The influence of the carbonate dissolution rate on the growth and composition of Co-rich ferromanganese crusts from Central Pacific seamount areas

The metal composition of oceanic ferromanganese deposits occurring in seamount regions (Line Islands chain and Mid-Pacific Mountains) varies with water depth and age. The results of metal determinations of carbonate plankton samples suggest that carbonate dissolution in the water column might have an important influence on the accretion and composition of hydrogenetic precipitates. Two ferromanganese crust generations of different age have been observed The precipitation of the older crust took probably place during early Oligocene, the younger crust began to form during middle Miocene. Between the two crust generations periods of carbonate sedimentation and of phosphorite deposition occur. The hydrogenetic formation of the crusts is controlled by the metal supply from the water column, according to the laws of colloidal surface chemistry.Dissolution experiments with carbonate plankton samples show that the main Fe source for the hydrogenetic crust formation are colloidal Fe-hydroxide particles being released in the water column from the dissolution of carbonate plankton skeletons. In the case of Mn, maximum dissolved Mn occurs in the oxygen minimum zone as the result of in-situ break-down of organic matter and the in-situ reduction of Mn-bearing solid phases. Closely beneath the oxygen minimum zone a Fe supply, mobilized within the oxygen minimum zone, has also to be taken into account. In the water column below the oxygen minimum zone, a mixture of colloidal particles of MnFe-oxyhydroxide and colloidal AlFe-silicate, precipitate together on the surface of substratum rocks. The mixing ratio of these colloidal phases controlling the metal composition of the ferromanganese precipitates, is depth-dependent and shows also temporal variations. In general, Mn/Fe ratio, Ni, and Co contents decrease with depth down to the calcite compensation depth.The most probable mechanism for the ultimate removal of Co and Ni from the water column might be a surface reaction. δ-MnO₂ is specifically able to absorb hydrous Co²⁺ and Ni²⁺ ions. Because of the surface enrichment of Co and the strong electrical field of Mn(IV), a subsequent oxidation of Co²⁺ to Co³⁺ takes place leading to higher enrichment of Co in comparison to Ni. The most important factor governing the high Co enrichment in the ferromanganese crusts is the growth rate: the lower the growth rate, the higher the Co content. Maximum values of up to 2% Co occurring in samples from water depths between 1500 and 1100 m [1] are related to lower carbonate dissolution rates and corresponding lower Fe supply.The metal supply from the water column is strongly related to distinct environmental factors such as bio-productivity, range of lysocline and calcite compensation depth, rate of carbonate dissolution, and activity of the Antarctic bottom water. Thus, our model shows that the growth periods and the metal composition of hydrogenetic seamount crusts are controlled by changes in the paleoceanography and reflect distinct environmental conditions.     

In-situ dissolution experiment of radiolaria in the central North Pacific ocean

Monospecific phaeodarian radiolarian assemblages of Castanidium longispinum were suspended in plastic cages built with 225 μm nylon mesh at different water depths from 378 to 5582 m in the central North Pacific. Weight losses of these samples after a suspension period of 61 days were used to determine dissolution rates. The highest weight losses were observed at 378 m where samples lost ～90% of their initial weight. Through the main thermocline weight losses decreased from 90 to 60% and reached a constant value of 40% below it. These weight losses are roughly an order of magnitude higher than those reported by earlier workers. The higher weight losses can be attributed in part to the more soluble nature of the phaeodarian radiolarian skeletons and in part to the improved experimental technique. Kinetic considerations show that temperature is the major factor that controls silica dissolution rates in the ocean. Using an Arrehnius plot for the apparent rate constants, it can be shown that in surface water dissolution rats should be two orders of magnitude higher than in deep water below the main thermocline.     

