Variation in calcite dissolution rates:: A fundamental problem?

A comparison of published calcite dissolution rates measured far from equilibrium at a pH of ∼ 6 and above shows well over an order of magnitude in variation. Recently published AFM step velocities extend this range further still. In an effort to understand the source of this variation, and to provide additional constraint from a new analytical approach, we have measured dissolution rates by vertical scanning interferometry. In areas of the calcite cleavage surface dominated by etch pits, our measured dissolution rate is 10^−10.95 mol/cm²/s (PCO₂ 10^−3.41 atm, pH 8.82), 5 to ∼100 times slower than published rates derived from bulk powder experiments, although similar to rates derived from AFM step velocities. On cleavage surfaces free of local etch pit development, dissolution is limited by a slow, “global” rate (10^−11.68 mol/cm²/s). Although these differences confirm the importance of etch pit (defect) distribution as a controlling mechanism in calcite dissolution, they also suggest that “bulk” calcite dissolution rates observed in powder experiments may derive substantial enhancement from grain boundaries having high step and kink density. We also observed significant rate inhibition by introduction of dissolved manganese. At 2.0 μM Mn, the rate diminished to 10^−12.4 mol/cm²/s, and the well formed rhombic etch pits that characterized dissolution in pure solution were absent. These results are in good agreement with the pattern of manganese inhibition in published AFM step velocities, assuming a step density on smooth terraces of ∼9 μm⁻¹.     

Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ^44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ^44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ^44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ^44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.     

Complex trajectories of aquatic and terrestrial ecosystem shifts caused by multiple human-induced environmental stresses

Large shifts in the isotopic compositions of organic matter (OM) in lake sediments, over the last few hundred years, are commonly interpreted as representing changes in photosynthetic productivity corresponding to eutrophication or in the input of terrestrial OM due to human disturbances. Based on multiple-proxy data (C:N ratio, δ¹³C and δ¹⁵N of OM, δ¹³C of calcite, lithology and fossil pollen) from a 700-year sediment core at White Lake, New Jersey (USA), we propose a new explanation that relates these large shifts in OM δ¹³C and δ¹⁵N to human-induced changes in aquatic OM producers. Combined records of geochronology, fossil pollen and lithology from White Lake reveal that the upland forest was cleared by European settlers for farmland beginning around 1745 A.D. and has gradually reforested since 1930 after the abandonment of the farmlands. For the pre-agricultural period, OM had relatively constant but extremely low δ¹³C_VPDB (−35.8 to −34.5‰) and δ¹⁵N_Air (−3.5 to −2.5‰) and high atomic C:N ratios (13.7 to 16.7), indicating a stable anoxic lake environment with prominent microbial producers. Following the human disturbance (since 1745), high OM mass accumulation rates and abundances of the green alga Pediastrum indicate an increase in aquatic photosynthetic productivity due to enhanced nutrient input from disturbed uplands. However, carbonate δ¹³C remains constant or even decreases during this period, implying that increasing productivity did not elevate the δ¹³C of dissolved inorganic carbon and thus cannot explain the observed large increase in OM δ¹³C (7.4‰) and δ¹⁵N (5.8‰) over this period. Instead, δ¹³C, δ¹⁵N and C:N ratios of OM and differences in δ¹³C between calcite and OM suggest that the large increase in OM δ¹³C and δ¹⁵N can be attributed to a human-induced ecological shift in the predominant organic source from anaerobic bacteria to autotrophic phytoplankton. During the post-agricultural period, mass accumulation rates of OM, carbonate and silicate, and the δ¹³C of OM and calcite all decreased significantly, corresponding to stabilization of the uplands. However, over the last 70 years, an intensifying aquatic stress from the deposition of ¹⁵N-enriched industrial pollutants has resulted in a steady increase of 1.9‰ in δ¹⁵N. Proxy records for lake (δ¹³C and δ¹⁵N of OM) and upland conditions (pollen and silicates) at White Lake show complex trajectories of the aquatic and terrestrial ecosystems in response to past human disturbances.     

