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DOE OSTI2022

Binder-Free Wood Converted Carbon for Enhanced Water Desalination Performance

Here, the design and synthesis of high-performance and economical carbon electrodes play a critical role in developing energy-efficient water desalination technologies. As a sustainable approach, low-cost and abundant biomass materials are promising candidates to prepare porous carbon for capacitive deionization. In this study, binder-free porous carbon sheets are successfully prepared using natural balsa, pine, and basswood by thermal carbonization and treated by chemical activation. The carbon electrode materials converted from balsa and pine exhibit a comparable salt adsorption performance by capacitive deionization due to the extensive surface area, substantial electrical property, and superior hydrophilic performance. The following activation treatment of the balsa-converted carbon further enhances the surface and electrical properties and benefits the desalination performance. The salt adsorption capacity of the activated balsa electrode exhibits 12.45 mg g -1 . Additionally, 19.52 mg g -1 Pb 2+ and 20.06 mg g -1 Cr 3+ heavy metal adsorption capacity is also observed with the activated balsa electrode in 100 mg L -1 PbCl 2 and 50 mg L -1 CrCl 3 , respectively. To the best of authors’ knowledge, this is the highest NaCl adsorption capacity performance reported thus far by using pure wood converted carbon as the electrode, and these promising results indicate that activated balsa is an extraordinary material for water desalination.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Briquetting characteristics of woody and herbaceous biomass blends: Impact on physical properties, chemical composition, and calorific value

Abstract Intercropping (or polyculture) is gaining a lot of interest as it increases yields, allows better utilization of resources (water and nutrients), and provides better land management. The objective of this study is to understand the briquetting characteristics of woody and herbaceous biomass blends, which might result from intercropping. Tests were conducted on blends of lodgepole pine, switchgrass, and corn stover biomass using three hammer mill screen sizes (i.e., 4.8, 12.7, and 19.05 mm), three blend moistures (12%, 15%, and 18%, w.b.), and two‐ and three‐blend ratios (i.e., 1:1 and 1:1:1) using a pilot‐scale hydraulic briquette press. The briquette properties, such as unit and bulk density, durability rating after 5 days of storage (as they tend to attain stable density), and the energy consumption of the process were measured. The results indicate that moisture content of 12% and 15% (w.b.) and smaller hammer mill screen size of 4.8 mm increased the unit and bulk densities to >750 and >430 kg/m 3 and moisture content (15% and 18% (w.b.)) and hammer mill screen size of 12.7 and 19.05 mm produced briquettes with durability rating values of >95%. The higher moisture content of 18% (w.b.) and the hammer mill screen size of 12.7 and 19.05 mm had the highest energy consumption. The proximate and ultimate analysis showed that energy content improved by blending lodgepole pine with both corn stover and switchgrass and also showed increased calorific value and reduced ash content. Scanning electron microscopy micrographs showed interlocking of particles and cracks in the briquettes. © 2020 Society of Chemical Industry and John Wiley & Sons, Ltd

Tumuluru, Jaya Shankar↗

DOE OSTI2015

Prolonged experimental drought reduces plant hydraulic conductance and transpiration and increases mortality in a piñon–juniper woodland

Abstract Plant hydraulic conductance ( k s ) is a critical control on whole‐plant water use and carbon uptake and, during drought, influences whether plants survive or die. To assess long‐term physiological and hydraulic responses of mature trees to water availability, we manipulated ecosystem‐scale water availability from 2007 to 2013 in a piñon pine ( Pinus edulis ) and juniper ( Juniperus monosperma ) woodland. We examined the relationship between k s and subsequent mortality using more than 5 years of physiological observations, and the subsequent impact of reduced hydraulic function and mortality on total woody canopy transpiration ( E C ) and conductance ( G C ). For both species, we observed significant reductions in plant transpiration ( E ) and k s under experimentally imposed drought. Conversely, supplemental water additions increased E and k s in both species. Interestingly, both species exhibited similar declines in k s under the imposed drought conditions, despite their differing stomatal responses and mortality patterns during drought. Reduced whole‐plant k s also reduced carbon assimilation in both species, as leaf‐level stomatal conductance ( g s ) and net photosynthesis ( A n ) declined strongly with decreasing k s . Finally, we observed that chronically low whole‐plant k s was associated with greater canopy dieback and mortality for both piñon and juniper and that subsequent reductions in woody canopy biomass due to mortality had a significant impact on both daily and annual canopy E C and G C . Our data indicate that significant reductions in k s precede drought‐related tree mortality events in this system, and the consequence is a significant reduction in canopy gas exchange and carbon fixation. Our results suggest that reductions in productivity and woody plant cover in piñon–juniper woodlands can be expected due to reduced plant hydraulic conductance and increased mortality of both piñon pine and juniper under anticipated future conditions of more frequent and persistent regional drought in the southwestern United States.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Life Cycle Analysis of Decentralized Preprocessing Systems for Fast Pyrolysis Biorefineries with Blended Feedstocks in the Southeastern United States

