ALBERT

Description: The release of exchangeable Mg in marine sediments from displacement by ammonium ions was estimated by way of experimentally determining the parameters that govern this ion-exchange equilibrium on solid geochemical phases: smectite, humic acid, illite and opal. We showed that: (a) both the conditional selectivity constant as well as the solid concentration are important parameters in determining the relative contribution of ammonium-exchangeable Mg from smectite, organic matter, illite and opal; and (b) that, except in the cases where opal or organic matter concentrations are very high, the clays are the dominant carrier phases for labile Mg which is exchangeable by ammonium. A model, based on the sum of the contributions from the major geochemical phases present in the sediment reliably predicts the amount of Mg released by exchange with ammonium in marine sediments.

Description: A radiotracer technique, employing 27Mg, is used to determine the Mg released by ammonium exchange on undis-solved humic acid in a seawater medium. This new method allows for the measurement of exchangeable Mg on the solid phase surface, which eliminates the problem caused by the high-Mg background in the seawater matrix. The precision calculated from the counting statistics is better than ±2%; the reproducibility among repeated counts ranged from ±1% to ±3%. The higher sensitivity of the method allows for monitoring the MgNH4 exchange at concentrations as low as 30 mM NH4. This is a major improvement relative to the data obtained with the analytical methods used so far, which allow detection of exchangeable Mg only at NH4 concentrations higher than 1 M. The lower experimental concentrations are more in accordance with the natural ammonium levels found in anoxic marine sediments. For the undissolved humic acid used in this experiment, the amount of exchangeable Mg in apparent equilibrium with an ammonium-free seawater matrix was found to be 96.6 ± 0.4 meq/100g. The Mg-NH4 exchange on humic acid in seawater comes to a steady-state value in 〈 18 min. The conditional equilibrium constant obtained for this reaction, Kcond = 0.039 ± 0.001 M−1. The technique can be expanded to other geochemical solid phases in seawater and it can be modified to study the behavior of the major cations by using 24Na, 42K and 49Ca.

Description: The observed distribution of dissolved magnesium in the pore water of rapidly accumulating sediments shows significant deviations from the seawater value. We have shown that deviations during early diagenesis can be explained by reactions occurring at the surface of sediment particles. In anoxic pore water environments with high levels of dissolved total carbon dioxide the formation of Mg+2·CO3−2 complexes significantly reduces the concentration of the free Mg+2 ion. This decrease in the Mg+2 activity results in desorption of magnesium from the solid surfaces due to the re-equilibration of the adsorbed Mg+2 with the dissolved species. The effect of increasing carbonate complexation of Mg+2 in anoxic environments is initially compensated by the loss of sulfate, which is also a strong Mg+2 ligand. Therefore, significant changes in free Mg+2 concentration and thus in the magnesium desorption from solid surfaces by ligand competition for Mg+2 are more pronounced in sulfate-depleted systems undergoing methanogenesis. Such conditions are characteristic of most continental margin sediments. Another consequence of the decomposition of organic matter in hemipelagic sediments is the accumulation of high levels of ammonium ions which also displace Mg+2 from sediment-particle surfaces by ion exchange. These equilibria in the pore water-sediment systems can be described by empirical parameters, which were experimentally obtained. A computer model was used to determine the equilibrium conditions for solid-solution reactions as a function of changes in the pore-water composition in organicrich hemipelagic environments. This model includes complex formation, competition for Mg+2 between dissolved ligands and exchange sites and Mg+2NH+4 exchange reactions. The relative proportion of desorbed and displaced Mg+2 from the solid surface depends on the characteristics of the sediment and on the ΣCO2:NH+4 regenerative ratio in the pore waters. In sediments from Bransfield Strait, the Gulf of California, and the Peru margin, both release mechanisms for Mg+2—ligand competition and ion exchange with ammonium—were evaluated as part of the complex reaction system in order to explain the observed maxima in the dissolved magnesium profiles. Overlying the Mg+2 maxima, the Bransfield Strait and Gulf of California pore waters show minima in the dissolved magnesium concentration, concurrent with a measured increase in the cation exchange capacity (CEC) of the sediments. By including the observed CEC changes in the multi-component model we show that the negative anomaly in the dissolved Mg+2 profiles is a consequence of changes in the CEC of sediments during the very early stages of anoxic diagenesis.