方解石和钾长石在模拟蚯蚓肠液中的初始溶解动力学机理及意义

蚯蚓肠道内小分子有机酸与摄入的土壤矿物相互作用,加速矿物溶解。摄入的土壤在蚯蚓肠道内平均停留时间约为12 h,不足以使土壤矿物产生显著的溶解特征,因此这一过程难以在蚯蚓体内进行评估。本研究通过体外实验控制pH值和有机酸浓度,模拟蚯蚓肠道中有机酸对土壤中常见矿物的溶解反应,探讨了方解石和钾长石在蚯蚓肠道环境中的初始溶解动力学。研究发现,矿物在混合有机酸中的溶解速率比在纯水中高一个数量级,说明有机配体和质子促进了矿物溶解。溶解速率及粒度分析表明,方解石(CaCO₃)溶解速率不受溶解过程中粒度变化的影响,而钾长石(KAlSi₃O₈)粒度在溶解期间未出现显著变化。在此基础上,采用初始速率法模拟了钾长石的初始溶解动力学,计算得出的溶解速率表明钾长石在溶解初期主要为表面K~+的释放。使用缩核模型(shrink core model)和Hixson-Crowell模型对方解石溶解过程进行动力学解析,发现方解石的溶解主要受溶液中反应物内扩散的速率影响。这定量描述了两种矿物在有机酸溶液和纯水中的溶解差异。现有研究表明,有机配体和质子协同促...     

Aqueous cadmium uptake by calcite: a stirred flow-through reactor study

Uptake of cadmium ions from solution by a natural Mg-containing calcite was investigated in stirred flow-through reactor experiments. Input NaCl solutions were pre-equilibrated with calcite (pH 8.0) or not (pH 6.0), prior to being spiked with CdCl₂. For water residence times in the reactor less than 0.5 h, irreversible uptake of Cd by diffusion into the bulk crystal had a minor effect on the measured cadmium breakthrough curves, hence allowing us to quantify “fast” Cd²⁺ adsorption. At equal aqueous activities of Cd²⁺, adsorption was systematically lower for the pre-equilibrated input solutions. The effect of variable solution composition on Cd²⁺ adsorption was reproduced by a Ca²⁺-Cd²⁺ cation exchange model and by a surface complexation model for the calcite-aqueous solution interface. For the range of experimental conditions tested, the latter model predicted binding of aqueous Ca²⁺ and Cd²⁺ to the same population of carbonate surface sites. Under these circumstances, both adsorption models were equivalent. Desorption released 80 to 100% of sorbed cadmium, confirming that fast uptake of Cd²⁺ was mainly due to binding at surface sites. Slow, irreversible cadmium uptake by the solid phase was measured in flow-through reactor experiments with water residence times exceeding 0.7 h. The process exhibited first-order kinetics with respect to the concentration of adsorbed Cd²⁺, with a linear rate constant at 25°C of 0.03 h⁻¹. Assuming that diffusion into the calcite lattice was the mechanism of slow uptake, a Cd²⁺ solid-state diffusion coefficient of 8.5×10⁻²¹ cm² s⁻¹ was calculated. Adsorbed Cd²⁺ had a pronounced effect on the dissolution kinetics of calcite. At maximum Cd²⁺ surface coverage (∼10⁻⁵ mol m⁻²), the calcite dissolution rate was 75% slower than measured under initially cadmium-free conditions. Upon desorption of cadmium, the dissolution rate increased again but remained below its initial value. Thus, the calcite surface structure and reactivity retained a memory of the adsorbed Cd²⁺ cations after their removal.     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

Far from equilibrium enstatite dissolution rates both open to atmospheric CO₂ and CO₂ purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO₂ conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO₂ was purged by performing the experiments in a N₂ atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO₃²⁻ above pH 10.33. It is argued that CO₃²⁻ forms a >Mg₂-CO₃ complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO₂-purged enstatite dissolution in moles per cm² per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.     