Blending biomass feedstock is an enticing approach to mitigate supply chain risks that are common challenges for large-scale biomass utilization. Understanding the potential environmental benefits of biofuels produced from blended biomass and identifying driving parameters are critical for the supply chain design. Herein, a cradle-to-gate life cycle analysis model for fast pyrolysis biorefineries converting blended feedstocks (pine residues and switchgrass) with traditional centralized and alternative decentralized preprocessing sites, so-called depots, is explained. Different scenarios are developed to investigate the impacts of parameters such as feedstock blending ratios, biorefinery and depot capacities, preprocessing technologies, and allocation methods. The life-cycle energy consumption and global warming potential (GWP) of biofuel production with depots vary between 0.7–1.1 MJ MJ -1 and 43.2–76.6 g CO 2 eq. MJ -1 , respectively. The results are driven by biorefinery processes and depot preprocesses. A decentralized design reduces the energy consumption of the biorefinery but increases the overall life-cycle energy and GWP. Such increases can be significantly mitigated by increasing switchgrass content as the energy consumption at the depot is driven largely by the higher moisture content of pine feedstocks. Allocation methods have a further impact on the results but do not change the major trends and overall conclusions.

09 BIOMASS FUELS↗

DOE OSTI2021

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

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

Fegel, Timothy S.↗

DOE OSTI2022

Effects of trunk injection with emamectin benzoate on arthropod diversity

Abstract BACKGROUND Pine wood nematode is a major plant quarantine object in the world. Trunk injection is an effective method for controlling pests that cause disease. To evaluate the ecological safety of trunk injection with emamectin benzoates in forests of Pinus massoniana , the community diversity and community composition of soil arthropods and flying insects (Hymenoptera) were studied at different stages of trunk injection. RESULTS The dominant taxonomic groups of soil arthropods were Collembola (30.80%), Insecta (26.42%), and Arachnida (23.84%). The taxonomic groups of flying insects (Hymenoptera) were Ichneumonidae (48.94%), Formicidae (14.10%), and Braconidae (8.44%). Trunk injection with emamectin benzoate has no significant effect on the community diversity indices of total soil arthropods and flying insects (Hymenoptera). However, it has a significant effect on the community diversity indices of detritivores for soil arthropods. It changed the community composition of soil arthropods but did not impact the community composition of flying insects (Hymenoptera). Redundancy analysis of arthropod community structure and environmental variables showed that total potassium, residual of green leaf, and residual of litter leaf have a significant impact on the community structure of soil arthropods, and total phosphorus, total nitrogen, water content, organic matter, and total potassium have a significant impact on the community structure of flying insects (Hymenoptera). CONCLUSION Trunk injection with emamectin benzoate is safe for the ecological environment. This study provides a new insight into the field for the prevention and control of pine wood nematode disease, which is of great significance to forest management and pest control. © 2022 Society of Chemical Industry.

Ouyang, Xianheng↗

DOE OSTI2015

Microbial lipid production by oleaginous Rhodococci cultured in lignocellulosic autohydrolysates

Metabolic synthesis of single cell oils (SCOs) for biodiesel application by heterotrophic oleaginous microorganisms is being hampered by the high cost of culture media. This study investigated the possibility of using loblolly pine and sweetgum autohydrolysates as economic feedstocks for microbial lipid production by oleaginous Rhodococcus opacus ( R. opacus ) PD630 and DSM 1069. Results revealed that when the substrates were detoxified by the removal of inhibitors (such as HMF—hydroxymethyl-furfural), the two strains exhibited viable growth patterns after a short adaptation/lag phase. R. opacus PD630 accumulated as much as 28.6 % of its cell dry weight (CDW) in lipids while growing on detoxified sweetgum autohydrolysate (DSAH) that translates to 0.25 g/l lipid yield. The accumulation of SCOs reached the level of oleagenicity in DSM 1069 cells (28.3 % of CDW) as well, while being cultured on detoxified pine autohydrolysate (DPAH), with the maximum lipid yield of 0.31 g/l. The composition of the obtained microbial oils varied depending on the substrates provided. These results indicate that lignocellulosic autohydrolysates can be used as low-cost fermentation substrates for microbial lipid production by wild-type R. opacus species. Furthermore, the variety of applications for aqueous liquors from lignocellulosic pretreatment has been expanded, allowing for the further optimization of the integrated biorefinery.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Evaluation of engineered sorbents for the sorption of mercury from contaminated bank soils: a column study

