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At least 271 records · Page 15

Industrial emission inventories of iron and phosphorus for past, present and future

Global emission inventories of aerosol iron by species, and of phosphorus, were developed for inclusion in Earth system modeling that includes atmospheric transport. The time period covered was 1850-2010 to evaluate human influence. A variety of approaches to compare measured and modeled values of aerosol iron was synthesized to estimate how well anthropogenic emissions are known. Anthropogenic emissions are constrained within a factor of two and if there is a bias, it is an overestimation. The exception is shipping emissions, which may be underestimated. Direct radiative forcing by iron aerosol is small in the global average (0.02 W m -2 ) but reaches 0.25 W m -2 around source regions. Regions of high direct radiative forcing are poorly constrained by observations. The central value of change in oceanic net primary productivity due to iron deposition is about 0.26 PgC yr -1 , also highly localized. This leads to a decrease in atmospheric CO2 accumulation that corresponds to a forcing of 0.008 W m -2 since 1850 (0.003-0.18 W m -2 ). Emissions of particulate matter to 2050 were estimated in response to different policy scenarios, including the need for renewable energy installations under decarbonization scenarios. Under the business-as-usual scenario, the total metal demand is 195 Mt/yr in 2020, peaking at 270 Mt/yr in years 2040-2045; under the Rapid Decarbonization scenario, total metal demand is nearly doubled at its peak: 480 Mt/yr in year 2040. Primary particulate matter emissions attributable to processing metals for renewable energy are also amplified under rapid decarbonization, but total atmospheric emissions are much lower because of the shift away from combustion.

58 GEOSCIENCES↗

Active layer depth and soil properties impact specific leaf area variation and ecosystem productivity in a boreal forest

Specific leaf area (SLA, leaf area per unit dry mass) is a key canopy structural characteristic, a measure of photosynthetic capacity, and an important input into many terrestrial process models. Although many studies have examined SLA variation, relatively few data exist from high latitude, climate-sensitive permafrost regions. We measured SLA and soil and topographic properties across a boreal forest permafrost transition, in which dominant tree species changed as permafrost deepened from 54 to >150 cm over 75 m hillslope transects in Caribou-Poker Creeks Research Watershed, Alaska. We characterized both linear and threshold relationships between topographic and edaphic variables and SLA and developed a conceptual model of these relationships. We found that the depth of the soil active layer above permafrost was significantly and positively correlated with SLA for both coniferous and deciduous boreal tree species. Intraspecific SLA variation was associated with a fivefold increase in net primary production, suggesting that changes in active layer depth due to permafrost thaw could strongly influence ecosystem productivity. While this is an exploratory study to begin understanding SLA variation in a non-contiguous permafrost system, our results indicate the need for more extensive evaluation across larger spatial domains. These empirical relationships and associated uncertainty can be incorporated into ecosystem models that use dynamic traits, improving our ability to predict ecosystem-level carbon cycling responses to ongoing climate change.

59 BASIC BIOLOGICAL SCIENCES↗

Chlamydomonas cells transition through distinct Fe nutrition stages within 48 h of transfer to Fe-free medium

