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DOE OSTI2021

Amount and reactivity of dissolved organic matter export are affected by land cover change from old-growth to second-growth forests in headwater ecosystems

Headwater forest ecosystems of the western USA generate a large portion of the dissolved organic matter (DOM) transported in streams across North America. Land cover changes that alter forest structure and species composition affect the quantity and composition of DOM transferred to aquatic ecosystems. Clear-cut harvesting affects ~1% of the forest area of North America annually, leaving most western forests in varying stages of regrowth and the total area of old-growth forest is decreasing. The consequences of this widespread management practice on watershed carbon cycling remain unknown. We investigated the role of land cover change, because of clear-cut harvesting, from mixed-species old-growth to lodgepole pine-dominated second-growth forest on the character and reactivity of hillslope DOM exports. We evaluated inputs of DOM from litter leachates and export of DOM collected at the base of trenched hillslopes during a 3-year period (2016–2018) at the Fraser Experimental Forest in north-central Colorado, USA. Dissolved organic carbon and total dissolved nitrogen were higher in lateral subsurface flow draining old- versus second-growth forest. Fluorescence spectroscopy showed that the DOM exported from the old-growth forest was more heterogeneous and aromatic and that proteinaceous, microbially processed DOM components were more prevalent in the second-growth forest. Biological oxygen demand assays revealed much lower microbial metabolism of DOM in litter leachate and subsurface exports from the old-growth forest relative to second growth. Old-growth and second-growth forests are co-mingled in managed ecosystems, and our findings demonstrate that land cover change from a mixture of conifer species to lodgepole pine dominance influences DOM inputs that can increase the reactivity of DOM transferred from terrestrial to aquatic ecosystems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Organic matter distribution in the icy environments of Taylor Valley, Antarctica

Glaciers can accumulate and release organic matter affecting the structure and function of associated terrestrial and aquatic ecosystems. Here we analyzed 18 ice cores collected from six locations in Taylor Valley (McMurdo Dry Valleys), Antarctica to determine the spatial abundance and quality of organic matter, and the spatial distribution of bacterial density and community structure from the terminus of the Taylor Glacier to the coast (McMurdo Sound). Our results showed that dissolved and particulate organic carbon (DOC and POC) concentrations in the ice core samples increased from the Taylor Glacier to McMurdo Sound, a pattern also shown by bacterial cell density. Fluorescence Excitation Emission Matrices Spectroscopy (EEMs) and multivariate parallel factor (PARAFAC) modeling identified one humic-like (C1) and one protein-like (C2) component in ice cores whose fluorescent intensities all increased from the Polar Plateau to the coast. The fluorescence index showed that the bioavailability of dissolved organic matter (DOM) also decreased from the Polar Plateau to the coast. Partial least squares path modeling analysis revealed that bacterial abundance was the main positive biotic factor influencing both the quantity and quality of organic matter. Marine aerosol influenced the spatial distribution of DOC more than katabatic winds in the ice cores. Certain bacterial taxa showed significant correlations with DOC and POC concentrations. Collectively, our results show the tight connectivity among organic matter spatial distribution, bacterial abundance and meteorology in the McMurdo Dry Valley ecosystem.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2010

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Fu, Qi↗

NASA NTRS2005

Microbiological Characterization and Concerns of the International Space Station Internal Active Thermal Control System

Since January 1999, the chemical the International Space Station Thermal Control System (IATCS) and microbial state of (ISS) Internal Active fluid has been monitored by analysis of samples returned to Earth. Key chemical parameters have changed over time, including a drop in pH from the specified 9.5 +/- 0.5 ta = 58.4, an increase in the level of total inorganic carbon (TIC), total organic carbon (TOC) and dissolved nickel (Ni) in the fluid, and a decrease in the phosphate (PO,) level. In addition, silver (AS) ion levels in the fluid decreased rapidly as Ag deposited on internal metallic surfaces of the system. The lack of available Ag ions coupled with changes in the fluid chemistry has resulted in a favorable environment for microbial growth. Counts of heterotrophic bacteria have increased from less than 10 colony-forming units (CFUs)/l00 mL to l0(exp 6) to l0(exp 7) CFUs/100 mL. The increase of the microbial population is of concern because uncontrolled microbiological growth in the IATCS can contribute to deterioration in the performance of critical components within the system and potentially impact human health if opportunistic pathogens become established and escape into the cabin atmosphere. Micro-organisms can potentially degrade the coolant chemistry; attach to surfaces and form biofilms; lead to biofouling of filters, tubing, and pumps; decrease flow rates; reduce heat transfer; initiate and accelerate corrosion; and enhance mineral scale formation. The micro- biological data from the ISS IATCS fluid, and approaches to addressing the concerns, are summarized in this paper.

