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Chemolithoautotroph distributions across the subsurface of a convergent margin

Subducting oceanic crusts release fluids rich in biologically relevant compounds into the overriding plate, fueling subsurface chemolithoautotrophic ecosystems. To understand the impact of subsurface geochemistry on microbial communities, we collected fluid and sediments from 14 natural springs across a ~200 km transect across the Costa Rican convergent margin and performed shotgun metagenomics. The resulting 404 metagenome-assembled genomes (MAGs) cluster into geologically distinct regions based on MAG abundance patterns: outer forearc-only (25% of total relative abundance), forearc/arc-only (38% of total relative abundance), and delocalized (37% of total relative abundance) clusters. In the outer forearc, Thermodesulfovibrionia, Candidatus Bipolaricaulia, and Firmicutes have hydrogenotrophic sulfate reduction and Wood-Ljungdahl (WL) carbon fixation pathways. In the forearc/arc, Anaerolineae, Ca. Bipolaricaulia, and Thermodesulfovibrionia have sulfur oxidation, nitrogen cycling, microaerophilic respiration, and WL, while Aquificae have aerobic sulfur oxidation and reverse tricarboxylic acid carbon fixation pathway. Transformation-based canonical correspondence analysis shows that MAG distribution corresponds to concentrations of aluminum, iron, nickel, dissolved inorganic carbon, and phosphate. While delocalized MAGs appear surface-derived, the subsurface chemolithoautotrophic, metabolic, and taxonomic landscape varies by the availability of minerals/metals and volcanically derived inorganic carbon. Furthermore, the WL pathway persists across all samples, suggesting that this versatile, energy-efficient carbon fixation pathway helps shape convergent margin subsurface ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗

Root exudates shift how N mineralization and N fixation contribute to the plant-available N supply in low fertility soils

Nitrogen (N) availability is a primary constraint to plant productivity, especially in marginal lands with inherently low fertility. Root exudates change with plant nutrient status, and are expected to affect the microbially-mediated N transformations (gross N mineralization vs N fixation) in low fertility soil (low soil organic matter). To explore this possibility, we sampled soils from two monoculture switchgrass (var. Cave-In-Rock) plot with and without N addition at two marginal land sites in Michigan, USA. In a two-week lab incubation, we quantified the effect of different root exudates on gross N mineralization and N fixation by adding simulated root exudates (carbohydrates, organic acids) at a rate of 100 μg C g –1 day –1 . On average, adding carbohydrates to low fertility soil increased the soil respiration by 254%, the dissolved organic carbon (DOC) by 366% and reduced dissolved organic N (DON) by 40%. In contrast, soils receiving organic acids had 159% more soil respiration, 163% higher DOC concentration and the DON concentration increased by 49%. Analysis of the C recovery in measured pools revealed that root exudates C inputs were nearly equivalent to the DOC, microbial biomass carbon (MBC), and soil respiration in sandy soil, but only 45–74% of the root exudate C was recovered in these pools in the sandy loam soil. This suggests that root exudate C may be adsorbed to mineral particles in the sandy loam soil. Soil treated with organic acids had higher gross N mineralization and N immobilization rates than soil with carbohydrates addition. Adding carbohydrates significantly increased the free-living N fixation rates, compared to organic acid addition. Changes in soil pH, and DON induced by root exudate addition had strong association with N transformation rates and N availability. Gross N mineralization produced more plant-available N than N fixation, as evidenced by higher inorganic N concentration in soils receiving organic acids than carbohydrates. Here, by quantifying how different root exudates affect the contribution of N mineralization and N fixation to the plant-available N pool in low fertility soils, this study enhances our understanding of the “C for N” exchange in the plant rhizosphere.

