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At least 109 records · Page 6

Gas Evolution in Water Electrolysis

Gas bubbles generated by the hydrogen evolution reaction and oxygen evolution reaction during water electrolysis influence the energy conversion efficiency of hydrogen production. Here we survey what is known about the interaction of gas bubbles and electrode surfaces and the influence of gas evolution on practicable devices used for water electrolysis. Here, we survey the physical processes occurring during the life cycle of a bubble, summarize techniques used to characterize gas evolution phenomena in-situ and in practical device environments, and discuss ways that electrodes can be tailored to facilitate gas removal at high current densities. Lastly, we summarize efforts to model the behavior of individual gas bubbles and multiphase flows produced at gas evolving electrodes. We conclude our review with a short summary of outstanding questions which could be answered by future efforts to characterize gas evolution in electrochemical device environments or by improved simulations of multiphase flows.

Bubbles↗

Land surface dynamics and meteorological forcings modulate land surface temperature characteristics

This study examines the effect of land cover, vegetation health, climatic forcings, elevation heat loads, and terrain characteristics (LVCET) on land surface temperature (LST) distribution over West Africa (WA). We employ fourteen machine-learning models, which preserve nonlinear relationships, to downscale LST and other predictands while preserving the geographical variability of WA. Our results showed that the random forest model performs best in downscaling predictands. This is important for the sub-region since it has limited access to mainframes to power multiplex machine-learning algorithms. In contrast to the northern regions, the southern regions consistently exhibit healthy vegetation. Also, areas with unhealthy vegetation coincide with hot LST clusters. The positive Normalized Difference Vegetation Index (NDVI) trends in the Sahel underscore rainfall recovery and subsequent Sahelian greening. The southwesterly winds cause the upwelling of cold waters, lowering LST in southern WA and highlighting the cooling influence of water bodies on LST. Identifying regions with elevated LST is paramount for prioritizing greening initiatives, and our study underscores the importance of considering LVCET factors in urban planning. Topographic slope-facing angles, heat loads, and diurnal anisotropic heat all contribute to variations in LST, emphasizing the need for a holistic approach when designing resilient and sustainable landscapes.

54 ENVIRONMENTAL SCIENCES↗

Overview of the earth resources program of the Jet Propulsion Laboratory

Proposed is an investigation to develop and correlate remote sensing from satellites and aircraft into an effective prototype system for California statewide water quality surveillance. Aircraft overflights, computer enhanced recognition of pollution signatures, ground truth measurements, and data processing will be employed to develop a simplified and automated monitoring system. ERTS A image data will be used for nine major drainage basins of California having unique water quality influences from waste discharges, thermal contributions, oil spills, turbidity, sea water intrusion, agricultural drainage, toxicity, biostimulation, and eutrophication.

Burcham, D. P.↗

Influence of fixed charge concentration and water uptake on ion sorption in AMPS/PEGDA membranes

Water content and charge density strongly influence ion sorption in charged membranes. However, isolating the individual effect of each parameter on ion sorption can be difficult due to experimental challenges associated with independently controlling these two variables during membrane synthesis. This frustrates development and validation of fundamental models and structure/property relationships. In this study, three series of uncharged and negatively charged hydrogel membranes were prepared using poly(ethylene glycol) diacrylate (PEGDA) as a cross-linker and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as an ionic monomer. Here, water content and charge density were controlled by varying AMPS content and PEGDA chain length. Ion sorption in these materials was measured using aqueous NaCl solutions at concentrations ranging from 0.01 to 1.0 M. At constant charge density, salt sorption increased as water content increased. At fixed water content, salt sorption decreased as charge density increased. Salt sorption in membranes with the highest water content and charge density was predicted using the Donnan/Manning model, which accounts for solution and membrane phase thermodynamic non-idealities. However, this approach could not predict sorption in weakly charged and uncharged membranes, presumably due to additional membrane phase thermodynamic non-idealities associated with ion solvation and uncharged polymer segments.

36 MATERIALS SCIENCE↗

Anthropogenically driven climate and landscape change effects on inland water carbon dynamics: What have we learned and where are we going?