Abstract As a global environmental pollutant, mercury (Hg) threatens our water resources and presents a substantial risk to human health. The rate and extent of immobilization of Hg 2+ (hereafter, Hg) on engineered sorbents (Thiol-SAMMS®, pine biochar, SediMite™, Organoclay™ PM-199, and quartz sand as a control) was evaluated using flow-through column experiments. The effectiveness of the sorbents was based on (1) the percentage of Hg removed in relation to the total amount of Hg passing the sorbent column, and (2) the rate of Hg uptake compared to the nonreactive tracer bromide (Br − ). All sorbents removed Hg to a certain extent, but none of the sorbents removed all the Hg introduced to the columns. Thiol-SAMMS showed the highest mean percentage of Hg removed (87% ± 2.9%), followed by Organoclay PM-199 (71% ± 0.4%), pine biochar (57% ± 22.3%), SediMite (61% ± 0.8%), and the control quartz sand (11% ± 5.6%). Thiol-SAMMS was the only sorbent to exhibit retardation of Hg in comparison to the conservative tracer Br − . For the remaining sorbents, Br − along with low concentrations of Hg were eluted within the first 3 pore volumes, indicating limited retardation of Hg. Overall, removal of Hg by sorbents was substantial, suggesting that sorbents might be suitable for deployment in contaminated environments. High concentrations of DOM leaching from the soil columns likely influenced the speciation of Hg and inhibited sorption to the sorbents. Incomplete removal of Hg by any sorbent suggests that additional optimization is needed to increase efficiency.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Allometric relationships between primary size measures and sapwood area for six common tree species in snow-dependent ecosystems in the Southwest United States

High-elevation, snow-dependent, semiarid ecosystems across southwestern United States are expected to be vulnerable to climate change, including drought and fire, with implications for various aspects of the water cycle. To that end, much less is known about the dynamics of transpiration, an important component of the water cycle across this region. At the individual-tree scale, transpiration is estimated by scaling mean sap flux density by the hydroactive sapwood area (SA). SA also remains a key factor in effectively scaling individual tree water-use to stand level. SA across large spatial scales is normally established by relating SA of a few trees to primary size measures, e.g., diameter at breast height (DBH), tree height ( H ), or canopy diameter (CD). Considering the importance of SA in scaling transpiration, the primary objective of this study was therefore to establish six species-specific (aspen, maple, white fir, ponderosa pine, Douglas fir, Englemann spruce) allometric relationships between SA and three primary size measures (DBH, CD, or H ) across two high-elevation, snow-dependent, semiarid ecosystems in New Mexico and Arizona. Based on multiple statistical criteria (coefficient of determination, index of agreement, Nash–Sutcliffe efficiency) and ease of measurement in the forest, we identified DBH as the primary independent variable for estimating SA across all sites. Based on group regression analysis, we found allometric relationships to be significantly ( p < 0.05) different for the same species (ponderosa pine, Douglas-fir) across different sites. Overall, our allometric relationships provide a valuable database for estimating transpiration at different spatial scales from sap flow data in some of our most vulnerable ecosystems.

Forestry↗

DOE OSTI2025

Enhancing the flowability of woody biomass slurries in wet biorefineries

Feeding wet lignocellulosic biomass (e.g., softwood and hardwood) slurries into high-pressure, high-temperature reactors at an industrially relevant scale presents significant challenges, such as process equipment plugging. Here, in this study, we investigate the possibility of improving the flowability of biomass slurries in an industrial scale wet biorefinery by tuning the physical and chemical characteristics of the biomass particles. To understand the effects of the chemical characteristics of woody biomass on flowability, cellulose pulp particles are produced from pulp sheets via knife milling, pelletizing, and crumbling. These cellulose pulp particles are processed for acid hydrolysis dehydration (AHDH) at one –tonne-per day pilot scale. The levulinic acid yield (a product of cellulose AHDH) and the flowability of the biomass particles are compared using market pulp, 1 mm crumbled pine softwood, a blend of 2 mm hammer-milled pine softwood with 10 wt.% bark, and 2 mm hammer-milled hardwood material with 10 wt.% bark (to represent forest residues). The results indicate that the presence of hemicellulose and lignin influences the flowability of lignocellulosic feedstocks. Crumbled wood particles show poor flowability at the pilot scale, while the presence of fine materials (less than 0.7 mm) and bark improves the flowability of biomass slurries without affecting the organic acid yields (based on C6 carbohydrate content).