54 ENVIRONMENTAL SCIENCES↗

Stable isotope laser spectroscopy

Recent advances in semiconductor laser technology have produced a reliable lightweight device ideally suited for a spacecraft high resolution molecular spectrometer. Lead-salt tunable diode lasers (TDL) emit in several spectral modes, each with a very narrow linewidth of -0.0003/cm. This spectral resolution is much narrower than typical Doppler broadened molecular linewidths in the mid-IR range. Thus it is possible to detect individual rotational lines within the vibrational band and measure their intensity, which can be used to determine gas concentration. The narrow spectral lines of any impurity gas tend to lie between the narrow lines of the gas of interest. This represents a major advantage over the accepted gas chromatograph mass spectrometer (GCMS) technique for measuring gas concentrations and isotope ratios. The careful and extensive gas purification procedures required to remove impurities for reliable GCMS measurements will not be required for an IR laser gas analysis. The infrared laser gas analysis technique is being developed to measure stable isotopic ratios of gases such as CO2, CH4, N2O, and NH3. This will eventually lead to development of instruments capable of in situ istopic measurements on planets such as Mars. The carbon (C-12, C-13) isotope ratio is indicative of the type of carbon fixation mechanisms (e.g., photosynthesis, respiration) in operation on a planet, while the nitrogen (N-14, N-15) isotope ratio can probably be used to date nitrogen-bearing Martian samples. The absorbance ratio of two adjacent lines of CO2 in the 2300/cm (4.3 micron) region of the spectrum was measured. The precision of the measurement is presently better than 1 percent and significant improvement is anticipated as rapid sweep-integration techniques and computer controlled data acquistion capabilities are incorporated.

Becker, J. F.↗

Leafweb: Leaf Gas Exchange and Pulse-Amplitude Modulated Fluorometry for C4 Species, June 2026 Release

This dataset contains leaf gas exchange and Pulse-Amplitude Modulated (PAM) fluorometry for 98 C4 species. The C4 photosynthetic pathway employs specialized CO2 concentration mechanisms and Kranz anatomy to enrich CO2 concentration around Rubisco, the enzyme that catalyzes carbon fixation in the Calvin-Benson cycle to suppress photorespiration and increase the use efficiencies of light, nitrogen, and water as compared to the C3 photosynthetic pathways. Large-scale C4 photosynthetic datasets are relatively scarce, which has affected C4 photosynthesis research. To improve C4 photosynthetic data availability, Leafweb organized an effort to systematically collect, compile, standardize, and organize measurements of leaf gas exchange and/or Pulse-Amplitude Modulated (PAM) fluorometry of C4 species. This derived a C4 photosynthetic dataset containing measurements made by independent researchers in multiple countries in various environments (field, garden, or greenhouse). It covers three biochemical subtypes – the nicotinamide adenine dinucleotide phosphate-malic enzyme (NADP-ME), nicotinamide adenine dinucleotide-malic enzyme (NAD-ME), and phosphoenolpyruvate carboxykinase (PEP-CK) subtypes. This dataset is useful for using Artificial Intelligence / Machine Learning and mechanistic models to study C4 photosynthesis and compare across different biochemical subtypes. This dataset contains 3 compressed (*.zip) folders containing 1,892 data files in comma-separate values (*.csv) format. Additional metadata are provided: one data dictionary and a file-level metadata file in comma-separate values (*.csv) format and a user guide in PDF (*.pdf) format.

Zhou, Haoran [Tianjin University, China]↗

The phototrophic purple non‐sulfur bacteria Rhodomicrobium spp. are novel chassis for bioplastic production

