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At least 577 records · Page 32

CO 2 Hydrogenation on ZrO 2 /Cu(111) Surfaces: Production of Methane and Methanol

The conversion and utilization of carbon dioxide is a critical challenge for the control of greenhouse gas pollution and in the production of high value chemicals in C1 chemistry. ZrO 2 /Cu(111) is an inverse oxide/metal catalyst that displays high activity and stability for the hydrogenation of CO 2 into methanol at 500-600 K. At elevated temperatures, ZrO 2 grows on a CuO x /Cu(111) substrate forming islands of 10-12 nm in size and an average height of ~ 3 Å. Reaction with H 2 leads to the removal of the copper oxide producing ZrO 2 /Cu(111) surfaces which are very active for the binding and dissociation of CO 2 into CO and C. After exposing ZrO 2 /Cu(111) to moderate or elevated pressures of a CO 2 /H 2 mixture at 300 K, atomic C and minor amounts of CH x O and CO x are deposited on the catalyst surface. The adsorbed CH x O and CO x disappear upon heating above 400 K. The catalytic tests for CO 2 hydrogenation give CO as the main reaction product and CH 4 and CH 3 OH as secondary products. The relative yields of methane and methanol change with time and track the amount of atomic C deposited on the active ZrO 2 /Cu(111) surface. The formation of methane stops once the catalyst surface is saturated with C. Under steady-state conditions, ZrO 2 /Cu(111) is a much better catalyst for methanol synthesis than ZnO/Cu(111). This trend reflects variations in the size of the oxide islands and in the strength of oxide-metal interactions. The use of an inverse oxide/metal configuration is an important synthetic tool when preparing active, selective, and stable catalysts for CO 2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Anti-Fouling Coatings to Improve the Efficiency of Coal Power Plants

As the total cost of carbon to generate energy has become a global concern, operators are increasingly looking at all parts of the generation cycle to find areas where efficiency gains may be found. It has been long identified that fouling of heat exchangers is a persistent cause of up to 2.5% of global CO 2 emissions. Unfortunately, practice has also demonstrated that unless a powerful economic driver exists to encourage preemptive mitigation of fouling, there will always be a strong tendency for operators to minimize any form of intervention due to high costs and challenges in scheduling downtime. The objective of this proposed research effort was to demonstrate how existing power plants could lower their carbon emissions and significantly improve heat transfer efficiency using new surface treatment materials to control fouling in a variety of heat exchange equipment. The surface treatment material which was optimized and deployed in this effort is now known commercially as HeatX. It is a low-surface energy, water- and oil-repellent, abrasion resistant material which can be applied in-situ to a wide variety of previously worn/used/in-service substrates. Once applied, it provides a barrier against corrosion, scale deposit formation, and biofilm adhesion on the circulating water-containing tube-side. Alternatively, if applied to the tube exterior, the non-wetting nature of the surface was demonstrated to promote dropwise condensation, subsequently lowering condenser backpressure and increasing overall plant efficiency. As part of this cooperative effort, the Department of Energy’s support was crucial to de-risk and demonstrate the concept of HeatX, while validating both the performance and economic benefit in multiple pilot field studies. The HeatX material properties were optimized in this effort for full field applicability to heat exchangers and condensers, and Oceanit developed the necessary procedures and protocols to provide enough material to support extended length, multi-year demonstrations in the power generation, desalination, and refining industries, making this technology broadly applicable and ready for commercial transition. Field deployment case studies at thermal power plants have shown that the HeatX treatment can provide economic savings of up to $15,000 per day for an operator based on avoiding maintenance costs and lowering fuel usage. The complete mitigation of fouling effects can increase the efficiency of equipment by up to 7%, in a field where gains of 0.5% are generally seen as operationally significant. The HeatX treatment has also demonstrated exceptional lifetime and compatibility with a wide variety of seawater and hydrocarbon environments, further increasing both the return on investment and the effective emission reduction. Such efficiency improvements correlate to massive carbon savings. For every 1 GW of capacity, operators can see carbon emissions reductions of 300,000 tons of CO 2 per year. When looking at the bigger picture, improved condenser function across the U.S. has the potential to prevent 221.3 million tons of CO 2 emissions, equivalent to the sequestration capacity of 129 million acres of forest. If applied on a global scale, 1.26 billion metric tons of CO 2 could be averted from the atmosphere, the same amount of carbon sequestrated by 1.5 billion acres of forest annually or 262,000 wind turbines operating annually. As businesses across multiple industries take a more active role in focusing on environmental, social, and governance (ESG) solutions as part of their core business operations, HeatX will be an attractive technology for commercial investment.

