Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

K–Ar and Ar/Ar ages of dikes emplaced in the onshore basement of the Santos Basin, Resende area, SE Brazil: implications for the south Atlantic opening and Tertiary reactivation

New K–Ar and ⁴⁰Ar/³⁹Ar data of tholeiitic and alkaline dike swarms from the onshore basement of the Santos Basin (SE Brazil) reveal Mesozoic and Tertiary magmatic pulses. The tholeiitic rocks (basalt, dolerite, and microgabbro) display high TiO₂ contents (average 3.65 wt%) and comprise two magmatic groups. The NW-oriented samples of Group A have (La/Yb)_N ratios between 15 and 32.3 and range in age from 192.9±2.2 to 160.9±1.9 Ma. The NNW-NNE Group B samples, with (La/Yb)_N ratios between 7 and 16, range from 148.3±3 to 133.9±0.5 Ma. The alkaline rocks (syenite, trachyte, phonolite, alkaline basalts, and lamprophyre) display intermediate–K contents and comprise dikes, plugs, and stocks. Ages of approximately 82 Ma were obtained for the lamprophyre dikes, 70 Ma for the syenite plutons, and 64–59 Ma for felsic dikes. Because Jurassic–Early Cretaceous basic dikes have not been reported in SE Brazil, we might speculate that, during the emplacement of Group A dikes, extensional stresses were active in the region before the opening of the south Atlantic Ocean and coeval with the Karoo magmatism described in South Africa. Group B dikes yield ages compatible with those obtained for Serra Geral and Ponta Grossa magmatism in the Paraná Basin and are directly related to the breakup of western Gondwana. Alkaline magmatism is associated with several tectonic episodes that postdate the opening of the Atlantic Ocean and related to the upwelling of the Trindade plume and the generation of Tertiary basins southeast of Brazil. In the studied region, alkaline magmatism can be subdivided in two episodes: the first one represented by lamprophyre dykes of approximately 82 Ma and the second comprised of felsic alkaline stocks of approximately 70 Ma and associated dikes ranging from 64 to 59 Ma.

Resumo

Novos dados K–Ar e ⁴⁰Ar/³⁹Ar de enxames de diques toleíticos e alcalinos localizados no embasamento onshore da Bacia de Santos (SE Brasil) apontam para diferentes pulsos magmáticos ocorridos entre o Jurássico e o Terciário. Os diques de rochas toleíticas (basalto, diabásio e microgabro), são mais velhos, exibem altos teores de TiO₂ (3,65% peso na média) e podem ser subdivididos em dois grupos magmáticos. O Grupo A aflora a norte da Bacia de Resende, compreende diques orientados na direção NW, com razões (La/Yb)_N entre 15 e 32,3, e idades entre 192.9±2.2 e 160.9±1.9 Ma. O Grupo B aflora a sul e a leste da Bacia de Resende, engloba diques orientados na direção NNW e NNE, com razões (La/Yb)_N entre 7 e 16, e idades obtidas entre 148.3±3 e 133.9±0.5 Ma. As rochas alcalinas (sienito, traquito, fonolito, basalto alcalino e lamprófiro) possuem teores médios de K, e afloram como diques, plugs e stocks.. As idades obtidas são de ca. 82 Ma para os diques lamprofíricos, de ca. 70 Ma para os plugs sieníticos, e entre 64 e 59 Ma para os diques félsicos. Como estas idades Jurássicas para diques toleíticos ainda não foram descritas para a região sudeste do Brasil, pode-se especular que durante o emplacement dos diques do GrupoA o cenário tectônico indicaria esforços extensionais anteriores à abertura do Oceano atlântico Sul, e contemporânea ao derrame basáltico do Karoo na África do Sul. Já os diques do Grupo B são contemporâneos ao magmatismo Serra Geral e ao enxame de diques de Ponta Grossa, e portanto este episódio está diretamente relacionado à separação entre o Brasil e África no Cretáceo. O magmatismo alcalino está associado a diversos episódios tectônicos que sucedem à abertura do Oceano Atlântico Sul e que resultaram no desenvolvimento das Bacias terciárias do sudeste brasileiro. Está provavelmente relacionado à chegada da Pluma de Trindade e as idades obtidas para a região em estudo indicam que o magmatismo lamprofírico é mais antigo (ca. 82 Ma), seguido pelos plútons sieníticos (ca. 70 Ma) e diques associados (64 a 59 Ma.)     