Abstract Petroleum‐based plastics levy significant environmental and economic costs that can be alleviated with sustainably sourced, biodegradable, and bio‐based polymers such as polyhydroxyalkanoates (PHAs). However, industrial‐scale production of PHAs faces barriers stemming from insufficient product yields and high costs. To address these challenges, we must look beyond the current suite of microbes for PHA production and investigate non‐model organisms with versatile metabolisms. In that vein, we assessed PHA production by the photosynthetic purple non‐sulfur bacteria (PNSB) Rhodomicrobium vannielii and Rhodomicrobium udaipurense. We show that both species accumulate PHA across photo‐heterotrophic, photo‐hydrogenotrophic, photo‐ferrotrophic, and photo‐electrotrophic growth conditions, with either ammonium chloride (NH 4 Cl) or dinitrogen gas (N 2 ) as nitrogen sources. Our data indicate that nitrogen source plays a significant role in dictating PHA synthesis, with N 2 fixation promoting PHA production during photoheterotrophy and photoelectrotrophy but inhibiting production during photohydrogenotrophy and photoferrotrophy. We observed the highest PHA titres (up to 44.08 mg/L, or 43.61% cell dry weight) when cells were grown photoheterotrophically on sodium butyrate with N 2 , while production was at its lowest during photoelectrotrophy (as low as 0.04 mg/L, or 0.16% cell dry weight). We also find that photohydrogenotrophically grown cells supplemented with NH 4 Cl exhibit the highest electron yields – up to 58.89% – while photoheterotrophy demonstrated the lowest (0.27%–1.39%). Finally, we highlight superior electron conversion and PHA production compared to a related PNSB, Rhodopseudomonas palustris TIE‐1. This study illustrates the value of studying non‐model organisms like Rhodomicrobium for sustainable PHA production and indicates future directions for exploring PNSB metabolisms.

59 BASIC BIOLOGICAL SCIENCES↗

BOREAS TE-9 PAR and Leaf Nitrogen Data for NSA Species

The Boreal Ecosystem-Atmospheric Study (BOREAS) TE-9 (Terrestrial Ecology) team collected several data sets related to chemical and photosynthetic properties of leaves in boreal forest tree species. This data set describes the relationship between photosynthetically active radiation (PAR) levels and foliage nitrogen in samples from six sites in the BOREAS Northern Study Area (NSA) collected during the three 1994 intensive field campaigns (IFCs). This information is useful for modeling the vertical distribution of carbon fixation for these different forest types in the boreal forest. The data were collected to quantify the relationship between PAR and leaf nitrogen of black spruce, jack pine, and aspen. The data are available in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

Hall, Forrest G.↗

INSIGHTS INTO MARINE UNICELLULAR CYANOBACTERIAL AND NON-CYANOBACTERIAL DIAZOTROPHS THROUGH SINGLE-CELL ANALYSES

Nutrient availability affects primary productivity, and nitrogen (N) is the limiting nutrient over large regions of the ocean. Biological N fixation (BNF) is the conversion of atmospheric dinitrogen (N2) to bioavailable forms of N (ammonium and amino acids). A select group of Bacteria and Archaea, known as diazotrophs, are the only organisms capable of this conversion. BNF is a critical source of N in nutrient-depleted (oligotrophic) marine waters. As such, BNF studies are a fundamental component for better understanding primary productivity and carbon cycling, as well as parameterizing predictive future global ocean models. Unicellular diazotrophs are widespread in marine systems and, in some cases, important contributors of BNF. This dissertation investigates unicellular diazotrophs at the single-cell level, including: UCYN-A, a cyanobacterial diazotroph that lives in symbiosis with an algal host, non-cyanobacterial diazotrophs (NCDs), which are putative heterotrophs, as well as a specific NCD known as Gamma A, a commonly occurring organism throughout the tropics and subtropics that belongs to the class Gammaproteobacteria. The single-cell investigations used in these studies can provide high-resolution insights that are not possible from community-level analyses of BNF, such as the N2 fixation rate of individual cells and cell morphology. Singlecell nanoscale secondary ion mass spectrometry (nanoSIMS) analyses were used in chapter 2 and 3 to investigate the cell-specific N2 fixation rates of (2) UCYN-A in the viii cold waters of the Bering and Arctic Seas where N2 fixation was not previously believed to be possible, and (3) NCDs in the North Pacific Subtropical Gyre where we demonstrated the first direct evidence of NCD N2 fixation on open ocean particles. Chapter 4 focused on the uncultivated NCD, Gamma A, using geneFISH to visualize single cells in natural seawater samples. We successfully identified Gamma A by developing a fluorescent in situ hybridization (FISH) probe targeting the diazotrophic functional marker gene nifH, revealing Gamma A cells are most often attached to particles. Together these studies provide new insights into the distributions, activities, and physiologies of geographically widespread, unicellular diazotrophs, thus improving our understanding of their roles as sources of fixed N in the surface ocean.