Roman, Monsi C.↗

DOE OSTI2024

Total metal, carbon, anion, iron speciation, and sulfide concentrations; Slate River, East River, and Trail Creek surface water and floodplains, Crested Butte, CO; May 2023–August 2023

This data package comprises analytical results and metadata from stream and groundwater samples collected from the Slate River, East River, Trail Creek, and their respective floodplains. This dataset contains five files: (1) a samples file (2023_SFA_Field_samples.csv) that contains site information; (2) a chemical analysis data file (2023_FieldWaterSampleData_IC__ICPOES__ICPMS__TOC__Fe__S_chem_data.csv) that contains sample analysis values; (3) a file-level metadata file (flmd.csv) that lists each file contained in the dataset with associated metadata; (4) a data dictionary file (dd.csv) that contains column/row headers used throughout the files along with definitions, units, and data types; and (5) a methods file (methods.csv) that contains ID, type, description, instrument, and lab information for each method.The samples’ anion concentrations were measured using ion chromatography (IC), total metal concentrations using inductively coupled plasma emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS), non-purgeable organic carbon using total organic carbon (TOC) analysis, dissolved sulfide concentration using methylene blue spectrophotometry, and iron speciation using the ferrozine assay. To support bulk chemical analyses and colloid characterization, samples were collected from multiple depths ranging from the surface to 3.5 meters below ground.Update on 2024-10-18: Updates were made to the 2023_FieldWaterSampleData_IC__ICPOES__ICPMS__TOC__Fe__S_chem_data.csv and dd.csv files to correct units (ppb instead of ppm).

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1982

Literature review of organic matter transport from marshes

A conceptual model for estimating a transport coefficient for the movement of nonliving organic matter from wetlands to the adjacent embayments was developed in a manner that makes it compatible with the Earth Resources Laboratory's Productive Capacity Model. The model, which envisages detritus movement from wetland pixels to the nearest land-water boundary followed by movement within the water column from tidal creeks to the adjacent embayment, can be transposed to deal with only the interaction between tidal water and the marsh or to estimate the transport from embayments to the adjacent coastal waters. The outwelling hypothesis postulated wetlands as supporting coastal fisheries either by exporting nutrients, such as inorganic nitrogen, which stimulated the plankton-based grazing food chain in the water column, or through the export of dissolved and particulate organic carbon which provided a benthic, detritus-based food web which provides the food source for the grazing food chain in a more indirect fashion.

Dow, D. D.↗

NASA NTRS2018

Arctic Ocean Primary Productivity: The Response of Marine Algae to Climate Warming and Sea Ice Decline

Highlights: 1. Satellite estimates of ocean primary productivity (i.e., the rate at which marine algae transform dissolved inorganic carbon into organic material) were higher in 2018 (relative to the 2003-17 mean) for three of the nine investigated regions (the Eurasian Arctic, Bering Sea, and Baffin Bay). 2. All regions continue to exhibit positive trends over the 2003-18 period, with the strongest trends for the Eurasian Arctic, Barents Sea, Greenland Sea, and North Atlantic. 3. The regional distribution of relatively high (low) chlorophyll-a concentrations can often be associated with a relatively early (late) breakup of sea ice cover.

Frey, K.E.↗

NASA NTRS2020

Arctic Ocean Primary Productivity: The Response of Marine Algae to Climate Warming and Sea Ice Decline

