A study on the dissolution rates of K-Cr(VI)-jarosites: kinetic analysis and implications

Background

The presence of natural and industrial jarosite type-compounds in the environment could have important implications in the mobility of potentially toxic elements such as lead, mercury, arsenic, chromium, among others. Understanding the dissolution reactions of jarosite-type compounds is notably important for an environmental assessment (for water and soil), since some of these elements could either return to the environment or work as temporary deposits of these species, thus would reduce their immediate environmental impact.

Results

This work reports the effects of temperature, pH, particle diameter and Cr(VI) content on the initial dissolution rates of K-Cr(VI)-jarosites (KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆). Temperature (T) was the variable with the strongest effect, followed by pH in acid/alkaline medium (H₃O⁺/OH^?). It was found that the substitution of CrO₄ ^2?in Y-site and the substitution of H₃O⁺ in M-site do not modify the dissolution rates. The model that describes the dissolution process is the unreacted core kinetic model, with the chemical reaction on the unreacted core surface. The dissolution in acid medium was congruent, while in alkaline media was incongruent. In both reaction media, there is a release of K⁺, SO₄ ^2? and CrO₄ ^2? from the KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ structure, although the latter is rapidly absorbed by the solid residues of Fe(OH)₃ in alkaline medium dissolutions. The dissolution of KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ exhibited good stability in a wide range of pH and T conditions corresponding to the calculated parameters of reaction order n, activation energy E _A and dissolution rate constants for each kinetic stages of induction and progressive conversion.

Conclusions

The kinetic analysis related to the reaction orders and calculated activation energies confirmed that extreme pH and T conditions are necessary to obtain considerably high dissolution rates. Extreme pH conditions (acidic or alkaline) cause the preferential release of K⁺, SO₄ ^2? and CrO₄ ^2? from the KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆ structure, although CrO₄ ^2? is quickly adsorbed by Fe(OH)₃ solid residues. The precipitation of phases such as KFe₃[(SO₄)_2 ? X(CrO₄)_X](OH)₆, and the absorption of Cr(VI) after dissolution can play an important role as retention mechanisms of Cr(VI) in nature.

     

Reproductive ecology of the seabob shrimp <Emphasis Type="Italic">Xiphopenaeus kroyeri</Emphasis> (Heller, 1862) in a coastal area of Southern Brazil

The predictability of certain environmental factors that affect the life cycle of the seabob shrimp Xiphopenaeus kroyeri (Heller, 1862) was evaluated in a study of its reproductive biology in an area adjacent to Babitonga Bay, State of Santa Catarina, Brazil. Monthly sampling was conducted from July 2010 through June 2011 at depths of 5, 8, 11, 14, and 17 m. 76 004 individuals were obtained, with a pronounced peak in absolute abundance in austral autumn (34 208), coinciding with the annual closed season from March to May. Grain size composition of the sediment showed the closest relationship to the distribution of individuals (multiple linear regression, P <0.05), related to their burying habit. The observed correlations between the abundance of reproductive males (bearing spermatophores) and females with spent gonads (cross-correlation, P <0.05), and between reproductive males and reproductive females (with a 1-month lag) suggest that the peak of reproductive males preceded the peak of female ones. This result agrees with the pattern expected for females, which copulate in post-ecdysis (spent gonads). Spawning seemed to take place at greater depths, as evidenced by the concentration of reproductive females in these areas. The reproductive activities observed here confirm that this species follows a tropical/subtropical reproductive pattern, spawning continuously throughout the year, with the highest peaks in spring and autumn. The data indicate that the juvenile recruitment period observed in August-September resulted from the reproductive output noted in April–May. Additionally, the reproductive period recorded in November led to the juvenile peak observed in March–May.     

Lateral terrestrial water flow contribution to summer precipitation at continental scale – A comparison between Europe and West Africa with WRF-Hydro-tag ensembles

It is well accepted that summer precipitation can be altered by soil moisture condition. Coupled land surface – atmospheric models have been routinely used to quantify soil moisture – precipitation feedback processes. However, most of the land surface models (LSMs) assume a vertical soil water transport and neglect lateral terrestrial water flow at the surface and in the subsurface, which potentially reduces the realism of the simulated soil moisture – precipitation feedback. In this study, the contribution of lateral terrestrial water flow to summer precipitation is assessed in two different climatic regions, Europe and West Africa, for the period June–September 2008. A version of the coupled atmospheric-hydrological model WRF-Hydro with an option to tag and trace land surface evaporation in the modelled atmosphere, named WRF-Hydro-tag, is employed. An ensemble of 30 simulations with terrestrial routing and 30 simulations without terrestrial routing is generated with random realizations of turbulent energy with the stochastic kinetic energy backscatter scheme, for both Europe and West Africa. The ensemble size allows to extract random noise from continental-scale averaged modelled precipitation. It is found that lateral terrestrial water flow increases the relative contribution of land surface evaporation to precipitation by 3.6% in Europe and 5.6% in West Africa, which enhances a positive soil moisture – precipitation feedback and generates more uncertainty in modelled precipitation, as diagnosed by a slight increase in normalized ensemble spread. This study demonstrates the small but non-negligible contribution of lateral terrestrial water flow to precipitation at continental scale.     

Fluvial carbon export and CO2 efflux in representative nested headwater catchments of the eastern La Plata River Basin

This study involved a baseline evaluation of fluvial carbon export and degas rates in three nested rural catchments (1 to 80 km²) in Taboão, a representative experimental catchment of the Upper Uruguay River Basin. Analyses of the carbon content in stream waters and the catchment carbon yield were based on 4‐year monthly in situ data and statistical modeling using the United States Geological Survey load estimator model. We also estimated p CO₂ and degas fluxes using carbonate equilibrium and gas‐exchange formulas. Our results indicated that the water was consistently p CO₂ saturated (~90% of the cases) and that the steep terrain favors high gas evasion rates. The mean calculated fluvial export was 5.4 tC·km^?2·year^?1 with inorganic carbon dominating (dissolved inorganic carbon:dissolved organic carbon ratio >4), and degas rates (~40 tC km^?2·year^?1) were nearly sevenfold higher than the downstream export. The homogeneous land use in this nested catchment system results in similar water‐quality characteristics, and therefore, export rates are expected to be closely related to the rainfall–runoff relationships at each scale. Although the sampling campaigns did not fully reproduce storm‐event conditions and related effects such as flushing or dilution of in‐stream carbon, our results indicated a potential link between dissolved inorganic carbon and slower hydrological pathways related to subsurface water storage and movement.