Solubility of rhodochrosite (MnCO3) in water and seawater

The solubility product of rhodochrosite (MnCO₃) was measured in seawater, deionized water and dilute NaCl solutions. The solubility product extrapolated to infinite dilution at 25.0 C was (2.60 ± 0.07)× 10^?11. The stoichiometric solubility product measured in seawater of 34.27%. salinity was (3.24 ± 0.23) × 10^?9 at 25.0 C and (2.28 ± 0.24) × 10^?9 at 3.3 C. The stoichiometric solubility product is in good agreement with the value calculated from an ion association model. The enthalpy of the reaction is in fair agreement with the estimated value.     

The solubility of calcite and aragonite in seawater of 35%. salinity at 25°C and atmospheric pressure

The solubilities of synthetic, natural and biogenic aragonite and calcite, in natural seawater of 35%. salinity at 25°C and 1 atm pressure, were measured using a closed system technique. Equilibration times ranged up to several months. The apparent solubility constant determined for calcite of 4.39(±0.20) × 10^?7 mol² kg^?2 is in good agreement with other recent solubility measurements and is constant after 5 days equilibration. When we measured aragonite solubility we observed that it decreased with increasing time of equilibration. The value of 6.65(±0.12) × 10^?7 mol² kg^?2, determined for equilibration times in excess of 2 months, is significantly less than that found in other recent measurements, which employed equilibration times of only a few hours to days. No statistically significant difference was found among the synthetic, natural and biogenic material. Solid to solution ratio, contamination of aragonite with up to 10 wt% calcite and recycling of the aragonite made no statistically significant difference in solubility when long equilibration times were used.Measured apparent solubility constants of aragonite and calcite are respectively 22( ± 3)% and 20( ± 2)% less than apparent solubility constants calculated from thermodynamic equilibrium constants and seawater total activity coefficients. These large differences in measured and calculated apparent solubility constants may be the result of the formation of surface layers of lower solubility than the bulk solid.     

Amorphous silica solubilities—II. Effect of aqueous salt solutions at 25°C

The solubility of amorphous silica was measured at 25°C in ten separate sets of aqueous salt solutions—potassium chloride, potassium nitrate, sodium chloride, lithium chloride, lithium nitrate, magnesium chloride, calcium chloride, magnesium sulfate, sodium bicarbonate and sodium sulfate. The concentrations of the salts were varied from zero to saturation with both salt and amorphous silica. With increasing concentration of salt, the solubility of amorphous silica always decreased as expected from an average value of 0.00218 m in water. Nevertheless, the extent of decrease differed greatly from a 6% decrease in a solution saturated with NaHCO₃ to a 95.7% decrease in a solution saturated with CaCl₂. A striking correlation was observed: In the 1-1 and 2-1 electrolyte salt solutions at a given molality the effect on the solubility of silica depended upon the cation in the order Mg²⁺, Ca²⁺ > Li⁺ > Na⁺ > K ⁺.     

Metasomatic Phase Relations in the System CaO-MgO-SiO2-H2O-NaCl at High Temperatures and Pressures

An equation of state of solute silica in NaCl brines at 500 to 900°C and 4 to 15 kbar is formulated by making use of two experimentally determined properties of quartz solubility: the silica molality decreases in direct proportion to the logarithm of the NaCl mole fraction (X(NaCl)) at pressures approaching 10 kbar, and the relative silica molality (molality at a given NaCl mole fraction, m_x, divided by the molality in pure H₂O at the same P and T, m_o) is independent of temperature in the evaluated range. These two properties are expressed in the relation:

log(m_x/m_o)? = A + BX(NaCI),

where log(m_x/m_o)? denotes the logarithm of the ideal molality ratio, and A and B are functions of pressure, but not temperature or salinity, such that B = ?1.730 ? 1.431 × 10?³P + 5.923 × 10?⁴P² ?9.243 × lO?⁵P³, and A = 0 at P>10 kbar, whereas A = 0.6131 ? 0.1256P + 6.431 × 10?³P² at P≤10 kbar, as derived from fits to experimental data (Newton and Manning, 1999). The parameter A decreases from 0.214 to 0 from 4 to 9.5 kbar, and remains zero to 15 kbar; B decreases from ?1.373 to ?1.571 from 4 to 15 kbar. With the above relationship defining a variable X(NaCl)-T-P standard-state of solute silica, the activity of SiO₂ can be replaced by its molality for calculations of mineral-fluid equilibria over most of the conditions for metasomatism in the deep crust and upper mantle. Significant departures from ideality occur only at the lowest pressures, and low salinities.

