Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.     

Tree-Ring δD as an Indicator of Asian Monsoon Intensity

Oxygen and hydrogen isotopic compositions of meteoric water are known to correlate with surface air temperature, except in tropical areas. This relationship has been described using a number of terms corresponding to specific observations, such as latitude, altitude and seasonal effects. However, these temperature effects do not seem to apply to precipitation in monsoonal areas of Asia. Questions have been raised as to whether the isotopic composition of meteoric water can be used to reconstruct paleomonsoon intensity. Tree rings of two modern spruce trees (Picea meyeri) and a 10,000-yr-old timber (Picea jezoensis) were analyzed for hydrogen isotopic composition. On average, the older tree is depleted in deuterium by 45‰ compared to the modern trees. We attribute this isotopic depletion to the strength of summer monsoons, which were more intense in the early Holocene than at present. Although this study is not definitive, it suggests that paleomonsoon intensity can be reconstructed by direct or proxy methods that yield the oxygen or hydrogen isotopic composition of meteoric water.     

Characterization of Quaternary faults by electric resistivity tomography in the Andean Precordillera of Western Argentina

El río San Juan, situado en la Provincia de San Juan (Argentina) cruza la Precordillera y otras unidades geológicas incluyendo la Depresión de Ullum y la Zona de La Laja, entre las latitudes 31°S y 32°S. El curso del río tiene un cierto caracter antecedente como puede deducirse por sus dos trazas perpendiculares unidas por otra casi paralela a las alineaciones estructurales principales. En la zona de la Precordillera, el valle del río San Juan muestra numerosos abanicos aluviales, situados en las zonas de confluencia entre el río principal y sus tributarios. Las superficies de los abanicos aluviales cuaternarios estan cortadas por una serie de escalones que consideramos como terrazas aluviales generadas por episodios repetitivos de agradación y degradación. El sector estudiado incluye una zona con una importante actividad sísmica reciente(La Laja), otra sin una importante actividad sísmica reciente (Precordillera), y una zona subsidente (Ullum) donde se formó un gran lago natural hace unos 6500 años. El antiguo río San Juan fue capturado por el valle de la Quebrada de Ullum mediante una incisión del orden de 25 m, que implicó una nueva adecuación del gradiente del río mediante los efectos de la erosión remontante. El gradiente del río San Juan muestra algunas irregularidades que, aunque no se presenten relacionadas directamente con las estructuras principales, estan relacionadas con la propia dinámica fluvial que acentúa la diferenciación litológica. La anchura del valle del río principal, la geometria y el gradiente de cada tributario, junto a las litologias del basamento y a las dimensiones de cada area fuente local, son los factores principales que controlan los procesos de la generación de las terrazas aluviales. En la zona de La Laja, donde la terraza mas alta soporta un nivel de travertino, la datación de los depósitos travertínicos proporciona datos como para suponer una tasa de incisión del orden de 0,9–1 mm/año, asociada a la actuación periódica de la falla de La Laja.

Comment and reply regarding Changyou Zhang (1995) A general formula and its inverse formula for gravimetric transformation by use of convolution and deconvolution techniques.

The incorrectness in the derivations of error formula (52) in Zhang's paper is pointed out and the correction is given. Table 3 [list of error formulae of Eqs (5)–(8)] in Zhang's paper is also corrected. Received: 25 February 1998 / Accepted: 30 June 1998     

Crustal structure beneath Spain from deep seismic sounding experiments

Major tectonic units of Spain have been investigated by deep seismic sounding experiments since 1974 to determine crustal structures and to delineate their differences. These areas are the central part of the Hercynian Meseta, and the Alpine chains: the Betic Cordillera in the south, including the Balearic promontory and the Alboran Sea, and the Pyrenees in the north.The main features of the crust and the upper mantle along a NNE-SSW cross-section from the Pyrenees to the Alboran Sea are described.The crust under the Meseta is typical of Hercynian areas found elsewhere in Europe, with an average thickness of 31 km, whereas the two Alpine regions are characterized by very large lateral inhomogeneities, such as rapid thickening of the crust to 50 and 40 km under the Pyrenees and the Betics, respectively. The deep-reaching E-W-trending North Pyrenean fault has a throw of 10–15 km at the base of the crust. A P_n velocity of 8.1 km s^?1 is found under the entire Iberian Peninsula.In the Alboran Sea, strongly varying thicknesses of sediments, shallow variable depths to the Moho (～ 13 km under the Alboran ridge), and strong variations of P_n velocity between 7.5 and 8.2 km s^?1 have been found.     