The distribution of particulate iodine in the Atlantic Ocean

The iodine content of marine suspended matter obtained from thirteen stations in the Atlantic between 75°N and 55°S has been measured. The concentration of particulate iodine is high in the surface, up to 127 ng/kg of seawater being observed. Below the euphotic zone, it drops sharply to 1–2 ng/kg. The iodine-containing particles are probably biogenic. A simple box-model calculation shows that only 3% of the particulate iodine produced in the surface water may reach the deep sea and that the residence time of these particles in the surface water is about 0.1 year.     

Investigations of gram quantities of Atlantic and Pacific surface particulates

Particulates amounting to 0.1–2.0 g efficiently collected from large volumes of Atlantic and Pacific surface waters have been analyzed for carbonate, opal, quartz and several natural and man-made radioisotopes.The concentrations of particles range between 10 and 600 μg/kg. In the equatorial regions particle concentrations are low and similar in both the oceans. At higher latitudes (>30°N or S), the Atlantic waters, however, have higher concentrations of particles compared to those in the Pacific. The latitudinal distribution exhibits a north-south symmetry with higher concentrations in the 30°–60° belt. Based on the particulate abundance for CaCO₃ and opal and their sedimentation, we have estimated their production and in-situ integrated dissolution rates for a few regions.Radioisotopes having different source functions, namely¹⁴C and²³⁹Pu injected due to nuclear weapon tests,²³⁴Th,²³⁰Th and²²⁸Th produced in-situ in seawater,²³²Th which derives primarily from land,²¹⁰Pb introduced via wet precipitations and²²⁶Ra introduced through diffusion from deep-sea sediments have been measured in the particulates. The relative enrichment factors for these nuclides in particles vary as Th ? Pu > Pb > Ra. The atmospheric bomb fallout pattern is discernible in the surface particulates; the²³⁹Pu concentration increases with latitude in both the hemispheres; however, the values are about a factor of two lower in the southern hemisphere.The distribution pattern of radioisotopes is found to be complex, even for²³⁴Th whose source function in the oceans is uniform. In view of the differences in the source functions it becomes possible to delineate the principal geochemical/geophysical processes which determine the concentrations of these nuclides in surface waters.     

Interstitial water profiles and sites of diagenetic reactions,Leg 35, DSDP,Bellingshausen Abyssal Plain

Discrepancies between predicted and observed interstitial water profiles for sites 322 and 323, Leg 35, Bellingshausen Abyssal Plain, were used to identify sites of reaction for further mineralogical and chemical investigations. Two major reaction sites were identified at site 323:(1) In the silicification zone between 410 and 505 m depth, where dissolution of biogenic (opaline) silica, plagioclase and a few coccoliths and the formation of opal-CT, Mg-rich smectite and K-feldspar are responsible for the observed silica, Ca²⁺, Mg²⁺, and K⁺ interstitial water gradients. Dissolution of biogenic silica provided most of the silica for the porcelanites.(2) In the basalt, weathering of pyroxene and plagioclase and the formation of celadonite, smectite, calcite, and goethite are probably responsible for the observed Ca²⁺, Mg²⁺, and K⁺ interstitial water gradients below the silicification zone.The chemistry of authigenic smectites reflects the composition of their precursor(s).     

Aragonite dissolution on the Bermuda pedestal: Its depth and geochemical significance

The depth distribution of pteropod and planktonic foram tests, and fine-grained (<62 μm) aragonite, high-Mg calcite (12 mode mol.% MgCO₃), and low-Mg calcite has been determined for surface sediments of an area of the eastern slope of the Bermuda pedestal. Over the range 1800–3000 m, fine-grained aragonite and fine-grained high-Mg calcite gradually disappear relative to fine-grained low-Mg calcite, and pteropods gradually disappear relative to planktonic forams. This is interpreted as preferential dissolution of aragonite (and high-Mg calcite) relative to low-Mg calcite over this depth range. Coarse aragonitic debris derived from shallow-water organisms living on the Bermuda platform does not show consistent disappearance over the same depth zone. Chemical analyses of bottom water samples taken at the same time as some of the sediment samples indicate that the degree of saturation with respect to aragonite Ω_A over the zone of aragonite disappearance ranges from 0.55 to 0.85; i.e. major dissolution occurs only at Ω_A values distinctly less than one. These results lend credence to the hypothesis that CaCO₃ dissolution in the oceans, both as aragonite and as calcite, takes place mainly as a response to complex chemical kinetic phenomena and not as a result of the simple attainment of undersaturation (thermodynamic hypothesis) or the resuspension of bottom sediment (hydrodynamic hypothesis).     