Harding, K.↗

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

The growth of crops to sustain astronauts will be critical to long-duration spaceflight missions. Carbon dioxide (CO 2 ) concentrations are very high in spaceflight cabin environments, often 5-10X the CO 2 concentration on Earth 1 . It is therefore crucial to understand how plants respond to elevated CO 2 (eCO 2 ). Nitrogen (N) is important for plant survival, though the effects of eCO 2 on plant uptake of different N forms remain poorly understood. Shoot nitrate assimilation may be reduced at eCO 2 due to a decrease in available reducing power through increased carbon fixation and inhibition of photorespiration 2 , suggesting that eCO 2 may increase plant ammonium preference (Figure 1). A deeper understanding of changes in plant nitrogen form preference in response to eCO 2 will inform nutrient optimization for future space crop production and wastewater processing system design requirements 3 in addition to developing future eCO 2 climate-ready crops.

nitrogen↗

Binding of isolated plant lectin by rhizobia during episodes of reduced gravity obtained by parabolic flight

Development of a legume root nodule is a complex process culminating in a plant/bacterial symbiosis possessing the capacity for biological dinitrogen fixation. Formation of root nodules is initiated by the binding and stabilization of rhizobia to plant root hairs, mediated in part by a receptor/ligand recognition system composed of lectins on the plant root surface and lectin-binding sites on the rhizobial cell surface. The dinitrogen fixation activity of these root nodules may be an important feature of enclosed, space-based life support systems, and may provide an ecological method to recycle nitrogen for amino acid production. However, the effects on nodule development of varied gravitational fields, or of root nutrient delivery hardware, remain unknown. We have investigated the effects of microgravity on root nodule formation, with preliminary experiments focused upon the receptor/ligand component. Microgravity, obtained during parabolic flight aboard NASA 930, has no apparent effect on the binding of purified lectin to rhizobia, a result that will facilitate forthcoming experiments using intact root tissues.

manned↗

State of Climate 2011 - Global Ocean Phytoplankton

Phytoplankton photosynthesis in the sun lit upper layer of the global ocean is the overwhelmingly dominant source of organic matter that fuels marine ecosystems. Phytoplankton contribute roughly half of the global (land and ocean) net primary production (NPP; gross photosynthesis minus plant respiration) and phytoplankton carbon fixation is the primary conduit through which atmospheric CO2 concentrations interact with the ocean s carbon cycle. Phytoplankton productivity depends on the availability of sunlight, macronutrients (e.g., nitrogen, phosphorous), and micronutrients (e.g., iron), and thus is sensitive to climate-driven changes in the delivery of these resources to the euphotic zone

Siegel, D. A.↗

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium 1. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties 2. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling 3. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security. References: 1. Bloom (2015). The increasing importance of distinguishing among plant nitrogen sources. Current Opinion in Plant Biology 25, 10-16. 2. Fountain (2023). Understanding interactions of barley (Hordeum vulgare) with soil nitrogen cycling activity and links to plant nitrogen preference. Ph.D. Thesis, The University of Sheffield. 3. Schiefloe et al. (2023). From urine to food and oxygen: effects of high and low NH4+:NO3- ratio on lettuce cultivated in a gas-tight hydroponic facility. Frontiers in Plant Science 14:1229476.

nitrogen↗

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security.

