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At least 307 records · Page 17

What explains the year-to-year variation in growing season timing of boreal black spruce forests?

Amplified climate warming in high latitudes is expected to affect growing season timing of the vast boreal biome. It is unclear whether the presence of permafrost (perennially frozen ground) might have an influence on changes in growing season timing. Here, this study examined how different environmental variables explained, either directly or indirectly, the variation in growing season timing of boreal forest stands with and without permafrost. We expected that environmental variables explaining the variation in growing season timing differed or had different explanatory power depending on permafrost presence or absence. The growing season was delineated from daily gross primary productivity (GPP) time series derived from 40 site-year data of net ecosystem carbon dioxide exchange measured with eddy covariance techniques over five black spruce (Picea mariana [Mill.])-dominated boreal forest stands in North America. In permafrost-free forest stands, a combination of start in canopy ‘green-up’ in spring and the timing of air and soil temperature increasing above freezing explained the start-of-season (SOS GPP ). Results from commonality analysis and structural equation modeling suggest that canopy ‘green-up’ and air temperature directly affected SOS GPP in permafrost-free forest stands. In addition, soil temperature acted as mediator for an indirect effect of air temperature on SOS GPP . In contrast, none of the environmental variables, or their combination, explained the variation in SOS GPP in forest stands with permafrost. The explanatory power of environmental variables was more consistent regarding the end-of-season (EOS GPP ). In both, forest stands with and without permafrost, EOS GPP was directly explained by mean soil water content in the fall and the first day of continuous snowpack formation. A better understanding how environmental variables control SOS GPP and EOS GPP in forest stands with and without permafrost will help to refine parameterizations of the boreal biome in Earth system models.

54 ENVIRONMENTAL SCIENCES↗

Causality guided machine learning model on wetland CH 4 emissions across global wetlands

Wetland CH 4 emissions are among the most uncertain components of the global CH 4 budget. The complex nature of wetland CH 4 processes makes it challenging to identify causal relationships for improving our understanding and predictability of CH 4 emissions. In this study, we used the flux measurements of CH 4 from eddy covariance towers (30 sites from 4 wetlands types: bog, fen, marsh, and wet tundra) to construct a causality-constrained machine learning (ML) framework to explain the regulative factors and to capture CH 4 emissions at sub-seasonal scale. We found that soil temperature is the dominant factor for CH 4 emissions in all studied wetland types. Ecosystem respiration (CO 2 ) and gross primary productivity exert controls at bog, fen, and marsh sites with lagged responses of days to weeks. Integrating these asynchronous environmental and biological causal relationships in predictive models significantly improved model performance. More importantly, modeled CH 4 emissions differed by up to a factor of 4 under a +1°C warming scenario when causality constraints were considered. These results highlight the significant role of causality in modeling wetland CH 4 emissions especially under future warming conditions, while traditional data-driven ML models may reproduce observations for the wrong reasons. Our proposed causality-guided model could benefit predictive modeling, large-scale upscaling, data gap-filling, and surrogate modeling of wetland CH 4 emissions within earth system land models.

54 ENVIRONMENTAL SCIENCES↗

Feasibility of enhancing carbon sequestration and stock capacity in temperate and boreal European forests via changes to management regimes

Forest management practices might act as nature-based methods to remove CO 2 from the atmosphere and slow anthropogenic climate change and thus support an EU forest-based climate change mitigation strategy. However, the extent to which diversified management actions could lead to quantitatively important changes in carbon sequestration and stocking capacity at the tree level remains to be thoroughly assessed. To that end, we used a state-of-the-science bio-geochemically based forest growth model to simulate effects of multiple forest management scenarios on net primary productivity (NPP) and potential carbon woody stocks (pCWS) under twenty scenarios of climate change in a suite of observed and virtual forest stands in temperate and boreal European forests. Previous modelling experiments indicated that the capacity of forests to assimilate and store atmospheric CO 2 in woody biomass is already being attained under business-as-usual forest management practices across a range of climate change scenarios. Nevertheless, we find that on the long-term, with increasing atmospheric CO 2 concentration and warming, managed forests show both higher productivity capacity and a larger potential pool size of stored carbon than unmanaged forests as long as thinning and tree harvesting are of moderate intensity.

