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1. Electrochemically induced metal- vs. ligand-based redox changes in mackinawite: identification of a Fe ³⁺ - and polysulfide-containing intermediate

   https://doi.org/10.1039/d1dt01684a  

   Sanden, Sebastian A.; Szilagyi, Robert K.; Li, Yamei; Kitadai, Norio; Webb, Samuel M.; Yano, Takaaki; Nakamura, Ryuhei; Hara, Masahiko; McGlynn, Shawn E. (August 2021, Dalton Transactions)

   Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H + , CO 2 and NO 3 − reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases. Here, we investigated the chemical properties of iron-sulfide by cyclic voltammetry, Raman and X-ray absorption spectroscopic techniques. Tracing oxidative maturation pathways by varying electrode potential, nanoparticulate n (Fe 2+ S 2− ) (s) was found to oxidize to a Fe 3+ containing FeS phase at −0.5 V vs. Ag/AgCl (pH = 7). In a subsequent oxidation, polysulfides are proposed to give a material that is composed of Fe 2+ , Fe 3+ , S 2− and polysulfide (S n 2− ) species, with its composition described as Fe 2+ 1−3 x Fe 3+ 2 x S 2− 1− y (S n 2− ) y . Thermodynamic properties of model compounds calculated by density functional theory indicate that ligand oxidation occurs in conjunction with structural rearrangements, whereas metal oxidation may occur prior to structural rearrangement. These findings together point to the existence of a metastable FeS phase located at the junction of a metal-based oxidation path between FeS and greigite (Fe 2+ Fe 3+ 2 S 2− 4 ) and a ligand-based oxidation path between FeS and pyrite (Fe 2+ (S 2 ) 2− ). 

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2. The core root microbiome of Spartina alterniflora is predominated by sulfur-oxidizing and sulfate-reducing bacteria in Georgia salt marshes, USA

   https://doi.org/10.1186/s40168-021-01187-7  

   Rolando, Jose L.; Kolton, Max; Song, Tianze; Kostka, Joel E. (December 2022, Microbiome)

   Abstract Background Salt marshes are dominated by the smooth cordgrass Spartina alterniflora on the US Atlantic and Gulf of Mexico coastlines. Although soil microorganisms are well known to mediate important biogeochemical cycles in salt marshes, little is known about the role of root microbiomes in supporting the health and productivity of marsh plant hosts. Leveraging in situ gradients in aboveground plant biomass as a natural laboratory, we investigated the relationships between S. alterniflora primary productivity, sediment redox potential, and the physiological ecology of bulk sediment, rhizosphere, and root microbial communities at two Georgia barrier islands over two growing seasons. Results A marked decrease in prokaryotic alpha diversity with high abundance and increased phylogenetic dispersion was found in the S. alterniflora root microbiome. Significantly higher rates of enzymatic organic matter decomposition, as well as the relative abundances of putative sulfur (S)-oxidizing, sulfate-reducing, and nitrifying prokaryotes correlated with plant productivity. Moreover, these functional guilds were overrepresented in the S. alterniflora rhizosphere and root core microbiomes. Core microbiome bacteria from the Candidatus Thiodiazotropha genus, with the metabolic potential to couple S oxidation with C and N fixation, were shown to be highly abundant in the root and rhizosphere of S. alterniflora . Conclusions The S. alterniflora root microbiome is dominated by highly active and competitive species taking advantage of available carbon substrates in the oxidized root zone. Two microbially mediated mechanisms are proposed to stimulate S. alterniflora primary productivity: (i) enhanced microbial activity replenishes nutrients and terminal electron acceptors in higher biomass stands, and (ii) coupling of chemolithotrophic S oxidation with carbon (C) and nitrogen (N) fixation by root- and rhizosphere-associated prokaryotes detoxifies sulfide in the root zone while potentially transferring fixed C and N to the host plant. 