Oligocene biogenic siliceous deposits on the slope of the northern South China Sea

The abundance of radiolarian, diatom and sponge spicule and H₄SiO₄ in pore-waters increase abruptly at the boundary between Early and Late Oligocene (about 30-27.5 Ma) at Site 1148 of the northern South China Sea (SCS), indicating high biogenic silica accumulation during this time. At the same time (about 30-28 Ma), high biogenic silica deposition occurred in the central equatorial Pacific. Comparison of the biogenic silica accumulation at Site 1148 of the SCS with that at Site 929 of the Atlantic verifies that the biogenic silica accumulation between the low latitude Pacific and Atlantic oceans expresses the evident relationship of compensation during the Oligocene. Biogenic silica accumulation decreased in the Atlantic, whereas it increased in the Pacific at the boundary between the Early and Late Oligocene. It resulted from the formation and presence of North Atlantic deep water (NADW) in the Atlantic basin, indicating an intensive basin-basin fractionation. XRD analysis and SEM observation of the samples from Site 1148 demonstrate that most of radiolarian, diatom and sponge spicule have suffered from dissolution and reprecipitation, suggested by the opal-A→opal-CT transformation. As a result of the transformation, porosity increased, but dry and bulk densities decreased, reflecting the consequence of diagenesis on the physical property of sediment.     

Calcium isotope fractionation in coccoliths of cultured Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa

Four species of marine calcifying algae, the coccolithophores Calcidiscus leptoporus, Helicosphaera carteri, Syracosphaera pulchra and Umbilicosphaera foliosa were grown in laboratory cultures under temperatures varying between 14 and 23 °C, and one species, C. leptoporus, under varying [CO₃²⁻], ranging from 105 to 219 μmol/kg. Calcium isotope compositions of the coccoliths resemble in both absolute fractionation and temperature sensitivity previous calibrations of marine calcifying species e.g. Emiliania huxleyi (coccolithophores) and Orbulina universa (planktonic foraminifera) as well as inorganically precipitated CaCO₃, but also reveal small species specific differences. In contrast to inorganically precipitated calcite, but similar to E. huxleyi and O. universa, the carbonate ion concentration of the medium has no statistically significant influence on the Ca isotope fractionation of C. leptoporus coccoliths; however, combined data of E. huxleyi and C. leptoporus indicate that the observed trends might be related to changes of the calcite saturation state of the medium. Since coccoliths constitute a significant portion of the global oceanic CaCO₃ export production, the Ca isotope fractionation in these biogenic structures is important for defining the isotopic composition of the Ca sink of the ocean, one of the key parameters for modelling changes to the marine Ca budget over time. For the present ocean our results are in general agreement with the previously postulated and applied mean value of the oceanic Ca sink (Δ_sed) of about − 1.3‰, but the observed inter- and intra-species differences point to possible changes in Δ_sed through earth history, due to changing physico-chemical conditions of the ocean and shifts in floral and faunal assemblages.     