Low iron (Fe) bioavailability can limit the biosynthesis of Fe-containing proteins, which are especially abundant in photosynthetic organisms, thus negatively affecting global primary productivity. Understanding cellular coping mechanisms under Fe limitation is therefore of great interest. We surveyed the temporal responses of Chlamydomonas (Chlamydomonas reinhardtii) cells transitioning from an Fe-rich to an Fe-free medium to document their short- and long-term adjustments. While slower growth, chlorosis and lower photosynthetic parameters are evident only after one or more days in Fe-free medium, the abundance of some transcripts, such as those for genes encoding transporters and enzymes involved in Fe assimilation, change within minutes, before changes in intracellular Fe content are noticeable, suggestive of a sensitive mechanism for sensing Fe. Promoter reporter constructs indicate a transcriptional component to this immediate primary response. With acetate provided as a source of reduced carbon, transcripts encoding respiratory components are maintained relative to transcripts encoding components of photosynthesis and tetrapyrrole biosynthesis, indicating metabolic prioritization of respiration over photosynthesis. In contrast to the loss of chlorophyll, carotenoid content is maintained under Fe limitation despite a decrease in the transcripts for carotenoid biosynthesis genes, indicating carotenoid stability. These changes occur more slowly, only after the intracellular Fe quota responds, indicating a phased response in Chlamydomonas, involving both primary and secondary responses during acclimation to poor Fe nutrition. Overall design: Sampling of Chlamydomonas CC-4532 cells cultivated photoheterotrophically (TAP) under Fe-starvation condition (0 uM Fe-EDTA). Samples were collected at multiple timepoints from biological duplicate cultures after washing in TAP medium lacking Fe. Two time courses were collected. A short time course with t=0 (pre-wash), 0 (post-wash), 5, 10, 15, 30, 60, 120, and 240 min. A long time course with t= 0, 0.5, 1, 2, 4, 8, 12, 24 and 48 hours. Please note that, for long time course, the GSE44611/PRJNA190650 samples were re-used/re-analyzed together with the short time course data: GSM1087792 C.reinhardtii_Fe_Long_0_hours SRX245324 SAMN01924672 GSM1087793 C.reinhardtii_Fe_Long_0.5_hours SRX245325 SAMN01924673 GSM1087794 C.reinhardtii_Fe_Long_1_hours SRX245326 SAMN01924674 GSM1087795 C.reinhardtii_Fe_Long_2_hours SRX245327 SAMN01924675 GSM1087796 C.reinhardtii_Fe_Long_4_hours SRX245328 SAMN01924676 GSM1087797 C.reinhardtii_Fe_Long_8_hours SRX245329 SAMN01924677 GSM1087798 C.reinhardtii_Fe_Long_12_hours SRX245330 SAMN01924678 GSM1087799 C.reinhardtii_Fe_Long_24_hours SRX245331 SAMN01924679 GSM1087800 C.reinhardtii_Fe_Long_48_hours SRX245332 SAMN01924680

Source record↗

Chlamydomonas cells transition through distinct Fe nutrition stages within 48 h of transfer to Fe-free medium

Low iron (Fe) bioavailability can limit the biosynthesis of Fe-containing proteins, which are especially abundant in photosynthetic organisms, thus negatively affecting global primary productivity. Understanding cellular coping mechanisms under Fe limitation is therefore of great interest. For this paper, we surveyed the temporal responses of Chlamydomonas ( Chlamydomonas reinhardtii ) cells transitioning from an Fe-rich to an Fe-free medium to document their short and long-term adjustments. While slower growth, chlorosis and lower photosynthetic parameters are evident only after one or more days in Fe-free medium, the abundance of some transcripts, such as those for genes encoding transporters and enzymes involved in Fe assimilation, change within minutes, before changes in intracellular Fe content are noticeable, suggestive of a sensitive mechanism for sensing Fe. Promoter reporter constructs indicate a transcriptional component to this immediate primary response. With acetate provided as a source of reduced carbon, transcripts encoding respiratory components are maintained relative to transcripts encoding components of photosynthesis and tetrapyrrole biosynthesis, indicating metabolic prioritization of respiration over photosynthesis. In contrast to the loss of chlorophyll, carotenoid content is maintained under Fe limitation despite a decrease in the transcripts for carotenoid biosynthesis genes, indicating carotenoid stability. These changes occur more slowly, only after the intracellular Fe quota responds, indicating a phased response in Chlamydomonas, involving both primary and secondary responses during acclimation to poor Fe nutrition.

