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All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Decadal-Scale Vegetation Change Driven by Salinity at Leading Edge of Rising Sea Level

As sea levels rise, low-lying coastal forests increasingly are subject to stressors such as inundation and saltwater exposure. At long timescales (for example, centuries), the extent of inundation and saltwater exposure will increase; however, on a decadal timescale, the role of these drivers may differ in both magnitude and direction. To investigate the drivers of decadal-scale vegetation change, we measured the changes in five metrics of vegetation composition and structure between 2003/2004 and 2016/ 2017 at 98 plots distributed across a vegetation gradient from coastal forest to brackish marshes (< 0.5–18 ppt). We used elevation as a proxy of inundation vulnerability and soil sodium concentration as a proxy of saltwater exposure, and we investigated relationships between these two variables and the change in vegetation conditions between the two sampling periods. Soil sodium concentration was a significant predictor of vegetation change for all five vegetation metrics, whereas the effect of elevation was not significant for any of the metrics. The one site that was affected by wildfire twice during the duration of the study shifted almost completely from forest to marsh with limited regeneration ofwoody vegetation observed in 2016/ 2017. Our results show that salinization in our system is a more important driver of vegetation change than inundation potential. Furthermore, the effects of drought-induced salinization could be amplified by the elevated risk of wildfire during droughts. Forecasting the response of coastal wetlands to rising sea levels will require a better understanding of the individual and combined effects of salinity, droughts, and wildfires on vegetation.

Taillie, Paul J.↗
NASA NTRSDate not supplied

Building a Bilingual Google Earth Engine Dashboard to Increase Accessibility to Long-term Time Series Remote Sensing Data for Monitoring Saline System Changes in Chile’s Atacama Desert

Saline systems, consisting of salt flats, ponds, and marshes, provide vital water resources to wildlife and communities in northern Chile’s Atacama Desert, one of the driest regions in the world. Mining is extensive in the Atacama, which contains 30% of the world’s lithium reserves and is abundant in potassium and boron. The groundwater that feeds into salt marshes and ponds is extracted in large volumes for mining operations, limiting the availability of water for ecosystems. However, identifying long-term and large-scale environmental impacts from local lithium mining on the saline systems is limited by region inaccessibility and terrain variability. Open access satellite imagery and cloud computing technology has made studying Atacama saline systems feasible and allowed for collaboration across different agencies and countries. The NASA DEVELOP Program partnered with Chile’s la Universidad de La Serena and Servicio Nacional de Geología y Minería (SERNAGEOMIN) to create the Saline Analysis Tool (SalT) in Google Earth Engine (GEE). SalT is used to analyze the extent and distribution of remote saline systems in the Atacama from 1986 to the present day. The tool filters Landsat 5 Thematic Mapper (TM) and Landsat 8 Operational Land Imager (OLI) data from GEE’s data catalog and creates a single composite image per year for analysis. Additional output analyses include land cover classification, Normalized Difference Vegetation Index (NDVI) and Normalized Difference Water Index (NDWI) raster images that can be displayed on the map interface or exported. The tool can also generate time-lapse videos and charts displaying NDVI, NDWI, and land cover over time. A key feature of the tool is the use of a bilingual graphical user interface to make analysis accessible and customizable to different users’ needs—SalT provides options to select an analysis area, analysis time period, and outputs to display or export. The tool also incorporates new Earth observations as they are added to GEE’s catalog. The ability to easily visualize and analyze long-term remote sensing imagery will enable SERNAGEOMIN and la Universidad de la Serena to continually monitor changes in these saline systems and inform future land management policy.