Inland waters serve as important hydrological connections between the terrestrial landscape and oceans but are often overlooked in global carbon (C) budgets and Earth System Models. Terrestrially derived C entering inland waters from the watershed can be transported to oceans but over 83% is either buried in sediments or emitted to the atmosphere before reaching oceans. Anthropogenic pressures such as climate and landscape changes are altering the magnitude of these C fluxes in inland waters. Here, we synthesize the most recent estimates of C fluxes and the differential contributions across inland waterbody types (rivers, streams, lakes, reservoirs, and ponds), including recent measurements that incorporate improved sampling methods, small waterbodies, and dried areas. Across all inland waters, we report a global C emission estimate of 4.40 Pg C/year (95% confidence interval: 3.95–4.85 Pg C/year), representing a 13% increase from the most recent estimate. In this work, we also review the mechanisms by which the most globally widespread anthropogenically driven climate and landscape changes influence inland water C fluxes. The majority of these drivers are expected to influence terrestrial C inputs to inland waters due to alterations in terrestrial C quality and quantity, hydrological pathways, and biogeochemical processing. We recommend four research priorities for the future study of anthropogenic alterations to inland water C fluxes: (1) before-and-after measurements of C fluxes associated with climate change events and landscape changes, (2) better quantification of C input from land, (3) improved assessment of spatial coverage and contributions of small inland waterbodies to C fluxes, and (4) integration of dried and drawdown areas to global C flux estimates. Improved measurements of inland water C fluxes and quantification of uncertainty in these estimates will be vital to understanding both terrestrial C losses and the “moving target” of inland water C emissions in response to rapid and complex anthropogenic pressures.

59 BASIC BIOLOGICAL SCIENCES↗

Influence of Initial fabric and water-wetting on particle fracture and force chain evolution in natural silica sand

Particle fracture has a significant influence on the engineering behavior of granular materials. However, the combined influence of the initial fabric and wetting on particle fracture and force chain evolution in granular materials, particularly in sands, remains insufficiently explored in the current literature. Here, in this paper, one-dimensional (1D) confined compression experiments were conducted on dry and wet specimens, and particle-level fracture was captured using three-dimensional (3D) in-situ Synchrotron Micro-Computed Tomography (SMT). A quantitative assessment of particle fracture revealed that wet specimens, which have disturbed fabric, exhibited a higher fracture percentage in comparison to dry specimens. Complementary 3D finite element (FE) simulations were performed using dry and wet (only solid fabric was considered and the influence of pore water is not considered) sand assemblies to assess interparticle contact forces and particle-scale stress distributions within the specimens. Force chain analysis was subsequently conducted, encompassing quantification of interparticle forces, characterization of force network structures, and monitoring the dynamic evolution of force chains under different strain levels. The results show that the specimens with disturbed fabric led to a more dynamic and less persistent force network, more fabric instability, and thus more reorganization of force chain structures. In addition, the frequent rearrangement of the force network in the presence of water (with reduced inter-particle contact friction) likely exacerbates localized stress concentrations, promoting failure in previously unengaged or weakly connected particles. The results reported in this paper offer a new insight into how the initial fabric and wetting cause different fracture behavior. The findings can also pave the way for more in-depth future investigations into the mechanics governing particle fracture in granular assemblies.

Finite element analysis↗

Nitrate Removal Across Ecogeomorphic Zones in Wax Lake Delta, Louisiana (USA)

Human activities have increased nitrate export from rivers, degrading coastal water quality. At deltaic river mouths, the flow of water through wetlands increases nitrate removal, and the spatial organization of removal rates influences coastal water quality. To understand the spatial distribution of nitrate removal in a river-dominated delta, in this study we deployed 23 benthic chambers across ecogeomorphic zones with varying elevation, vegetation, and sediment properties in Wax Lake Delta (Louisiana, USA) in June 2018. Regression analyses indicate that normalized difference vegetation index is a useful predictor of summertime nitrate removal. Mass transfer velocity were approximately three times greater on a vegetated submerged levee (13 mm hr –1 ), where normalized difference vegetation index was greatest, compared to other locations (4.6 mm hr –1 ). Two methods were developed to upscale nitrate removal across the delta. The flooded-delta method integrates spatially explicit potential removal rates across submerged portions of the delta and suggests that intermediate elevations on the delta—including submerged levees—are responsible for 70% of potential nitrate removal despite covering only 33% of the flooded area. The channel network method treats the delta as a network of river channels and suggests that although secondary channels are more efficient than primary channels at removing received nitrate, primary channels collectively contribute more to overall removal because they convey more of the total nitrate load. The two upscaling methods predict similar rates of nitrate removal, equivalent to less than 4% of nitrate entering the delta. To protect coastal waters against high nitrate loads, management policies should aim to reduce upstream nutrient loads.