59 BASIC BIOLOGICAL SCIENCES↗

Amazon drought resilience – emerging results point to new empirical needs

Will climate change turn tropical forests from a carbon sink to a source (Pan et al., 2011)? Tropical forests cycle more carbon, water, and energy than any other biome (Bonan, 2008). The Amazon is the largest tropical forest, spanning one-third of South America, and any perturbation in its function has repercussions on the global climate. Mild and severe droughts in the Amazon are predicted to double and triple in area, respectively, by 2100, while the area under wet extremes will increase (Duffy et al., 2015). Our understanding of the role of plants' hydrological environments in determining their drought response, however, is limited (Chitra-Tarak et al., 2018, 2021). An important review by Costa et al. (2023; pp. 714–733) published in this issue of New Phytologist highlights that shallow-water table (WT) forests constitute c. 50% of the Amazon and may act as hydrological refugia during droughts, yet they have been neglected in Amazon forest research to date. Emerging results suggest that the shallow-WT forests that dominate the Amazon basin may increase in productivity under moderate droughts due to relief from hypoxia, suggesting a potential buffer from drought relative to deeper WT forests (Fig. 1). During severe droughts, however, shallow-WT forests may be vulnerable to collapse due to drought-intolerant traits. Addressing the underrepresentation of relatively drought-resilient shallow-WT forests in the Amazon's forest inventories may help resolve the much-debated incongruence in recent studies of the Amazon's drought resilience. Data from forest inventories (biased toward deep-WT forests) indicate that the Amazon's carbon sink is declining, partially because of drought impacts (Phillips et al., 2009; Brienen et al., 2015), whereas basin-wide satellite-based measures of gross primary productivity, which include shallow-WT forests, indicate varied regional responses to droughts (Saleska et al., 2007; Brando et al., 2010). Costa et al.'s (2023) descriptive insights of the intricate balance of geology, topography, hydrology, vegetation, and drought on ecosystem function, as well as their conceptual predictive framework, are useful for developing new empirical research in these understudied ecosystems and improving Earth system models.

54 ENVIRONMENTAL SCIENCES↗

Beyond the visible: Accounting for ultraviolet and far‐red radiation in vegetation productivity and surface energy budgets

Photosynthetically active radiation (PAR) is typically defined as light with a wavelength within 400–700 nm. However, ultra-violet (UV) radiation within 280–400 nm and far-red (FR) radiation within 700–750 nm can also excite photosystems, though not as efficiently as PAR. Vegetation and land surface models (LSMs) typically do not explicitly account for UV's contribution to energy budgets or photosynthesis, nor FR's contribution to photosynthesis. However, whether neglecting UV and FR has significant impacts remains unknown. Here, we explored how canopy radiative transfer (RT) and photosynthesis are impacted when explicitly implementing UV in the canopy RT model and accounting for UV and FR in the photosynthesis models within a next-generation LSM that can simulate hyperspectral canopy RT. We validated our improvements using photosynthesis measurements from plants under different light sources and intensities and surface reflection from an eddy-covariance tower. Our model simulations suggested that at the whole plant level, after accounting for UV and FR explicitly, chlorophyll content, leaf area index (LAI), clumping index, and solar radiation all impact the modeling of gross primary productivity (GPP). At the global scale, mean annual GPP within a grid would increase by up to 7.3% and the increase is proportional to LAI; globally integrated GPP increases by 4.6 PgC year −1 (3.8% of the GPP without accounting for UV + FR). Further, using PAR to proxy UV could overestimate surface albedo by more than 0.1, particularly in the boreal forests. Our results highlight the importance of improving UV and FR in canopy RT and photosynthesis modeling and the necessity to implement hyperspectral or multispectral canopy RT schemes in future vegetation and LSMs.

energy budget↗

A Multiyear Gridded Data Ensemble of Surface Biogenic Carbon Fluxes for North America: Evaluation and Analysis of Results