NASA DEVELOP↗
NASA NTRSDate not supplied

The Global Water Monitor: Wetland surface height dynamics for Ecology, Conservation, and Resource Management

The Global Water Monitor (GWM) offers surface water-related products for lakes, river reaches and wetland zones. The surface elevation change products are derived from satellite radar altimeters, such as the Jason/Sentinel series, and can span multiple decades. While the current instruments are profiling, they offer surface water height at specific locations, thus contributing to parallel observation of wetland surface water extent. GWM wetland products are “operational” with routine updates within 1-2days of satellite overpass. There is also assurance of product continuity to at least the end of 2030. Currently, the GWM holds products for a small selection (~40) of diverse wetlands for objectives that focus on conservation and water/fisheries resource monitoring. These sites have been requested by various organizations also looking to the effects of climate change and anthropogenic influences. Many of the current GWM wetland regions are in National Parks such as the Everglades (USA), the Wasur (Rep. Indonesia), and the Kakadu marshes (Australia). They also include coastal river deltas of the Danube, Mekong, Amazon, Orinoco and Ganges Rivers, and the internal Okavango Delta in Botswana. The preliminary set also ensures a diverse range of wetlands e.g., the shallow pot-hole lake region of the Sand Hills and the coastal Black Swamp of the USA, the peat fields of Malaysia and rice growing fields of Yilinzhen in China. Extensive wetlands in Brazil (the Pantanal), South Sudan (the Sudd Marshes) and Belarus (the Pinsk) are also featured, as are the mangrove regions of the Sundarbans (India) and the Laguna Terminos (Mexico). The Usangu wetland (Tanzania) is also included, a focus region where wetland ecology strongly competes with demands from irrigation, livestock, and the needs of downstream hydro-electric power. The nadir-pointing altimeter instruments record height variations regardless of vegetation or canopy cover, and height dynamics at 10-day or monthly resolution reveal seasonal and inter-annual variations as well as longer-term declining or re-charging trends. These products provide a unique, multi-decadal data set that can stand-alone or serve with cross-validation or image-fusion efforts.

Charon Birkett↗
DOE OSTI2022

Role of copper in nitrous oxide accumulation in wetland soils from Illinois and South Carolina and stream sediments from Tennessee

Denitrification is microbially-mediated through enzymes containing metal cofactors. Laboratory studies of pure cultures have highlighted that the availability of copper (Cu), required for the multicopper enzyme nitrous oxide reductase, can limit nitrous oxide (N2O) reduction. However, in natural aquatic systems, such as wetlands and hyporheic zones in stream beds, the role of Cu in controlling denitrification remains incompletely understood. In this study, we collected soils and sediments from three natural environments -- riparian wetlands, marsh wetlands, and a stream -- to investigate their nitrogen species transformation activity at background Cu levels and different supplemented Cu loadings. All of the systems contained solid-phase associated Cu below or around geological levels (40–280 nmol g-1) and exhibited low dissolved Cu (3–50 nM), which made them appropriate sites for evaluating the effect of limited Cu availability on denitrification.The dataset contains the variation in the nutrient (nitrate (NO3-), nitrite (NO2-), and ammonium (NH4+)) and N2O concentrations during the incubation experiments to evaluate the effect of Cu. We have also reported the variation in metal concentrations (Cu, iron(Fe) and manganese (Mn)) and dissolved organic carbon (DOC) concentrations during the incubations. The parameters obtained using a kinetic model to quantitatively report the effect of Cu on nitrogen species conversion in natural aquatic systems are also added in the dataset. The dataset also contains the labile concentration of Cu estimated using a speciation model in MINTEQ. All data are provided in text-based CSV format with header sections indicating the data contained in each file and the corresponding units.Our study suggests that high concentrations of N2O accumulated in all microcosms lacking Cu amendment except for one stream sediment sample. With Cu added to provide dissolved concentrations at trace levels (10–300 nM), the reduction rate of N2O to N2 in the wetland soils and stream sediments was enhanced. A kinetic model could account for the trends in nitrogen species by combining the reactions for microbial reduction of NO3- to NO2-/N2O/N2 and abiotic reduction of NO2 to nitrogen (N2_. The model revealed that the rate of N2O to N2 conversion increased significantly in the presence of Cu. For riparian wetland soils and stream sediments, the kinetic model also suggested that overall denitrification is driven by abiotic reduction of NO2- in the presence of inorganic electron donors. This study demonstrated that natural aquatic systems containing Cu at concentrations less than or equal to crustal abundances may display incomplete reduction of N2O to N2 that would cause N2O accumulation and release to the atmosphere.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1985