Autotrophic single-celled algae living in sea ice (ice algae) and water column (phytoplankton) are the main primary producers in the Arctic Ocean. Through photosynthesis, they transform dissolved inorganic carbon into organic material. Consequently, primary production provides a key ecosystem service by providing energy to the entire food web in the oceans. Primary productivity is strongly dependent upon light availability and the presence of nutrients, and thus is highly seasonal in the Arctic. The melting and retreat of sea ice during spring are strong drivers of primary production in the Arctic Ocean and its adjacent shelf seas, owing to enhanced light availability and stratification (Barber et al. 2015; Leu et al. 2015; Ardyna et al. 2017). Recent studies have emphasized that primary production occurs under lower light conditions and earlier in the seasonal cycle than previously recognized (Randelhoff et al. 2020). Other studies suggest that increased nutrient supply have also influenced overall production (Henley et al. 2020; Lewis et al. 2020). Furthermore, while declines in Arctic sea ice extent over the past several decades (see essay Sea Ice) have contributed substantially to shifts in primary productivity throughout the Arctic Ocean, the response of primary production to sea ice loss has been both seasonally and spatially variable (e.g., Tremblay et al. 2015; Hill et al. 2018). Here we present satellite-based estimates of algal chlorophyll-a (occurring in all species of phytoplankton), based on ocean color, and subsequently provide calculated primary production estimates. These results are shown for ocean areas with less than 10% sea ice concentration and, therefore, do not include production by sea ice algae or under-ice phytoplankton blooms, which can be significant (e.g., Lalande et al. 2019).

K. E. Frey↗

NASA NTRS1974

Raw Liquid Waste Treatment System and Process

A raw sewage treatment process is disclosed in which substantially all the non-dissolved matter, suspended in the sewage water is first separated from the water, in which at least organic matter remains dissolved. The non-dissolved material is pyrolyzed to form an activated carbon and ash material without the addition of any conditioning agents. The activated carbon and ash material is added to the water from which the non-dissolved matter was removed. The activated carbon and ash material adsorbs the organic matter dissolved in the water and is thereafter supplied in a counter flow direction and combined with the incoming raw sewage to at least facilitate the separation of the non-dissolved settleable materials from the sewage water. Carbon and ash material together with the non-dissolved matter which was separated from the sewage water are pyrolyzed to form the activated carbon and ash material.

Humphrey, M. F.↗

DOE OSTI2022

Exposure pathways and bioaccumulation of per- and polyfluoroalkyl substances in freshwater aquatic ecosystems: Key considerations

We report that due to the bioaccumulative behavior, toxicity, and recalcitrance to degradation, per- and polyfluoroalkyl substances (PFAS) are a focus for many researchers investigating freshwater aquatic ecosystems. PFAS are a diverse set of chemicals that accumulate and transport quite differently in the environment depending on the length of their fluoroalkyl chains and their functional groups. This diversity in PFAS chemical characteristics combined with varying environmental factors also impact the bioaccumulation of these compounds in different organisms. In this review, we evaluate environmental factors (such as organic carbon, proteins, lipids, and dissolved cations) as well as PFAS characteristics (head group, chain-length, and concentration) that contribute to the significant variation seen in the literature of bioaccumulation metrics reported for organisms in aquatic ecosystems. Of the factors evaluated, it was found that PFAS concentration, dissolved organic matter, sediment organic matter, and biotransformation of precursor PFAS tended to significantly impact reported bioaccumulation metrics the most. Based on this review, it is highly suggested that future studies provide sufficient details of important environmental factors, specific organism traits/ behavior, and PFAS concentrations/compounds when reporting on bioaccumulation metrics to further fill data gaps and improve our understanding of PFAS in aquatic ecosystems.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1980

Raw liquid waste treatment process

A raw sewage treatment process is disclosed in which substantially all the non-dissolved matter, which is suspended in the sewage water is first separated from the water, in which at least organic matter is dissolved. The non-dissolved material is pyrolyzed to form an activated carbon and ash material without the addition of any conditioning agents. The activated carbon and ash material is added to the water from which the non-dissolved matter was removed. The activated carbon and ash material absorbs organic matter and heavy metal ions, it is believed, are dissolved in the water and is thereafter supplied in a counter current flow direction and combined with the incoming raw sewage to facilitate the separation of the non-dissolved settleable materials from the sewage water. The used carbon and ash material together with the non-dissolved matter which was separated from the sewage water are pyrolyzed to form the activated carbon and ash material.