Accurate and fine-scale estimates of biogenic carbon fluxes are critical for measuring and monitoring the biosphere's responses and feedback to the climate system. Currently available data products from flux towers and model-intercomparison projects struggle to adequately represent spatiotemporal dynamics of surface biogenic carbon fluxes, and to quantify their uncertainties, which also are crucial to atmospheric inversion systems. To address these gaps, we introduce a new perturbed-parameter model ensemble with the CASA model to estimate surface biogenic carbon fluxes at monthly and 3-hourly scales for North America at ~500-m and 5-km resolutions. We first use the Extended Fourier Amplitude Sensitivity Testing to choose the three most sensitive parameters to be perturbed, maximum light use efficiency (E max ), optimal temperature of photosynthesis (T opt ), and temperature response of respiration (Q 10 ). The initial range for each parameter is broadly sampled for the L1 ensemble, but then we pruned E max with site-level primary productivity to derive an L2 ensemble with narrower uncertainty ranges. Ensembles are strongly correlated with site-level results at both monthly and 3-hourly scales, and the spread across L1/L2 ensemble members encompasses the range of AmeriFlux observations. Monthly variability in the L2 ensemble mean is 85% of the observed variability. The L2 ensemble outperforms diverse data products with the highest Taylor skill scores at diurnal to annual scales. Finally, the ensemble's seasonality agrees well with other models for most biome types and in high and middle latitudes, but inconsistencies are found in subtropical and tropical ecoregions and for annual totals over North America.

54 ENVIRONMENTAL SCIENCES↗

Quantifying carbon budget, crop yields and their responses to environmental variability using the ecosys model for U.S. Midwestern agroecosystems

As one of the major agricultural production areas in the world, the United States (U.S.) Midwest plays a vital role in the global food supply and agricultural ecosystem services. Although significant efforts have been made in modeling the carbon cycle dynamics over this area, large uncertainty still exists in the previous simulations in terms of reproducing individual components of the carbon cycle and their responses to environmental variability. Here we evaluated the performance of an advanced agroecosystem model, ecosys, in simulating carbon budgets over the U.S. Midwest, considering both the magnitude of carbon flux/yield and its response to environmental (climate and soil) variability. We conducted model simulations and evaluations at 7 cropland eddy-covariance sites as well as over 293 counties of Illinois, Indiana, and Iowa in the U.S. Midwest. The site-level simulations showed that ecosys captured both the magnitude and seasonal patterns of carbon fluxes (i.e., net ecosystem carbon exchange (NEE), ecosystem gross primary production (GPP), and ecosystem respiration (Reco)), leaf area index (LAI), and dynamic plant carbon allocation processes, with R2 equal to 0.92, 0.87, 0.87, and 0.78 for GPP, NEE, Reco, and LAI, respectively across all the sites compared with the observations. For regional scale simulations, ecosys reproduced the spatial distribution and interannual variability of corn and soybean yields with the constraints of observed yields and a new remotely sensed GPP product, with R2 of multi-year averaged simulated and observed yield equal 0.83 and 0.80 for corn and soybean, respectively. The simulated responses of carbon cycle dynamics to environmental variability were consistent with that from the empirical observations at both site and regional scales. Furthermore, our results demonstrated the applicability of ecosys in simulating the carbon cycle and soil carbon dynamics of the U.S. Midwestern agroecosystems under different climate and soil conditions.

54 ENVIRONMENTAL SCIENCES↗

Amplified bottom water acidification rates on the Bering Sea shelf from 1970–2022