Depth distribution of calcareous sediments in the Mesozoic and Cenozoic North Atlantic Ocean

The upper Mesozoic and Cenozoic distribution of calcareous, biogenic particles which are produced by planktonic foraminifers and nannoplankton and which are the most important components of pelagic sediments since mid-Mesozoic times, has been reconstructed using data from North Atlantic deep-sea drill sites. Two phases of sedimentation of carbonate-rich sediments are separated by an interval from 100 to 80 m.y. B.P. when CaCO₃ particles were diluted by chiefly terrigenous material. Prior to 100 m.y. B.P. the highest concentrations of calcareous matter were confined to the deepest part of the then 4–4.5 km deep North Atlantic. After 80 m.y. B.P. sediments with high concentrations of calcareous matter have been deposited above 3 km paleodepth, but during the last 25 m.y. also between 4 and 5.5 km paleo-water depth. The latter occurrence is associated with indications of downslope displacement of calcareous material into the abyssal plains of the deepest parts of the North Atlantic.     

Hydrogeochemical Evolution Along Groundwater Flow Paths in the Manas River Basin,Northwest China

The impacts of long-term pumping on groundwater chemistry remain unclear in the Manas River Basin, Northwest China. In this study, major ions within five surface water and 105 groundwater samples were analyzed to identify hydrogeochemical processes affecting groundwater composition and evolution along the regional-scale groundwater flow paths using the multivariate techniques of hierarchical cluster analysis (HCA) and principal components analysis (PCA) and traditional graphical methods for analyzing groundwater geochemistry. HCA classified the groundwater samples into four clusters (C1 to C4). PCA reduced the dimensionality of geochemical data into three PCs, which explained 86% of the total variance. The results of HCA and PCA were used to identify three zones: “recharge,” “transition,” and “discharge.” In the recharge zone the groundwater type is Ca-HCO₃-SO₄ and is primarily impacted by the dissolution of calcite and silicate weathering. In the transition zone the groundwater type is Ca-HCO₃-SO₄-Cl and is impacted by rock dissolution and reverse ion exchange. In the discharge zone the groundwater type is Na-Cl and is impacted by evaporation and reverse ion exchange. In addition, anthropogenic activities impact the groundwater chemistry in the study area. The groundwater type generally changes from Ca-HCO₃-SO₄ in the recharge area to Na-Cl in the discharge area along the regional-scale groundwater flow paths. This study provides a process-based knowledge for understanding the interaction of groundwater flow patterns and geochemical evolution within the Manas River Basin.     

A numerical system to study the transport properties in the Ria de Aveiro lagoon

This work presents results from numerical modelling studies on the hydrodynamics and sediments and passive particles transport properties in Ria de Aveiro, a shallow lagoon located on the Portuguese Northwest Atlantic coast. The hydrodynamic of the lagoon was systematically studied, from both the Eulerian and Lagragian point of view, in order to understand the overall circulation in the lagoon, characterize the dynamics of its different channels and assess the transport of suspended cohesive sediments.Responsible Editor: Hans Burchard     

Late Holocene annual growth in three Alpine stalagmites records the influence of solar activity and the North Atlantic Oscillation on winter climate

Annual growth rates and the ratio of dark to light-colored calcite within single annual laminae in three contemporaneously deposited Holocene speleothems from Grotta di Ernesto, an Alpine cave in northern Italy, respond to changes in surface temperature rather than precipitation. Based on monitoring of present-day calcite growth, and correlation with instrumental data for surface climatic conditions, we interpret a higher ratio of dark to light-colored calcite and the simultaneous thinning of annual laminae as indicative of colder-than-present winters. Such dark and thin laminae occur in those parts of the three stalagmites deposited from AD 1650 to 1713 and from AD 1798 to 1840, as reconstructed through lamina counting. These periods correspond to the well-known Maunder and Dalton Minima of solar activity. An 11-yr cyclicity in growth rate, coupled with reduced calcite deposition during the historic minima of solar activity, is indicative of a solar influence on lamina thickness. Spectral analysis of the lamina thickness data also suggests that the North Atlantic Oscillation variability influenced winter temperatures. Based on the present-day controls on cave calcite formation, we infer that high-frequency changes in solar activity modulated the seasonal duration of soil CO₂ production.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