54 ENVIRONMENTAL SCIENCES↗

Distribution of Bound and Free Water in Anatomical Fractions of Pine Residues and Corn Stover as a Function of Biological Degradation

Biomass quality is influenced by water’s abundance, distribution, and status in relation to other chemical species within the polymer matrix. Water interacts with polymers that make up the cell walls, and these interactions govern the physical and chemical changes that occur during the storage and preprocessing of biomass feedstocks. Time-domain nuclear magnetic resonance (TD-NMR) was employed to explore variations in the physical constraints of water within the lignocellulosic microstructure in distinct anatomical fractions of biomass and as a function of biological degradation. The Carr–Purcell–Meiboom–Gill sequence, when combined with knowledge of the chemical composition and physical structure of pine residues and corn stover anatomical fractions, gives an accurate measurement of the bound and free water. In this work, the impacts of storage and biological degradation were investigated to elucidate changes in the status and distribution of water within distinct plant tissues. We also investigate how degradation during storage affects water interactions in different pine residues (e.g., bark, branch, and needle) and corn stover (e.g., cob, leaf, and stalk) anatomical fractions using transverse relaxation times (T2). As demonstrated herein, TD-NMR provides quantitative data on lignocellulosic biomass–water interactions within anatomical fractions, which can further aid in the investigation of preprocessing effects on feedstock quality. Our findings suggest that biological heating enhances biomass–water interactions at the cellular and macromolecular scale. In addition, analysis of three-dimensional scanning electron microscopy reconstructions indicates that surface roughness wavelengths align with microscale roughness, suggesting that pine forestry residue and corn stover particles have primarily hydrophobic exterior surfaces. Furthermore, this study offers multiscale insights into understanding the microstructure, wettability, and chemical environment that dictate diffusion, enzyme access, and recalcitrance of lignocellulosic biomass.

09 BIOMASS FUELS↗

Exploring the elevated water vapor signal associated with the free tropospheric biomass burning plume over the southeast Atlantic Ocean

In southern Africa, widespread agricultural fires produce substantial biomass burning (BB) emissions over the region. The seasonal smoke plumes associated with these emissions are then advected westward over the persistent stratocumulus cloud deck in the southeast Atlantic (SEA) Ocean, resulting in aerosol effects which vary with time and location. Much work has focused on the effects of these aerosol plumes, but previous studies have also described an elevated free tropospheric water vapor signal over the SEA. Water vapor influences climate in its own right, and it is especially important to consider atmospheric water vapor when quantifying aerosol-cloud interactions and aerosol radiative effects. Here we present airborne observations made during the NASA ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) campaign over the SEA Ocean. In observations collected from multiple independent instruments on the NASA P-3 aircraft (from near-surface to 6-7 km), we observe a strongly linear correlation between pollution indicators (carbon monoxide (CO) and aerosol loading) and atmospheric water vapor content, seen at all altitudes above the boundary layer. The focus of the current study is on the especially strong correlation observed during the ORACLES-2016 deployment (out of Walvis Bay, Namibia), but a similar relationship is also observed in the August 2017 and October 2018 ORACLES deployments. Using reanalyses from the European Centre for Medium-Range Weather Forecasts (ECMWF) and Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2), and specialized WRF-Chem simulations, we trace the plume-vapor relationship to an initial humid, smoky continental source region, where it mixes with clean, dry upper tropospheric air and then is subjected to conditions of strong westward advection, namely the southern African easterly jet (AEJ-S). Our analysis indicates that air masses likely left the continent with the same relationship between water vapor and carbon monoxide as was observed by aircraft. This linear relationship developed over the continent due to daytime convection within a deep continental boundary layer (up to ~5-6 km) and mixing with higher-altitude air, which resulted in fairly consistent vertical gradients in CO and water vapor, decreasing with altitude and varying in time, but this water vapor does not originate as a product of the BB combustion itself. Due to a combination of conditions and mixing between the smoky, moist continental boundary layer and the dry and fairly clean upper-troposphere air above (~6 km), the smoky, humid air is transported by strong zonal winds and then advected over the SEA (to the ORACLES flight region) following largely isentropic trajectories. Hybrid Single-Particle Lagrangian Integrated Trajectory model (HYSPLIT) back trajectories support this interpretation. This work thus gives insights into the conditions and processes which cause water vapor to covary with plume strength. Better understanding of this relationship, including how it varies spatially and temporally, is important to accurately quantify direct, semi-direct, and indirect aerosol effects over this region.