54 ENVIRONMENTAL SCIENCES↗

Remote sensing of seasonal variation of LAI and fAPAR in a deciduous broadleaf forest

Climate change is affecting the phenology of terrestrial ecosystems. In deciduous forests, phenology in leaf area index (LAI) is the primary driver of seasonal variation in the fraction of absorbed photosynthetically active radiation (fAPAR), which drives photosynthesis. Remote sensing has been widely used to estimate LAI and fAPAR. However, while many studies have examined both empirical and model-based relationships among LAI, fAPAR, and spectral vegetation indices (SVI) from remote sensing, few studies have systematically and empirically examined how relationships among these variables change over the growing season. In this study, we examine how and why seasonal-scale covariation differs among time series of remotely sensed SVIs and both LAI and fAPAR based on current understanding and theory. To do this we use newly available remote sensing data sets in combination with time series of in-situ measurements and a canopy radiative transfer model to analyze how seasonal variation in canopy and environmental conditions affect relationships among remotely sensed SVIs, LAI, and fAPAR at a temperate deciduous forest site in central Massachusetts. Our results show that accounting for seasonal variation in canopy shadowing, which is driven by variation in solar zenith angle, improved remote sensing-based estimates of LAI, fAPAR, and daily total APAR. Specifically, we show that the phenology of SVIs is strongly influenced by seasonal variation in near infrared (NIR) reflectance arising from systematic variation in the canopy shadow fraction that is independent of changes in LAI or fAPAR. Therefore, results of this work provide a refined basis for understanding how remote sensing can be used to monitor and model the phenology of LAI, fAPAR, APAR, and gross primary productivity in temperate deciduous forests.

54 ENVIRONMENTAL SCIENCES↗

Editorial special issue: Advancing foundational sun-induced chlorophyll fluorescence science

The first research on the possibilities offered by chlorophyll-a fluorescence to track the daily course of CO 2 assimilation by leaves dates back to the last century (Kautsky and Hirsch, 1931). In the second half of the XXth Century, the development of the field of active fluorescence, which relies mainly on the pulse amplitude modulation (PAM) fluorimetry technique, allowed the unraveling of the relationship between the yield of chlorophyll-a fluorescence and photochemistry (linear electron transport), which is modulated by a third process known as non-photochemical quenching (Genty et al., 1989). Since then, active fluorescence has been regularly used in ecophysiology, forestry, and crop sciences to understand the plant response to stress (Schreiber, 2004). Since the beginning of the 2000s, the development of portable field spectrometers allows for measuring passive sun-induced fluorescence (SIF) at strong solar or telluric absorption features, which do not rely on the use of artificial excitation light (e.g., Meroni and Colombo, 2006; Meroni et al., 2009; Perez-Priego et al., 2005). Since then, the field has rapidly evolved, and now fluorescence is measurable with automated field spectrometers in the field (Grossmann et al., 2018; Gu et al., 2019b; Rossini et al., 2010), airborne platforms (Rascher et al., 2015; Zarco-Tejada et al., 2000), and satellites (Guanter et al., 2012; Sun et al., 2018). These advances offer the potential to couple ecosystem-scale measurements of CO 2 fluxes and SIF to probe new aspects related to ecosystem structural impacts on SIF andphotosynthesis processes at different time-scales and on different ecosystems (e.g., Damm et al., 2010; Magney et al., 2019; Porcar-Castell et al., 2021). While SIF has been proven as a good proxy of gross primary productivity (GPP), mainly across large spatial and temporal gradients, a series of studies showed that different factors could confound this relationship, namely different canopy structures (e.g., Dechant et al., 2020; Migliavacca et al., 2017), stress conditions (e.g., Martini et al., 2022; Wieneke et al., 2018; Wohlfahrt et al., 2018), nutritional conditions (Cendrero-Mateo et al., 2015; Martini et al., 2019), species-specific differences (e.g., Van Wittenberghe et al., 2013) and light regimes (e.g., Liu and Liu, 2018). At the same time, the modeling of SIF developed rapidly (Gu et al., 2019a; Han et al., 2022; Han et al., 2021; van der Tol et al., 2014; van der Tol et al., 2009) and with an increasing degree of realism, offering the possibility to retrieve important vegetation parameters from remote sensing (Pacheco-Labrador et al., 2019; Verrelst et al., 2015; Verrelst et al., 2016; Zhang et al., 2014). Excellent and comprehensive reviews of the field are by (Mohammed et al., 2019; Porcar-Castell et al., 2021; Porcar-Castell et al., 2014; Sun et al., 2023a; Sun et al., 2023b). Despite the exponential increase in the number of publications in the field, significant progress is still needed. Here, this special issue aims to report foundational SIF science, including theoretical modeling and measurement-based research that is urgently needed to unleash the full potential of SIF for physiological and ecological applications at scales spanning from leaf to globe. The 14 articles collected in this special issue reported on the following specific aspects: first, technical capabilities enabling spectrally resolved SIF observations and their inter-comparability in space and time; second, theoretical developments in SIF-photosynthesis relationships to correctly interpret the signal and extract mechanistic information on vegetation structure and function; third, evaluation of the potential of SIF to track process beyond photosynthesis, such as transpiration; fourth, large scale-applications of SIF observations; and finally, upscaling fluorescence from leaf to canopy scales.