Humphrey, Marshall F.↗

DOE OSTI2020

Using Community Science to Reveal the Global Chemogeography of River Metabolomes

River corridor metabolomes reflect organic matter (OM) processing that drives aquatic biogeochemical cycles. Recent work highlights the power of ultrahigh-resolution mass spectrometry for understanding metabolome composition and river corridor metabolism. However, there have been no studies on the global chemogeography of surface water and sediment metabolomes using ultrahigh-resolution techniques. Here, we describe a community science effort from the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium to characterize global metabolomes in surface water and sediment that span multiple stream orders and biomes. We describe the distribution of key aspects of metabolomes including elemental groups, chemical classes, indices, and inferred biochemical transformations. We show that metabolomes significantly differ across surface water and sediment and that surface water metabolomes are more rich and variable. We also use inferred biochemical transformations to identify core metabolic processes shared among surface water and sediment. Finally, we observe significant spatial variation in sediment metabolites between rivers in the eastern and western portions of the contiguous United States. Our work not only provides a basis for understanding global patterns in river corridor biogeochemical cycles but also demonstrates that community science endeavors can enable global research projects that are unfeasible with traditional research models.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Decoupling of redox processes from soil saturation in Arctic tundra

Permafrost thaw in warming Arctic landscapes alters hydrology and saturation-driven biogeochemical processes. Models assume that aerobic respiration occurs in drained soils while saturated soils support methanogenesis; however, saturated soils maintain redox gradients that host a range of anaerobic metabolisms. We evaluated how redox potential and redox-active solutes vary with soil moisture in the active layer of permafrost-affected acidic and non-acidic tundra hillslopes. Oxidizing conditions persisted in highly permeable organic horizons of both unsaturated tussock tundra and saturated wet sedge meadows. Redox potential decreased with depth in all soils as increasing soil bulk density restricted groundwater flow and oxygen diffusion. High concentrations of dissolved iron, phosphate, and organic carbon coincided with redox boundaries below the soil surface in acidic tundra, indicating active iron redox cycling and potential release of adsorbed phosphate during iron (oxyhydr)oxide dissolution. In non-acidic tundra, weatherable minerals affected nutrient dynamics more than redox-driven iron cycling, especially in low-lying, saturated areas where thaw reached mineral soils. The role of thaw depth and the ability of saturated soils to maintain oxidizing conditions in organic surface layers highlight the importance of soil physical properties and hydrology in predicting biogeochemical processes and greenhouse gas emissions.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2000

Sensor Needs for Advanced Life Support

Sensors and feedback systems are critical to life support flight systems and life support systems research. New sensor capabilities can allow for new system architectures to be considered, and can facilitate dramatic improvements in system performance. This paper will describe three opportunities for biosensor researchers to develop sensors that will enable life support system improvements. The first opportunity relates to measuring physical, chemical, and biological parameters in the Space Station Water Processing System. Measuring pH, iodine, total organic carbon, microbiological activity, total dissolved solids, or conductivity with a safe, effective, stable, reliable microsensor could benefit the water processing system considerably. Of special interest is a sensor which can monitor biological contamination rapidly. The second opportunity relates to sensing microbiological contamination and water condensation on the surface of large inflatable structures. It is the goal of large inflatable structures used for habitation to take advantage of the large surface area of the structure and reject waste heat passively through the walls of the structure. Too much heat rejection leads to a cold spot with water condensation, and eventually microbiological contamination. A distributed sensor system that can measure temperature, humidity, and microbiological contamination across a large surface would benefit designers of large inflatable habitable structures. The third opportunity relates to sensing microbial bioreactors used for waste water processing and reuse. Microbiological bioreactors offer considerable advantages in weight and power compared to adsorption bed based systems when used for long periods of time. Managing and controlling bioreactors is greatly helped if distributed microsensors measured the biological populations continuously in many locations within the bioreactor. Nitrifying bacteria are of special interest to bioreactor designers, and any sensors that could measure the populations of these types of bacteria would help the control and operation of bioreactors. J

Graf, John C.↗

NASA NTRS1978

Breadboard wash water renovation system

A total wash water renovation system concept was developed for removing objectionable materials from spacecraft wash water in order to make the water reusable. The breadboard model system described provides for pretreatment with ferric chloride to remove soap by chemical precipitation, carbon adsorption to remove trace dissolved organics, and ion exchange for removal of dissolved salts. The entire system was put into continuous operation and carefully monitored to assess overall efficiency and equipment maintenance problems that could be expected in actual use. In addition, the capacity of the carbon adsorbers and the ion-exchange resin was calculated and taken into consideration in the final evaluation of the system adequacy. The product water produced was well within the Tentative Wash Water Standards with regard to total organic carbon, conductivity, urea content, sodium chloride content, color, odor, and clarity.