Calculations on peridotite mineral stability in the simple system CaO-MgO-SiO₂-H₂O-NaCl at high T and P show that antigorite, brucite, and diopside are stable at 500°C and pressures of 5 to 15 kbar in the presence of concentrated NaCl solutions at low SiO₂ activities. At 700°C, anthophyllite is stable over a wide range of salinities at 5 kbar with tremolite but not with diopside. The presence of anthophyllite buffers silica solubility at a high, salinity-independent value close to quartz saturation. At 10 and 15 kbar and 700°C, talc replaces anthophyllite as the stable hydrate, and talc-trem-olite assemblages buffer SiO₂ fluid concentrations at high values nearly independent of salinity. At 900°C hydrates are unstable and diopside again becomes stable and coexists with enstatite in peridotites. These stability calculations correspond well to the observed progressive metamorphic sequence in peridotite bodies in the Central Alps.

This method of analysis may be useful in interpretation of metamorphosed ultramafic bodies in general, including the basal portions of obducted ophiolitic mantle lithosphere and the mantle wedge above subduction zones. More detailed calculations, including rocks containing feldspars, must take into account the more soluble major components of rocks, especially alkalis, as these will affect the activity coefficient of SiO₂ in NaCl solutions. The solubility of silica in the presence of minerals containing these components must be determined by additional measurements.     

Structural change and mineralogical transformation mechanism of aluminum hydroxide gels from forced hydrolysis Al（Ⅲ） solutions containing AlO4Al12（OH）24（H2O）12^7＋ polyoxycation during aging

The structural change and mineralogy of Al gel during aging time were investigated by using spectroscopy techniques. The results indicated that: 1) the aggregation extent of solution-gel system increases with aging time, and the structure of amorphous gel becomes more short-ordered; 2) after six months, the gel formats nordstrandite and little gibbsite; 3) a marked decrease in the number of (Al-OH)_oh bands occurring at 610 cm⁻¹ and increase in the number of (Al-OH₂)_oh bands occurring at 555 cm⁻¹ indicate that the gel undergoes rearrangement-like process during aging; 4) the gel constantly contains Al-O tetrahedron of Keggin structure, but the signal peak occurring at ≈61×10⁻⁶ of ²⁷Al MAS NMR have a slight shift to downfield with aging time. A mineralogical transformation mechanism for hydrolysis Al(III) solution was proposed.     

Amorphous silica solubilities—I. Behavior in aqueous sodium nitrate solutions; 25–300°C, 0–6 molal

The solubility of amorphous silica was obtained in aqueous sodium nitrate solutions up to six molal and at temperatures from 25 to 300°C. It was expected that solubilities in aqueous sodium chloride solutions would be similar. At 25°C, the solubility of amorphous silica is lowered from that in water to 0.00086 m in 6.12 m sodium nitrate, or a decrease of 60%. At 300°C, the corresponding decrease is only 27% from a solubility of 0.0269 m in H₂O. From the change in solubility with temperature at a given constant molality of sodium nitrate, the molal heat of solution over the range, 100 to 300°C, increases from + 2.93 kcal mol^?1 in water to + 3.64 kcal mol^?1 in 6m sodium nitrate. The value approaches a constant of +3.8 kcal mol^?1 as sodium nitrate approaches saturation at 10.8 molal.     

A method of calculating quartz solubilities in aqueous sodium chloride solutions

The aqueous silica species that form when quartz dissolves in water or saline solutions are hydrated. Therefore, the amount of quartz that will dissolve at a given temperature is influenced by the prevailing activity of water. Using a standard state in which there are 1,000 g of water (55.51 moles) per 1,000 cm³ of solution allows activity of water in a NaCl solution at high temperature to be closely approximated by the effective density of water, p_e, in that solution, i.e. the product of the density of the NaCl solution times the weight fraction of water in the solution, corrected for the amount of water strongly bound to aqueous silica and Na⁺ as water of hydration. Generally, the hydration of water correction is negligible.The solubility of quartz in pure water is well known over a large temperature-pressure range. An empirical formula expresses that solubility in terms of temperature and density of water and thus takes care of activity coefficient and pressure-effect terms. Solubilities of quartz in NaCl solutions can be calculated by using that equation and substituting p_e, for the density of pure water. Calculated and experimentally determined quartz solubilities in NaCl solutions show excellent agreement when the experiments were carried out in non-reactive platinum, gold, or gold plus titanium containers. Reactive metal containers generally yield dissolved silica concentrations higher than calculated, probably because of the formation of metal chlorides plus NaOH and H₂. In the absence of NaOH there appears to be no detectable silica complexing in NaCl solutions, and the variation in quartz solubility with NaCl concentration at constant temperature can be accounted for entirely by variations in the activity of water.The average hydration number per molecule of dissolved SiO₂ in liquid water and NaCl solutions decreases from about 2.4 at 200°C to about 2.1 at 350°C. This suggests that H₄SiO₄ may be the dominant aqueous silica species at 350°C, but other polymeric forms become important at lower temperatures.     