54 ENVIRONMENTAL SCIENCES↗

SIF-based GPP modeling for evergreen forests considering the seasonal variation in maximum photochemical efficiency

Solar-induced chlorophyll fluorescence (SIF) has shown great potential in estimating gross primary production (GPP). However, their quantitative relationship is not invariant, which undermines the reliability of empirical SIF-based GPP estimation at fine spatiotemporal scales, especially under extreme conditions. In this study, we developed a parsimonious mechanistic model for SIF-based GPP estimation in evergreen needle forests (ENF) by employing the Mechanistic Light Response framework and Eco-Evolutionary theory to describe the light and dark reactions during photosynthesis, respectively. Specifically, we found that considering the seasonal variation in a key parameter of the MLR framework, the maximum photochemical efficiency of photosystem II (Φ PSIImax ), can avoid the GPP overestimation in winter and early spring due to the relatively low environmental sensitivity of SIF. Compared to the estimates from other benchmark models, our GPP estimates were closer to the 1: 1 line and had higher accuracy (average R 2 = 0.86, RMSE=1.99 μmol m -2 s -1 ) across sites. Furthermore, the changes in the relationship between SIF and J (refers to the electron transport rate) contribute a lot to the dynamic SIF–GPP relationship in this study, while the J–GPP relationship is less variant when the temperature drops. Further, the seasonal variation in the SIF–J relationship, especially the reduction in its slope at low temperatures, is found largely explained by the Φ PSIImax . These results indicate the importance of the uncertainty caused by the variation in the SIF–J relationship for SIF-based GPP estimation, and the consideration of changes in Φ PSIImax under extreme conditions (such as severe winter in this study) is crucial for the improvement of GPP estimation via SIF.

59 BASIC BIOLOGICAL SCIENCES↗

Oxidation of n-alkanes using TS-1 and H 2 O 2 : Effects of chain length and solvents

The selective oxidation of n-C 8 H 18 , n-C 12 H 26 , n-C 16 H 34 , n-C 20 H 42 , and n-C 36 H 74 was studied with a goal of using these as models to provide insight into how to functionalize polyolefins. Reactions were carried out using a TS-1 catalyst and H 2 O 2 in a batch reactor with different cosolvents, including methanol, acetone, acetonitrile, methyl ethyl ketone, and methyl butyl ketone. Rates decreased with increasing alkane size, possibly due to the reduced solubility of larger alkanes into the water-rich phases. Cosolvents that promote the partitioning of alkanes in the aqueous phase increased the rates. 1 H NMR spectroscopy demonstrated that ketones were the primary products, although some alcohols also formed. There was preferential reaction at the 2 position in the alkanes, but reaction at central carbons was also observed. The results of this study suggest strategies for using this catalytic chemistry to functionalize polyolefins.

