The impact of solution chemistry on Mytilus edulis calcite and aragonite

Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.     

A multivariate design framework for river confluences

ABSTRACT

Throughout the last decade copula functions were widely used to assess a wide range of hydrological problems, often focusing on two distinct variables. In many of these studies it was ignored whether the two variables of interest actually occurred simultaneously (e.g. two annual maximum time series were analysed in a multivariate statistical framework). Here we introduce a novel approach to derive bivariate design events using copula functions allowing both simultaneous and non-simultaneous occurrence of the variables to be modelled. The methodology is exemplarily applied to assess the combined flood occurrence at the confluence of the rivers Rhine and Sieg (Germany). The results underline the validity of the methodology. Employing a hydrodynamic numerical model furthermore shows that commonly used statistical approaches to select a single design event out of a vast number of possible combinations can be critical for practical design purposes.

Editor Z.W. Kundzewicz; Associate editor S. Grimaldi     

The stability of the pristine magnetopause

A MHD theory of combined Kelvin-Helmholtz (KH) and Rayleigh-Taylor (RT) instabilities for a transition layer with two different scale lengths (Δ and δ for the variation of velocity/magnetic fields and density, respectively) is presented. The study is motivated by reports of magnetopauses with no low latitude boundary layer, in which a sharp density drop over a distance δ?Δ is observed (“pristine” magnetopauses (J. Geophys. Res. 101 (1996) 49). The theory ignores compressibility effects and applies to subsonic regions of the dayside magnetopause. The RT effect is included to account for temporary periods of acceleration of the magnetopause, caused by sudden changes of the solar wind dynamic pressure. For small wavelengths λ, such that δ?λ?Δ, a WKB solution shows that the velocity gradient operates, together with magnetic tensions, to attenuate or even stabilize the Rayleigh-Taylor instability within a certain wavelength range. An exact dispersion relation for flute modes, valid for all λ, in the form of a fourth order polynomial for the complex frequency ω, is obtained from a model with a constant velocity gradient, dV/dy within Δ, and with δ→0. Flute modes are possible because of the existence of bands of very small magnetic shear on the dayside magnetopause (J. Geophys. Res. 103 (1998) 6703). The exact solution allows for a study of the change of the action of the velocity gradient with λ from the long-λ range where dV/dy is KH destabilizing to the short-λ range where dV/dy produces a stabilizing effect. Both, the WKB approximation and the well known tangential discontinuity model (Δ→0) are recovered as limiting cases of the exact solution. Properties of the KH and RT instabilities, for different density ratios on either side of the magnetopause, are described. For flute modes, at very small λ the RT instability grows faster and becomes the dominant effect. However, it is shown that the growth rate remains bounded at a finite value as λ→0, when a theory with a finite δ model is considered. To study configurations with finite, arbitrary, δ/Δ ratios, the MHD perturbation equations are solved numerically, using hyperbolic tangent functions for both the density and velocity transitions across the magnetopause. To examine the influence of different δ/Δ ratios on the growth rates of KH and RT, calculations are performed for different δ/Δ, with and without acceleration, and for two different density ratios. It is found that the general features exhibited by the constant dV/dy model, are confirmed by these numerical solutions. The stability of pristine magnetopauses, and the possibility of observing some theoretical predictions during magnetopause crossings in ongoing missions, are discussed.     

Remediation of coal-mine drainage by a sulfate-reducing bioreactor: A case study from the Illinois coal basin,USA

This study reports changes in coal-mine drainage constituent concentrations through an anaerobic SO₄-reducing bioreactor monitored over a 3-a period. The purpose of the study was to identify and monitor over time the biogeochemical mechanisms that control the attenuation of toxic compounds in the mine drainage. This information is needed to investigate bioreactor performance and longevity. The water treated at the case example site, the Tab-Simco Mine, was highly acidic with an average pH of 2.9, a net acidity of 1674 mg/L CaCO₃ equivalent-CCE, and high levels of dissolved ${\text{SO}}_4^{2-}$, Al, Fe and Mn. The results of this study indicated that the treatment system increased the pH of the acid mine drainage (AMD) to 6.2 and decreased the median acidity to 22.7 mg/L CCE, ${\text{SO}}_4^{2-}$ from 2981 to 1750 mg/L, Fe from 450.6 to 1.76 mg/L, Al from 113 to 0.42 mg/L, and Mn from 36.4 to 23.3 mg/L. Geochemical modeling indicates that the bioreactor discharge is saturated with respect to the minerals alunite, gibbsite, siderite, rhodochrosite, jarosite, and Fe hydroxide precipitates. The observed trends also include seasonal variations in ${\text{SO}}_4^{2-}$ reduction and a general decline in the amount of alkalinity produced. The average δ³⁴S value of the ${\text{SO}}_4^{2-}$ in the untreated AMD was +7.3‰. In the bioreactor, δ³⁴S value of ${\text{SO}}_4^{2-}$ increased from an average of +6.9‰ to +9.2‰, suggesting the presence of bacterial SO₄ reduction processes. Preliminary results of a bacterial community analysis show that DNA sequences corresponding to bacteria capable of SO₄ reduction were present in the bioreactor outflow sample. However, these sequences were outnumbered by sequences similar to bacteria capable of reoxdizing reduced sulfur species. This study illustrates the dynamic nature of metal removal in SO₄-reducing bioreactor-based treatment systems.