01 COAL, LIGNITE, AND PEAT↗

Rational design of high-performance low-loading oxygen reduction catalysts for alkaline fuel cells

The lack of mechanistic understanding and catalyst design principles for alkaline electrolytes, especially for the sluggish oxygen reduction reaction, has impeded the advancement of alkaline fuel cells. Here, in this study, we propose a modified volcano plot and apply this rationale to strategically design Pt nanosheets with PdH x nanosheets substrates. This catalyst exhibited high stability with a specific activity of 1.71 mA cm −2 at 0.95 V versus the reversible hydrogen electrode, surpassing the benchmark of Pt/C by 49-fold. Spectroscopic, electrochemical and electron microscopic characterizations revealed that such performance enhancement originated from tensile-strained Pt{111} facets, improving oxidative stability and suppressing carbon corrosion. In fuel cell testing, the catalyst enabled a peak power density of 1.67 W cm −2 with a loading of 10 µg PGM Cathode cm −2 . Further optimization delivered a peak power density of 21.7 W mg −1 PGM Cathode+Anode with a total specific catalyst cost US$\$$1.27 kW −1 , surpassing the US Department of Energy’s Pt group metal loading and cost targets. This study provides valuable insights into catalyst design for the alkaline oxygen reduction reaction.

36 MATERIALS SCIENCE↗

Synthesis of (hemi)cellulosic lubricant base oils via catalytic coupling and deoxygenation pathways

The past decade has witnessed a significant growth in bioproduct development due to the strong interest in creating a more diverse energy supply, environmental sustainability, and a carbon neutral bioeconomy. The initial biorefinery strategy, which focused mainly on the production of low carbon number drop-in bioproducts, has recently shifted its focus on the production of high carbon number and high performance bioproducts with unique properties and value propositions. One such product is lubricant base oil (LBO), which represents over $150 billion global lubricant market and is used for various industrial, automotive, marine, metal-working, consumer, and specialized applications. The application landscape of lubricants has changed significantly over the past decade because of environmental regulations and the growing demand for sustainable lubricants to mitigate regulatory challenges and improve carbon footprint. Currently, only 3% LBOs are produced from bio-based triglycerides/fatty acids. Because of low oxidation stability and high hydrolytic susceptibility, these bio-based LBOs have limited applications. Thus, research and development and commercialization efforts for (hemi)cellulosic LBOs to meet the market demand have received momentum over the past few years. This review describes strategies to produce (hemi)cellulosic LBOs via carbon–carbon coupling and hydrodeoxygenation chemistries. We emphasize the coupling strategies to create LBOs with a branched architecture to surrogate petroleum-based poly-α-olefins. Here, a structure–property relationship for tuning the key specifications of LBOs as a function of molecular architecture is illustrated. Mechanistic understanding and molecular interactions of multi-furan substrates with the active sites of complex multifunctional catalysts are described. Furthermore, techno-economic and life-cycle analysis is summarized along with standing challenges and future opportunities.

09 BIOMASS FUELS↗

Asgard archaea modulate potential methanogenesis substrates in wetland soil

The roles of Asgard archaea in eukaryogenesis and marine biogeochemical cycles are well studied, yet their contributions in soil ecosystems remain unknown. Of particular interest are Asgard archaeal contributions to methane cycling in wetland soils. To investigate this, we reconstructed two complete genomes for soil-associated Atabeyarchaeia, a new Asgard lineage, and a complete genome of Freyarchaeia, and predicted their metabolism in situ. Metatranscriptomics reveals expression of genes for [NiFe]-hydrogenases, pyruvate oxidation and carbon fixation via the Wood-Ljungdahl pathway. Also expressed are genes encoding enzymes for amino acid metabolism, anaerobic aldehyde oxidation, hydrogen peroxide detoxification and carbohydrate breakdown to acetate and formate. Overall, soil-associated Asgard archaea are predicted to include non-methanogenic acetogens, highlighting their potential role in carbon cycling in terrestrial environments.