nitrogen↗

Plant Nitrogen Uptake Responses to Elevated Carbon Dioxide

Future long-duration missions will require a sustainable supply of food to support human crews. The spaceflight cabin environment often contains very high concentrations of CO 2 due to release of CO 2 by astronauts that is not completely scrubbed from the cabin, and it is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Much focus has been given to changes in plant photosynthetic and performance parameters in response to eCO 2 , but the effects of eCO 2 on nitrogen (N) uptake are poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , likely due to less reductant available for nitrate reduction because of reduced photorespiration and increased carbon fixation 1. Relative growth rate can be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium. However, N uptake in response to eCO 2 has, to our knowledge, not yet been studied. An increased ‘preference’ for plants to take up N as ammonium at eCO 2 could have important implications for growth in the space environment, where N is currently only supplied as nitrate. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of eCO 2 on N preference for ammonium or nitrate in spring barley and lettuce when both N forms are provided equally. Several varieties of spring barley displayed increased ammonium preference at eCO 2 (720 ppm) compared to ambient CO 2 (410 ppm), though this was not true for all varieties. In most cases, increases in ammonium preference were driven by increases in ammonium uptake at eCO 2 and not decreases in nitrate uptake. Current research is assessing whether similar responses are observed in the candidate space crop lettuce, at levels of CO 2 like those observed on ISS (3000 ppm), and these results will also be presented. This work will enable the development of optimized nutrient regimes for candidate crops in space environments and the selection of crop varieties adapted to eCO 2 environments. Plants adapted to ammonium nutrition may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling. Moreover, this research will further our understanding of plant responses to the eCO 2 environment brought about by climate change, allowing the development of future-proof crops that will help to maintain food security.

nitrogen↗

Unraveling metabolism underpinning biomass composition shift in Scenedesmus obliquus under simulated outdoor conditions using 13 C-fluxomics

To render the resulting biomass more attractive and amenable for utilization as the basis for low-carbon intensity bioproducts, single-celled algae need to be biochemically and metabolically poised to assimilate and store the delivered carbon in the fastest and most efficient manner. Accelerating biochemical carbon storage, as primarily carbohydrates or lipids, is critical to achieve the high carbon capture potential that is assigned to algae. To guide strain optimization and engineering for maximizing carbon capture and storage, it is essential to elucidate the link between carbon metabolism and biomass composition. Most published metabolomics work in algae remains largely restricted to ideal and simplified environmental conditions in model organisms, thereby limiting their translation to outdoor implementation. In this work, we utilize 13 C isotopic labeling to characterize distinct intracellular metabolic fluxes before, during, and after nitrogen depletion-induced compositional shifts in Scenedesmus obliquus UTEX 393. The results indicate that a transition to carbohydrates is characterized by diverting flux to starch instead of replenishing the Calvin cycle for CO 2 fixation whereas the subsequent transition to lipids is fueled by NADPH produced by upregulating the phosphoenolpyruvate carboxylase (PEPC)–malic enzyme (ME) cycle flux. Our work highlights bottlenecks to carbohydrate- and lipid-rich biomass and can guide implementable strategies to control the fate of fixed carbon in S. obliquus.

09 BIOMASS FUELS↗

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source

Long-duration exploration missions will require a sustainable supply of food to support human crews. The spaceflight environment contains high concentrations of CO 2 due to release by astronauts that cannot be completely scrubbed. It is therefore crucial to understand plant responses to elevated CO 2 (eCO 2 ) environments. Nitrogen (N) is crucial for plant survival, though the effects of eCO 2 on plant N uptake remain poorly understood. Shoot nitrate reduction may be reduced at eCO 2 , due to reduced reductant availability for nitrate reduction due to reduced photorespiration and increased carbon fixation. Relative growth rate may be reduced at eCO 2 when N is provided only as nitrate and can be unaffected when N is supplied as ammonium, suggesting eCO 2 may drive increased plant ‘preference’ for ammonium. However, changes in N preference in response to eCO 2 have, to our knowledge, not yet been studied. In this study, novel stable isotope approaches were used in conjunction with hydroponics and isotope ratio mass spectrometry to determine the effect of space station-like eCO 2 (3000 ppm) on preference for ammonium or nitrate in several lettuce varieties previously grown in space, when both N forms are provided equally. All varieties displayed significant ammonium preference irrespective of CO 2 concentration, however the extent of this preference varied. Increased ammonium preference was observed for all varieties at eCO 2 compared to ambient CO 2 (410 ppm), driven by increases in nitrogen uptake which plants disproportionately took up as ammonium. These results suggest that future nutrient formulations should favor ammonium as a major N source for space crop production. Moreover, increased ammonium preference may play a role in future plant-based bioregenerative life support systems with higher ammonium concentrations due to waste recycling. Additionally, this research furthers our understanding of plant responses to future high CO 2 climates, allowing the development of future-proof crops to maintain food security.