Multi-Modal Monitoring of Slip Along Frictional Discontinuities

Seismic wave transmission and digital image correlation (DIC) are employed to study slip processes along frictional discontinuities. A series of biaxial compression experiments are performed on gypsum specimens with non-homogeneous contact surfaces. The specimens are composed of two blocks with perfectly mated contact surfaces with a smooth surface with low frictional strength on the upper half and a rough surface with high frictional strength on the lower half. Compressional, P, and shear, S, wave pulses were transmitted through the discontinuity while digital images of the specimen surface were acquired during the test. A distinct peak in the amplitude of transmitted wave occurs prior to the peak shear strength and is considered a “precursor” to the failure. Precursors indicate that slip initiates from the smooth surface and extends to the rough surface as the shear load is increased. From the DIC data, slip is identified as a jump in the displacement field along the fracture that initiates from the smooth surface and propagates to the rough surface. Precursors are associated with an increase in the rate of slip across the discontinuity and are a measure of the reduction in the fracture shear stiffness.     

Crystallization conditions of Los Angeles, a basaltic Martian meteorite

The texture of Los Angeles (stone 1) is dominated by relatively large (0.5−2.0 mm) anhedral to subhedral grains of pyroxene, and generally subhedral to euhedral shocked plagioclase feldspar (maskelynite). Minor phases include subhedral titanomagnetite and ilmenite, Fe-rich olivine, olivine+augite-dominated symplectites [some of which include a Si-rich phase and some which do not], pyrrhotite, phosphate(s), and an impact shock-related alkali- and silica-rich glass closely associated with anhedral to euhedral silica grains. Observations and model calculations indicate that the initial crystallization of Mg-rich pigeonitic pyroxenes at ≤1150 °C, probably concomitantly with plagioclase, was followed by pigeonitic and augitic compositions between 1100 and 1050 °C whereas between 1050 and 920 to 905 °C pyroxene of single composition crystallized. Below 920 to 905 °C, single composition Fe-rich clinopyroxene exsolved to augite and pigeonite. Initial appearance of titanomagnetite probably occurred near 990 °C and FMQ-1.5 whereas at and below 990 °C and ≥FMQ-1.5 titanomagnetite and single composition Fe-rich clinopyroxene may have started to react, producing ilmenite and olivine. However, judging from the most common titanomagnetite compositions, we infer that most of this reaction likely occurred between 950 and 900 °C at FMQ-1.0±0.2 and nearly simultaneously with pyroxene exsolution, thus producing assemblages of pigeonite, titanomagnetite, olivine, ilmenite, and augite. We deem this reaction as the most plausible explanation for the formation of the olivine+augite-dominated symplectites in Los Angeles. But we cannot preclude possible contributions to the symplectites from the shock-related alkali- and silica-rich glass or shocked plagioclase, and the breakdown of Fe-rich pigeonite compositions to olivine+augite+silica below 900 °C. Reactions between Fe-Ti oxides and silicate minerals in Los Angeles and other similar basaltic Martian meteorites can control the T-fO₂ equilibration path during cooling, which may better explain the relative differences in fO₂ among the basaltic Martian meteorites.     

Surface dynamic deformation estimates from local seismicity: the Itoiz reservoir,Spain

We analyze the ground motion time histories due to the local seismicity near the Itoiz reservoir to estimate the near-source, surface 3D displacement gradients and dynamic deformations. The seismic data were obtained by a semipermanent broadband and accelerometric network located on surface and at underground sites. The dynamic deformation field was calculated by two different methodologies: first, by the seismo-geodetic method using the data from a three-station microarray located close to the dam, and second, by single station estimates of the displacement gradients. The dynamic deformations obtained from both methods were compared and analyzed in the context of the local free-field effects. The shallow 1D velocity structure was estimated from the seismic data by modeling the body wave travel times. Time histories obtained from both methods result quite similar in the time window of body wave arrivals. The strain misfits between methods vary from 1.4 to 35.0 % and rotational misfits vary from 2.5 to 36.0 %. Amplitudes of displacement gradients vary in the range of 10^?8 to 10^?7 strains. From these results, a new scaling analysis by numerical modeling is proposed in order to estimate the peak dynamic deformations for different magnitudes, up to the expected maximum M _w in the region (M5.5). Peak dynamic deformations due to local M _w5.5 earthquakes would reach amplitudes of 10^?5 strain and 10^?3 radians at the Itoiz dam. The single station method shows to be an adequate option for the analysis of local seismicity, where few three-component stations are available. The results obtained here could help to extend the applicability of these methodologies to other sites of engineering interest.     