09 - BIOMASS FUELS↗

DOE OSTI2018

Restoring ZSM-5 performance for catalytic fast pyrolysis of biomass: Effect of regeneration temperature

Zeolite catalysts used for biomass catalytic fast pyrolysis (CFP) deactivate rapidly, similar to a fluidized catalytic cracking (FCC) catalyst used in refining. To operate effectively when there is rapid deactivation, biomass CFP can take place in a riser FCC-style reactor in which the catalyst has a short contact time (seconds) with reactants before it is regenerated. The regeneration, therefore, has two major needs for effective operation: 1) heat balance, since the heat required for the CFP reactions is brought into the reactor by the hot catalyst and 2) relatively short (minutes) regeneration to restore the catalyst activity to be near its initial state. In order to understand effective conditions to regenerate zeolites used for CFP, a series of experiments were performed to determine the effect of regeneration temperature on the activity of ZSM-5 (SiO 2 /Al 2 O 3 = 30). After use for pine pyrolysis vapor upgrading, the catalyst was oxidized in 4% O 2 at temperatures between 500-700 °C and reevaluated for the upgrading of pine pyrolysis vapors to assess the extent of regeneration. Additional testing was performed using ethylene aromatization as a surrogate reaction to probe regeneration efficiency. Regeneration experiments were performed for either a fixed length of time (20 min) or until there was no further CO 2 measured in the effluent gas. Results from the ethylene aromatization reactions were shown to serve as an excellent surrogate for CFP reactivity and indicated that the use of model compound studies can effectively be used to understand reaction and regeneration processes from biomass CFP. Both sets of results indicate that a spent ZSM-5 used for biomass CFP could be fully regenerated at 650 degrees C and 700 °C within 20 min, whereas regeneration temperatures of 550 °C and 600 °C required longer regeneration temperatures and in the case of regeneration at 500 °C, there may be coke species that are not removed and the catalyst activity may never be fully restored. Characterization by pyridine diffuse reflectance infrared spectroscopy, thermogravimetric analysis coupled with infrared spectroscopy, and N 2 physisorption showed that higher regeneration temperatures are more effective for restoring Bronsted acid sites and catalyst mesoporosity by rapidly removing aromatic coke deposits. In conclusion, regeneration at 650 °C and 700 °C led to a slightly higher total porosity as compared to the pristine catalyst, which was attributed to the formation of additional mesoporosity from catalyst steaming.

09 BIOMASS FUELS↗

DOE OSTI2024

Investigation of Cyrene organosolv fractionation of softwood biomass and alkaline post-incubation

Cyrene organosolv fractionation effectively extracted 78% of lignin from recalcitrant softwood biomass pine at a mild temperature of 120°C. However, the enzymatic conversion of the fractionated cellulose-rich solid did not improve significantly. Alkali post-incubation of the fractionated cellulose fraction notably enhanced the glucan conversion. This phenomenon has also been observed in other organosolv processes, but how this approach transforms pretreated biomass has not yet been comprehensively investigated. In this study, small-angle X-ray scattering (SAXS) was employed to understand the structural changes in biomass during fractionation and post-incubation at the nanometer scale. Further, no lignin aggregation was found on the microfibrils, whereas the distance between the microfibrils increased after pretreatment and decreased after alkaline post-incubation. These results suggests that the Cyrene molecules remained between the microfibrils and were removed by post-incubation. In addition, the pine lignin recovered after pretreatment was characterized by NMR to understand the impact of Cyrene pretreatment on the lignin structure.