Precision geodesy and geodynamics using Starlette laser ranging

The French Starlette satellite, launched in February 1975, was the first satellite specifically designed to minimize the effects of nongravitational forces and to obtain the highest possible accuracy for laser range measurements. It has been found that Starlette represents a valuable complement to the U.S. geodetic satellites. In an analysis of Starlette laser ranging data conducted by Marsh and Williamson (1978), it was concluded that by tailoring a gravity model to a specific satellite and observation period, substantial improvements in data fits and, therefore, in orbit accuracy could be achieved. In the present analyses, a tailored gravity model has been derived for Starlette from the data acquired for the 4-year period, 1975-1978. Attention is given to the solution for geodetic and geodynamic parameters and polar motion.

Marsh, J. G.↗
DOE OSTI2020

Ecohydrology of wetland plant communities along an estuarine to tidal river gradient

Abiotic filters that interact with wetland plant communities along tidal–fluvial gradients are highly dynamic, and understanding their quantitative thresholds and relationships to interspecific competition is important during an era of sea-level rise and watershed hydrologic change. Yet, landscape-scale studies of major coastal rivers from the river mouth to the head of tide, such as this study, remain rare. Here, we develop a new predictive framework for estuarine–tidal river research and management using a river-specific low-water datum and the wetland inundation indicator SEVg, the growing-season sum exceedance value of hourly surface-water depth. The distribution and variability of the wetland species pool (n = 203) on the 234 river kilometer (rkm) lower Columbia River and estuary floodplain are described for the first time. 4,940 quadrats at 50 marshes were surveyed (2005–2016). Throughout the estuarine–tidal river system, SEVg was well suited to describe the wetland inundation regime and its variability based on the combination of longitudinal river position and elevation. SEVg increased significantly landward. Two primary wetland inundation regimes were identified: the seaward-tidal, usually greatest during the winter months, and landward-fluvial, greatest during the growing season. Nearest the ocean, salinity is the abiotic factor limiting species richness and non-native species. Farther upriver, the daily, seasonal, and interannual variability of the wetting and drying cycle encourage disturbance-tolerant species and non-natives and limit the number of hydrophytes and total vegetative cover. Hence, the average between-year similarity of site-scale areal cover significantly decreased landward. Hierarchical cluster analysis indicated five vegetative groups and five ecohydrologic zones between rkm 0 and 234 were discriminated with 76 significant species–zone associations. All zones had unique indicator species. Species with high indicator values were Carex lyngbyei throughout the estuarine zones, and Eleocharis palustris, Sagittaria latifolia, and the invasive non-native Phalaris arundinacea in the upper estuarine and lower, middle, and upper tidal river zones (IV > 0.90). Competition from C. lyngbyei nearest the ocean and P. arundinacea in the tidal river was associated with reduced species richness when total cover was >65%. This framework of filters informs the design and prediction of future wetland plant communities on coastal river floodplains.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Integrating Aquatic Metabolism and Net Ecosystem CO2 Balance in Short- and Long-Hydroperiod Subtropical Freshwater Wetlands

Abstract How aquatic primary productivity influences the carbon (C) sequestering capacity of wetlands is uncertain. We evaluated the magnitude and variability in aquatic C dynamics and compared them to net ecosystem CO 2 exchange (NEE) and ecosystem respiration ( R eco ) rates within calcareous freshwater wetlands in Everglades National Park. We continuously recorded 30-min measurements of dissolved oxygen (DO), water level, water temperature ( T water ), and photosynthetically active radiation (PAR). These measurements were coupled with ecosystem CO 2 fluxes over 5 years (2012–2016) in a long-hydroperiod peat-rich, freshwater marsh and a short-hydroperiod, freshwater marl prairie. Daily net aquatic primary productivity (NAPP) rates indicated both wetlands were generally net heterotrophic. Gross aquatic primary productivity (GAPP) ranged from 0 to − 6.3 g C m −2 day −1 and aquatic respiration ( R Aq ) from 0 to 6.13 g C m −2 day −1 . Nonlinear interactions between water level, T water , and GAPP and R Aq resulted in high variability in NAPP that contributed to NEE. Net aquatic primary productivity accounted for 4–5% of the deviance explained in NEE rates. With respect to the flux magnitude, daily NAPP was a greater proportion of daily NEE at the long-hydroperiod site (mean = 95%) compared to the short-hydroperiod site (mean = 64%). Although we have confirmed the significant contribution of NAPP to NEE in both long- and short-hydroperiod freshwater wetlands, the decoupling of the aquatic and ecosystem fluxes could largely depend on emergent vegetation, the carbonate cycle, and the lateral C flux.