54 ENVIRONMENTAL SCIENCES↗

Exploring the Elevated Water Vapor Signal Associated With the Free Tropospheric Biomass Burning Plume Over the Southeast Atlantic Ocean

In southern Africa, widespread agricultural fires produce substantial biomass burning (BB) emissions over the region. The seasonal smoke plumes associated with these emissions are then advected westward over the persistent stratocumulus cloud deck in the southeast Atlantic (SEA) Ocean, resulting in aerosol effects which vary with time and location. Much work has focused on the effects of these aerosol plumes, but previous studies have also described an elevated free tropospheric water vapor signal over the SEA. Water vapor influences climate in its own right, and it is especially important to consider atmospheric water vapor when quantifying aerosol–cloud interactions and aerosol radiative effects. Here we present airborne observations made during the NASA ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) campaign over the SEA Ocean. In observations collected from multiple independent instruments on the NASA P-3 aircraft (from near-surface to 6–7 km), we observe a strongly linear correlation between pollution indicators (carbon monoxide (CO) and aerosol loading) and atmospheric water vapor content, seen at all altitudes above the boundary layer. The focus of the current study is on the especially strong correlation observed during the ORACLES-2016 deployment (out of Walvis Bay, Namibia), but a similar relationship is also observed in the August 2017 and October 2018 ORACLES deployments. Using reanalyses from the European Centre for Medium-Range Weather Forecasts (ECMWF) and Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2), and specialized WRF-Chem simulations, we trace the plume–vapor relationship to an initial humid, smoky continental source region, where it mixes with clean, dry upper tropospheric air and then is subjected to conditions of strong westward advection, namely the southern African easterly jet (AEJ-S). Our analysis indicates that air masses likely left the continent with the same relationship between water vapor and carbon monoxide as was observed by aircraft. This linear relationship developed over the continent due to daytime convection within a deep continental boundary layer (up to ∼5–6 km) and mixing with higher-altitude air, which resulted in fairly consistent vertical gradients in CO and water vapor, decreasing with altitude and varying in time, but this water vapor does not originate as a product of the BB combustion itself. Due to a combination of conditions and mixing between the smoky, moist continental boundary layer and the dry and fairly clean upper-troposphere air above (∼6 km), the smoky, humid air is transported by strong zonal winds and then advected over the SEA (to the ORACLES flight region) following largely isentropic trajectories. Hybrid Single-Particle Lagrangian Integrated Trajectory model (HYSPLIT) back trajectories support this interpretation. This work thus gives insights into the conditions and processes which cause water vapor to covary with plume strength. Better understanding of this relationship, including how it varies spatially and temporally, is important to accurately quantify direct, semi-direct, and indirect aerosol effects over this region.

Kristina Pistone↗

Organic matter transformations are disconnected between surface water and the hyporheic zone

Abstract. Biochemical transformations of organic matter (OM) are a primary driver of river corridor biogeochemistry, thereby modulating ecosystem processes at local to global scales. OM transformations are driven by diverse biotic and abiotic processes, but we lack knowledge of how the diversity of those processes varies across river corridors and across surface and subsurface components of river corridors. To fill this gap we quantified the number of putative biotic and abiotic transformations of organic molecules across diverse river corridors using ultra-high-resolution mass spectrometry. The number of unique transformations is used here as a proxy for the diversity of biochemical processes underlying observed profiles of organic molecules. For this, we use public data spanning the contiguous United States (ConUS) from the Worldwide Hydrobiogeochemical Observation Network for Dynamic River Systems (WHONDRS) consortium. Our results show that surface water OM had more biotic and abiotic transformations than OM from shallow hyporheic zone sediments (1–3 cm depth). We observed substantially more biotic than abiotic transformations, and the numbers of biotic and abiotic transformations were highly correlated with each other. We found no relationship between the number of transformations in surface water and sediments and no meaningful relationships with latitude, longitude, or climate. We also found that the composition of transformations in sediments was not linked with transformation composition in adjacent surface waters. We infer that OM transformations represented in surface water are an integrated signal of diverse processes occurring throughout the upstream catchment. In contrast, OM transformations in sediments likely reflect a narrower range of processes within the sampled volume. This indicates decoupling between the processes influencing surface water and sediment OM, despite the potential for hydrologic exchange to homogenize OM. We infer that the processes influencing OM transformations and the scales at which they operate diverge between surface water and sediments.