Americium interaction with calcite and aragonite surfaces in seawater

Observations of the distribution of ²⁴¹Am in the marine environment indicate that Am has a high affinity for solid surfaces. The adsorption of Am onto calcite and aragonite surfaces from seawater and related solutions has been studied, in order to establish the interaction of Am with a major component of many marine sediments. Results indicate that Am is rapidly and strongly adsorbed. This occurs even when both dissolved Am concentrations and solid to solution ratios are low. The minimum value for $\text{K}{}_{\mathrm{D}}$ determined is 2 × 10⁵. Measurements of reaction kinetics established that Am is adsorbed from seawater at 40 times the rate per unit surface area on synthetic aragonite that it is on synthetic calcite. Approximately 15% of the difference is attributable to epitaxial influences, with the remainder being due to enhanced site competition by Mg on calcite relative to aragonite. The adsorption rate is first order with respect to Am concentration, but follows approximately the square root of the solid surface area to solution volume ratio.Adsorption rate of Am on biogenic aragonite and Mg-calcites are, within a given particle size range, close to equal. It is not possible to normalize these adsorption rates to surface area due to the differing microporous structure of biogenic carbonates. The Am adsorption rates on a shallow water calcium carbonate-rich sediment gave results which were predicted from, its mineralogie mixture of components.     

Evaluation of silica-water surface chemistry using NMR spectroscopy

We have combined traditional batch and flow-through dissolution experiments, multinuclear nuclear magnetic resonance (NMR) spectroscopy, and surface complexation modeling to re-evaluate amorphous silica reactivity as a function of solution pH and reaction affinity in NaCl and CsCl solutions. The NMR data suggest that changes in surface speciation are driven by solution pH and to a lesser extent alkali concentrations, and not by reaction time or saturation state. The ²⁹Si cross-polarization NMR results show that the concentration of silanol surface complexes decreases with increasing pH, suggesting that silanol sites polymerize to form siloxane bonds with increasing pH. Increases in silica surface charge are offset by sorption of alkali cations to ionized sites with increasing pH. It is the increase in these ionized sites that appears to control silica polymorph dissolution rates as a function of pH. The ²³Na and ¹³³Cs NMR results show that the alkali cations form outersphere surface complexes and that the concentration of these complexes increases with increasing pH. Changes in surface chemistry cannot explain decreases in dissolution rates as amorphous silica saturation is approached. We find no evidence for repolymerization of the silanol surface complexes to siloxane complexes at longer reaction times and constant pH.     

Hydrothermal serpentinization of peridotite within the oceanic crust: Experimental investigations of mineralogy and major element chemistry

Mantle derived ultramafic rocks form a significant portion of lithosphere created at slow-spreading mid-ocean ridges. These rocks are ubiquitously serpentinized, due at least in part to interaction with seawater, at temperatures below approximately 500°C. To evaluate reaction pathways, primary mineral reaction rates, major element exchange between rock and solution, and alteration mineral formation, interaction of equigranular peridotites with seawater and seawater derived solutions has been investigated experimentally at 200°C and 300°C, 500 bars.Seawater chemistry changed greatly during the experiments. Initially, the concentrations of Mg, Ca, and SO₄ decreased, as did pH. During Iherzolite experiments, however, the trend of dissolved Ca concentrations reversed with time, first decreasing, then increasing. pH also increased during the latter part of the experiments. Mg, Ca, SiO₂, Fe, Cl and ΣCO₂ decreased as pH increased Fe^II oxidation is shown to be affected by solution pH, being greatly enhanced under alkaline conditions. Resulting solution composition and reaction pathway are dependent on initial solution composition, particularly initial concentrations of Mg in solution. Consistent with changes in solution chemistry, the peridotites were significantly altered. Substantial amounts of olivine, relatively minor amounts of diopside and all the enstatite dissolved. Alteration products included serpentine + anhydrite ± magnesium hydroxide sulfate hydrate ± magnetite ± brucite ± tremolite-actinolite or truscottite.From the changes in solution chemistry and examination of the alteration products, the reaction rates (moles per unit time) of olivine to enstatite to diopside during 300°C Iherzolite-seawater experiments are estimated to be approximately 1.0/1.0/0.1. These rates correspond to constant surface area rates of 1.5:5:1 (moles per unit time per unit surface area), which are consistent with experimental data on the dissolution kinetics of these minerals and emphasize the importance of initial rock texture on reaction rates.     