Alkane oxidation↗

A one-pot synthesis of high-density biofuels through bifunctional mesoporous zeolite-encapsulated Pd catalysts

Developing a powerful bifunctional catalyst for tandem reactions is essential to the future carbon neutrality by reducing the energy consumption in chemical industries. Herein, mesoporous zeolite-encapsulated palladium (Pd) nanoparticles (Pd@meso-ZSM-5) synthesized via emulsification-demulsification followed by a dry-gel transformation method were demonstrated to have a remarkable catalytic performance for a one-pot multiple tandem reaction of cyclic ketones (cyclopentanone, cyclohexanone) to bicyclic alkanes (bicyclopentane, bicyclohexane). Compared with supported catalysts (Pd/meso-ZSM-5) and microporous zeolite-encapsulated catalysts (Pd@ZSM-5) with a primary product of monocyclic alkane (cyclopentane, cyclohexane), Pd@meso-ZSM-5 shows much higher catalytic efficiency for the bicyclic alkanes synthesis, which was previously unattainable in the conventional two-step synthesis route. Controlled experiments and detailed characterizations show that mesoporosity provides sufficient space for the generation and diffusion of large molecular intermediates, and the intimate acid-Pd interface promotes the conversion of intermediates. As a result, this work proposes a design strategy for a mesoporous zeolite-encapsulated metal catalyst, which efficiently provides cooperative acid-hydrogenation catalysis.

09 BIOMASS FUELS↗

Coupling hydropyrolysis and vapor-phase catalytic hydrotreatment to produce biomethane from pine sawdust

Here, this study investigated hydropyrolysis and subsequent vapor-phase hydrotreatment over a NiAl 2 O 4 catalyst to produce biomethane (CH 4 ) from pine sawdust. The non-catalytic pressurized hydropyrolysis generated tar, CO 2 , and CO as the primary products. However, using a NiAl 2 O 4 catalyst in the second-stage reactor significantly increased the formation of CH 4 and reduced CO and CO 2 in gas products. The catalyst also fully converted tar intermediates to produce CH 4 , resulting in a maximum carbon yield of 77.7% with 97.8% selectivity. The temperature plays a crucial role in CH 4 generation, with both its yield and selectivity showing a positive correlation with the reaction temperature. Increasing the reaction pressure from 0.2 to 1.2 MPa notably inhibited the production of CH 4 , leading to a shift towards cycloalkanes due to a competitive reaction. This tandem approach shows great potential as an innovative technique for producing alternative fuels from biomass wastes.

09 BIOMASS FUELS↗

Applicability of the Delplot method for the determination of catalytic reaction sequences: Hydrodeoxygenation of $\gamma$-valerolactone on Ni 2 P/MCM-41

Contact-time measurements based on sites are used to investigate the reaction sequence of the hydrodeoxygenation of γ-valerolactone (GVL) on Ni 2 P/MCM-41. Here the study is carried out at 300 °C and 0.5 MPa with site times of 0.29–6.1 s. A reaction network is proposed in which pentanoic acid and 2-methyltetrahydrofuran (2-MTHF) are formed in parallel initially and pentanal, butane and pentane are formed subsequently. A first-rank Delplot analysis (selectivity) gives a good fit, but higher-rank Delplots do not. The lack of applicability is explained by the magnitude of the rate constants, in which the rate constant for one of the later steps (the consumption of pentanal) is substantially larger than those for the preceding steps. For this reason, pentanal demonstrated the characteristics of a primary product and consequently affected the discrimination of higher rank products. A simulation of a model sequence with assumed rate constants confirms the reason why the Delplot method does not work for this reaction. Since the rate constants cannot be determined a priori to be of close magnitude, the Delplot method cannot be generally used to ascertain reaction sequences.

42 ENGINEERING↗

Estimating soybean yields from high-temporal-resolution multi-source data using deep learning

