Fluxes of high- versus low-temperature water-rock interactions in aerial volcanic areas: Example from the Kamchatka Peninsula, Russia

Volcanic areas play a key role in the input of elements into the ocean and in the regulation of the geological carbon cycle. The aim of this study is to investigate the budget of silicate weathering in an active volcanic area. We compared the fluxes of the two major weathering regimes occurring at low temperature in soils and at high temperature in the active volcanic arc of Kamchatka, respectively. The volcanic activity, by inducing geothermal circulation and releasing gases to the surface, produces extreme conditions in which intense water-rock interactions occur and may have a strong impact on the weathering budgets. Our results show that the chemical composition of the Kamchatka river water is controlled by surface low-temperature weathering, atmospheric input and, in some limited cases, strongly imprinted by high-temperature water-rock reactions. We have determined the contribution of each source and calculated the rates of CO₂ consumption and chemical weathering resulting from low and high-temperature water/rock interactions. The weathering rates (between 7 and 13.7 t/km²/yr for cations only) and atmospheric CO₂ consumption rates (∼0.33-0.46 × 10⁶ mol/km²/yr for Kamchatka River) due to rock weathering in soils (low-temperature) are entirely consistent with the previously published global weathering laws relating weathering rates of basalts with runoff and temperature. In the Kamchatka River, CO₂ consumption derived from hydrothermal activity represents about 11% of the total HCO₃ flux exported by the river. The high-temperature weathering process explains 25% of the total cationic weathering rate in the Kamchatka River. Although in the rivers non-affected by hydrothermal activity, the main weathering agent is carbonic acid (reflected in the abundance of in rivers), in the region most impacted by hydrothermalism, the protons responsible for minerals dissolution are provided not only by carbonic acid, but also by sulphuric and hydrochloric acid. A clear increase of weathering rates in rivers impacted by sulphuric acid can be observed. In the Kamchatka River, 19% of cations are released by hydrothermal acids or the oxidative weathering of sulphur minerals.Our results emphasise the important impact of both low and high-temperature weathering of volcanic rocks on global weathering fluxes to the ocean. Our results also show that besides carbonic acid derived from atmospheric CO₂, hydrochloric acid and especially sulphuric acid are important weathering agents. Clearly, sulphuric acid, with hydrothermal activity, are key parameters that cause first-order increases of the chemical weathering rates in volcanic areas. In these areas, accurate determination of weathering budgets in volcanic area will require to better quantify sulphuric acid impact.     

In situ adsorption of mercury,methylmercury and other elements by iron oxyhydroxides and organic matter in lake sediments

Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (K_Fe–M) and anionic (K_Fe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of K_Fe–M and K_Fe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (K_POM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of K_POM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.     

Measuring Venus’ winds using the Absolute Astronomical Accelerometer: Solid super-rotation model of Venus’ clouds

We present a new method of measuring the Venus winds by Doppler velocimetry on the full visible spectrum of solar light scattered by the clouds. In January 2003, we carried out observations to measure the winds of Venus, using the EMILIE high-resolution, cross-dispersed spectrograph and its associated calibrating instrument the Absolute Astronomical Accelerometer (AAA), at Observatoire de Haute-Provence, France. The motivation of this type of measurements is that it measures the actual velocity of cloud particles, while the other method (track of cloud features) may be sensitive to the deformation of the clouds. During observations, Venus was near maximum western elongation, at a phase angle near 90°. The EMILIE-AAA system allows us to measure accurately the Doppler shift induced in the reflected solar spectrum by the radial component of the motion of the clouds of Venus. We present the measurements and compare them with a forward simulation of a solid super-rotation of the atmosphere of Venus. Taking into account the Doppler shift relative to the Sun and that relative to the Earth, the theoretical total Doppler shift induced in the solar spectra is easily computed as a function of the velocity of the reflecting target. A first forward simulation is computed, with a wind model considering a purely horizontal and zonal wind. The magnitude of the wind is assumed to depend on cos(latitude), as for a solid-body rotation. The comparison with the measurements at various points on the illuminated semi-disc allowed us to determine an equatorial velocity of 66, 75, 91 and 85 m/s on 4 consecutive mornings, consistent with previous ultraviolet cloud tracking wind measurements, showing that wave propagation is not a major factor in the apparent motion of the cloud marks. Further, we discuss the effect of the finite angular size of the Sun and its rapid equatorial rotation (that we call the Young effect). It mainly affects measurements taken near the terminator, where the largest discrepancies are found. These discrepancies are alleviated when the Young effect is taken into account in the model but then the retrieved Venus equatorial velocity is reduced to only 48±3 m/s. This is well below classical ultraviolet markings velocities, but the altitude at which the visible photons are scattered (66 km) that we use is 5 km below the UV markings, confirming the vertical gradient of the horizontal winds shown by previous in-situ measurements.     

