Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3 h) and low concentrations of phosphate (?50 μM). Sorption of phosphate on calcite was studied in 11 different calcite-equilibrated solutions that varied in pH, P_CO2, ionic strength and activity of Ca²⁺, and . Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2-3 h while desorption is complete in less than 0.5 h. The reversibility of the sorption process indicates that phosphate is not incorporated into the calcite crystal lattice under our experimental conditions. Precipitation of phosphate-containing phases does not seem to take place in systems with ?50 μM total phosphate, in spite of a high degree of super-saturation with respect to hydroxyapatite (SI_HAP ? 7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the activity decreases (at constant pH) and as pH increases (at constant activity). The primary effect of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO₄Ca⁰ and either >CaHPO₄Ca⁺ or > as the adsorbed surface species. Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms.     

Geochemical processes and solute transport at the seawater/freshwater interface of a sandy aquifer

Geochemical processes occurring at a seawater/freshwater interface were studied in a shallow coastal siliclastic aquifer containing minor amounts of calcite. Data were collected from 106 piezometers in a 120-m transect from the coastline and landward. In the first 40 m from the coastline, a wedge of saltwater is intruding below the freshwater aquifer. The aquifer is strongly reduced with mineralization of organic matter by methanogenesis in the freshwater aquifer, and sulfate reduction dominating in the most seaward part of the saline aquifer. The spatial separation of cations in the aquifer indicated a slow freshening process where Ca²⁺ from freshwater displaced the marine cations Na⁺ and Mg²⁺ from the exchanger complex. The resulting loss of Ca²⁺ from solution decreases the saturation state for calcite and possibly causes calcite dissolution. A storm-flooding event was recorded where pulses of dense seawater sank through the fresh aquifer. As a result, the terminal electron accepting process switched from methanogenesis to sulfate reduction. The pulses of sinking seawater also triggered cation exchange reactions where Ca²⁺ was expelled from the exchanger by seawater Na⁺ and Mg²⁺. The released Ca²⁺ is being flushed from the aquifer by groundwater flow, and this export of Ca²⁺ will, in the long term, cause decalcification of the sediment. The water composition in the aquifer is in a transient state as the result of various processes that operate on different timescales. Oxidation of organic matter occurs continuously but at a rate decreasing on a geological time scale. The freshening of the aquifer operates on the timescale of a few years. The episodic flooding and sinking of seawater through the aquifer proceeds in the course of days to weeks, but occurs irregularly with years in between.     

Fluvial response to sea-level changes: a quantitative analogue, experimental approach

ABSTRACT Quantitative evaluation of fluvial response to allogenic controls is crucial for further progress in understanding the stratigraphic record in terms of processes that control landscape evolution. For instance, without quantitative insight into time lags that are known to exist between sea‐level change and fluvial response, there is no way to relate fluvial stratigraphy to the sea‐level curve. It is difficult to put firm constraints on these time‐lag relationships on the basis of empirical studies. Therefore, we have started to quantify time‐averaged erosion and deposition in the fluvial and offshore realms in response to sea‐level change by means of analogue modelling in a 4 × 8‐m flume tank. The rate of sea‐level change was chosen as an independent variable, with other factors such as sediment supply, discharge and initial geometry kept constant over the course of 18 experiments. Our experimental results support the common view that neither fall nor rise in sea level affects the upstream fluvial system instantaneously. An important cause for the delayed fluvial response is that a certain amount of time is required to connect initial incisions on the newly emergent shelf (canyons) with the fluvial valley. Lowering of the fluvial longitudinal profile starts only after the connection of an active shelf canyon with the fluvial valley; until that moment the profile remains steady. We quantified the process of connection and introduced the quantity ‘connection rate’. It controlled, in conjunction with the rate of sea‐level fall: (1) the amount of fluvial degradation during sea‐level fall; (2) the total sediment volume that bypasses the shelf edge; (3) the percentage of fluvial relative to shelf sediment in the lowstand delta; (4) the volume of the transgressive systems tract and (5) the amount of diachroneity along the sequence boundary. Our experiments demonstrate also that the sequence‐stratigraphic concept is difficult to apply to continental successions, even when these successions have been deposited within the influence of sea level.     

The reactivity of iron oxides towards reductive dissolution with ascorbic acid in a shallow sandy aquifer (Rømø, Denmark)

The pool of iron oxides, available in sediments for reductive dissolution, is usually estimated by wet chemical extraction methods. Such methods are basically empirically defined and calibrated against various synthetic iron oxides. However, in natural sediments, iron oxides are present as part of a complex mixture of iron oxides with variable crystallinity, clays and organics etc. Such a mixture is more accurately described by a reactive continuum covering a range from highly reactive iron oxides to non-reactive iron oxide. The reactivity of the pool of iron oxides in sediment can be determined by reductive dissolution in 10 mM ascorbic acid at pH 3. Parallel dissolution experiments in HCl at pH 3 reveal the release of Fe(II) by proton assisted dissolution. The difference in Fe(II)-release between the two experiments is attributed to reductive dissolution of iron oxides and can be quantified using the rate equation J/m₀ = k′(m/m₀)^γ, where J is the overall rate of dissolution (mol s⁻¹), m₀ the initial amount of iron oxide, k′ a rate constant (s⁻¹), m/m₀ the proportion of undissolved mineral and γ a parameter describing the change in reaction rate over time. In the Rømø aquifer, Denmark, the reduction of iron oxides is an important electron accepting process for organic matter degradation and is reflected by the steep increase in aqueous Fe²⁺ over depth. Sediment from the Rømø aquifer was used for reductive dissolution experiments with ascorbic acid. The rate parameters describing the reactivity of iron oxides in the sediment are in the range k′ = 7·10⁻⁶ to 1·10⁻³ s⁻¹ and γ = 1 to 2.4. These values are intermediate between a synthetic 2-line ferrihydrite and a goethite. The rate constant increases by two orders of magnitude over depth suggesting an increase in iron oxide reactivity with depth. This increase was not captured by traditional oxalate and dithionite extractions.