Accurate and timely crop yield prediction is crucial for ensuring food security and maintaining stable agricultural markets. In recent years, there has been a surge in interest in leveraging high-temporal-resolution, multi-source data for effective crop growth monitoring and yield estimation. A notable challenge arises from the difficulty in capturing the intricate interactions between variables across different time steps within these high-temporal-resolution time series datasets. This complexity hinders the reliable extraction of yield information from voluminous and often noisy datasets, especially during periods of extreme weather events. Here, in this study, we propose an Attention and Graph Isomorphism Network-enhanced Bi-directional Long Short-Term Memory network (AGB-LSTM) for estimating county-level soybean yield in the United States. This model integrates a diverse set of remote sensing data, including Near-Infrared Reflectance of Vegetation (NIRv), Sun-Induced chlorophyll Fluorescence (SIF), and Gross Primary Productivity (GPP), along with environmental covariates. The AGB-LSTM effectively leverages information related to crop yield from high-temporal-resolution time series data (5-days), achieving an accuracy of R²= 0.67 and rRMSE = 14.46%. This approach significantly outperforms traditional machine learning methods such as Random Forest (RF) (R²= 0.52, rRMSE = 17.36%) and Bi-LSTM (R²= 0.58, rRMSE = 16.17%). Sensitivity experiments with different time steps and ranges demonstrated that our model could accurately and stably predict yields 1 to 2 months before harvest. Moreover, data with a finer temporal resolution consistently improved prediction performance, resulting in an approximately 20% increase in and an approximately 20% decrease in rRMSE compared to using monthly composites. We also evaluated the robustness of the model under extreme climate events and observed strong performance (R²= 0.50, rRMSE = 21.32%). Finally, yield mapping for major soybean-producing regions in North America in 2023 revealed spatial patterns that closely matched USDA yield reports. Our findings suggest that the AGB-LSTM model is a promising and effective method for estimating yield and has notable potential for global crop yield forecasting.

Deep learning↗

A new phenomenological model to describe root-soil interactions based on percolation theory

In his paper on net primary productivity of terrestrial communities predicted from climatological data, Rosenzweig (1968) argued that variability in productivity is well accounted for by (evapo)-transpiration, and that water from transpiration is, on global scales, the most variable component in the photosynthesis reaction. The goal of this paper is to investigate whether variability in plant growth on local scales and within species is primarily related to transpiration under several scenarios including different terrain curvature, slope aspect, soil characteristics, and climate ranges. Here, we test the hypothesis that this relationship exists because root growth into the surface soil layers (0–2 m) tends to follow paths with minima in resistance, which in turn maximizes water flow and nutrient delivery rates that regulate growth. The set of all connected paths with individual pore-to-pore flow resistances less than a critical, percolating, value forms a cluster with mass fractal dimensionality, d f . We propose that roots follow paths through the 2D percolation cluster, defining the set of all optimal flow paths, making the 2D value of d f from percolation relevant to root fractal dimensionality. The tortuosity of such optimal paths as defined in percolation theory should then relate root length to root radial extent, linking the parameters of root tortuosity and plant productivity. Our analysis of large data sets across species implies that root radial extent and tree height are both proportional to cumulative transpiration until trees approached maximum height, and their growth rates are proportional to the transpiration rate, not to the moisture content. Local variations in tree height as functions of the variables investigated appear generally consistent with deduced variations in transpiration. Here this correlation is investigated more closely in the context of studies addressing individual tree species.

54 ENVIRONMENTAL SCIENCES↗

Solid-phase Mn speciation in suspended particles along meltwater-influenced fjords of West Greenland

Manganese (Mn) is an essential micro-nutrient that can limit or, along with iron (Fe), co-limit phytoplankton growth in the ocean. Glacier meltwater is thought to be a key source of trace metals to high latitude coastal systems, but little is known about the nature of Mn delivered to glacially-influenced fjords and adjacent coastal waters. In this work, we combine in-situ dissolved Mn (dMn) measurements of surface waters with Mn K-edge X-ray absorption spectroscopy (XAS) data of suspended particles in four fjords of West Greenland. Data were collected from transects of up to 100 km in fjords with different underlying bedrock geology from 64 to 70°N. We found that dMn concentrations generally decreased conservatively with increasing salinity (from 80 to 120 nM at salinity < 8 to < 40 nM at salinities > 25). Dissolved Fe (dFe) trends in these fjords similarly declined with increasing distance from glacier outflows (declining from > 20 nM to < 8 nM). However, the dMn/dFe ratio increased rapidly likely due to the greater stability of dMn at intermediate salinities (i.e. 10–20) compared to rapid precipitation of dFe across the salinity gradient. The XAS data indicated a widespread presence of Mn(II)-rich suspended particles near fjord surfaces, with structures akin to Mn(II)-bearing phyllosilicates. However, a distinct increase in Mn oxidation state with depth and the predominance of birnessite-like Mn(IV) oxides was observed for suspended particles in a fjord with tertiary basalt geology. The similar dMn behaviour in fjords with different suspended particle Mn speciation (i.e., Mn(II)-bearing phyllosilicates and Mn(IV)-rich birnessite) is consistent with the decoupling of dissolved and particulate Mn and suggests that dMn concentrations on the scale of these fjords are controlled primarily by dilution of a freshwater dMn source rather than exchange between dissolved and particle phases. This work provides new insights into the Mn cycle in high latitude coastal waters, where small changes in the relative availabilities of dMn, dFe and macronutrients may affect the identity of the nutrient(s) proximally limiting primary production.