Seasonal variability of surface and internal M<Subscript>2</Subscript> tides in the Arctic Ocean

The modeling results of surface and internal M₂ tides for summer and winter periods in the Arctic Ocean (AO) are presented. We employed a modified version of the three-dimensional finite-element hydrothermodynamic model QUODDY-4 differing from the original model by using a rotated (instead of spherical) coordinate system and by considering the equilibrium-tide effects. It has been shown that the modeling results for the surface tide differs little from the results obtained earlier by other authors. According to these results, the amplitudes of internal tidal waves (ITWs) in the AO are significantly lower than in other oceans and the ITWs proper have the character of trapped waves. Their source of generation is located at the continental slope northwest of the New Siberian Islands. Our results are consistent with the fields of average (over a tidal cycle) and integral (by depth) densities of baroclinic tidal energy, the maximum baroclinic tidal velocity, and the coefficient of diapycnic mixing. The local rate of baroclinic tidal energy dissipation at the AO ridges increases as it approaches the bottom, as was observed on Mid-Atlantic and Hawaii ridges (but merely within the bottom boundary layer) and is two to three orders of magnitude lower than in other oceans. The ITW degeneration scale in the AO is several hundreds of kilometers in summer and winter, remaining within the range of its values between 100 and 1000 km in mid- and low-latitude oceans. In both seasons, the integral (over the AO area) rate of baroclinic tidal energy dissipation is two orders of magnitude lower than the global estimate (2.5 × 10¹² W).     

Global high resolution versus Limited Area Model climate change projections over Europe: quantifying confidence level from PRUDENCE results

Four high resolution atmospheric general circulation models (GCMs) have been integrated with the standard forcings of the PRUDENCE experiment: IPCC-SRES A2 radiative forcing and Hadley Centre sea surface temperature and sea-ice extent. The response over Europe, calculated as the difference between the 2071–2100 and the 1961–1990 means is compared with the same diagnostic obtained with nine Regional Climate Models (RCM) all driven by the Hadley Centre atmospheric GCM. The seasonal mean response for 2m temperature and precipitation is investigated. For temperature, GCMs and RCMs behave similarly, except that GCMs exhibit a larger spread. However, during summer, the spread of the RCMs—in particular in terms of precipitation—is larger than that of the GCMs. This indicates that the European summer climate is strongly controlled by parameterized physics and/or high-resolution processes. The temperature response is larger than the systematic error. The situation is different for precipitation. The model bias is twice as large as the climate response. The confidence in PRUDENCE results comes from the fact that the models have a similar response to the IPCC-SRES A2 forcing, whereas their systematic errors are more spread. In addition, GCM precipitation response is slightly but significantly different from that of the RCMs.     

Estimating the influence of filtering during the operation of the Pauzhetka and Mutnovskii high-temperature geothermal fields,Kamchatka, Russia

It is shown that the productive reservoir received considerable quantities of meteoric water during the operation of the Pauzhetka geothermal field (1960–2007), which amounted to 30% of the total with-drawal of heat carrier. This led to cooling of the productive reservoir and reduced steam extraction. Modeling the operation process with the infiltration zones sealed shows that steam extraction can be enhanced by 23.2%. Multi-option modeling for the operation of the Dachnyi site of the Mutnovskii geothermal field shows that the most-likely scenario is infiltration of meteoric water with a discharge of about 60 kg/s into the productive reservoir from above. These results are consistent with the decrease in the steam concentration during the first 4 years of operation.