09 BIOMASS FUELS↗

DOE OSTI2025

Synergistic torrefaction of plastic polymers and biomass

This study explores the synergistic torrefaction of biomass and plastics, aimed at enhancing bioenergy production and promoting a circular economy. By leveraging the unique properties of both materials, we investigated the thermochemical transformations occurring during the torrefaction process, from material preparation to the final characteristics of the torrefied product. The biomass used included corn stover (CS) and loblolly pine (LP), while various plastics were categorized from #1 to #7. Torrefaction was conducted at temperatures of 200, 225, and 250 °C, with subsequent extrusion of the torrefied materials and raw materials to produce composite filaments. The results show a consistent decrease in mass yield with increased torrefaction temperature, with notable variations among different biomass-plastic combinations. Co-torrefaction of biomass with polyvinyl chloride and polypropylene resulted in accelerated reaction kinetics, with an observed mass loss rate increase of 15 % at 250 °C compared to the expected rates for individual components. This synergy was quantified, indicating a 20.3 % increase in mass loss for the loblolly pine-polypropylene combination and 23.9 % for corn stover-polypropylene. In contrast, other plastics, including polyethylene terephthalate, high-density polyethylene, low-density polyethylene, polystyrene, and polycarbonate, did not exhibit significant synergistic effects. Mechanical testing indicated that the torrefaction process alters the strength and brittleness of the resulting materials, with implications for their application in bioenergy production and bio-renewable materials. Overall, this research highlights the potential of synergistic torrefaction as a viable strategy for co-processing biomass and plastics, paving the way for innovative solutions in waste management and renewable energy resource development.

09 - BIOMASS FUELS↗

DOE OSTI2025

Wood template-supported phase change material composites for durable and form-stable thermal energy storage in buildings

Here, to reduce and shift peak energy loads in buildings, phase change materials (PCMs) with high transition enthalpies and transition temperatures near human thermal comfort are desirable for thermal energy storage (TES). Traditional solid/liquid PCMs suffer from leakage during thermal cycling, requiring encapsulation that lowers heat storage capacity. Wood templates (WTs), with porous and hierarchical structures, provide natural encapsulation scaffolds for PCM containment. Polyethylene glycol (PEG) is a compatible PCM with WTs, but when infiltrated alone, ~30 wt% of PEG binds to wood with no detectable phase change, limiting TES efficiency. To address this, we developed a method to (1) improve the form stability of balsa and pine-based composites (BWT + PCMs and PWT + PCMs) and (2) reduce inactive PCM within the composites to ~10 wt%. BWT + PCMs exhibit transition properties upwards of 114.2 J/g at 25.4 degrees C, with no degradation after 1000 thermal cycles, and similar stiffness compared to raw balsa. Meanwhile, PWT + PCMs exhibit 25 % higher storage efficiency with the addition of poly(ethylene glycol) diacrylate compared to solely PEG-infiltrated PWT. PWT + PCM retains 84 % of raw pine's mechanical stiffness, sufficient for light-duty construction. Our shape-stabilized WT + PCM composites enrich the functionality of wood materials as both ideal TES material candidates and light-duty building construction applications.

25 ENERGY STORAGE↗

DOE OSTI2016

Size, shape and flow characterization of ground wood chip and ground wood pellet particles

Size, shape and density of biomass particles influence their transportation, fluidization, rates of drying and thermal decomposition. Pelleting wood particles increases the particle density and reduces the variability of physical properties among biomass particles. In this study, pine chips prepared for pulping and commercially produced pine pellets were ground in a hammer mill using grinder screens of 3.2, 6.3, 12.7 and 25.4mmperforations. Pellets consumed about 7 times lower specific grinding energy than chips to produce the same size of particles. Grinding pellets produced the smaller particles with narrower size distribution than grinding chips. Derived shape factors in digital image analysis showed that chip particles were rectangular and had the aspect ratios about one third of pellet particles. Pellet particles were more circular shape. The mechanical sieving underestimated the actual particle size and did not represent the size of particles correctly. Instead, digital imaging is preferred. Angle of repose and compressibility tests represented the flow properties of ground particles. Pellet particles made a less compacted bulk, had lower cohesion and did flow easier in a pile of particles. In conclusion, particle shape affected the flow properties more than particle size

09 BIOMASS FUELS↗

DOE OSTI2018

Inhibitory effects of lignin on enzymatic hydrolysis: The role of lignin chemistry and molecular weight