Malone, Sparkle L.↗
DOE OSTI2020

The practice and economics of hybrid poplar biomass production for biofuels and bioproducts in the Pacific Northwest

Hybrid poplar demonstration-scale farms were managed in Oregon, Washington, Idaho, and California to establish management practices, yields, harvesting methods, and the economics of biomass production. Yield during the 2-year establishment cycle averaged 3.5 dry Mg ha –1 year –1 increasing to 11.6 Mg ha –1 year –1 in the ensuing 3-year coppice cycle. Populus deltoides (Bartram ex Marsh.) × P. maximowiczii (Henry) varieties preformed best in Oregon during the coppice cycle with the best variety producing 18.1 Mg ha –1 year –1 , while P. ×generosa (Henry) varieties maximized yields in Washington at 22.1 Mg ha –1 year –1 . P. ×canadensis (Moench) varieties excelled in Idaho and California with upper yields of 13.6 Mg ha –1 year –1 and 12.9 Mg ha –1 year –1 , respectively. Stands were cut with a single-pass harvester 2 years after planting and a second time after 3 years of coppice growth; material capacity, limited by poor ground conditions, varied between 21.7 to 31.3 green Mg h –1 . Chemical composition averaged 1.87% inorganics, 7.74% extractives, 26.90% lignin, 38.07% glucan, 13.66% xylan, 1.61% galactan, 1.14% arabinan, and 2.76% mannan. Production costs (USD) projected over a 20-year rotation of six coppice cycles were $71.81 Mg –1 in Washington, $89.91 Mg –1 in Oregon, $98.76 Mg–1 in Idaho, and 179.07 Mg–1 in California. Here, land rental, establishment, crop care, harvest, transportation, and land restoration, respectively, accounted for 23%, 5%, 19%, 30%, 17%, and 6% of total feedstock cost. Farms were successfully restored to conditions existing before poplar conversion. In the absence of fertilization, increases in soil pH and decreases in nitrate-nitrogen, zinc, iron, and organic matter were consistently noted but could not be associated with poplar production alone.

09 BIOMASS FUELS↗
DOE OSTI2023

Rapidly Changing Range Limits in a Warming World: Critical Data Limitations and Knowledge Gaps for Advancing Understanding of Mangrove Range Dynamics in the Southeastern USA

Climate change is altering species’ range limits and transforming ecosystems. For example, warming temperatures are leading to the range expansion of tropical, cold-sensitive species at the expense of their cold-tolerant counterparts. In some temperate and subtropical coastal wetlands, warming winters are enabling mangrove forest encroachment into salt marsh, which is a major regime shift that has significant ecological and societal ramifications. Here, we synthesized existing data and expert knowledge to assess the distribution of mangroves near rapidly changing range limits in the southeastern USA. We used expert elicitation to identify data limitations and highlight knowledge gaps for advancing understanding of past, current, and future range dynamics. Mangroves near poleward range limits are often shorter, wider, and more shrublike compared to their tropical counterparts that grow as tall forests in freeze-free, resource-rich environments. The northern range limits of mangroves in the southeastern USA are particularly dynamic and climate sensitive due to abundance of suitable coastal wetland habitat and the exposure of mangroves to winter temperature extremes that are much colder than comparable range limits on other continents. Thus, there is need for methodological refinements and improved spatiotemporal data regarding changes in mangrove structure and abundance near northern range limits in the southeastern USA. Advancing understanding of rapidly changing range limits is critical for foundation plant species such as mangroves, as it provides a basis for anticipating and preparing for the cascading effects of climate-induced species redistribution on ecosystems and the human communities that depend on their ecosystem services.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Iron(II) monosulfide (FeS) minerals reductively transform the insensitive munitions compounds 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO)