The distribution of13C in the Atlantic Ocean

Individual vertical profiles and north-south sections for the distribution of theδ¹³C of total dissolved inorganic carbon are presented for the Atlantic stations of the GEOSECS program. In most cases theδ¹³C data parallel the distribution of dissolved O₂. Differences are attributed to in-situ oxidation of organic matter and dissolution of particles of CaCO₃. Antarctic Bottom and Intermediate Waters have aδ¹³C value of near 0.5‰ relative to the PDB isotopic standard. The lowest values in the Atlantic ocean were found in the Antarctic Circumpolar waters which haveδ¹³C values as low as 0.2‰. The core of the North Atlantic Deep Water has aδ¹³C value of 1.0‰.     

In-situ investigation on growth and dissolution of crystals in aqueous solution

In-situ observation methods to investigate the physics involved in growth and dissolution processes of crystals in aqueous solution at ordinary temperature and pressure are described. The methods visualize insitu the phenomena relating to clustering of nanometer sized embryonic particles, the mass transport from bulk solution and from a crystal, the concentration gradient in the diffusion boundary layer and its distribution around a crystal, and spiral growth steps with height of one nanometer. The techniques measure at the nanometer scale the growth and dissolution rates of individual spiral growth hillocks and etch pits whose dislocation characters are identified in-situ.     

Plagioclase weathering in the groundwater system of a sandy,silicate aquifer

The weathering rate of plagioclase was estimated in the groundwater system of a sandy, silicate aquifer formed after the Wisconsin Glacial Stage. The study area is an isthmus lying between Crystal and Big Muskellunge Lakes in northern Wisconsin, USA. Plagioclase occupies 3% of the quartz and K‐feldspar dominated sediments. Groundwater in the study area is recharged in part by precipitation through the isthmus soils and in part by seepage from Crystal Lake, which is of low ionic strength and chemically in steady state. Water analysis revealed that the chemistry of groundwater recharged from Crystal Lake is regulated by mineral dissolution reactions. The rate constant for plagioclase was estimated using mass balances for sodium concentrations along a groundwater flowline from Crystal Lake. For this calculation, various kinds of hydrological/mineralogical information were used: groundwater flow path from oxygen isotope analysis, groundwater travel times from flow modelling, mineral composition from microprobe analysis and surface area of minerals from BET (Brunauer–Emmett–Teller) analysis. The overall range of the estimation was less than an order of magnitude (3·5 × 10^?16 to 3·4 × 10^?15 mol/m²/s). The result is up to three orders of magnitude slower than the previous field estimates, which applied geometric methods in measuring mineral surface areas. However, this result is somewhat higher than the estimates reported by other BET area‐based studies, which were undertaken on soil profiles having different hydrological conditions. This rate difference is interpreted as a result of higher mineral reactivity owing to younger sediment age. The rate difference is smaller when this result is compared with the estimates from the soils of similar age, indicating that the differences in hydrological condition are not sufficient to explain the weathering rate discrepancy between the laboratory and field studies, which is up to five orders of magnitude. Copyright © 2002 John Wiley & Sons, Ltd.     

Role of fractures in weathering of solid rocks: narrowing the gap between laboratory and field weathering rates