Pore water fluoride in Peru continental margin sediments: Uptake from seawater

Fluoride analyses display downward decreasing pore water gradients in Peru shelf phosphatic muds that require diffusion from the overlying seawater into the sediment column and removal by reaction within the upper few tens of centimeters, presumably by incorporation into carbonate fluorapatite. The profiles can be modeled as first-order F-removal with rate constants of ~3 yr^?1 and asymptotic F-concentrations deep in the cores of 35–45 μM, almost one-half the seawater value. The integrated flux of fluoride from seawater into organic-rich shelf sediments in coastal-upwelling zones (phosphatic muds) yields a contemporaneous global F-burial of 0.54 × 10¹⁰ mol-F yr^?1, about one-fifth the burial in other sinks (mostly carbonates and opal). The associated burial flux of phosphorus in shelf phosphorites is about 1.6 × 10¹⁰ mol-P yr^?1, comparable to P-burial in the deep sea with organic matter (~1.4 × 10¹⁰ mol yr^?1) and biogenic carbonates (~1.4 × 10¹⁰ mol yr^?1). Thus phosphorite formation on the Peru shelf is a significant contemporaneous process.     

Silica in Lake Superior: mass balance considerations and a model for dynamic response to eutrophication

The dissolved silica concentration in waters of Lake Superior probably is in a steady state because it is not influenced significantly by man, and the climate, topography and vegetation in the drainage area of the lake have been stable for the past 4000 years. Therefore the rate at which dissolved silica is introduced to the lake should equal the output rate.The primary inputs are: tributaries (4.1–4.6 × 10⁸kgSiO₂/yr), diffusion from sediment pore waters (0.21?0.78 × 10⁸kgSiO₂/yr) and atmospheric loading (0.26 × 10⁸kgSiO₂/yr). Silica is lost from the lake waters by: outflow through the St. Marys River, diatom deposition, adsorption onto particulates in the sediments, and authigenic formation of new silicate minerals. Tributary outflow accounts for less than one half the annual input of silica, and diatom deposition and silica adsorption withdraw less than 10% of the annual input. Therefore the formation of new silicate phases must be the dominant sink for dissolved silica in Lake Superior. The specific phases formed are not identified in the bottom sediments. X-ray diffraction studies suggest that smectite is one product, and amorphous ferroaluminum silicates may be another product.Mathematical modeling of the dissolved silica response to lake eutrophication suggests that the phosphate loading to Lake Superior would have to increase by about 250-fold to cause a silica depletion rate equal to that reported for Lake Michigan, assuming no change in the rate of upwelling of deep waters.     

Steady-state kinetics and equilibrium between ground water and granitic rock

A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D_25°C = 3 × 10^?22 and 1.5 × 10^?20 cm²sec^?1 at P_CO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10^?8 to n × 10^?5 cm according to the temperature and P_CO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)₃](_1?x)[SiO₂]_x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al³⁺] + xlog [H₄SiO₄] ? (3 ? 3x) log [H⁺] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.     

Amorphous silica solubilities IV. Behavior in pure water and aqueous sodium chloride,sodium sulfate,magnesium chloride,and magnesium sulfate solutions up to 350°C

Solubilities of amorphous silica were determined in separate aqueous solutions of sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate at temperatures up to 350°C. These salts, of strong interest in hydrothermal oceanography and geothermal energy, generally ranged in concentration from zero to saturation. Solubilities in the sodium chloride solutions followed closely earlier observed decreases in sodium nitrate solutions at high temperatures.Amorphous silica solubilities were depressed most by magnesium chloride, followed by magnesium sulfate, and less by sodium chloride. As the temperature rose the relative decrease in solubility caused by added salt became smaller. Surprisingly, sodium sulfate solutions, showing little effect at 25°C, sharply raised the solubility as the temperature increased to 350°C. Plots of the logarithms of derived activity coefficients against molalities of added salt gave approximately straight lines. These plots allow simple predictions of amorphous silica solubility in single salt solutions.     