As military applications of the insensitive munitions compounds (IMCs) 2,4-dinitroanisole (DNAN) and 3-nitro-1,2,4-triazol-5-one (NTO) increase, there is a growing need to understand their environmental fate and to develop remediation strategies to mitigate their impacts. Iron (II) monosulfide (FeS) minerals are abundant in freshwater and marine sediments, marshes, and hydrothermal environments. Here, this study shows that FeS solids can reduce DNAN and NTO to their corresponding amines under anoxic ambient conditions. The reactions between IMCs and the FeS minerals were surface-mediated since they did not occur when only dissolved Fe 2+ (aq) and S 2– (aq) were present. Mackinawite, a tetragonal FeS with a layered structure, reduced DNAN mainly to 2-methoxy-5-nitroaniline (MENA), which in turn was partially reduced to 2-4-diaminoanisole (DAAN). The layered structure of mackinawite provided intercalation sites likely responsible for partial adsorption of MENA and DAAN. Mackinawite entirely reduced NTO to 3-amino-1,2,4-triazol-5-one (ATO). The reduction of IMCs showed concurrent oxidation of mackinawite to goethite and elemental sulfur. A commercial FeS product, composed mainly of pyrrhotite and troilite, reduced DNAN to DAAN and NTO to ATO. At pH 6.5, DNAN and NTO transformation rates were 667 and 912 μmol h –1 m –2 , respectively, on the mackinawite surface and 417 and 1344 μmol h –1 m –2 , respectively, on the commercial FeS surface. This is the first report of the reduction of a nitro-heterocyclic compound (NTO) by FeS minerals. The evidence indicates that DNAN and NTO can be rapidly transformed to their succeeding amines in anoxic subsurface environments and aquatic sediments rich in FeS minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Copper availability governs nitrous oxide accumulation in wetland soils and stream sediments

Denitrification is microbially-mediated through enzymes containing metal cofactors. Laboratory studies of pure cultures have highlighted that the availability of Cu, required for the multicopper enzyme nitrous oxide reductase, can limit N2O reduction. However, in natural aquatic systems, such as wetlands and hyporheic zones in stream beds, the role of Cu in controlling denitrification remains incompletely understood. In this study, we collected soils and sediments from three natural environments -- riparian wetlands, marsh wetlands, and a stream -- to investigate their nitrogen species transformation activity at background Cu levels and different supplemented Cu loadings. All of the systems contained solid-phase associated Cu below or around geological levels (40 - 280 nmol g-1) and exhibited low dissolved Cu (3-50 nM), which made them appropriate sites for evaluating the effect of limited Cu availability on denitrification. In laboratory incubation experiments, high concentrations of N2O accumulated in all microcosms lacking Cu amendment except for one stream sediment sample. With Cu added to provide dissolved concentrations at trace levels (10-300 nM), reduction rate of N2O to N 2 in the wetland soils and stream sediments was enhanced. A kinetic model could account for the trends in nitrogen species by combining the reactions for microbial reduction of NO 3 - to NO 2 -/N 2 O/N 2 and abiotic reduction of NO 2 - to N 2 . The model revealed that the rate of N 2 O to N 2 conversion increased significantly in the presence of Cu. For riparian wetland soils and stream sediments, the kinetic model also suggested that overall denitrification is driven by abiotic reduction of NO2- in the presence of inorganic electron donors. This study demonstrated that natural aquatic systems containing Cu at concentrations less than or equal to crustal abundances may display incomplete reduction of N 2 O to N 2 that would cause N 2 O accumulation and release to the atmosphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