Carbonate and silicate weathering in two presently glaciated, crystalline catchments in the Swiss Alps

We present a weathering mass balance of the presently glaciated Rhône and Oberaar catchments, located within the crystalline Aar massif (central Switzerland). Annual chemical and physical weathering fluxes are calculated from the monthly weighted means of meltwater samples taken from July, 1999 to May, 2001 and are corrected for precipitation inputs. The meltwater composition issuing from the Oberaar and Rhône catchments is dominated by calcium, which represents 81% and 55% of the total cation flux respectively (i.e. 555 and 82-96 keq km⁻² yr⁻¹). The six to seven times higher Ca²⁺ denudation flux from the Oberaar catchment is attributed to the presence of a strongly foliated gneissic zone. The gneissic zone has an elevated calcite content (as reflected by the 4.6 times higher calcite content of the suspended sediments from Oberaar compared to Rhône) and a higher mechanical erosion rate (resulting in a higher flux of suspended sediment). The mean flux of suspended calcite of the Oberaar meltwaters during the ablation period is 7 times greater than that of the Rhône meltwaters. Taking the suspended calcite as a proxy for the total (including sub-glacial sediments) weathering calcite surface area, it appears that the available surface area is an important factor in controlling weathering rates. However, we also observe an increased supply of protons for carbonate dissolution in the Oberaar catchment, where the sulphate denudation flux is six times greater. Carbonic acid is the second important source of protons, and we calculate that three times as much atmospheric CO₂ is drawn down (short term) in the Oberaar catchment. Silica fluxes from the two catchments are comparable with each other, but are 100 kmol km² yr⁻¹ lower than fluxes from physically comparable, non-glaciated basins.     

Do organic ligands affect calcite dissolution rates?

Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO₂ sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA⁴⁻, succinate, d-glucosaminate, l-glutamate, d-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA⁴⁻. The presence of 0.05 mol/kg citrate and EDTA⁴⁻ increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.     

Ca isotopes in carbonate sediment and pore fluid from ODP Site 807A: The Ca(aq)-calcite equilibrium fractionation factor and calcite recrystallization rates in Pleistocene sediments

The calcium isotopic compositions (δ⁴⁴Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (α_s−f) between calcite and dissolved Ca²⁺ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of α_s−f at equilibrium in the marine sedimentary section is 1.0000 ± 0.0001, which is significantly different from the value (0.9987 ± 0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ∼14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in δ⁴⁴Ca of +0.15‰ for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.     

The role of background electrolytes on the kinetics and mechanism of calcite dissolution

The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl⁻ < I⁻ < F⁻ for salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F⁻ and Li⁺ are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F⁻, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.     

An atomic force microscopy study of calcite dissolution in saline solutions: The role of magnesium ions

In situ Atomic Force Microscopy, AFM, experiments have been carried out using calcite cleavage surfaces in contact with solutions of MgSO₄, MgCl₂, Na₂SO₄ and NaCl in order to attempt to understand the role of Mg²⁺ during calcite dissolution. Although previous work has indicated that magnesium inhibits calcite dissolution, quantitative AFM analyses show that despite the fact that Mg²⁺ inhibits etch pit spreading, it increases the density and depth of etch pits nucleated on calcite surfaces and, subsequently, the overall dissolution rates: i.e., from 10^−11.75 mol cm⁻² s⁻¹ (in deionized water) up to 10^−10.54 mol cm⁻² s⁻¹ (in 2.8 M MgSO₄). Such an effect is concentration-dependent and it is most evident in concentrated solutions ([Mg²⁺] >> 50 mM). These results show that common soluble salts (especially Mg sulfates) may play a critical role in the chemical weathering of carbonate rocks in nature as well as in the decay of carbonate stone in buildings and statuary.     

Microbial dissolution of calcite at T = 28 °C and ambient pCO2

This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species (Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO₂ over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH₄⁺ as an N source, and H₂PO₄⁻ as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H₂O-CO₂-CaCO₃ system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH₄⁺ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H₂CO₃ generated by dissolution of atmospheric CO₂ (H₂CO₃ + CaCO₃ → Ca²⁺ + 2HCO₃⁻) and H⁺ released during NH₄⁺ uptake (H⁺ + CaCO₃ → Ca²⁺ + HCO₃⁻). Reaction with H₂CO₃ and H⁺ supplied ∼45% and 55% of the total Ca²⁺ and ∼60% and 40% of the total HCO₃⁻, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH₄⁺ was ∼2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H₂CO₃. In lactate bearing reactors, most H⁺ generated by NH₄⁺ uptake reacted with HCO₃⁻ produced by lactate oxidation to yield CO₂ and H₂O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H₂CO₃ at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH₄⁺ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.     