Source record↗

DOE OSTI2020

Culturing of “Unculturable” Subsurface Microbes: Natural Organic Carbon Source Fuels the Growth of Diverse and Distinct Bacteria From Groundwater

Recovery and cultivation of diverse environmentally-relevant microorganisms from the terrestrial subsurface remain a challenge despite recent advances in modern molecular technology. Here, we applied complex carbon (C) sources, i.e., sediment dissolved organic matter (DOM) and bacterial cell lysate, to enrich groundwater microbial communities for 30 days. As comparisons, we also included enrichments amended with simple C sources including glucose, acetate, benzoate, oleic acid, cellulose, and mixed vitamins. Our results demonstrate that complex C is far more effective in enriching diverse and distinct microorganisms from groundwater than simple C. Simple C enrichments yield significantly lower biodiversity, and are dominated by few phyla (e.g., Proteobacteria and Bacteroidetes ), while microcosms enriched with complex C demonstrate significantly higher biodiversity including phyla that are poorly represented in published culture collections (e.g., Verrucomicrobia , Planctomycetes , and Armatimonadetes ). Subsequent isolation from complex C enrichments yielded 228 bacterial isolates representing five phyla, 17 orders, and 56 distinct species, including candidate novel, rarely cultivated, and undescribed organisms. Results from this study will substantially advance cultivation and isolation strategies for recovering diverse and novel subsurface microorganisms. Obtaining axenic representatives of “once-unculturable” microorganisms will enhance our understanding of microbial physiology and function in different biogeochemical niches of terrestrial subsurface ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1986

Oxidation and reduction rates for organic carbon in the Amazon mainstream tributary and floodplain, inferred from distributions of dissolved gases

Concentrations of CO2, O2, CH4, and N2O in the Amazon River system reflect an oxidation-reduction sequence in combination with physical mixing between the floodplain and the mainstem. Concentrations of CO2 ranged from 150 microM in the Amazon mainstem to 200 to 300 microM in aerobic waters of the floodplain, and up to 1000 microM in oxygen-depleted environments. Apparent oxygen utilization (AOU) ranged from 80 to 250 microM. Methane was highly supersaturated, with concentrations ranging from 0.06 microM in the mainstem to 100 microM on the floodplain. Concentrations of N2O were slightly supersaturated in the mainstem, but were undersaturated on the floodplain. Fluxes calculated from these concentrations indicated decomposition of 1600 g C sq m y(-1) of organic carbon in Amazon floodplain waters. Analysis of relationships between CH4, O2, and CO2 concentrations indicated that approximately 50 percent of carbon mineralization on the floodplain is anaerobic, with 20 percent lost to the atmoshphere as CH4. The predominance of anaerobic metabolism leads to consumption of N2O on the flood plane. Elevated concentrations of CH4 in the mainstem probably reflect imput from the floodplain, while high levels of CO2 in the mainstem are derived from a combination of varzea drainage and in situ respiration.

Richey, Jeffrey E.↗

NASA NTRS2012

Alternative Water Processor Test Development

The Next Generation Life Support Project is developing an Alternative Water Processor (AWP) as a candidate water recovery system for long duration exploration missions. The AWP consists of biological water processor (BWP) integrated with a forward osmosis secondary treatment system (FOST). The basis of the BWP is a membrane aerated biological reactor (MABR), developed in concert with Texas Tech University. Bacteria located within the MABR metabolize organic material in wastewater, converting approximately 90% of the total organic carbon to carbon dioxide. In addition, bacteria convert a portion of the ammonia-nitrogen present in the wastewater to nitrogen gas, through a combination of nitrogen and denitrification. The effluent from the BWP system is low in organic contaminants, but high in total dissolved solids. The FOST system, integrated downstream of the BWP, removes dissolved solids through a combination of concentration-driven forward osmosis and pressure driven reverse osmosis. The integrated system is expected to produce water with a total organic carbon less than 50 mg/l and dissolved solids that meet potable water requirements for spaceflight. This paper describes the test definition, the design of the BWP and FOST subsystems, and plans for integrated testing.

Pickering, Karen D.↗