58 GEOSCIENCES↗

Photosynthetic adaptation to polar life: Energy balance, photoprotection and genetic redundancy

The persistent low temperature that characterize polar habitats combined with the requirement for light for all photoautotrophs creates a conundrum. The absorption of too much light at low temperature can cause an energy imbalance that decreases photosynthetic performance that has a negative impact on growth and can affect long-term survival. The goal of this review is to survey the mechanism(s) by which polar photoautotrophs maintain cellular energy balance, that is, photostasis to overcome the potential for cellular energy imbalance in their low temperature environments. Photopsychrophiles are photosynthetic organisms that are obligately adapted to low temperature (0⁰- 15 °C) but usually die at higher temperatures (≥20 °C). In contrast, photopsychrotolerant species can usually tolerate and survive a broad range of temperatures (5⁰- 40 °C). First, we summarize the basic concepts of excess excitation energy, energy balance, photoprotection and photostasis and their importance to survival in polar habitats. Second, we compare the photoprotective mechanisms that underlie photostasis and survival in aquatic cyanobacteria and green algae as well as terrestrial Antarctic and Arctic plants. We show that polar photopsychrophilic and photopsychrotolerant organisms attain energy balance at low temperature either through a regulated reduction in the efficiency of light absorption or through enhanced capacity to consume photosynthetic electrons by the induction of O 2 as an alternative electron acceptor. Finally, we compare the published genomes of three photopsychrophilic and one photopsychrotolerant alga with five mesophilic green algae including the model green alga, Chlamydomonas reinhardtii. We relate our genomic analyses to photoprotective mechanisms that contribute to the potential attainment of photostasis. Finally, we discuss how the observed genomic redundancy in photopsychrophilic genomes may confer energy balance, photoprotection and resilience to their harsh polar environment. Primary production in aquatic, Antarctic and Arctic environments is dependent on diverse algal and cyanobacterial communities. Although mosses and lichens dominate the Antarctic terrestrial landscape, only two extant angiosperms exist in the Antarctic. Furthermore, the identification of a single ‘molecular key’ to unravel adaptation of photopsychrophily and photopsychrotolerance remains elusive. Since these photoautotrophs represent excellent biomarkers to assess the impact of global warming on polar ecosystems, increased study of these polar photoautotrophs remains essential.

59 BASIC BIOLOGICAL SCIENCES↗

A quantal diffusion approach for multinucleon transfer in heavy-ion collisions

The stochastic mean-field (SMF) approach beyond the time-dependent-Hartree-Fock theory is used to explore the primary production cross sections in 64 Ni + 130 Te at the bombarding energy E c.m. = 184.3 MeV and 206 Pb + 118 Sn at E c.m. = 436.8 MeV. Secondary production cross-sections in the same systems are calculated using a statistical de-excitation model with GEMINI++ code. Furthermore, the obtained results are compared with available experimental data. Analysis employing SMF and GEMINI++ exhibit a good agreement with the experimental data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Plankton energy flows using a global size-structured and trait-based model