59 BASIC BIOLOGICAL SCIENCES↗

Revisiting the activity of two poly(vinyl chloride)- and polyethylene-degrading enzymes

Biocatalytic degradation of non-hydrolyzable plastics is a rapidly growing field of research, driven by the global accumulation of waste. Enzymes capable of cleaving the carbon-carbon bonds in synthetic polymers are highly sought-after as they may provide tools for environmentally friendly plastic recycling. Despite some reports of oxidative enzymes acting on non-hydrolyzable plastics, including polyethylene or poly(vinyl chloride), the notion that these materials are susceptible to efficient enzymatic degradation remains controversial, partly driven by a general lack of studies independently reproducing previous observations. Here, we attempt to replicate two recent studies reporting that deconstruction of polyethylene and poly(vinyl chloride) can be achieved using an insect hexamerin from Galleria mellonella (so-called “Ceres”) or a bacterial catalase-peroxidase from Klebsiella sp., respectively. Reproducing previously described experiments, we do not observe any activity on plastics using multiple reaction conditions and multiple substrate types. Digging deeper into the discrepancies between the previous data and our observations, we show how and why the original experimental results may have been misinterpreted.

36 MATERIALS SCIENCE↗

Combined Effects of Stream Hydrology and Land Use on Basin‐Scale Hyporheic Zone Denitrification in the Columbia River Basin

Abstract Denitrification in the hyporheic zone (HZ) of river corridors is crucial to removing excess nitrogen in rivers from anthropogenic activities. However, previous modeling studies of the effectiveness of river corridors in removing excess nitrogen via denitrification were often limited to the reach‐scale and low‐order stream watersheds. We developed a basin‐scale river corridor model for the Columbia River Basin with random forest models to identify the dominant factors associated with the spatial variation of HZ denitrification. Our modeling results suggest that the combined effects of hydrologic variability in reaches and substrate availability influenced by land use are associated with the spatial variability of modeled HZ denitrification at the basin scale. Hyporheic exchange flux can explain most of spatial variation of denitrification amounts in reaches of different sizes, while among the reaches affected by different land uses, the combination of hyporheic exchange flux and stream dissolved organic carbon (DOC) concentration can explain the denitrification differences. Also, we can generalize that the most influential watershed and channel variables controlling denitrification variation are channel morphology parameters (median grain size (D50), stream slope), climate (annual precipitation and evapotranspiration), and stream DOC‐related parameters (percent of shrub area). The modeling framework in our study can serve as a valuable tool to identify the limiting factors in removing excess nitrogen pollution in large river basins where direct measurement is often infeasible.

54 ENVIRONMENTAL SCIENCES↗

High-temperature phonon-mediated superconductivity in monolayer Mg 2 B 4 C 2

A two-dimensional material – Mg 2 B 4 C 2 , belonging to the family of the conventional superconductor MgB 2 , is theoretically predicted to exhibit superconductivity with critical temperature T c estimated in the 47–48 K range (predicted using the McMillian-Allen-Dynes formula) without any tuning of external parameters such as doping, strain, or substrate-induced effects. The origin of such a high intrinsic T c is ascribed to the presence of strong electron-phonon coupling and large density of states at the Fermi level. This system is obtained after replacing the chemically active boron-boron surface layers in a MgB 2 slab by chemically inactive boron-carbon layers. Hence, the surfaces of this material are inert. Our calculations confirm the stability of 2D Mg 2 B 4 C 2 . We also find that the key features of this material remain essentially unchanged when its thickness is increased by modestly increasing the number of inner MgB 2 layers.

36 MATERIALS SCIENCE↗

Broad substrate-specific phosphorylation events are associated with the initial stage of plant cell wall recognition in Neurospora crassa

Fungal plant cell wall degradation processes are governed by complex regulatory mechanisms, allowing the organisms to adapt their metabolic program with high specificity to the substrate at hand. While the uptake of representative plant cell wall mono- and disaccharides is known to induce specific transcriptional and translational responses, the processes related to early signal reception and transduction are still enigmatic. A fast and reversible way of transmitting extracellular signals throughout the cell are protein phosphorylations, which could initiate adaptations of the fungal metabolism on a post-translational level. In an effort to elucidate how changes in the initial substrate recognition phase of Neurospora crassa affect the global phosphorylation pattern, phosphoproteomics was performed after a short (2 minute) induction period with several plant cell wall-related mono- and disaccharides. The MS/MS-based peptide analysis revealed a large number of proteins that are phosphorylated or de-phosphorylated in a substrate-specific manner. A protein-protein-interaction network was constructed based on the proteins identified by MS/MS. Using this network, putative interaction partners of several phosphorylated proteins of interest were determined. This led to the discovery of substrate-specific protein-interactions that might be involved in mediating the substrate recognition of N. crassa. Besides a high number of kinases, phosphatases and transcription factors to be affected by differential phosphorylation, our data demonstrate, for example, that the cAMP signaling pathway is heavily modified by substrate-specific phosphorylations, including the key component adenylate cyclase CR-1 as well as several G-protein-coupled receptors. In addition, four differentially phosphorylated F-Box proteins were identified in the phospho-proteome. When physiologically characterized using the respective gene deletion strains, Fbx-19 and Fbx-22 were found to be involved in carbon catabolite repression responses. Overall, these results improve our understanding of how fungi respond to environmental cues and provide novel insights into the mechanisms of sensory perception and signal transduction during lignocellulose degradation.