Lignocellulose is a promising feedstock for biofuel production, while lignin poses a grand challenge on the entire process, especially enzymatic hydrolysis. In this study, different types of lignin inhibited enzymatic hydrolysis by different mechanisms. Organosolv lignin from Loblolly pine adsorbed enzyme nonproductively and reduced the available enzyme for cellulose, therefore decreasing hydrolysis rate and ultimate sugar yield. Kraft pine lignin precipitated on the surface of cellulose, preventing it from contacting with enzyme. The molecular weight influenced the inhibition effect of lignin. Lignin of lower molecular weight could bind enzyme nonproductively and when the molecular weight increased, the steric repulsion caused by lignin deposition on cellulose became more significant. The NMR analysis revealed that lignin structural features, e.g., functional groups, S/G ratio, determined the behaviors of lignin in enzymatic hydrolysis. High content of aliphatic hydroxyl groups, or low content of carboxylic groups led to high surface hydrophobicity, increasing the adsorption between lignin and enzyme. In addition, the substrate reactivity is also an important factor that affects enzymatic hydrolysis. Cellulose with higher crystallinity exhibited slower hydrolysis rate and lower conversion. When the crystallinity index increased from 0.43 to 0.72 and 0.81, the ultimate conversion decreased from 80 to 68% and 57%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Airborne measurements of isoprene and monoterpene emissions from southeastern U.S. forests

Isoprene and monoterpene emission rates are essential inputs for atmospheric chemistry models that simulate atmospheric oxidant and particle distributions. Process studies of the biochemical and physiological mechanisms controlling these emissions are advancing our understanding and the accuracy of model predictions but efforts to quantify regional emissions have been limited by a lack of constraints on regional distributions of ecosystem emission capacities. We used an airborne wavelet-based eddy covariance measurement technique to characterize isoprene and monoterpene fluxes with high spatial resolution during the 2013 SAS (Southeast Atmosphere Study) in the southeastern United States. The fluxes measured by direct eddy covariance were comparable to emissions independently estimated using an indirect inverse modeling approach. Isoprene emission factors based on the aircraft wavelet flux estimates for high isoprene chemotypes (e.g., oaks) were similar to the MEGAN2.1 biogenic emission model estimates for landscapes dominated by oaks. Aircraft flux measurement estimates for landscapes with fewer isoprene emitting trees (e.g., pine plantations), were about a factor of two lower than MEGAN2.1 model estimates. The tendency for high isoprene emitters in these landscapes to occur in the shaded understory, where light dependent isoprene emissions are diminished, may explain the lower than expected emissions. This result demonstrates the importance of accurately representing the vertical profile of isoprene emitting biomass in biogenic emission models. Airborne measurement-based emission factors for high monoterpene chemotypes agreed with MEGAN2.1 in landscapes dominated by pine (high monoterpene chemotype) trees but were more than a factor of three higher than model estimates for landscapes dominated by oak (relatively low monoterpene emitting) trees. This results suggests that unaccounted processes, such as floral emissions or light dependent monoterpene emissions, or vegetation other than high monoterpene emitting trees may be an important source of monoterpene emissions in those landscapes and should be identified and included in biogenic emission models.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

Dissolved organic matter reduces the effectiveness of sorbents for mercury removal

Mercury (Hg) contamination of soils and sediments impacts numerous environments worldwide and constitutes a challenging remediation problem. In this study, we evaluate the impact of dissolved organic matter (DOM) on the effectiveness of eight sorbent materials considered for Hg remediation in soils and sediments. The materials include both engineered and unmodified materials based on carbon, clays, mesoporous silica and a copper alloy. Initially, we investigated the kinetics of Hg(II) complexation with DOM for a series of Hg:DOM ratios. Steady-state Hg-DOM complexation occurred within 48 to 120 h, taking longer time at higher Hg:DOC (dissolved organic carbon) molar ratios. In subsequent equilibrium experiments, Hg(II) was equilibrated with DOM at a defined Hg:DOC molar ratio (2.4 · 10 –6 ) for 170 h and used in batch experiments to determine the effect of DOM on Hg partition coefficients and sorption isotherms by comparing Hg(II) and Hg-DOM. Hg sorption capacities of all sorbents were severely limited in the presence of DOM as a competing ligand. Thiol-SAMMS®, SediMite™ and pine biochar were most effective in reducing Hg concentrations. While pine biochar and lignin-derived carbon processed at high temperatures released negligible amounts of anions into solution, leaching of sulfate and chloride was observed for most engineered sorbent materials. Sulfate may stimulate microbial communities harboring sulfate reducing bacteria, which are considered one of the primary drivers of microbial mercury methylation in the environment. Here, the results highlight potential challenges arising from the application of sorbents for Hg remediation in the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