58 GEOSCIENCES↗

Evidence for Dry Carbonatite Metasomatism in the Oceanic Lithosphere from Peridotite Xenoliths of Samoa and Lanzarote

Water in Earth’s mantle affects processes like magmatism and plate tectonics. Experiments show that CO2-rich fluids lower the water solubility in olivine, implying that CO2-rich melts/fluids may dehydrate the lithosphere during metasomatism. To test this hypothesis, we report water concentrations (by polarized FTIR) of olivines, orthopyroxenes (OPX) and clinopyroxenes (CPX) from Savai’i (Samoa) and Lanzarote (Canary Islands) peridotite xenoliths with evidence of carbonatite metasomatism. Savai’i peridotites are highly depleted harzburgites and dunites with spinel Cr# (Cr/(Cr+Al)) ranging from 0.4 to 0.76 (estimated degree of melting: 191.5%). Strong Light Rare Earth Element (LREE) enrichments with Ti and Zr depletions in OPX and CO2-rich fluid inclusions (via Raman spectroscopy) are consistent with carbonatite metasomatism. Olivine, OPX and reconstructed bulk rock water concentrations (0.67-3.8, 17-89 and 4-26 ppm H2O, respectively) are low and show no apparent relationship with extent of carbonatite metasomatism. Calculated water concentrations of melts in equilibrium with Savai’i OPX (OPX/melt partitioning of water 0.0063 to 0.011) are, on average (0.540.32 wt% H2O), lower than host Samoan lavas (0.63 to 1.5 wt% H2O), despite the LREE enrichments in OPX. Lanzarote peridotites are also highly depleted (degree of melting from spinel Cr#: 171.8%).Water concentrations are low in olivines (1.7-5.3 ppm H2O) and variable in pyroxenes (OPX: 42-103 ppm H2O; CPX: 105-301 ppm H2O), and show no apparent correlation with indicators of carbonatite metasomatism. Both Savai’i and Lanzarote peridotites show negative correlations between water and degree of melting (i.e. Mg/(Mg+Fe), Cr#), suggesting melt depletion rather than metasomatism may have influenced their water concentrations. Calculated water concentrations of melts in equilibrium with Lanzarote CPX (average 1.90.75 wt% H2O; CPX/melt partitioning of water 0.011 to 0.012) are similar to those for Western Canaries lavas (average 1.80.31 wt%; CPX/melt partitioning of water 0.016 to 0.021) inferred from their CPX phenocrysts. However, calculated Ce concentrations in such melts (352 to 378 ppm; CPX/melt partitioning of Ce 0.07) are an order of magnitude greater than the lavas, and similar to carbonatites. This leads to H2O/Ce to be an order of magnitude lower in the inferred melts (26 to 57) than estimates for Western Canary lavas (280150). These low H2O/Ce ratios may suggest H2O loss from CPX during ascent, but the lack of strong water diffusion gradients in Lanzarote minerals does not support this. Instead we hypothesize that carbonatite metasomatism resulted in greater enrichment of Ce over H2O. Assuming carbonatite magmas are water rich, this implies a lower partitioning of water between minerals and melts during metasomatism, as suggested by experiments. Our data suggests carbonatite metasomatism does not result in significant re-hydration of the lithosphere, in contrast to silicate metasomatism as previously observed in Hawaiian peridotites.

