait

TOPEX/POSEDIENT-ERS satellite altimeter data along with the mean state from the Parallel Ocean Climate Model result have been used to investigate the variation of Kuroshio intrusion and eddy shedding at Luzon Strait during 1992–2001. The Kuroshio penetrates into the South China Sea and forms a bend. The Kuroshio bend varies with time, periodically shedding anticyclonic eddies. Criteria of eddy shedding are identified: 1) When the shedding event occurs, there are usually two centers of high Sea Surface Height (SSH) together with negative geostrophic vorticity in the Kuroshio Bend (KB) area. 2) Between the two centers of high SSH there usually exists positive geostrophic vorticity. These criteria have been used to determine the eddy shedding times and locations. The most frequent eddy shedding intervals are 70, 80 and 90 days. In both the winter and summer monsoon period, the most frequent locations are 119.5°E and 120°E, which means that the seasonal variation of eddy shedding location is unclear.     

Geodynamics of the deep sedimentary basin of the Caspian Sea region: paragenetic correlation of seismicity and mud volcanism

In this paper we analyze seismic regime and earthquake depth distribution and correlation of seismicity and mud volcanism in the Azerbaijan and the Caspian Sea region. For the present region we have calculated accurate source locations, seismic activity, earthquake repetition and released earthquake energy parameters. It is shown that the active tectonic processes in the region are concentrated within the thick sedimentary cover that we consider as a general source of contemporary stress and a main structural element responsible for the origin of regional earthquakes. The correlation of seismicity and mud volcanism is of paragenetic character.     

The Effect of Human Exclusion on the Population Structure of Key-Hole Limpets Fissurella crassa and F. limbata on the Coast of Central Chile

Abstract. We describe the basic ecology of two key-hole limpets, Fissurella crassa and Fissurella limbata , which are heavily harvested by coastal shellfishermen (mariscadores) at the rocky intertidal of central Chile. The ecological role of human predation on these species was assessed. Anthropic exclusion from a stretch of the rocky intertidal at Las Cruces (non-harvested area) for about two and a half years resulted in changes of the densities and size distributions of these fissurelid species as compared to populations in control zones (harvested area). Differential human predation generates, on key-hole limpets, responses of different intensities related to the accessibility of man to the mesohabitats (sheltered platforms, exposed platforms and vertical walls) and fringes of the intertidal (mid-low intertidal and Lessonia nigrescens fringe). Thus, size distributions and mean densities of both fissurelids differ widely between the harvested and non-harvested areas on both platform habitats but not on vertical walls. In the mid-low intertidal fringe, differences are greater than in the less accessible L. nigrescens intertidal fringe. Moreover, we discuss the way in which other species, directly harvested by mariscadores (i. e., the mollusc Concholepas concholepas) can affect the keyhole limpet populations of central Chile rocky shores. Finally, we highlight the ecological role of these limpets on the dynamics of intertidal ecosystems and how they can modify community landscape.     

Estimates of heat flow and heat production and a thermal model of the São Francisco craton

An updated analysis of geothermal data from the highland area of eastern Brazil has been carried out and the characteristics of regional variations in geothermal gradients and heat flow examined. The database employed includes results of geothermal measurements at 45 localities. The results indicate that the Salvador craton and the adjacent metamorphic fold belts northeastern parts of the study area are characterized by geothermal gradients in the range of 6–17°C/km. The estimated heat flow values fall in the range of 28–53 mW/m², with low values in the cratonic area relative to the fold belts. On the other hand, the São Francisco craton and the intracratonic São Francisco sedimentary basin in the southwestern parts are characterized by relatively higher gradient values, in the range of 14–42°C/km, with the corresponding heat flow values falling in the range of 36–89 mW/m². Maps of regional variations indicate that high heat flow anomaly in the São Francisco craton is limited to areas of sedimentary cover, to the west of the Espinhaço mountain belt. Crustal thermal models have been developed to examine the implications of the observed intracratonic variations in heat flow. The thermal models take into consideration variation of thermal conductivity with temperature as well as change of radiogenic heat generation with depth. Vertical distributions of seismic velocities were used in obtaining estimates of radiogenic heat production in crustal layers. Crustal temperatures are calculated based on a procedure that makes simultaneous use of the Kirchoff and Generalized Integral Transforms, providing thereby analytical solutions in 2D and 3D geometry. The results point to temperature variations of up to 300°C at the Moho depth, between the northern Salvador and southern São Francisco cratons. There are indications that differences in rheological properties, related to thermal field, are responsible for the contrasting styles of deformation patterns in the adjacent metamorphic fold belts.     

Eta carinae nebulosities in 1963

The purpose of this note is to give further information regarding the positions of some condensations around Carinae in 1963, an epoch not yet considered in the literature. The new information is unable to confirm the deceleration hypothesis of theeir motion.     

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S₂ generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S₂ generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S₂ generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.     

The behavior of trace elements during schwertmannite precipitation and subsequent transformation into goethite and jarosite

Schwertmannite is a ubiquitous mineral formed from acid rock drainage (ARD), and plays a major role in controlling the water chemistry of many acid streams. The formation of schwertmannite was investigated in the acid discharge of the Monte Romero abandoned mine (Iberian Pyrite Belt, SW, Spain). Schwertmannite precipitated from supersaturated solutions mainly owing to the oxidation of Fe(II) to Fe(III) and transformed with time into goethite and jarosite. In a few hours, schwertmannite precipitation removed more than half of the arsenic load from solution, whereas the concentration of divalent trace metals (Zn, Cu, Pb, Cd, Ni, and Co) remained almost unchanged. In the laboratory, natural schwertmannite was kept in contact with its coexisting acid water in a flask with a solid-liquid mass ratio of 1:5 for 353 days. During this time, the pH of the solution dropped from 3.07 to 1.74 and the concentrations of sulfate and Fe increased. During the first 164 days, schwertmannite transformed into goethite plus H₃O-jarosite but, subsequently, goethite was the only mineral to form. Some of the trace elements, such as Al, Cu, Pb, and As were depleted in solution during the first stage as schwertmannite transformed into goethite plus H₃O-jarosite. On the contrary, the transformation of schwertmannite to goethite (with no jarosite) during the second stage released Al, Cu, and As to the solution. Despite the variation in their concentrations in solution, approximately 80% of the total Al and Cu inventories and more than 99% As and Pb remained in the solid phase throughout the entire aging process.