space crop production↗

Rock-Sourced Nitrogen in Semi-Arid, Shale-Derived California Soils

Models suggest that rock-derived nitrogen (N) inputs are of global importance to ecosystem N budgets; however, field studies demonstrating the significance of rock N inputs are rare. We examined rock-derived N fluxes in soils derived from sedimentary rocks along a catena formed under a semi-arid climate. Our measurements demonstrate that there are distinct and traceable pools of N in the soil and bedrock and that the fraction of rock-derived N declines downslope along the catena. We used geochemical mass balance weathering flux measurements to estimate a rock-derived N flux of 0.145 to 0.896 kg ha -1 yr -1 at the ridgecrest. We also developed independent N flux estimates using a 15 N-based isotope mixing model. While geochemical mass-balance-based estimates fell within the 95% confidence range derived from the isotope mixing model (-1.1 to 44.3 kg ha -1 yr -1 ), this range was large due to uncertainty in values for atmospheric 15 N deposition. Along the catena, N isotopes suggest a diminishing effect of rock-derived N downslope. Overall, we found that despite relatively large N pools within the saprolite and bedrock, slow chemical weathering and landscape denudation limit the influence of rock-derived N, letting atmospheric N deposition (7.1 kg ha -1 yr -1 ) and N fixation (0.9-3.1 kg ha -1 yr -1 ) dominate N inputs to this grassland ecosystem.

54 ENVIRONMENTAL SCIENCES↗

Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency

The electrochemical dinitrogen (N 2 ) reduction reaction (NRR) under ambient conditions has gained significant interest as an environmentally friendly alternative to the traditional Haber–Bosch process for the synthesis of ammonia (NH 3 ). However, up to now, most of the reported NRR electrocatalysts with satisfactory catalytic activities have been hindered by the large overpotential in N 2 activation. The preparation of highly efficient Mo-based NRR electrocatalyst in acidic electrolytes under ambient conditions is demonstrated here, consisting of stabilized single Mo atoms anchored on holey nitrogen-doped graphene synthesized through a convenient potassium-salt-assisted activation method. At -0.05 V versus a reversible hydrogen electrode (RHE), an electrode consisting of the resultant electrocatalyst immobilized on carbon fiber paper can attain an exceptional Faradaic efficiency of 50.2% and a NH3 yield rate of 3.6 µg h -1 mg cat -1 with low overpotentials. Density functional theory calculations further unveil that compared to the original graphene without holes, the edge coordinated Mo atoms and the existence of vacancies on holey graphene lower the overpotential of N 2 reduction, thereby promoting the NRR catalytic activity. Finally, this work could provide new guidelines for future designs in single-atom catalysis that would be beneficial to ambient N 2 fixation, and replacement of classical synthesis processes that are very energy-intensive.

36 MATERIALS SCIENCE↗

BOREAS TE-9 NSA Photosynthetic Capacity and Foliage Nitrogen Data

The Boreal Ecosystem-Atmospheric Study (BOREAS) TE-9 (Terrestrial Ecology) team collected several data sets related to chemical and photosynthetic properties of leaves in boreal forest tree species. This data set describes the spatial and temporal relationship between foliage nitrogen concentration and photosynthetic capacity in the canopies of black spruce, jack pine, and aspen located within the Northern Study Area (NSA). The data were collected from June to September 1994 and are useful for modeling the vertical distribution of carbon fixation for different forest types in the boreal forest. The data are available in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

Hall, Forrest G.↗