59 BASIC BIOLOGICAL SCIENCES↗

High temperature and high beam current compatible targets and methods thereof for generating noble gas/radiohalogen generators for medical isotopes

A method of providing alpha particle emitters and materials suitable for use in generating the alpha particles for medical treatment is disclosed. Metal oxide targets, preferentially Bi 2 O 3 pellets and Bi 2 O 3 coatings on metallic or metal oxide substrates are formed. The targets placed in a heated vacuum chamber subjecting to irradiation using a 6 Li beam at an elevated temperature below the melting point of the target generate a radioactive gas, such as 211 Rn, the radioactive gas is carried by an inert gas which is delivered a carrier for, such as a carbon column or oil for delivery to a treatment facility. The radioactive gas such as 211 Rn generates 211 At, which has a useable half-life of at least about 14 hours, in turn releases alpha particles which are effective for use in medical procedures.

Sampathkumaran, Uma↗

Atomically dispersed palladium catalyses Suzuki–Miyaura reactions under phosphine-free conditions

Single-atom catalysts have emerged as a new frontier in catalysis science. However, their applications are still limited to small molecule activations in the gas phase, the classic organic transformations catalyzed by single-atom catalysts are still rare. Here, we report the use of a single-atom Pd catalyst for the classic Suzuki–Miyaura carbon–carbon coupling reaction under phosphine-free and open-air conditions at room temperature. The single-atom Pd catalyst is prepared through anchoring Pd on bimetal oxides (Pd-ZnO-ZrO 2 ). The significant synergetic effect of ZnO and ZrO 2 is observed. The catalyst exhibits high activity and tolerance of a wide scope of substrates. Characterization demonstrates that Pd single atoms are coordinated with two oxygen atoms in Pd-ZnO-ZrO 2 catalyst. The catalyst can be fabricated on a multi-gram scale using a simple in situ co-precipitation method, which endows this catalytic system with great potential in practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of moisture on microbial decomposition phenotypes and enzyme dynamics

Soil organic matter decomposition is a complex process reflecting microbial composition and environmental conditions. Moisture can modulate the connectivity and interactions of microbes. Due to heterogeneity, a deeper understanding of the influence of soil moisture on the dynamics of organic matter decomposition and resultant phenotypes remains a challenge. Soils from a long-term field experiment exposed to high and low moisture treatments were incubated in the laboratory to investigate organic matter decomposition using chitin as a model substrate. By combining enzymatic assays, biomass measurements, and microbial enrichment via activity-based probes, we determined the microbial functional response to chitin amendments and field moisture treatments at both the community and cell scales. Chitinolytic activities showed significant responses to the amendment of chitin, independent of differences in field moisture treatments. However, for other measurements of carbon metabolism and cellular functions, soils from high moisture field treatments had greater potential enzyme activity than soils from low moisture field treatments. A cell tagging approach was used to enrich and quantify bacterial taxa that are actively producing chitin-degrading enzymes. By integrating organism, community, and soil core measurements we show that (i) a small subset of taxa compose the majority (>50%) of chitinase production despite broad functional redundancy, (ii) the identity of key chitin degraders varies with moisture level, and (iii) extracellular enzymes that are not cell-associated account for most potential chitinase activity measured in field soil.

activity-based probes↗

Lambda-PFLOTRAN 1.0: a workflow for incorporating organic matter chemistry informed by ultra high resolution mass spectrometry into biogeochemical modeling