The Bering Sea shelf supports a highly productive marine ecosystem that is vulnerable to ocean acidification (OA) due to the cold, carbon-rich waters. Previous observational evidence suggests that bottom waters on the shelf are already seasonally undersaturated with respect to aragonite (i.e. Ω arag <1) and that OA will continue to increase the spatial extent, duration, and intensity of these conditions. Here, we use a regional ocean biogeochemical model to simulate changes in ocean carbon chemistry for the Bering Sea shelf from 1970–2022. Over this timeframe, model results suggest that surface Ω arag decreases by −0.043 per decade and surface pH by −0.014 per decade, comparable to observed global rates of OA. However, bottom water pH decreases at twice the rate of surface pH, while bottom [H + ] decreases at nearly 3 times the rate of surface [H + ]. This amplified bottom water acidification has emerged over the past 25 years and is likely driven by a combination of anthropogenic carbon accumulation and increasing primary productivity and subsurface respiration and remineralization. Due to this enhanced bottom water acidification, the spatial extent of bottom waters with Ω arag <1 has greatly expanded over the past 2 decades, along with pH conditions harmful to red king crab. Interannual variability in surface and bottom Ω arag , pH, and [H + ] has also increased over the past 2 decades, resulting in part from the increased physical climate variability. We also find that the Bering Sea shelf is a net annual carbon sink of 1.1–7.9 Tg C yr −1 , with the range resulting from the difference in the two different atmospheric forcing reanalysis products used. Seasonally, the shelf is a significant carbon sink from April–October but a somewhat weaker carbon source from November–March.

54 ENVIRONMENTAL SCIENCES↗

Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

Abstract Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure‐selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N 2 , reaching a current density of 20 mA cm geo −2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in‐situ spectroscopies and scattering experiments reveal a unique in situ generated Cu (2‐x)+ ‐OO −• active sites in CuCo, which initiates nucleophilic substitution of NH 2 from the amide, leading to N‐N coupling between * NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high‐valence Ni 3+ and Ni 4+ , which facilitates N‐H activation. This process, in conjunction with the excessive accumulation of OH − ions on Jahn‐Teller (JT) distorted Co sites, leads to the generation of NO 2 − as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

36 MATERIALS SCIENCE↗

Strong Local Evaporative Cooling Over Land Due to Atmospheric Aerosols

Abstract Aerosols can enhance terrestrial productivity through increased absorption of solar radiation by the shaded portion of the plant canopy—the diffuse radiation fertilization effect. Although this process can, in principle, alter surface evaporation due to the coupling between plant water loss and carbon uptake, with the potential to change the surface temperature, aerosol‐climate interactions have been traditionally viewed in light of the radiative effects within the atmosphere. Here, we develop a modeling framework that combines global atmosphere and land model simulations with a conceptual diagnostic tool to investigate these interactions from a surface energy budget perspective. Aerosols increase the terrestrial evaporative fraction, or the portion of net incoming energy consumed by evaporation, by over 4% globally and as much as ∼40% regionally. The main mechanism for this is the increase in energy allocation from sensible to latent heat due to global dimming (reduction in global shortwave radiation) and slightly augmented by diffuse radiation fertilization. In regions with moderately dense vegetation (leaf area index >2), the local surface cooling response to aerosols is dominated by this evaporative pathway, not the reduction in incident radiation. Diffuse radiation fertilization alone has a stronger impact on gross primary productivity (+2.18 Pg C y −1 or +1.8%) than on land evaporation (+0.18 W m −2 or +0.48%) and surface temperature (−0.01 K). Our results suggest that it is important for land surface models to distinguish between quantity (change in total magnitude) and quality (change in diffuse fraction) of radiative forcing for properly simulating surface climate.

Chakraborty, TC↗

Temporal nitrogen dynamics in intensively managed loblolly pine early stand development

Forest production is strongly dependent on nutrient uptake; however, sustainable management of intensively managed plantations requires an improved understanding of this relationship when fertilization occurs frequently across short rotations. Here, we studied temporal nitrogen (N) concentration ([N]) and content (Nc) dynamics under different silvicultural practices (herbicide, fertilization, and planting density) throughout early loblolly pine (Pinus taeda) stand development (5 years). We describe relationships of [N] and Nc of different stand components (foliage, branches, stem, roots, and competing vegetation) with carbon and biomass. Our results demonstrate that [N] of perennial loblolly tissues do not respond to silvicultural practices and progressively decrease through development. While foliar [N] was most responsive to resource availability, it was not consistent across time. Controlling competing vegetation was crucial to promote the use of site resources by the crop tree and increased loblolly Nc by >500%. However, increased N uptake and expedited growth is dependent upon fertilization early in stand development. At age 5, herbicide plus reduced and full fertilization rates exhibited similar aboveground Nc, which was 32% higher than with herbicide only. Increasing planting density resulted in increased above- and belowground loblolly Nc; however, increases in Nc were not proportional with increases in planting density. Net primary productivity and N uptake were linearly related, but age/development strongly controlled N use efficiency. Our study helps to understand complex relationships between N, biomass, and silvicultural practices during early stand development and demonstrates that temporal evaluation of nutrient dynamics is crucial to better understand loblolly pine growth, carbon sequestration potential, and to inform sustainable silvicultural practices across short rotations.