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↗
DOE OSTI2024

Microbe of the month: Methanococcus maripaludis

Methanococcus maripaludis was first isolated in 1983 from the anoxic sediment of a salt marsh in South Carolina, USA. M. maripaludis grows by using H 2 or formate to reduce CO 2 to CH 4 and is an autotroph that assimilates CO 2 via the archaeal version of the Wood–Ljungdahl pathway. In some strains, supplementation of growth medium with acetate or propionate can increase biomass yield. Furthermore, this microorganism is strictly anaerobic, has a pleomorphic coccoid shape, and forms translucent, pale yellow, smooth colonies within 3 days on agar plates. The optimum temperature for growth is 38°C with optimal pH between 6.8 and 7.2.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

Hydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly of organic building blocks by means of hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature of the hydrogen-bond formation endows HOFs with the attributes of solution processability and simple regeneration. High-quality single crystals of HOFs can be grown easily for unambiguous superstructure determination by single-crystal X-ray diffraction, which is crucial for the elucidation of superstructure–property relationships. During the past decade, considerable progress has been achieved in realizing stable HOFs with permanent porosities by focusing on the design of molecular building blocks in order to introduce rigidity, auxiliary [π···π] interactions, and interpenetration of their frameworks to sustain the extended networks. The applications of HOFs are far-reaching, spanning catalysis, energy, and biomedical products as well as the storage and separation of fine chemicals. In this paper, we, first of all, provide an overview of the chronological development of HOFs, starting from the seminal work by Marsh and Duchamp in 1969 on the crystal superstructure of the hydrogen-bonded networks of trimesic acid. We identify the development of novel hydrogen-bonding motifs such as diaminotriazine (DTA), the introduction of the concept of molecular tectonics, and the establishment of permanent porosity in HOFs as being some of the milestones, which incentivized the current burgeoning research endeavors on developing HOFs as multifunctional materials. This Account is focused primarily on surveying the strategies for constructing porous 3D HOFs based on organic building blocks with peripheral carboxyl groups. These strategies are presented in the following categories: (1) the polycatenation of 2D networks by trigonal building blocks to form global 3D frameworks, (2) the utilization of building blocks with 3D geometries—tetrahedral and trigonal prismatic—that are predisposed to form 3D networks, and (3) the docking by shape-fitting of geometrically labile building blocks. We emphasize how the molecular geometry of the building blocks plays an important role in modulating the superstructures of extended frameworks so as to address specific applications. Recognizing that the in silico design of HOFs is the ultimate goal of researchers in this field, we also discuss the recent advances in superstructure prediction that lead to the formation of porous supramolecular crystals and assess the complications in implementing computational methods for HOFs with complex superstructures. We hope this Account will inspire the development of new supramolecular designs and creative approaches to crystal engineering that aid and abet the assembly of multifunctional HOFs with customizable properties.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Linking Hydrology and Dissolved Organic Matter Characteristics in a Subtropical Wetland: A Long-Term Study of the Florida Everglades

Dissolved organic matter (DOM) acts as an important biogeochemical component of aquatic ecosystems that controls nutrient cycling, influences water quality, and links terrestrial and oceanic carbon pools, yet long-term studies of how changing environmental drivers alter its abundance and composition are rare. Using a ten-year, spatially explicit dataset from Everglades National Park (ENP), a globally significant wetland, we investigated the relationships between DOM quality/quantity and hydrologic/climatic drivers along two contrasting marsh-estuarine transects based on generalized linear modeling and a cumulative sums analysis. Analyses revealed distinct spatial, seasonal, and interannual patterns in variability of DOC and optical properties. Landscape-scale seasonal patterns showed an enrichment in microbial-like and protein-like DOM during the dry season relative to the wet season. We found that, while some compositional constituents varied with the solar calendar, responsive to temperature and photoperiod, others varied with the hydrologic calendar. Independent water level and discharge effects indicated strong hydrologic control on DOM quality that differed between the two transects, evidencing differences in their connectivity to areas of high agricultural activity. Across all sites, a significant long-term increasing trend in the fluorescence index was observed, associated with a positive correlation with precipitation and also potential changes in agricultural inputs, with other features associated with drought and hurricanes. Lastly, the cumulative sums analysis revealed differences between the two transects in the sensitivity of DOM composition to decreased water levels associated with 30-year climate scenarios, with the less hydrologically dynamic transect exhibiting greater potential sensitivity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