Ashley, Aaron↗

Depth and microtopography influence microbial biogeochemical processes in a forested peatland

Background and aims: Peat-accumulating wetlands have undulating surfaces of raised areas (hummocks) and depressions (hollows). Hummock-hollow microtopography in relation to the water table influences the distribution of plant species, root density, and microbial community composition, which could in turn alter carbon (C) and nitrogen (N) cycling within peatlands. We used paired hummock and hollow cores from a boreal, forested peatland to assess how microtopography influences peatland microbial function and, in turn, ecosystem C and N cycling. Methods: The peat was analyzed for microbial biomass and potential enzyme activity in 10 cm depth increments relative to the water table, resulting in two increments for hollows and three for hummocks, which has a raised increment above the water table. Results: Across hummocks and hollows, microbial C and N and fungal biomass generally decreased with depth from the peat surface. In contrast, potential enzyme activity often increased with depth, but this varied within enzyme functional groups according to topography, depth, or both. The potential enzyme activity of C-N degrading peptidases, for example, differed across the five topography × depth increments with the lowest rate in the aerated hummocks. Hummocks compose approximately 66% of the land area at our study site and would therefore underestimate C turnover by an average of 25% if solely used to extrapolate patterns across a forested bog. Conclusion: In conclusion, our results suggest that asynchrony in C and N cycling across the undulating surface of forested peatlands impacts our ability to accurately predict biogeochemical cycling across this important ecosystem.

54 ENVIRONMENTAL SCIENCES↗

Convective Influence on the Lower Stratospheric Water Vapor in the Boreal Summer Asian Monsoon Region

Processes maintaining the localized maxima in lower stratospheric watervapor over the boreal summer Asian monsoon region are investigated usingtrajectory and cloud models that resolve the detailed cloudmicrophysical processes, with observation-based convection and radiationschemes. We examine the impact of convective influence along parceltrajectories on cloud formation and dehydration by tracing thetrajectories through time-dependent fields of convective cloud topheights estimated from global rainfall and geostationary brightnesstemperatures. Parameters such as the rainfall threshold used foridentification of deep convection are derived by comparison with theCloudSat deep convective cloud top product as enhanced by colocatedCALIOP measurements. The simulated water vapor field at the 100 hPalevel and cloud occurrence frequencies in the tropical tropopause layer(TTL) are constrained by corresponding observations from MLS andCALIPSO, respectively. The observed maximum in the 100 hPa level watervapor field over the Asian monsoon region is only present in thesimulation with convective influence, indicating the importance ofconvective hydration for the summertime water vapor distribution.Convection moistens the 100 hPa level over the Asian monsoon by 1 ppmv,where 75 of this moistening is due to convection occurring locallywithin the monsoon region. Convection also increases the cloudoccurrence frequency in the TTL over the southern sector of the Asianmonsoon anticyclone by 20. Parcels are convectively hydrated in thesoutheastern sector of the anticyclone, transported westward by theanticyclonic circulation, and dehydrated in the southwestern sector. Therelative importance of extreme convective events that inject ice andwater vapor near or above the tropopause will also be examined.

convection↗

Water level changes in Lake Erie drive 21st century CO 2 and CH 4 fluxes from a coastal temperate wetland

Wetland water depth influences microbial and plant communities, which can alter the above- and below-ground carbon cycling of a wetland. Wetland water depths are likely to change due to shifting precipitation patterns, which will affect projections of greenhouse gas emissions; however, these effects are rarely incorporated into wetland greenhouse gas models. Seeking to address this gap, we used a mechanistic model, ecosys, to simulate a range of water depth scenarios in a temperate wetland, and analyzed simulated predictions of carbon dioxide (CO 2 ) andmethane (CH 4 ) fluxes over the 21st century. We tested our model using eddy covariance measurements of CO 2 and CH 4 fluxes collected at the Old Woman Creek National Estuarine Research Reserve (OWC) during 2015 and 2016. OWC is a lacustrine, estuarine, freshwater, mineral-soil marsh. An empirical model found that the wetland water depth is highly dependent on the water depth of the nearby Lake Erie. Future wetland surface water depths were modeled based on projection of Lake Erie's water depth using four separate NOAA projections, resulting in four wetland water-depth scenarios. Two of the four 21st century projections for Lake Erie water depths used in this study indicated that the water depth of the wetland would remain nearly steady; however, the other two indicated decreases in the wetland water depth. In our scenario where the wetland dries out, we project the wetland's climatological warming effect will decrease due to smaller CH 4 fluxes to the atmosphere and larger CO 2 uptake by the wetland. We also found that increased water level can lower emissions by shifting the site towards more open water areas, which have lower CH 4 emissions. We found that decreased water depths would cause more widespread colonization of the wetland by macrophyte vegetation. Using an empirical relationship, we also found that further drying could result in other, non-wetland vegetation to emerge, dramatically altering soil carbon cycling. In three of our four projections, we found that in general the magnitude of CO 2 and CH 4 fluxes steadily increase over the next 100 years in response to higher temperatures. However, in our driest simulations, we projected a different response due to increased oxidation of soil carbon, with CH 4 emissions decreasing substantially from an annual cumulative peak of 224.6 to a minimum of 104.7 gC m –2 year –1 . In that same simulation, net cumulative flux of CO 2 changed from being a sink of 56.5 gC m –2 year –1 to a source of 369.6 gCm –2 year –1 over the same period, despite a temperature increase from 13.7 °C to 14.2 °C. This temperature shift in our other three cases with greater water depths increased the source strength of CH 4 and the sink strength of CO 2 . Here, we conclude that the magnitude of wetland greenhouse-gas fluxes depended on the water depth primarily as it affected the areal percentage of the wetland available for plant colonization, but dramatic decreases in water depths could cause significant reductions in the wetland CH 4 fluxes, while simultaneously altering the wetland vegetation.