Abstract. Organic matter (OM) composition plays a central role in microbial respiration of dissolved organic matter and subsequent biogeochemical reactions. Here, a direct connection of organic matter chemistry and thermodynamics to reactive transport simulators has been achieved through the newly developed Lambda-PFLOTRAN workflow tool that succinctly incorporates carbon chemistry data generated from Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) into reaction networks to simulate organic matter degradation and the resulting biogeochemistry. Lambda-PFLOTRAN is a Python-based workflow, executed through a Jupyter notebook interface, that digests raw FTICR-MS data, develops a representative reaction network based on substrate-explicit thermodynamic modeling (also termed lambda modeling due to its key thermodynamic parameter λ used therein), and completes a biogeochemical simulation with the open source, reactive flow and transport code PFLOTRAN. The workflow consists of the following five steps: configuration, thermodynamic (lambda) analysis, sensitivity analysis, parameter estimation, and simulation output and visualization. Two test cases are provided to demonstrate the functionality of the Lambda-PFLOTRAN workflow. The first test case uses laboratory incubation data of temporal oxygen depletion to fit lambda parameters (i.e., maximum utilization rate and microbial carrying capacity). A slightly more complex second test case fits multiple lambda formulation and soil organic matter release parameters to temporal greenhouse gas generation measured during a soil incubation. Overall, the Lambda-PFLOTRAN workflow facilitates upscaling by using molecular-scale characterization to inform biogeochemical processes occurring at larger scales.

58 GEOSCIENCES↗

Superhydrophobic coating and process of making same

An improved superhydrophobic coating and a process of making it is provided herein. More particularly, a robust superhydrophobic coating is produced by using carbon dioxide to enhance the integration of a binder material into the superhydrophobic coating. The carbon dioxide may be used to infiltrate and fill the interstitial voids of a superhydrophobic material, such as diatomaceous earth. Consequently, occupying these voids in the superhydrophobic material effectively blocks other components (e.g., binders) from entering the voids. As a result, the coating formulations of the present invention are more robust and may strongly adhere to the substrates to which they are applied.

36 MATERIALS SCIENCE↗

Engineering Escherichia coli to produce medium chain oleochemicals from C 2 substrates

Many strategies to create a circular bioeconomy have been proposed. To be successful, CO 2 must be reduced with renewable energy into chemical building blocks, from which the chemical industry can be supported. Circular strategies include leveraging photosynthesis to produce sugar and lipid intermediates or renewable electricity to produce hydrogen or other electron carriers to support CO 2 reduction. Acetogens can anaerobically reduce CO 2 with H 2 to produce mixtures of small organic molecules in gas fermentations. We previously demonstrated that acetate, a common product of gas fermentation, can be converted to the model oleochemical dodecanol in engineered Escherichia coli. Here, we explored the conversion of ethanol and mixtures of ethanol and acetate to the same model oleochemicals. Co-feeding ethanol can supply both carbon and additional reducing power relative to acetate alone. In this work, we engineered E. coli to catabolize ethanol and expressed two distinct ethanol metabolism pathways in different operons and combined them with improved engineered acetate activation. We evaluated the performance of these operons in dodecanol-producing strains when fed ethanol or acetate and found ethanol to be a better carbon source when judged by product titers. The engineered strains fed ethanol produced about two-fold more dodecanol than the strains fed acetate. This increase was in part, due to change in product distribution. Cells fed ethanol produced predominantly dodecanol, whereas cells fed acetate generated a mixture of dodecanol and dodecanoic acid. Dodecanol titers were further improved by employing feeding strategies in controlled bioreactors.

Escherichia coli↗

Genomic insights into redox-driven microbial processes for carbon decomposition in thawing Arctic soils and permafrost

Climate change is rapidly transforming Arctic landscapes where increasing soil temperatures speed up permafrost thaw. This exposes large carbon stocks to microbial decomposition, possibly worsening climate change by releasing more greenhouse gases. Understanding how microbes break down soil carbon, especially under the anaerobic conditions of thawing permafrost, is important to determine future changes. Here, we studied the microbial community dynamics and soil carbon decomposition potential in permafrost and active layer soils under anaerobic laboratory conditions that simulated an Arctic summer thaw. The microbial and viral compositions in the samples were analyzed based on metagenomes, metagenome-assembled genomes, and metagenomic viral contigs (mVCs). Following the thawing of permafrost, there was a notable shift in microbial community structure, with fermentative Firmicutes and Bacteroidota taking over from Actinobacteria and Proteobacteria over the 60-day incubation period. The increase in iron and sulfate-reducing microbes had a significant role in limiting methane production from thawed permafrost, underscoring the competition within microbial communities. We explored the growth strategies of microbial communities and found that slow growth was the major strategy in both the active layer and permafrost. Our findings challenge the assumption that fast-growing microbes mainly respond to environmental changes like permafrost thaw. Instead, they indicate a common strategy of slow growth among microbial communities, likely due to the thermodynamic constraints of soil substrates and electron acceptors, and the need for microbes to adjust to post-thaw conditions. The mVCs harbored a wide range of auxiliary metabolic genes that may support cell protection from ice formation in virus-infected cells.