54 ENVIRONMENTAL SCIENCES↗

A micrometeorological flux perspective on brush management in a shrub-encroached Sonoran Desert grassland

Woody plant encroachment typically limits the forage productivity of managed rangelands and alters a panoply of semiarid ecosystem processes and services. Intervention strategies to reduce woody plant abundance, collectively termed “brush management”, often lack observations to quantify and interpret changes in ecosystem processes. Furthermore, comparative studies between treated and untreated areas should account for heterogeneity since plant composition, microclimate, topoedaphic factors, and historical land use can substantially vary over short distances in drylands. Here, in this work, we quantify ecosystem responses to brush management after a single aerial herbicide application on an 18 hectare shrub-encroached grassland (savanna) in southern Arizona, USA. We conducted a pre- and post-treatment comparison of a flux tower site in the treated area with that of a tower in a nearby control site. The comparison, spanning a seven year period, included: (1) ground, airborne, and satellite-based measurements of vegetation structure, and (2) eddy covariance measurements. The herbicide treatment defoliated the dominant shrub (velvet mesquite, Prosopis velutina) and led to a temporary reduction in summer greening, but full foliar recovery occurred within two years. Contrary to expectations, perennial grass cover decreased and bare soil cover increased on the treated site. Relative amounts of evapotranspiration were reduced, while carbon uptake increased during the 2 year post-treatment period at the treated site due to a higher water use efficiency in the following spring. During mesquite recovery, carbon uptake was enhanced by higher gross primary productivity and accompanied by a decrease in ecosystem respiration relative to the untreated site. Mesquite recovery was facilitated by access to deep soil water, carbohydrate reserves in rooting systems, and a lower competition from reduced perennial grass cover.

54 ENVIRONMENTAL SCIENCES↗

Integrated parameter and process learning for hydrologic and biogeochemical modules in Earth System Models

Focus area: Primary focal area #2; secondary focal area #3: Learning about parameters and processes of land surface hydrologic and biogeochemical models in Earth System models by integrating machine learning, physics, and big data. Science challenges: How do we maximally leverage big-data observations to improve hydrobiogeochemical process description and parameterization so that such modules more realistically capture hydrologic and vegetation responses and feedbacks under the future climate? For example, how can we leverage physics, limited observations of vegetation and streamflow to better estimate evapotranspiration, and, relatedly, net primary productivity, especially for drought areas? Vegetation plays a critical role in regional and global water cycles; however, existing vegetation models have failed to predict vegetation response to droughts (McDowell & Xu, 2017) , arctic greening (Keenan & Riley, 2018) , and critical transitions between forest and savanna (Hirota et al., 2011) . These studies suggest that when we build process-based models (PBM) parameterized from regional and global plant traits, we tend to poorly describe plant adaptation and local-scale competition processes. The models and their associated parameters assigned for different regions in the world are not capturing essential heterogeneity in vegetation responses at finer spatial scales. Many parameters of the land surface models control hydrology and vegetation dynamics at the same time. The heterogeneity in vegetation response is a function of (i) plant type, (ii) plant size, (iii) competition and succession, (iv) environmental controls, and (v) local variations due to the unique ecological community that are very difficult to describe (e.g., the size of gaps resulting from fire that facilitated the coexistence of pioneering species). In the demographic models, only factors (i) and (iv) were captured, and plant types were generally described only by leaf phenology and climate zones. With current demographic models, we generally consider more traits to define plant types (i) and calibrate these traits to consider factors (ii), (iii) and (iv); however, it is substantially challenging to scale to regional and global simulations due to trait variations across space (Ali et al., 2016). Moreover, it has been noted that hillslope processes, including ridge-to-valley flow and sunny vs. shady slopes are primary organizers of water, energy, and vegetation (Clark et al., 2015; Fan et al., 2019) . Although gradual improvements in the hydrologic model component in earth system models may reduce this error (at a remarkably slow pace), the long-term, gradual impact of hydrology on plant traits are not well captured. Recent work showed that the hydrologic controls exerted by groundwater and lateral flow are primary regulators of rooting depth (Fan et al., 2017) . Such hydrologic controls have seldom been reflected in vegetation model parameterizations.