Plankton community models are critical tools for understanding the processes that shape marine plankton communities, how plankton communities impact biogeochemical cycles, and the feedbacks between community structure and function. Here, using the flexible Marine Biogeochemistry Library (MARBL), we present the Size-based Plankton ECological TRAits (MARBL-SPECTRA) model, which is designed to represent a diverse plankton community while remaining computationally tractable. MARBL-SPECTRA is composed of nine phytoplankton and six zooplankton size classes represented using allometric scaling relationships for physiological traits and interactions within multiple functional types. MARBL-SPECTRA is embedded within the global ocean component of the Community Earth System Model (CESM) and simulates large-scale, emergent patterns in phytoplankton growth limitation, plankton phenology, plankton generation time, and trophic transfer efficiency. The model qualitatively reproduces observed global patterns of surface nutrients, chlorophyll biomass, net primary production, and the biogeographies of a range of plankton size classes. In addition, the model simulates how predator:prey dynamics and trophic efficiency vary across gradients in total ecosystem productivity. Shorter food chains that export proportionally more carbon from the surface to the ocean interior occur in productive, eutrophic regions, whereas in oligotrophic regions, the food chains are relatively long and export less organic matter from the surface. The union of functional type modeling with size-resolved, trait-based modeling approaches allows MARBL-SPECTRA to capture both large-scale elemental cycles and the structure of planktonic food webs affecting trophic transfer efficiency.

59 BASIC BIOLOGICAL SCIENCES↗

Pulse radiolysis and transient absorption spectra of aqueous solutions of sodium sulfamate

Chemical kinetics for the reactions of sulfamate ions (NH 2 SO 3 − ) with the primary products of water and nitric acid radiolysis were measured in aqueous solutions at ambient temperature. Using time-resolved electron pulse radiolysis techniques with a custom multichannel detection system, we examined the reactivity of NH 2 SO 3 − with the hydroxyl radical ( • OH), hydrogen atom (H • ), and nitrate radical (NO 3 • ). The sulfamate ion was found to react with • OH and H • with second-order rate coefficients of k • OH = (5.60 ± 0.04) × 10 6 M −1 s −1 and k H • = (7.96 ± 0.10) × 10 6 M −1 s −1 , respectively, and with NO 3 • with a rate coefficient of k NO 3 • = (1.67 ± 0.06) × 10 7 M −1 s −1 . The reactions of NH 2 SO 3 − with • OH and H • resulted in the formation of two transient radical species, one with maximum absorbance at 300 nm and a second with maxima at both 300 nm and 600 nm. These spectra are tentatively assigned to • NH 2 SO 3 and • NHSO 3 − , respectively. By measuring the absorbance of these radicals as a function of pH, the radical pK a was determined to be 9.5 ± 0.1. Overall, this work has implications for the longevity and performance of ferrous sulfamate, Fe(NH 2 SO 3 ) 2 , as a plutonium reductant in the reprocessing of used nuclear fuel.

Conrad, Jacy K. [Idaho National Laboratory (INL), ↗

A radiative transfer model for solar induced fluorescence using spectral invariants theory

Solar Induced chlorophyll Fluorescence (SIF) shows promise as an approach for estimating gross primary production (GPP) remotely. However, sun-target-sensor geometry and within-canopy absorption of SIF can alter the relationship between measured SIF and GPP, because sensors can only retrieve some unknown fraction of the total emitted SIF. Radiative transfer models that allow for variation in canopy structure and sensor angles are therefore needed to properly interpret SIF measurements. Spectral invariants allow decoupling of the wavelength-independent canopy structure and the wavelength-dependent leaf and soil spectrum in the radiative transfer process. Here we develop a simple analytical Fluorescence Radiative Transfer model based on Escape and Recollision probability (FluorRTER) to investigate the impact of canopy structure and sun-target-sensor geometry on SIF emissions. SIF simulations using the FluorRTER model agreed well the one-dimensional Soil-Canopy Observation of Photochemistry and Energy balance (SCOPE) model and the three-dimensional Fluorescence model with Weighted Photon Spread (FluorWPS) model. The fractional vegetation cover (FVC) and clumping effect have a large influence the SIF emission of 3D discontinuous canopies. For a moderate solar zenith angle (30°) and a clumped canopy (FVC?=?0.6), the difference between the directional observed SIF of a 3D discontinuous canopy and a 1D homogeneous canopy was as large as 43.2% and 38.4% for Photosystem I?+?II fluorescence at 685?nm and at 740?nm, respectively. By bridging the gap between observed SIF and total emitted SIF over 3D heterogeneous vegetation canopies, the FluorRTER model can assist with the angular normalization of SIF measurements and enable the more robust interpretation of how variations in SIF from directional and hemispherical in-situ, airborne and satellite observations relate to leaf and whole-canopy physiological processes.

Zeng, Yelu↗