Unique episodic groundwater recharge event in a South American sedimentary aquifer and its long-term impact on baseflow

The anomalous entrance of water into groundwater systems can affect storage throughout long periods and normally relies on infrequent and irregular pulses of groundwater recharge defined by the term episodic recharge. Recently there was a groundwater recharge of large magnitude with unknown circumstances in the Caiuá aquifer. This unique event was explored in detail here and allowed to better understand the occurrence of such events in humid subtropical climates in South America. For this study, groundwater monitoring daily data from the Integrated Groundwater Monitoring Network was used combined with a specific yield obtained from geophysical wireline logging to obtain groundwater recharge rates. To improve the investigation, we also used a baseflow separation method to obtain the groundwater contribution into local rivers. The groundwater storage variations were also assessed by remote sensing with the GRACE data. Results showed the importance of high soil moisture storage on the occurrence of large episodic recharge events. We estimated that the groundwater recharger volumes derived from 1 year that included the unique episodic recharge observed (total of 866 mm for April 2015–March 2016) were comparable with the sum of 7 years of groundwater recharge (total of 867 mm). Atypical rainfall in winter periods were responsible for the increase in soil moisture that explained that unique event. GRACE-based GWS showed concordance detecting the occurrence of the unique episodic recharge. However, the variation in terms of volumes obtained by GRACE does not represent the behaviour observed in the aquifer by the WTF method. The results also indicated that changes in aquifer storage caused by episodic recharge events directly affect low flows in rivers over long periods. The main knowledge gap addressed here relates to exploring a unique episodic recharge event quite rare to observe with its long-term impacts on hydroclimatic variability over a humid subtropical portion of the Caiuá aquifer.     

Eutrophication and hypoxia in four streams discharging in Guanabara Bay, RJ, Brazil, a case study

Four streams in the city of São Gonçalo, were sampled to evaluate their potential as sources of nutrients to Guanabara Bay aiming to contribute with the government program to decrease the levels of pollution in this area. Imbuaçu, Guaxindiba, Marimbondo and Brandoas streams were sampled in 2007, 2008 and 2009. The streams revealed to be hipereutrophic with severe limitation of primary production by nitrogen, as shown by the N/P molar ratio. Phosphate levels were abnormally high varying between 4.35 and 130.82 μM, whereas nitrate and nitrite ranged from 0.06 to 54.05 μM and from 0.28 to 19.23 μM, respectively. The streams also presented severe hypoxia and anoxia, with oxygen values varying from non-detected to 3.72 ml l⁻¹. Heavy loads of particulate suspended material were recorded in the studied streams, ranging between 6.00 and 400.00 mg l⁻¹. The streams were considered inexorable sources of nutrients, enhancing the severe eutrophication process in Guanabara Bay.     

Characterizing the Navidad current interannual variability using coastal altimetry

In this study, the Navidad current, which flows along the northern coast of Spain in winter, is observed and characterized using coastal altimetry data over the period 1992–2002. This coastal current, marked by a strong interannual variability, is associated with eastward transport of warm waters along the shelf slope. Specific data editing and processing strategies have been applied to the along-track altimeter data, which allows us to retrieve altimetric sea level anomalies closer to the coast, with a better spatial coverage and improved quality when compared with standard altimetric products. The current variability observed upstream by in situ time series after November 1996 is well reproduced by the satellite across-track surface geostrophic current anomalies up until September 1999; this agreement degrades later in time. The combined use of satellite-derived current anomalies and sea-surface temperature anomalies allows us to develop indices of Navidad occurrences, in the first long-term, systematic survey of that current based on a multi-sensor approach. The satellite analyses confirm the previously identified Navidad occurrences in winter of 1995–1996, 1997–1998, and 2000–2001. Furthermore, a weak Navidad event was identified in winter 1996–1997. These four winters are associated with a negative North Atlantic Oscillation index in the previous fall, but the intensity of the Navidad is not correlated to the amplitude of that index.     

An experimental approach to investigate mercury species transformations under redox oscillations in coastal sediments

This work describes a laboratory experiment designed to unravel mercury species reactivity in superficial coastal sediments oscillating between oxic and anoxic conditions. The experimental set-up has been applied to a sediment slurry from the Arcachon Bay (France) to follow the evolution of both naturally occurring (i.e. endogenous) and isotopically enriched added mercury species (i.e. exogenous, 1??IHg and 2?1MMHg) at environmental levels. The transformation and partition between the different phases (aqueous, solid and gaseous) of the endogenous and exogenous mercury species (inorganic Hg (IHg), monomethyl Hg (MMHg), elemental Hg (Hg?) and dimethyl Hg (DMHg)) have been investigated by isotopic speciation methods throughout the experiment. The results demonstrate that the experimental approach is able to promote sediment redox oscillations and to simultaneously follow the biogeochemical fate of naturally occurring or added mercury species. Experimentally driven redox transition events were found to significantly enhance the aqueous Hg species concentrations, while the MMHg burden is not greatly affected. Indeed, during the anoxic-oxic transition, while aqueous endogenous IHg and MMHg exhibited a two-fold increase, aqueous exogenous IHg and MMHg increased 7 and 4 times, respectively. Transient increases of the net IHg methylation were recorded during the redox transitions with the largest increase of the MMHg contents (factor 1.8) observed during the oxic-anoxic transition. High resolution in situ redox experiments have not been performed up to now, therefore the developed experimental set-up provides novel insights in both the influence of redox conditions on Hg methylation/demethylation and adsorption/desorption processes and kinetics in superficial sediments.     

The use of natural and archeological analogues for understanding the long-term behavior of nuclear glasses

The knowledge of the long-term behavior of nuclear waste in anticipation of ultimate disposal in a deep geological formation is of prime importance in a waste management strategy. If phenomenological models have been developed to predict the long-term behavior of these materials, validating these models remains a challenge, when considering the time scale of radioactive decay of radionuclides of environmental concern, typically 10⁴–10⁵ yrs. Here we show how natural or archaeological analogues provide critical constraints not only on the phenomenology of glass alteration and the mechanisms involved, but also on the ability of experimental short-term data to predict long-term alteration in complex environments.