54 ENVIRONMENTAL SCIENCES↗

Catalytic Activation of Polyethylene Model Compounds Over Metal-Exchanged Beta Zeolites

Decomposition of polymers by heterogeneous catalysts presents a promising approach for reuse of waste plastics. Here, we demonstrated non-hydrogenative decomposition of model polyolefins over proton-form and metal (Cu, Ni) ion-exchanged beta zeolites at moderate temperatures (ca. 300 degrees C). Near complete polyolefin decomposition was observed in batch reactions monitored by thermogravimetric analysis, while decomposition at partial conversion was studied in flow reactions. Ni-exchanged zeolites produced H 2 at substantially higher rates (> 10x) than other catalysts while also uniquely resisting deactivation over time. Application of the delplot formalism offered insights into the reaction network for polyolefin decomposition over Ni/BEA, most notably that H 2 is solely a primary product. We deduce that H 2 production is catalyzed by activation of C-H bonds at ionic Ni sites, and H 2 prevents buildup of polyaromatic coke species in Ni-exchanged zeolites that deactivate Cu-exchanged and protonic zeolites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nitrification, denitrification, and competition for soil N : Evaluation of two Earth System Models against observations

Abstract Earth System Models (ESMs) have implemented nitrogen (N) cycles to account for N limitation on terrestrial carbon uptake. However, representing inputs, losses, and recycling of N in ESMs is challenging. Here, we use global rates and ratios of key soil N fluxes, including nitrification, denitrification, mineralization, leaching, immobilization, and plant uptake (both NH 4 + and NO 3 − ), from the literature to evaluate the N cycles in the land model components of two ESMs. The two land models evaluated here, E3SM Land Model version 1 (ELMv1)‐ECA and CLM5.0, originated from a common model but have diverged in their representation of plant–microbe competition for soil N. The models predict similar global rates of gross primary productivity (GPP) but have approximately two‐fold to three‐fold differences in their underlying global mineralization, immobilization, plant N uptake, nitrification, and denitrification fluxes. Both models dramatically underestimate the immobilization of NO 3 − by soil bacteria compared with literature values and predict dominance of plant uptake by a single form of mineral nitrogen (NO 3 − for ELM, with regional exceptions, and NH 4 + for CLM5.0). CLM5.0 strongly underestimates the global ratio of gross nitrification:gross mineralization and both models are likely to substantially underestimate the ratio of nitrification:denitrification. Few experimental data exist to evaluate this last ratio, in part because nitrification and denitrification are quantified using different techniques and because denitrification fluxes are difficult to measure at all. More observational constraints on soil nitrogen fluxes such as nitrification and denitrification, as well as greater scrutiny of the functional impact of introducing separate NH 4 + and NO 3 − pools into ESMs, could help to improve confidence in present and future simulations of N limitation on the carbon cycle.