Silica biogeochemical cycle in temperate ecosystems of the Pampean Plain,Argentina

Silicophytoliths were produced in the plant communities of the Pampean Plain during the Quaternary. The biogeochemistry of silicon is scarcely known in continental environments of Argentina. The aim of this work is to present a synthesis of: the plant production and the presence of silicophytoliths in soils with grasses, and its relationship with silica content in soil solution, soil matrix and groundwaters in temperate ecosystems of the Pampean Plain, Argentina. We quantified the content of silicophytoliths in representative grasses and soils of the area. Mineralochemical determinations of the soils' matrix were made. The concentration of silica was determined in soil solution and groundwaters. The silicophytoliths assemblages in plants let to differenciate subfamilies within Poaceae. In soils, silicophytoliths represent 40–5% of the total components, conforming a stock of 59–72 × 10³ kg/ha in A horizons. The concentration of SiO₂ in soil solution increases with depth (453–1243 μmol/L) in relation with plant communities, their nutritional requirements and root development. The average concentration of silica in groundwaters is 840 umol/L. In the studied soils, inorganic minerals and volcanic shards show no features of weathering. About 10–40% of silicophytoliths were taxonomically unidentified because of their weathering degrees. The matrix of the aggregates is made up by microaggregates composed of carbon and silicon. The weathering of silicophytoliths is a process that contributes to the formation of amorphous silica-rich matrix of the aggregates. So, silicophytoliths could play an important role in the silica cycle being a sink and source of Si in soils and enriching soil solutions and groundwaters.     

The partial molal volume of silicic acid in 0.725 m NaCl

The partial molal volume ($\text{V}\text{?}$) of silicic acid in 0.725 m NaCl at 20°C has been calculated from (1) direct volume changes due to the dissolution of anhydrous sodium silicate and (2) some literature values for the partial molal volumes of NaOH and water. , unconnected for electrostriction effects, was found to be 53 ± 2 ml mole^?1. , corrected for volume changes due to solvent electrostriction by charged Si species, was estimated to be in the range 58–62 ml mole^?1; this range is 7–11 ml mole^?1 greater than the calculated from Willey's (Mar. Chem. 2, 239–250, 1974) solubility data obtained from the dissolution, in seawater, of amorphous silica subjected to hydrostatic pressure. Our does, however, agree within experimental error with the calculated from Jones and Pytkowicz's (Bull. Soc. Roy. Sci. Liege 42, 118–120, 1973) data for the solubility of amorphous silica in seawater at high pressure and is nearly in agreement with Willey's (Ph.D. thesis, Dalhousie University, 1975) solubility data for amorphous silica in 0.6 m NaCl.     

Pressure dependence ot SrSO4 solubility

The solubilities of SrSO₄ in seawater, 0.65 M NaCl and and distilled water were measured as a function of pressure at 2°C. The thermodynamic solubility product was determined from the distilled water measurements and stoichiometric solubility products were determined from the seawater and Nad measurements. The equilibrium quotient for SrSO₄ dissolution at ionic strength of 0.65 was calculated from the NaCl measurements, using the known NaSO₄^? ionpairing association constant. For each of the solubility products values of $\text{Θ V}$ were determined. These experimental values were all $\text{11.0 ± 0.3}\text{ml}$ mole_? lower than the theoretical values based on anhydrous SrSO₄. This difference may be due to the equilibrating solid phase being a hydrated form of SrSO₄.     

Solubility of the buffer assemblage pyrite + pyrrhotite + magnetite in NaCl solutions from 200 to 350°C

In the design of hydrothermal solubility studies it is important that the system be completely defined chemically. If the solubilities of minerals containing m metallic elements are to be determined in hydrothermal NaCl solutions, the phase rule requires that a total of m + 6 independent intensive parameters be controlled or measured in order to determine completely the system.In this study the solubility of the univariant assemblage pyrite + pyrrhotite + magnetite has been determined in vapor saturated hydrothermal solutions from 200 to 350°C for NaCl concentrations ranging from 0.0 to 5.0 molal. At any temperature, oxygen and sulfur fugacities were buffered by the chosen assemblage. System pH was determined from excess CO₂ partial pressures and computed ionic equilibria. Equilibrium constants were calculated by regression analysis of solubility data. The results show that more than 10 ppm of each mineral can dissolve in typical hydrothermal solutions under geologically realistic conditions. Solubilities were best represented by the species Fe²⁺ and FeCl⁺ at 200 and 250°C; Fe²⁺, FeCl⁺ and FeCl₂⁰ at 300°C; and Fe²⁺ and FeCl₂⁰ at 350°C. Ore deposition would occur by lowering temperature, diluting chloride concentration, or by raising pH through wall rock alteration reactions.     

Deposition of deep-sea manganese nodules

Manganese at equilibrium in seawater occurs dominantly as Mn²⁺ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O₂ and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 10⁸ ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn²⁺ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)₃⁰ and Fe(OH)₄^?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)₃.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.