The effect of Congo River freshwater discharge on Eastern Equatorial Atlantic climate variability

The surface ocean explains a considerable part of the inter-annual Tropical Atlantic variability. The present work makes use of observational datasets to investigate the effect of freshwater flow on sea surface salinity (SSS) and temperature (SST) in the Gulf of Guinea. In particular, the Congo River discharges a huge amount of freshwater into the ocean, affecting SSS in the Eastern Equatorial Atlantic (EEA) and stratifying the surface layers. The hypothesis is that an excess of river runoff emphasize stratification, influencing the ocean temperature. In fact, our findings show that SSTs in the Gulf of Guinea are warmer in summers following an anomalously high Congo spring discharge. Vice versa, when the river discharges low freshwater, a cold anomaly appears in the Gulf. The response of SST is not linear: temperature anomalies are considerable and long-lasting in the event of large freshwater flow, while in dry years they are less remarkable, although still significant. An excess of freshwater seems able to form a barrier layer, which inhibits vertical mixing and the entrainment of the cold thermocline water into the surface. Other processes may contribute to SST variability, among which the net input of atmospheric freshwater falling over EEA. Likewise the case of continental runoff from Congo River, warm anomalies occur after anomalously rainy seasons and low temperatures follow dry seasons, confirming the effect of freshwater on SST. However, the two sources of freshwater anomaly are not in phase, so that it is possible to split between atypical SST following continental freshwater anomalies and rainfall anomalies. Also, variations in air-sea fluxes can produce heating and cooling of the Gulf of Guinea. Nevertheless, atypical SSTs cannot be ascribed to fluxes, since the temperature variation induced by them is not sufficient to explain the SST anomalies appearing in the Gulf after anomalous peak discharges. The interaction processes between river runoff, sea surface salinity and temperature play an effective role in the interannual variability in the EEA region. Our results add a new source of variability in the area, which was often neglected by previous studies.     

Extreme climatic events in the Amazon basin

During 2009 the Amazon basin was hit by a heavy flooding with a magnitude and duration few times observed in several decades. Torrential rain in northern and eastern Amazonia during the austral summer of 2008–2009 swelled the Amazon River and its tributaries. By July 2009, water levels of the Rio Negro, a major Amazon tributary, reached at Manaus harbor a new record, the highest mark of the last 107?years. During the 2008–2009 hydrological year, the rainy season on northern and northwestern Amazonia started prematurely, and was followed by a longer-than-normal rainy season. An anomalously southward migration of the ITCZ during May–June 2009, due to the warmer than normal surface waters in the tropical South Atlantic, was responsible for abundant rainfall in large regions of eastern Amazonia and Northeast Brazil from May to July 2009. We also compared the flood of 2009 with other major events recorded in 1989 and 1999. The hydrological consequences of this pattern were earlier than normal floods in Amazon northern tributaries, which peak discharges at their confluences with the main stem almost coincided with the peaks of southern tributaries. Since the time displacement of the contribution to the main stem of northern and southern Amazon tributaries is fundamental for damping flood waves in the main stem, the simultaneous combinations of peak discharges of tributaries resulted in an extreme flood.     

Techniques for the Eduction of Coherent Structures from Flow Measurements in the Atmospheric Boundary Layer

Two empirical methods to detect coherent motions embedded in the flow field have been compared, namely the variable interval time average (VITA) method and a wavelet-based technique, both with artificial signals as well as velocity measurements from the atmospheric boundary layer over a forest canopy. It has been found that the wavelet method is slightly better than the VITA approach in coherent structure eduction, even if the results of both techniques are comparable. Also the application of the present approach to simultaneous conditionally sampled wind data has highlighted some important features of coherent structures and gust generation in canopy flows.     

A Monte Carlo Model Of The Nocturnal Surface Temperatures In Urban Canyons

A model for the urban canyon is formulated for meteorologicalconditions of weak winds at night time. Thermal radiation, conductivity and convection are simulated by means of the Monte Carlo method. These are the main physical processesof energy transfer that give rise to the characteristic temperaturedistribution in these systems. The model has been satisfactory tested under ideal conditions for which analytical solutions exist.The predictions of the model under morerealistic conditions accurately reproduce the observationalresults. A strong temperature gradient across streets, with the canyon corners up to 4 °C warmer than the canyon centre, is found for the deepest canyons. This theoretical predictionhas been successfully verified with measurementstaken in a number of streets of the city of Granada in Spain.