A Remote Sensing Technique to Upscale Methane Emission Flux in a Subtropical Peatland

Abstract Quantification of methane (CH 4 ) gas emission from peat is critical to understand CH 4 budget from natural wetlands under a climate warming scenario. Previous studies have focused on prediction and mapping of CH 4 emission flux using process‐based models, while application of statistical‐empirical models for upscaling spatially sparse in situ measurements is scarce. In this study, we developed an empirical remote sensing upscaling approach to estimate CH 4 emission flux in the Everglades using limited in situ point‐based CH 4 emission flux measurements and Landsat data during 2013–2018. We spatially and temporally linked in situ data with Landsat surface reflectance based on temporally composite data sets and developed an object‐based machine learning framework to model and map CH 4 emission flux. An ensemble analysis of two machine learning models, k ‐Nearest Neighbor ( k ‐NN) and Support Vector Machine (SVM), shows that the upscaling approach is promising for predicting CH 4 emission flux with a R 2 of 0.65 and 0.87 based on a fivefold cross‐validation for a dry season and wet season estimation, respectively. We generated emission flux map products that successfully revealed the spatial and temporal heterogeneity of CH 4 emission within the dominant freshwater marsh ecosystem in the Everglades. We conclude that Landsat is promising for upscaling and monitoring CH 4 emission flux and reducing the uncertainty in emission estimates from wetlands.

Zhang, Caiyun↗
DOE OSTI2022

Interplay of River and Tidal Forcings Promotes Loops in Coastal Channel Networks

We report the dense populations that inhabit global coastlines have an uncertain future due to increased flooding, storms, and human modification. The channel networks of deltas and marshes that plumb these coastlines present diverse architectures, including well-studied dendritic topologies. However, the quasi-stable loops that exist in nearly all coastal networks have not yet been explained. We present a model for self-organizing networks inspired by vascular biophysics to show that loops emerge when the relative forcings between rivers and tides are comparable, resulting in interplay between hydrodynamic forcings at short time scales relative to network evolution. Using field data and satellite imaging, we confirm this control on 21 field networks. Our comparison provides compelling evidence that hydrodynamic fluctuations are capable of stabilizing loops in geophysical systems.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Detecting Hot Spots of Methane Flux Using Footprint‐Weighted Flux Maps

Abstract In this study, we propose a new technique for mapping the spatial heterogeneity in gas exchange around flux towers using flux footprint modeling and focusing on detecting hot spots of methane (CH 4 ) flux. In the first part of the study, we used a CH 4 release experiment to evaluate three common flux footprint models: the Hsieh model (Hsieh et al., 2000), the Kljun model (Kljun et al., 2015), and the K & M model (Kormann and Meixner, 2001), finding that the K & M model was the most accurate under these conditions. In the second part of the study, we introduce the Footprint‐Weighted Flux Map, a new technique to map spatial heterogeneity in fluxes. Using artificial CH 4 release experiments, natural tracer approaches and flux chambers we mapped the spatial flux heterogeneity, and detected and validated a hot spot of CH 4 flux in a oligohaline restored marsh. Through chamber measurements during the months of April and May, we found that fluxes at the hot spot were on average as high as 6589 ± 7889 nmol m −2 s −1 whereas background flux from the open water were on average 15.2 ± 7.5 nmol m −2 s −1 . This study provides a novel tool to evaluate the spatial heterogeneity of fluxes around eddy‐covariance towers and creates important insights for the interpretation of hot spots of CH 4 flux, paving the way for future studies aiming to understand subsurface biogeochemical processes and the microbiological conditions that lead to the occurrence of hot spots and hot moments of CH 4 flux.

54 ENVIRONMENTAL SCIENCES↗