54 ENVIRONMENTAL SCIENCES↗

Upcycling plastic waste into polyhydroxyalkanoates with high carbon conversion via CO 2 plasma-enabled deconstruction

Plastic deconstruction into fermentable intermediates is a key step for microbial bio-upcycling into value-added products. In this study, CO 2 plasma deconstruction was used as an electrified route to convert polyethylene into oxygenated intermediates and liquid (OIL). The resulting OIL was rich in fatty acids, fatty alcohols, and hydrocarbons, making it a suitable feedstock for medium-chain-length polyhydroxyalkanoate (mcl-PHA) production by Pseudomonas putida NRRL B-14688 and Pseudomonas resinovorans NRRL B-2649. Compared with batch fermentation and monocultures, fed-batch co-cultivation markedly improved biomass formation and PHA accumulation, likely due to complementary substrate utilization, particularly hydrocarbon conversion by P. resinovorans. Using virgin polyethylene-derived OIL (Vir-OIL), the co-culture achieved 40.11% mcl-PHA content and about 18% PHA yield based on total OIL fed. More importantly, OIL produced from post-consumer single-use plastic films (PCR-OIL) was directly fermented and well supported the cell growth and PHA accumulation, achieving 38.11% PHA content and about 14.7% PHA yield. Based on emulsified OIL fractions, PHA yields for Vir-OIL and PCR-OIL were comparable (∼28%). PHA granules were extracted from PCR-OIL-grown cells with high recovery (88.25%) and purity (94.8%). Five monomers were identified in the polymer, including 3-hydroxyhexanoate (3HHx), 3-hydroxyoctanoate (3HO), 3-hydroxydecanoate (3HD), 3-hydroxydodecanoate (3HDD), and 3-hydroxytetradecanoate (3HTD), with 3HO (44.28%) and 3HD (40.60%) as the dominant units. The polymer exhibited moderate molecular weight and narrow dispersity (M n = 65.4 kDa, M w = 92.1 kDa, Đ = 1.40) and low crystallinity (T m ≈ 76.6 °C, X c ≈ 15.5%). These characteristics indicate elastomer-like behavior, making the material suitable for flexible applications such as films, coatings, adhesives, and blend modifiers. Overall, this study establishes a CO 2 plasma-assisted route for generating fermentable polyethylene-derived intermediates and demonstrates that fed-batch co-culture fermentation can effectively funnel plastic-derived carbon into mcl-PHA.

42 ENGINEERING↗

Substantial carbon loss respired from a corn–soybean agroecosystem highlights the importance of careful management as we adapt to changing climate

Understanding agroecosystem carbon (C) cycle response to climate change and management is vital for maintaining their long-term C storage. We demonstrate this importance through an in-depth examination of a ten-year eddy covariance dataset from a corn–corn–soybean crop rotation grown in the Midwest United States. Ten-year average annual net ecosystem exchange (NEE) showed a net C sink of –0.39 Mg C ha –1 yr –1 . However, NEE in 2014 and 2015 from the corn ecosystem was 3.58 and 2.56 Mg C ha –1 yr –1 , respectively. Most C loss occurred during the growing season, when photosynthesis should dominate and C fluxes should reflect a net ecosystem gain. Partitioning NEE into gross primary productivity (GPP) and ecosystem respiration (ER) showed this C 'burp' was driven by higher ER, with a 51% (2014) and 57% (2015) increase from the ten-year average (15.84 Mg C ha –1 yr –1 ). GPP was also higher than average (16.24 Mg C ha –1 yr –1 ) by 25% (2014) and 37% (2015), but this was not enough to offset the C emitted from ER. This increased ER was likely driven by enhanced soil microbial respiration associated with ideal growing season climate, substrate availability, nutrient additions, and a potential legacy effect from drought.

54 ENVIRONMENTAL SCIENCES↗