Why is calcite a strong phosphorus sink in freshwater? Investigating the adsorption mechanism using batch experiments and surface complexation modeling.

One of the primary drivers of Phosphorus (P) limitation in aquatic systems is P adsorption to sediments. Sediments adsorb more P in freshwater compared to other natural solutions, but the mechanism driving this difference is poorly understood. To provide insights into the mechanism, we conducted batch experiments of P adsorption to calcite in freshwater and seawater, and used computer software to develop complexation models. Our simulations revealed three main reasons that, combining together, may explain the greater P adsorption to calcite in freshwater vs. seawater. First, aqueous speciation of P makes a difference. The ion pair CaPO4- is much more abundant in freshwater; although seawater has more Ca2+ ions, MgHPO40 and NaHPO40 are more thermodynamically favored. Second, the adsorbing species of P make a difference. The ion pair CaPO4- (the preferred adsorbate in freshwater) is able to access adsorption sites that are not available to HPO42- (the preferred adsorbate in seawater), thereby raising the maximum concentration of P that can adsorb to the calcite surface in freshwater. Third, water chemistry affects the competition among ions for surface sites. Other ions (including P) compete more effectively against CO32- when immersed in freshwater vs. seawater, even when the concentration of HCO3-/CO32- is higher in freshwater vs. seawater. In addition, we found that under oligotrophic conditions, P adsorption is driven by the higher energy adsorption sites, and by the lower energy sites in eutrophic conditions. This study is the first to model P adsorption mechanisms to calcite in freshwater and seawater.

Carbon and nitrogen pools and mobile fractions in surface soils across a mangrove saltmarsh ecotone.

In the subtropics, climate change is pushing woody mangrove forests into herbaceous saltmarshes, altering soil carbon (C) and nitrogen (N) pools, with implications for coastal wetland productivity and C and N exports. We quantified total C and N pools, and mobile fractions including extractable mineral N, extractable organic C and N, and active (aerobically mineralizable) C and N, in surface soils (top 7.6 cm) of adjacent mangrove (primarily Avicennia germinans) and saltmarsh (Juncus roemerianus) vegetation zones in tidal wetlands of west-central Florida (USA). We tested whether surface-soil accumulations of C, N, and their potentially mobile fractions are greater in mangrove than in saltmarsh owing to greater accumulations in the mangrove zone of soil organic matter (SOM) and fine mineral particles (C- and N-retaining soil constituents). Extractable organic fractions were 39-45% more concentrated in mangrove than in saltmarsh surface soil, and they scaled steeply and positively with SOM and fine mineral particle (silt + clay) concentrations, which themselves were likewise greater in mangrove soil. Elevation may drive this linkage. Mangrove locations were generally at lower elevations, which tended to have greater fine particle content in the surface soil. Active C and extractable mineral N were marginally (p < 0.1) greater in mangrove soil, while active N, total N, and total C showed no statistical differences between zones. Extractable organic C and N fractions composed greater shares of total C and N pools in mangrove than in saltmarsh surface soils, which is meaningful for ecosystem function, as persistent leaching of this fraction can perpetuate nutrient limitation. The active (mineralizable) C and N fractions we observed constituted a relatively small component of total C and N pools, suggesting that mangrove surface soils may export less C and N than would be expected from their large total C and N pools.

Shifting Ground: Landscape-Scale Modeling of Biogeochemical Processes under Climate Change in the Florida Everglades.

Scenarios modeling can be a useful tool to plan for climate change. In this study, we help Everglades restoration planning to bolster climate change resiliency by simulating plausible ecosystem responses to three climate change scenarios: a Baseline scenario of 2010 climate, and two scenarios that both included 1.5 °C warming and 7% increase in evapotranspiration, and differed only by rainfall: either increase or decrease by 10%. In conjunction with output from a water-use management model, we used these scenarios to drive the Everglades Landscape Model to simulate changes in a suite of parameters that include both hydrologic drivers and changes to soil pattern and process. In this paper we focus on the freshwater wetlands; sea level rise is specifically addressed in prior work. The decreased rainfall scenario produced marked changes across the system in comparison to the Baseline scenario. Most notably, muck fire risk was elevated for 49% of the period of simulation in one of the three indicator regions. Surface water flow velocity slowed drastically across most of the system, which may impair soil processes related to maintaining landscape patterning. Due to lower flow volumes, this scenario produced decreases in parameters related to flow-loading, such as phosphorus accumulation in the soil, and methylmercury production risk. The increased rainfall scenario was hydrologically similar to the Baseline scenario due to existing water management rules. A key change was phosphorus accumulation in the soil, an effect of flow-loading due to higher inflow from water control structures in this scenario.

Visioning the Future: Scenarios Modeling of the Florida Coastal Everglades.

In this paper, we provide screening-level analysis of plausible Everglades ecosystem response by 2060 to sea level rise (0.50 m) interacting with macroclimate change (1.5 °C warming, 7% increase in evapotranspiration, and rainfall that either increases or decreases by 10%). We used these climate scenarios as input to the Ecological Landscape Model to simulate changes to seven interactive hydro-ecological metrics. Mangrove forest and other marine influences migrated up to 15 km inland in both scenarios, delineated by the saltwater front. Freshwater habitat area decreased by 25-30% under our two climate change scenarios and was largely replaced by mangroves and, in the increased rainfall scenario, open water as well. Significant mangroves drowned along northern Florida Bay in both climate change scenarios due to sea level rise. Increased rainfall of 10% provided significant benefits to the spatial and temporal salinity regime within the marine-influenced zone, providing a more gradual and natural adjustment for at-risk flora and fauna. However, increased rainfall also increased the risk of open water, due to water depths that inhibited mangrove establishment and reduced peat accumulation rates. We infer that ecological effects related to sea level rise may occur in the extreme front-edge of saltwater intrusion, that topography will control the incursion of this zone as sea level rises, and that differences in freshwater availability will have ecologically significant effects on ecosystem resilience through the temporal and spatial pattern of salinity changes.