A weathering study of a fractured environment composed of granites and metasediments was conducted in Trás-os-Montes and Alto Douro (north of Portugal) and covered the hydrographic basin of Sordo river. Within the basin, a number of perennial springs were monitored for discharge rate, which allowed for the estimation of annual recharges. A small area of the basin was characterized for parameters such as hydraulic conductivity and effective porosity, which, in combination with the previously calculated recharges, allowed for the calculation of a fracture surface area. The monitored springs were also sampled and analyzed for major inorganic compounds, and using a mole balance model the chemistry of the water samples was explained by weathering to kaolinite of albite–oligoclase plus biotite (granites) or of albite plus chlorite (metasediments). The number of moles of dissolved primary minerals (e.g. albite) could be calculated using this method. These mass transfers were then multiplied by the spring's median discharge rate and divided by the fracture surface area to obtain a weathering rate. Another weathering rate was determined, but using a BET surface area as normalizing factor. Comparing both rates with a representative record of laboratory as well as of field-based weathering rates, it has been noted that rates normalized by the BET were, as expected, similar to commonly reported field-based rates, whereas rates normalized by the fracture surface area were unexpectedly relatively close to laboratory rates (one order of magnitude smaller). The monitored springs are of the fracture artesian type, which means that water emerging at the spring site flowed preferentially through joints and fractures and that weathering took place predominantly at their walls. Consequently, it was concluded that the most realistic weathering rates are those normalized by the fracture surface area, and as a corollary that the gap between laboratory and field weathering rates might not be as wide as usually is reported to be.     

Conduit properties and karstification in the unconfined Floridan aquifer

Exchange of water between conduits and matrix is an important control on regional chemical compositions, karstification, and quality of ground water resources in karst aquifers. A sinking stream (Santa Fe River Sink) and its resurgence (River Rise) in the unconfined portion of the Floridan Aquifer provide the opportunity to monitor conduit inflow and outflow. The use of temperature as a tracer allows determination of residence times and velocities through the conduit system. Based on temperature records from two high water events, flow is reasonably represented as pipe flow with a cross-sectional area of 380 m2, although this model may be complicated by losses of water from the conduit system at higher discharge rates. Over the course of the study year, the River Rise discharged a total of 1.9 x 10(7) m3 more water than entered the River Sink, reflecting net contribution of ground water from the matrix into the conduit system. However, as River Sink discharge rates peaked following three rainfall events during the study period, the conduit system lost water, presumably into the matrix. Surface water in high flow events is typically undersaturated with respect to calcite and thus may lead to dissolution, depending on its residence time in the matrix. A calculation of local denudation is larger than other regional estimates, perhaps reflecting return of water to conduits before calcite equilibrium is reached. The exchange of matrix and conduit water is an important variable in karst hydrology that should be considered in management of these water resources.     

Factors Controlling In Situ Biogeochemical Transformation of Trichloroethene: Field Survey

We have previously defined in situ biogeochemical transformation as the biogenic formation of reactive minerals that are capable of abiotically degrading chlorinated solvents such as trichloroethene without accumulation of degradation products such as vinyl chloride (AFCEE et al. 2008 ). This process has been implemented in biowalls used to intercept contaminated groundwater. Abiotic patterns of contaminant degradation were observed at Altus Air Force Base (AFB) and in an associated column study, but not at other sites including Dover AFB. These abiotic patterns were associated with biogenic formation of reactive iron sulfide minerals. Iron sulfides in the form of small individual grains, coatings on magnetite, and sulfur‐deficient pyrite framboids were observed in samples collected from the Altus AFB biowalls and one of the EPA columns. Larger iron sulfide grains coated with oxide layers were observed in samples collected from Dover AFB. Altus AFB and the EPA column differed from Dover AFB in that groundwater flow at Dover AFB was relatively slow and potentially reversing. High volumetric sulfate consumption rates, an abiotic pattern of trichloroethene (TCE) degradation, and the formation of small, high surface area iron sulfide particles were associated with relatively high rates of TCE removal via an abiotic pattern. Geochemical modeling demonstrated that iron monosulfides such as mackinawite were near saturation, and iron disulfides such as pyrite were supersaturated at all sites. This environmental condition can be supportive of nucleation of small particles rather than crystal growth leading to larger particles. When nucleation is dominant, small, high surface area, and reactive particles result. When crystal growth dominates the crystals are larger and have lower specific surface area and reactivity. These results taken together suggest that creation of a dynamic environment can promote biogeochemical transformation based on generation of reactive iron sulfides.