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3. An assessment of future tidal marsh resilience in the San Francisco Estuary through modeling and quantifiable metrics of sustainability

   https://doi.org/10.3389/fenvs.2022.1039143  

   Morris, James T.; Drexler, Judith Z.; Vaughn, Lydia J.; Robinson, April H. (November 2022, Frontiers in Environmental Science)

   Quantitative, broadly applicable metrics of resilience are needed to effectively manage tidal marshes into the future. Here we quantified three metrics of temporal marsh resilience: time to marsh drowning, time to marsh tipping point, and the probability of a regime shift, defined as the conditional probability of a transition to an alternative super-optimal, suboptimal, or drowned state. We used organic matter content (loss on ignition, LOI) and peat age combined with the Coastal Wetland Equilibrium Model (CWEM) to track wetland development and resilience under different sea-level rise scenarios in the Sacramento-San Joaquin Delta (Delta) of California. A 100-year hindcast of the model showed excellent agreement ( R 2 = 0.96) between observed (2.86 mm/year) and predicted vertical accretion rates (2.98 mm/year) and correctly predicted a recovery in LOI ( R 2 = 0.76) after the California Gold Rush. Vertical accretion in the tidal freshwater marshes of the Delta is dominated by organic production. The large elevation range of the vegetation combined with high relative marsh elevation provides Delta marshes with resilience and elevation capital sufficiently great to tolerate centenary sea-level rise (CLSR) as high as 200 cm. The initial relative elevation of a marsh was a strong determinant of marsh survival time and tipping point. For a Delta marsh of average elevation, the tipping point at which vertical accretion no longer keeps up with the rate of sea-level rise is 50 years or more. Simulated, triennial additions of 6 mm of sediment via episodic atmospheric rivers increased the proportion of marshes surviving from 51% to 72% and decreased the proportion drowning from 49% to 28%. Our temporal metrics provide critical time frames for adaptively managing marshes, restoring marshes with the best chance of survival, and seizing opportunities for establishing migration corridors, which are all essential for safeguarding future habitats for sensitive species. 

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4. Salt marsh nitrogen cycling: where land meets sea

   https://doi.org/10.1016/j.tim.2023.09.010  

   Bowen, Jennifer L.; Spivak, Amanda C.; Bernhard, Anne E.; Fulweiler, Robinson W.; Giblin, Anne E. (October 2023, Trends in Microbiology)

   Iyer, Shankar Chandrashekar (Ed.)

   Salt marshes sit at the terrestrial–aquatic interface of oceans around the world. Unique features of salt marshes that differentiate them from their upland or offshore counterparts include high rates of primary production from vascular plants and saturated saline soils that lead to sharp redox gradients and a diversity of electron acceptors and donors. Moreover, the dynamic nature of root oxygen loss and tidal forcing leads to unique biogeochemical conditions that promote nitrogen cycling. Here, we highlight recent advances in our understanding of key nitrogen cycling processes in salt marshes and discuss areas where additional research is needed to better predict how salt marsh N cycling will respond to future environmental change. 

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5. The Effect of Runnels on Salt Marsh Sediment Dynamics, Vegetation, and Nitrogen Cycling

   https://doi.org/10.1007/s12237-025-01511-6  

   Sullivan, Hillary_L; Holtzer, Julia; Deegan, Linda_A; Bowen, Jennifer_L (February 2025, Estuaries and Coasts)

   Abstract Runnels, a climate adaptation technique that drains surface water to restore marsh vegetation and habitat, are increasingly being used to prevent the formation of shallow water impoundments or pannes in salt marshes that result in the loss of important ecosystem services. However, we know little about the effect of runnels on salt marsh biogeochemistry. This study measured how sediment characteristics and rates of nitrogen cycle processes were altered by impounded water and vegetation loss, and whether runnels can restore these marsh attributes to reference conditions. Impounded areas were 52 ± 4% less vegetated than nearby intact marsh, with 11 ± 2% less organic matter and 24 ± 5% higher bulk density. Additionally, impoundments removed 32 ± 32 µmol N m⁻²d⁻¹less than reference marsh areas via denitrification. At six of the 11 runneled sites, vegetation percent cover increased by 40 ± 5%, accompanied by a 7 ± 3% recovery of organic matter and a 9 ± 6% reduction of bulk density. At sites where vegetation recovered to within 70% of reference plots at a site, runneled plots removed 97 ± 31 µmol more N m⁻²d⁻¹than impoundments, which was also 82 ± 31 µmol more N m⁻²d⁻¹than reference areas. The driver of recovery is related to initial site conditions, including higher redox potentials and lower porewater salinities, compared with sites where revegetation was unsuccessful. The extent of runnel effectiveness and the recovery of vegetation, sediment characteristics, and nitrogen cycle processes was variable among runneled marshes, and the effectiveness of runnels may depend on initial site-specific characteristics and degree of initial degradation. 

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