Composition and origin of organic matter in surface sediments of Lake Sarbsko: A highly eutrophic and shallow coastal lake (northern Poland)

We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ¹³C_TOC and δ¹⁵N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ¹³C_DIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH₄ and CO₂ in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO₃.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.     

Modeling of subsurface calcite dissolution, including the respiration and reoxidation processes of marine sediments in the region of equatorial upwelling off Gabon

Mineralization of organic matter and the subsequent dissolution of calcite were simulated for surface sediments of the upper continental slope off Gabon by using microsensors to measure O₂, pH, pCO₂ and Ca²⁺ (in situ), pore-water concentration profiles of NO₃⁻, NH₄⁺, Fe²⁺, and Mn²⁺ and SO₄²⁻ (ex situ), as well as sulfate reduction rates derived from incubation experiments. The transport and reaction model CoTReM was used to simulate the degradation of organic matter by O₂, NO₃⁻, Fe(OH)₃ and SO₄²⁻, reoxidation reactions involving Fe²⁺ and Mn²⁺, and precipitation of FeS. Model application revealed an overall rate of organic matter mineralization amounting to 50 μmol C cm⁻² yr⁻¹, of which 77% were due to O₂, 17% to NO₃⁻ and 3% to Fe(OH)₃ and 3% to SO₄²⁻. The best fit for the pH profile was achieved by adapting three different dissolution rate constants of calcite ranging between 0.01 and 0.5% d⁻¹ and accounting for different calcite phases in the sediment. A reaction order of 4.5 was assumed in the kinetic rate law. A CaCO₃ flux to the sediment was estimated to occur at a rate of 42 g m⁻² yr⁻¹ in the area of equatorial upwelling. The model predicts a redissolution flux of calcite amounting to 36 g m⁻² yr⁻¹, thus indicating that ∼90% of the calcite flux to the sediment is redissolved.     

Interferometric study of the dolomite dissolution: a new conceptual model for mineral dissolution

The dissolution rate and mechanism of three different cleavage faces of a dolomite crystal from Navarra (near Pamplona), Spain, were studied in detail by vertical scanning interferometry techniques. A total of 37 different regions (each about 124 × 156 μm in size) on the three sample surfaces were monitored as a function of time during dissolution at 25°C and pH 3. Dissolution produced shallow etch pits with widths reaching 20 μm during 8 h of dissolution. Depth development as a function of time was remarkably similar for all etch pits on a given dolomite surface.On the basis of etch pit distribution and volume as a function of time, the calculated dissolution rate increases from near zero to 4 × 10⁻¹¹ mol cm⁻² s⁻¹ over 5 h. The time variation is different for each of the three cleavage surfaces studied. In addition, the absolute dissolution rates of different parts of the dolomite crystal surface can be computed by using a reference surface. The different surfaces yield an “average” rate of 1.08 × 10⁻¹¹ mol cm⁻² s⁻¹ with a standard deviation of 0.3 × 10⁻¹¹ mol cm⁻² s⁻¹ based on about 60 analyses. The mean absolute rate of the dolomite surface is about 10 times slower than the rate calculated from etch pit dissolution alone. On the other hand, earlier batch rate data that used BET surface areas yield rates that are at least 30 to 60 times faster than our directly measured mean dissolution rate for the same pH and temperature.A conceptual model for mineral dissolution has been inferred from the surface topography obtained by the interferometry investigations. In this model, mineral dissolution is not dominated by etch pit formation itself but rather by extensive dissolution stepwaves that originate at the outskirts of the etch pits. These stepwaves control the overall dissolution as well as the dependence on temperature and saturation state.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.