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23 records · Page 2

Integrating Tide‐Driven Wetland Soil Redox and Biogeochemical Interactions Into a Land Surface Model

Abstract Redox processes, aqueous and solid‐phase chemistry, and pH dynamics are key drivers of subsurface biogeochemical cycling and methanogenesis in terrestrial and wetland ecosystems but are typically not included in terrestrial carbon cycle models. These omissions may introduce errors when simulating systems where redox interactions and pH fluctuations are important, such as wetlands where saturation of soils can produce anoxic conditions and coastal systems where sulfate inputs from seawater can influence biogeochemistry. Integrating cycling of redox‐sensitive elements could therefore allow models to better represent key elements of carbon cycling and greenhouse gas production. We describe a model framework that couples the Energy Exascale Earth System Model (E3SM) Land Model (ELM) with PFLOTRAN biogeochemistry, allowing geochemical processes and redox interactions to be integrated with land surface model simulations. We implemented a reaction network including aerobic decomposition, fermentation, sulfate reduction, sulfide oxidation, methanogenesis, and methanotrophy as well as pH dynamics along with iron oxide and iron sulfide mineral precipitation and dissolution. We simulated biogeochemical cycling in tidal wetlands subject to either saltwater or freshwater inputs driven by tidal hydrological dynamics. In simulations with saltwater tidal inputs, sulfate reduction led to accumulation of sulfide, higher dissolved inorganic carbon concentrations, lower dissolved organic carbon concentrations, and lower methane emissions than simulations with freshwater tidal inputs. Model simulations compared well with measured porewater concentrations and surface gas emissions from coastal wetlands in the Northeastern United States. These results demonstrate how simulating geochemical reaction networks can improve land surface model simulations of subsurface biogeochemistry and carbon cycling.

54 ENVIRONMENTAL SCIENCES↗

Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated under suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. In this paper, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl–SO 4 –HCO 3 anion effects. Emergence of Lp/Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions without HCO 3 – ; whereas Lp and Gt concomitantly nucleate in SO 4 2– -rich solutions, and also when co-solute HCO 3 – is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO 4 ) or acicular needle-shaped (in HCO 3 ) Gt crystals nucleate and grow radially outward from the Fh aggregates. Stages of transformation monitored by in situ μ-XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by the onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelmingly support dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that the iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.

54 ENVIRONMENTAL SCIENCES↗

Environmental controls on the kinetics of iron-sulfur cluster nucleation and nanoparticle formation

Anoxic, sulfidic conditions have been prevalent since the early Proterozoic and favor aqueous iron-sulfur (FeS aq ) clusters as a major fraction of the soluble, reduced iron and sulfur pool. FeS aq cluster formation and nucleation is driven by the high affinity between ferrous iron (Fe(II)) and sulfide (HS − ), ultimately yielding particles that precipitate as iron sulfide minerals. FeS aq clusters were recently shown to be bioavailable sources of iron and sulfur for a variety of anaerobes, yet little is known of the factors that influence the kinetics of their formation and nucleation. Here we apply computational and spectroscopic approaches to investigate the dynamics of FeS aq nucleation, cluster growth, precipitation, and redissolution as a function of Fe(II)/HS − concentration, temperature, and pH. Experiments were conducted under excess HS − to mimic euxinic conditions common to contemporary anaerobic aquatic ecosystems and those of the Proterozoic. Density functional theory calculations reveal the key role of water oxygen-iron interactions in stabilizing small FeS aq clusters and promoting solubility. Dynamic light scattering revealed a concentration-dependent increase in the kinetics of FeS aq nucleation and cluster aggregation. Increasing temperature promoted FeS aq cluster nucleation and aggregation while also enhancing dissolution. Alkaline pH also promoted FeS aq nucleation and cluster aggregation. At 25 °C, pH 7.0, and at reactant concentrations of 30 µM, FeS aq clusters < 10 nm in diameter remained in solution for > 2 h. These results underscore the importance of temperature, pH, and reactant concentration in the kinetics of FeS aq nucleation and cluster growth that, in turn, influence their bioavailability in anaerobic ecosystems.

Aquatic ecosystems↗

Nanoscale trace-element zoning in pyrite framboids and implications for paleoproxy applications

Pyrite framboids (spherical masses of nanoscale pyrite) are among the earliest textures of pyrite to form in sediments. It has been proposed that their trace-element (TE) contents can be used to track the TE composition of the water column in which they formed. However, it is not clear how these TEs are associated with the framboidal pyrite grains. For instance, it is important to know whether they are incorporated uniformly or are enriched in different regions of the framboid. Here, we used high-resolution scanning transmission electron microscopy to identify chemical zoning within pyrite framboids. We found that initial, nanoscale pyrite euhedral crystals, which make up the volumetric majority of the framboids, are covered/infilled by later pyrite that templates on the earlier pyrite. Further, this later pyrite is enriched in TEs, suggesting that many TEs are incorporated in pyrite relatively late (during early diagenesis; not in the water column). This observation suggests that although chemical analyses of pyrite framboids may provide ocean-water chemistry trends through time, the details are complex. Specifically, the TEs found in pyrite may be linked to adsorption onto organic matter, detrital material, and authigenic minerals such as Fe- and Mn-oxide phases followed by desorption in the sediments or release via dissolution and incorporation into pyrite as overgrowths on the initial nanoscale euhedral crystals that make up framboids. While the use of pyrite chemistry to understand past ocean conditions remains promising, and even diagenetic additions may not preclude the utility of pyrite for reconstructing ancient ocean conditions, care must be taken in interpretations because the end concentration may be influenced by diagenesis.

58 GEOSCIENCES↗

Water film-driven Mn (oxy)(hydr)oxide nanocoating growth on rhodochrosite

Minerals exposed to moist air stabilize thin water films that drive a score of chemical reactions of great importance to water-unsaturated terrestrial environments. In this study, we identified Mn (oxy)(hydr)oxide nanocoatings formed by the dissolution, oxidation and precipitation of Mn in oxygenated water films grown on rhodochrosite (MnCO 3 ) microparticles. Nanocoatings that could be identified by vibrational spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and (scanning and transmission) electron microscopy formed in water films containing the equivalent of at least 7 monolayers (~84 H 2 O/nm 2 ). These films were formed by exposing microparticles to moist air with at least 50% relative humidity (RH). Films of neutral pH reacted up to 14% of the Mn II located in the topmost ~5 nm region of the microparticles in atmospheres of up to 90% RH for 7 d. These reactions produced MnOOH, birnessite (MnO 2 ) and hausmannite (Mn 3 O 4 ) nanoparticles of low crystallinity, while exposure to atmospheric air for 1 yr. converted only 2% of Mn II in this region to MnOOH. In contrast, reactions in alkaline water films converted up to ~75% of the Mn II but only after 16 d of reaction. These films produced MnOOH and MnO 2 of low crystallinity, as well as crystalline hausmannite. Kinetic modeling of the time-resolved growth of the Mnsingle bondO stretching vibrational bands of these nanocoatings revealed two concurrent reaction processes. A 1 rst -order process was assigned to nucleation events terminating only after a few hours, and a 0-order process was assigned to the sustained growth of nanocoatings from these nuclei over longer reaction time. By identifying nanocoatings formed by water film-driven reactions on rhodochrosite, our study adds new insight into mineralogical transformations relevant to anoxic–oxic boundaries in water-unsaturated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