Nevison, Cynthia↗

Beyond carbon flux partitioning: Carbon allocation and nonstructural carbon dynamics inferred from continuous fluxes

Carbon (C) allocation and nonstructural carbon (NSC) dynamics play essential roles in plant growth and survival under stress and disturbance. However, quantitative understanding of these processes remains limited. Here, in this work, we propose a framework where we connect commonly measured carbon cycle components (eddy covariance fluxes of canopy CO 2 exchange, soil CO 2 efflux, and allometry-based biomass and net primary production) by a simple mass balance model to derive ecosystem-level NSC dynamics (NSC i ), C translocation (dC i ), and the biomass production efficiency (BPE i ) in above- and belowground plant (i = agp and bgp) compartments. We applied this framework to two long-term monitored loblolly pine (Pinus taeda) plantations of different ages in North Carolina and characterized the variations of NSC and allocation in years under normal and drought conditions. The results indicated that the young stand did not have net NSC flux at the annual scale, whereas the mature stand stored a near-constant proportion of new assimilates as NSC every year under normal conditions, which was comparable in magnitude to new structural growth. Roots consumed NSC in drought and stored a significant amount of NSC post drought. The above- and belowground dC i and BPE i varied more from year to year in the young stand and approached a relatively stable pattern in the mature stand. The belowground BPE bgp differed the most between the young and mature stands and was most responsive to drought. With the internal C dynamics quantified, this framework may also improve biomass production estimation, which reveals the variations resulting from droughts. Overall, these quantified ecosystem-scale dynamics were consistent with existing evidence from tree-based manipulative experiments and measurements and demonstrated that combining the continuous fluxes as proposed here can provide additional information about plant internal C dynamics. Given that it is based on broadly available flux data, the proposed framework is promising to improve the allocation algorithms in ecosystem C cycle models and offers new insights into observed variability in soil–plant–climate interactions.

54 ENVIRONMENTAL SCIENCES↗

The climate change mitigation potential of annual grasslands under future climates

Abstract Composted manure and green waste amendments have been shown to increase net carbon (C) sequestration in rangeland soils and have been proposed as a means to help lower atmospheric CO 2 concentrations. However, the effect of climate change on soil organic C (SOC) stocks and greenhouse gas emissions in rangelands is not well understood, and the viability of climate change mitigation strategies under future conditions is even less certain. We used a process‐based biogeochemical model (DayCent) at a daily time step to explore the long‐term effects of potential future climate changes on C and greenhouse gas dynamics in annual grassland ecosystems. We then used the model to explore how the same ecosystems might respond to climate change following compost amendments to soils and determined the long‐term viability of net SOC sequestration under changing climates. We simulated net primary productivity (NPP), SOC, and greenhouse gas fluxes across seven California annual grasslands with and without compost amendments. We drove the DayCent simulations with field data and with site‐specific daily climate data from two Earth system models (CanESM2 and HadGEM‐ES) and two representative concentration pathways (RCP4.5 and RCP8.5) through 2100. NPP and SOC stocks in unamended and amended ecosystems were surprisingly insensitive to projected climate changes. A one‐time amendment of compost to rangeland acted as a slow‐release organic fertilizer and increased NPP by up to 390–814 kg C ha −1 year −1 across sites. The amendment effect on NPP was not sensitive to Earth system model or emissions scenario and endured through the end of the century. Net SOC sequestration amounted to 1.96 ± 0.02 Mg C ha −1 relative to unamended soils at the maximum amendment effect. Averaged across sites and scenarios, SOC sequestration peaked 22 ± 1 years after amendment and declined but remained positive throughout the century. Though compost stimulated nitrous oxide (N 2 O) emissions, the cumulative net emissions (in CO 2 equivalents) due to compost were far less than the amount of SOC sequestered. Compost amendments resulted in a net climate benefit of 69.6 ± 0.5 Tg CO 2 e 20 ± 1 years after amendment if applied to similar ecosystems across the state, amounting to 39% of California's rangeland. These results suggest that the biogeochemical benefits of a single amendment of compost to rangelands in California are insensitive to climate change and could contribute to decadal‐scale climate change mitigation goals alongside emissions reductions.

Mayer, Allegra↗