54 ENVIRONMENTAL SCIENCES↗

Lattice-scale variations in viscosity are correlated with solution structure at mineral-water interfaces

At solid-liquid interfaces, the viscosity increases markedly from the bulk due to the collective interactions of ions and water molecules, influencing phenomena relevant to nanofluidics, colloidal dynamics, and electrochemistry. Here, in this study, we investigated dissipative forces at the boehmite-water interface using 3D atomic force microscopy. We observed an increase in interfacial solution viscosity, η, by 10-100-fold as the nanoprobe approached the surface in normal direction, with up to four oscillatory features showing average peaks of η/η bulk = 44-71. Moreover, the viscosity showed sub-nanometer variations within 0.5 nm from the interface, templated by the underlying crystal lattice and correlated with the interfacial solution structure. Beyond a near-wall region of approximately 1.2 nm, the dissipative response was comparable to that in bulk solution. Molecular dynamics simulations, along with statistical mechanical analyses, provided details on hydrodynamic structures near the interface. Specifically, the lattice-dependent dissipative responses are correlated with extensive hydrogen bonding by interfacial water molecules, which increased friction, particularly along the [001] direction. These results demonstrate how solution viscosity at mineral-water interfaces is anisotropic and correlated with the local solution structure, providing insights into the dynamics of nanocrystal attachment.

Viscosity↗

Lagged Wetland CH 4 Flux Response in a Historically Wet Year

While a stimulating effect of plant primary productivity on soil carbon dioxide (CO 2 ) emissions has been well documented, links between gross primary productivity (GPP) and wetland methane (CH 4 ) emissions are less well investigated. Determination of the influence of primary productivity on wetland CH 4 emissions (FCH 4 ) is complicated by confounding influences of water table level and temperature on CH 4 production, which also vary seasonally. Here, in this work, we evaluate the link between preceding GPP and subsequent FCH 4 at two fens in Wisconsin using eddy covariance flux towers, Lost Creek (US-Los) and Allequash Creek (US-ALQ). Both wetlands are mosaics of forested and shrub wetlands, with US-Los being larger in scale and having a more open canopy. Co-located sites with multi-year observations of flux, hydrology, and meteorology provide an opportunity to measure and compare lag effects on FCH4 without interference due to differing climate. Daily average FCH4 from US-Los reached a maximum of 47.7 ηmol CH 4 m -2 s -1 during the study period, while US-ALQ was more than double at 117.9 ηmol CH 4 m -2 s -1 . The lagged influence of GPP on temperature-normalized FCH4 (T air -FCH 4 ) was weaker and more delayed in a year with anomalously high precipitation than a following drier year at both sites. FCH 4 at US-ALQ was lower coincident with higher stream discharge in the wet year (2019), potentially due to soil gas flushing during high precipitation events and lower water temperatures. Better understanding of the lagged influence of GPP on FCH 4 due to this study has implications for climate modeling and more accurate carbon budgeting.

59 BASIC BIOLOGICAL SCIENCES↗